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

Abstract

To provide a carboxylate that can produce a resist pattern having excellent CD uniformity (CDU), a carboxylic acid generator and a resist composition comprising the same.SOLUTION: The present invention discloses, for example, a carboxylate represented by formula (I-2).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. TIFF0007716900000001.tif2643 Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator. TIFF0007716900000002.tif2579 Patent Document 3 describes a resist composition containing a salt represented by the following formula as an acid generator. TIFF0007716900000003.tif2786 Patent Document 4 describes a resist composition containing a salt represented by the following formula as an acid generator. TIFF0007716900000004.tif2687

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention provides a carboxylate salt that forms a resist pattern with better CD uniformity (CDU) 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] A carboxylate salt represented by formula (I). TIFF0007716900000005.tif85118[In formula (I), R 1 , R 2 and R 3 each independently represents -O-R 10 [[ID=2l]]-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 represents a halogen atom, a fluorinated alkyl 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 -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. R 10 represents an acid-stable hydrocarbon group. X 1 , X 2 and X 3 each independently represents an oxygen atom or a sulfur atom. m1 represents any integer from 1 to 5, and when m1 is 2 or more, the groups within multiple parentheses may be the same or different from each other. m2 represents any integer from 0 to 5, and when m2 is 2 or more, the groups within multiple parentheses may be the same or different from each other. m3 represents an 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, the plurality of Rs 10 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 the -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. [2] X 1 , X 2 and X 3 is an oxygen atom, and the carboxylate salt according to [1]. [3] R 1 , R 2 and R 3 is -O-CO-O-R 10 or -O-L 1 -CO-O-R 10 and the carboxylate salt according to [1] or [2]. [4] R 10The carboxylate salt according to any one of [1] to [3], wherein the acid-stable hydrocarbon group is a group represented by the formula (3a). TIFF0007716900000006.tif2057[In the formula (3a), R 1a and R 2a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R 1a and R 2a are bonded to each other to form a hydrocarbon ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms. R 3a represents a hydrogen atom, or R 1a and R 2a and R 3a are bonded to each other to form a hydrocarbon ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms. * represents a bond.] [5] The carboxylate salt according to any one of [1] to [4], wherein m1 is 1 or 2, and m2 and m3 are each 0 or 1. [6] The carboxylate salt according to any one of [1] to [5], wherein either m2 or m3 is 0, and when m2 is 0, m8 is 1, and when m3 is 0, m9 is 1. [7] When m2 is 0, the bonding position of R 8 is in the p-position with respect to the bonding position of S + , and when m3 is 0, the bonding position of R 9 is in the p-position with respect to the bonding position of S + The carboxylate salt according to [6]. [8] X 0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that -CH2- contained in the aliphatic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. The carboxylate salt according to any one of [1] to [7]. [9] X 0is a carboxylate salt according to any one of [1] to [8], which is an alicyclic hydrocarbon group having 3 to 36 carbon atoms that may have a fluorine atom or a hydroxy group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or an aromatic hydrocarbon group having 6 to 36 carbon atoms that may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms.

[10] X 0 is a carboxylate salt according to any one of [1] to [9], which is an aromatic hydrocarbon group having 6 carbon atoms that may have a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 4 carbon atoms.

[11] X 0 is a carboxylate salt according to any one of [1] to [9], which is a group represented by formula (aa). TIFF0007716900000007.tif2737[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms that 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 that may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. * represents the bonding position to the carbon atom of -COO - .]

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

[11] .

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

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

[14] The resist composition according to

[13] , wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). TIFF0007716900000008.tif46102[In formulas (a1-1) and (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -CO-O-, k1 represents an integer from 1 to 7, and * represents the bonding position to -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 from 0 to 14. n1 represents an integer from 0 to 10. n1’ represents an integer from 0 to 3.]

[15] The resist composition according to

[13] or

[14] , wherein the resin having an acid-labile group contains a structural unit represented by formula (a2-A). TIFF0007716900000009.tif4653[In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or * -X a51 -(A a52 -X a52 ) nb -, * is -R a50represents the bonding site with the carbon atom to which it is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents 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.

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

[13] to

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

Advantages of the Invention

[0006] By using the resist composition using the carboxylate of the present invention, a resist pattern can be manufactured with good CD uniformity (CDU).

Modes for Carrying Out the Invention

[0007] In this specification, the term “(meth)acrylic monomer” means “at least one of acrylic monomers and methacrylic monomers”. Expressions such as “(meth)acrylate” and “(meth)acrylic acid” also represent the same meaning. Among the groups described in this specification, those that can take both a linear structure and a branched structure may be either of them. When -CH2- contained in a hydrocarbon group or the like is replaced by -O-, -S-, -CO- or -SO2-, the same examples shall 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 “derived” 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. In this specification, the “solid content of the resist composition” means the total of the components excluding the solvent (E) described later from the total amount of the resist composition.

[0008] [Carboxylate represented by formula (I)] The present invention relates to a carboxylate represented by formula (I) (hereinafter sometimes referred to as “salt (I)”). Among salts (I), the side having a negative charge may be referred to as “anion (I)”, and the side having a positive charge may be referred to as “cation (I)”. TIFF0007716900000010.tif85118[wherein all the symbols have the same meanings as described above.]

[0009] In formula (I), R 1 , R 2 and R 3 The alkane diyl group in L 1 contained in includes 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 Examples of the branched alkanediyl group include an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. L 1 is preferably an alkanediyl group having 1 to 3 carbon atoms, more preferably a methylene group.

[0010] R 1 , R 2 and R 3 The acid-stable hydrocarbon group of R contained in 10 means a group in which the group represented by R does not leave even when contacted with an acid (for example, trifluoromethanesulfonic acid). 10 As the acid-stable hydrocarbon group, a group represented by the formula (3a) (hereinafter, sometimes referred to as "acid-stable hydrocarbon group (3a)") is preferable. TIFF0007716900000011.tif2057[In the formula (3a), R 1a and R 2a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R 1a and R 2a are bonded to each other to form a hydrocarbon ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms. R 3a represents a hydrogen atom, or R 1a and R 2a and R 3a are bonded to each other to form a hydrocarbon ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms. * represents a bond.]

[0011] R 1a and R 2a Examples of the hydrocarbon group of 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 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 and the like. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 1 to 12, more preferably 1 to 9, still more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 2. The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include the groups represented below. The bonding site can be at any position. TIFF0007716900000012.tif44168Specifically, examples of the alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, and polycyclic cycloalkyl groups such as norbornyl group and adamantyl group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and 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, and still more preferably 6 to 10.

[0012] Examples of the group formed by combining these include groups formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group such as cyclopentylmethyl group and adamantylmethyl group, and groups formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group such as benzyl group and phenethyl group. In the case of a group formed by combination, two or more of the above groups may be combined, and groups having different valences (such as divalent or trivalent groups (chain hydrocarbon group, alicyclic saturated hydrocarbon group, aromatic hydrocarbon group)) may be included in the above groups. R 1a and R 2aor R 1a and R 2a and R 3a When the hydrocarbon ring formed by the bonding of them to each other has an alkyl group, the number of carbon atoms excluding the carbon atoms of the alkyl group is defined as the total number of carbon atoms of the hydrocarbon ring. R 1a or R 2a When it is a hydrocarbon group, the number of carbon atoms of the hydrocarbon group is preferably 1 to 16, more preferably 1 to 14, and even more preferably 1 to 12, respectively independently. R 1a and R 2a or R 1a and R 2a and R 3a When they are bonded to each other to form a hydrocarbon ring, the number of carbon atoms of the hydrocarbon ring is preferably 3 to 24, more preferably 3 to 18, and even more preferably 3 to 16, respectively independently. R 1a and R 2a or R 1a and R 2a and R 3a Examples of the alkyl group that may be possessed when they are bonded to each other to form a hydrocarbon ring include the same groups as described above. R 1a and R 2a or R 1a and R 2a and R 3a When they are bonded to each other to form a hydrocarbon ring, examples of -C(R 1a )(R 2a )(R 3a ) include the following groups, etc. * represents the bonding site. TIFF0007716900000013.tif27162R 1a and R 2a are each independently a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, or R 1a and R 2a are preferably bonded to each other to form a hydrocarbon ring having 3 to 24 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms, and are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, or R 1a and R 2aIt is more preferable that they are bonded to each other to form a hydrocarbon ring having 3 to 16 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms. R 3a is each independently a hydrogen atom, or R 1a and R 2a and R 3a are preferably bonded to each other to form a hydrocarbon ring having 3 to 24 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms, and is a hydrogen atom, or R 1a and R 2a and R 3a are more preferably bonded to each other to form a hydrocarbon ring having 3 to 16 carbon atoms which may have an alkyl group having 1 to 6 carbon atoms. When the hydrocarbon ring has an alkyl group, the bonding position of the alkyl group is to be bonded to a carbon atom other than the carbon atom to which the bond to the oxygen atom or the carbonyl group is bonded. R 1 , R 2 and R 3 are preferably -O-CO-R 10 , -O-CO-O-R 10 , -O-L 1 -CO-O-R 10 and more preferably -O-CO-O-R 10 or -O-L 1 -CO-O-R 10 . R 1 , R 2 and R 3 may each be bonded to the ortho, meta or para position with respect to the bonding positions of X 1 , X 2 and X 3 . Among them, it is preferably bonded to the para position with respect to the bonding positions of X 1 , X 2 and X 3 .

[0013] R 4 , R 5 , R 6 , R 7 , R 8 and R 9Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 The fluorinated alkyl group having 1 to 12 carbon atoms refers to an alkyl group having 1 to 12 carbon atoms and containing a fluorine atom, and examples thereof include perfluoroalkyl groups having 1 to 12 carbon atoms (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), as well as 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of the hydrocarbon group having 1 to 18 carbon atoms include chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups. 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, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9, even more preferably 1 to 6, and still more preferably 1 to 4. 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 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 groups represented below and the like. The bonding site can be at any position. 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, and still more preferably 6 to 10. Examples of the group formed by combination include a group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group - alkanediyl group - *, alkyl group - aromatic hydrocarbon group - *), a group formed by 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 formed by 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 the bonding site. Examples of the aromatic hydrocarbon group - alkanediyl group - * include aralkyl groups such as benzyl group and phenethyl group. Examples of the alkyl group - aromatic hydrocarbon group - * include tolyl group, xylyl group, cumenyl group and the like. Examples of the alicyclic hydrocarbon group - alkanediyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1-yl)-1-methylethyl and the like. Examples of the alkyl group - alicyclic hydrocarbon group - * include cycloalkyl groups having an alkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, and a 2-alkyladamantan-2-yl group. Examples of the aromatic hydrocarbon group - alicyclic hydrocarbon group - * include a phenylcyclohexyl group. Examples of the alicyclic hydrocarbon group - aromatic hydrocarbon group - * include a cyclohexylphenyl group. In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined. Further, -CH2- contained in the cyclic hydrocarbon group and the chain hydrocarbon group (alkanediyl group, alkyl group) may be replaced with -O-, -S-, -CO-, or -SO2-. Any of the combined groups may be bonded to the benzene ring. Examples of the group in which -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2- include a hydroxy group (a group in which -CH2- contained in the methyl group is replaced with -O-), a carboxy group (a group in which -CH2-CH2- contained in the ethyl group is replaced with -O-CO-), a thiol group (a group in which -CH2- contained in the methyl group is replaced with -S-), an alkoxy group (a group in which -CH2- at an arbitrary position contained in the alkyl group is replaced with -O-), an alkylthio group (a group in which -CH2- at an arbitrary position contained in the alkyl group is replaced with -S-), an alkoxycarbonyl group (a group in which -CH2-CH2- at an arbitrary position contained in the alkyl group is replaced with -O-CO-), an alkylsulfonyl group (a group in which -CH2- at an arbitrary position contained in the alkyl group is replaced with -SO2-), an alkylcarbonyl group (a group in which -CH2- at an arbitrary position contained in the alkyl group is replaced with -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at an arbitrary position contained in the alkyl group is replaced with -CO-O-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group - carbonyloxy group, and a group formed by combining two or more of these groups. Examples of the alkoxy group include alkoxy groups having 1 to 17 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkylthio group include alkylthio groups having 1 to 17 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group and the like. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, and still more preferably 1 to 4. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group represent groups in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl group, propionyl group and butyryl group and the like. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, etc. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. Examples of aromatic hydrocarbon group-carbonyloxy groups include aromatic hydrocarbon group-carbonyloxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. Examples of groups in which -CH2- in an alicyclic hydrocarbon group is replaced with -O- or -CO- include the groups shown below. The -O- or -CO- position in the groups shown below may be replaced with -S- or -SO2-, respectively. The bonding site may be at any position. When a -CH2- in a hydrocarbon group is replaced with -O- or -CO-, the number of carbon atoms before the replacement is the total number of carbon atoms in the hydrocarbon group. The number may be 1 or 2 or more. R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Examples of the substituent that the hydrocarbon group may have include a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms (-CH2- contained in the alkyl group may be replaced with -O- or -CO-). Examples of the halogen atom include the same groups as those mentioned above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those mentioned above. When -CH2- contained in an 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.

[0014] X 1 is preferably an oxygen atom. X 2 is preferably an oxygen atom. X 3 is preferably an oxygen atom. X 1 X 2 and X 3 may be bonded to the o-position, m-position, or p-position with respect to the bonding position of S + . Among them, it is preferably bonded to the p-position or m-position with respect to the bonding position of S + , and more preferably bonded to the p-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. When m1 to m3 are 2 or more, the groups in the plurality of parentheses may be the same as or different from each other, that is, X 1 ~X 3 When there are a plurality of each, R 1 ~R 3 When there are a plurality of each, R 4 ~R 6 When there are a plurality of each, all of these may be the same as or different from each other. R 4 、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 still more preferably a C1-C4 alkyl group. R 7 、R 8 and R 9 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-), still more preferably a fluorine atom, an iodine 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, an iodine atom, a trifluoromethyl group, a methyl group, a t-butyl group, a hydroxy group or a methoxy group. R 7 、R 8 and R 9The bonding position is not particularly limited. When m2 is 0, R 8 The bonding position of + may be any of the ortho, meta, and para positions with respect to the bonding position of S + and, among them, it is more preferable that it is bonded to the para position with respect to the bonding position of S 9 When m3 is 0, the bonding position of R + may be any of the ortho, meta, and para positions with respect to the bonding position of S + and, among them, it is more preferable that it is bonded to the para position with respect to the bonding position of S

[0015] Examples of the cation of the salt (I) include cations represented by the following formulas (I-c-1) to (I-c-52). TIFF0007716900000016.tif243147

[0016] TIFF0007716900000017.tif197145

[0017] TIFF0007716900000018.tif250147

[0018] TIFF0007716900000019.tif252142

[0019] TIFF0007716900000020.tif225143

[0020] TIFF0007716900000021.tif235152

[0021] In formula (I), the hydrocarbon group represented by X 0 includes aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups combining these. -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-), alkylsulfonyl group (the group in which -CH2- at any position contained in the alkyl group is replaced by -SO2-), 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, alkylcarbonyl group, alkylcarbonyloxy group, and alkylthio group are the same as those described above. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, and propylsulfonyl group. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 4. In addition, substitution in the alkenyl group and alkynyl group may be any group containing a carbon-carbon double bond or a carbon-carbon triple bond at an arbitrary position in the examples of substitution in the above-described alkyl group. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spiro, 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, and cyclododecyl group, and polycyclic cycloalkyl groups such as norbornyl group and adamantyl group. Specific examples of the group in which the alicyclic hydrocarbon group and -CH2- contained in the alicyclic hydrocarbon group are replaced by -O-, -S-, -CO-, or -SO2- include the following groups. The bonding site can be at any position.

[0022] As the alicyclic hydrocarbon group or a group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-, the groups represented by the formulas (y1) to (y71) are preferable, the groups represented by any of the formulas (y1) to (y20), formula (y26), formula (y27), formula (y30), formula (y31), formula (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), formula (y49) to (y58), formula (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.

[0023] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, binaphthyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 36, more preferably 6 to 24, even more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. In the case of a combined group, groups having different valences (alkanediyl group, alkanetriyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) may be included in the above-mentioned groups.

[0024] The combined group means a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a group formed by combining a chain hydrocarbon group and an aromatic hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), and A group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). In the combination, 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 - * (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), such as a tolyl group or a xylyl group, 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 - * (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), such as a benzyl group, a chain hydrocarbon group - aromatic hydrocarbon group - chain hydrocarbon group - * (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), such as a tolylmethyl group, Chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group - *, such as methyladamantylmethyleneadamantyl group, di(methyladamantylmethylene)adamantyl 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 - *(where -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 - *(where -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 - *(where -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.

[0025] 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 number of carbon atoms of the hydrocarbon group. X 0 The hydrocarbon group represented by may have one or more substituents. Examples of the substituent include a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a group 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 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 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, and 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. TIFF0007716900000023.tif17162 As the aromatic hydrocarbon group having 6 to 10 carbon atoms, aryl groups such as phenyl group and naphthyl group can be mentioned.

[0026] As the combined group, a group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, a group combining an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, etc. can be mentioned. As the group 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 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 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.

[0027] 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 which may have a hydroxy group or a fluorine atom (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group), a halogen atom, an aromatic hydrocarbon group which may have a hydroxy group or a C1-C4 perfluoroalkyl group, a group represented by formula (aa) or a group represented by formula (bb), Even more preferably, it is a *-alicyclic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * represents the bonding position with the carbon atom of -COO - .), a *-alicyclic hydrocarbon group-chain hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position with the carbon atom of -COO - .), a *-chain hydrocarbon group-alicyclic hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * represents the bonding position with the carbon atom of -COO - .), a fluorine atom or an aromatic hydrocarbon group which may have a hydroxy group, a group represented by formula (aa) or a group represented by formula (bb), More preferably, it is a polycyclic alicyclic hydrocarbon group (wherein -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. * is -COO - represents the bonding position with the carbon atom of). A polycyclic alicyclic hydrocarbon group - a chain hydrocarbon group (wherein -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the polycyclic alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxy group. * is -COO - represents the bonding position with the carbon atom of). A chain hydrocarbon group - a polycyclic alicyclic hydrocarbon group (wherein -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and -CH2- contained in the polycyclic alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group may have a fluorine atom or a hydroxy group. * 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 the formula (aa) or a group represented by the formula (bb), Particularly preferably, it is an adamantanone group, a hydroxyadamantyl group, a group combining an adamantyl group and an alkyl group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), a group represented by the formula (Y30F) or a phenyl group having a hydroxy group.

[0028] 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. TIFF0007716900000024.tif26132[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 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 - .

[0029] X a and X b are preferably the same atom, and more preferably both are oxygen atoms.

[0030] X 1a and X 2a Examples of the hydrocarbon group represented by X and X include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining two or more of these. Note that these hydrocarbon groups may have a substituent. Further, -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 substituent and no replacement.

[0031] X 1a Examples of the aliphatic hydrocarbon group of X 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.

[0032] 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 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.

[0033] 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 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.

[0034] 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). TIFF0007716900000025.tif46131[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.

[0035] X 2a The number of carbon atoms of the hydrocarbon group represented by is preferably 2 to 48, more preferably 4 to 48, still more preferably 6 to 44, even more preferably 8 to 40, and even more preferably 10 to 38.

[0036] 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.

[0037] 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. may be mentioned. In the case of combined groups, groups with different valences (alkyl group, alkanetriyl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cycloalkanetetrayl group, etc.) in the above-mentioned groups may be included. Examples of the combined groups include a group combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group, a group combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group, a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group, etc. Specifically, groups 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.), groups 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.), groups 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.

[0038] 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-) is more preferable. The group may have a substituent. 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-) is even more preferable. The group may have a substituent.

[0039] Specifically, the hydrocarbon group in X 2a includes: An alkanediyl group having 2 to 18 carbon atoms which may have a substituent (wherein -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), An alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), A group composed of an alkanediyl group having 1 to 12 carbon atoms which may have a substituent (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 which may have a substituent (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or An alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), and it is preferably a group composed of these, An alkane diyl group having 4 to 18 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), A group composed of an alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or More preferably, it is a group composed of an alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), An alkane diyl group having 6 to 14 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-), A group composed of an alkane diyl group having 1 to 12 carbon atoms which may have a substituent (wherein -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-) and an adamantane diyl group which may have a substituent (wherein -CH2- contained in the adamantane diyl group may be replaced by -O- or -CO-), or An alkane diyl group having 1 to 12 carbon atoms which may have a substituent (in the alkane diyl group, -CH2- contained therein may be replaced by -O- or -CO-), an adamantane diyl group which may have a substituent, and an alkyl group having 1 to 12 carbon atoms which may have a substituent (in the alkyl group, -CH2- contained therein may be replaced by -O- or -CO-). It is more preferably a group consisting of

[0040] Specifically, X 2a is preferably a group represented by formula (X 2 -1), a group represented by formula (X 2 -2), a group represented by formula (X 2 -3) or a group represented by formula (X 2 -4). TIFF0007716900000026.tif34158[wherein, 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 of 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.

[0041] 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). 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) is more preferable.

[0042] 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 carbon number 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 -CH2- at any position contained in an alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -CO-O-), an alkanediyl-oxy group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -O-), an alkanediyl-oxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkanediyl group is replaced by -O-CO-), an alkanediylcarbonyl group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -CO-), or an alkanediylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkanediyl group is replaced by -CO-O-). Examples of the alkanediyl-oxy group include a methyleneoxy group, an ethyleneoxy group, a propanediyl-oxy group, a butanediyl-oxy group, and a pentanediyl-oxy group. Examples of the alkanediyl-oxycarbonyl group include a methyleneoxycarbonyl group, an ethyleneoxycarbonyl 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.

[0043] 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, alkylsulfonyl group and the like. Examples of the alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group, alkylsulfonyl group and alkylthio group include, for example, an alkoxy group having 1 to 17 carbon atoms, an alkoxycarbonyl group having 2 to 17 carbon atoms, an alkylcarbonyl group having 2 to 18 carbon atoms, an alkylcarbonyloxy group having 2 to 17 carbon atoms, an alkylsulfonyl group having 1 to 17 carbon atoms and an alkylthio group having 1 to 17 carbon atoms, and groups similar to the above-described groups. The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, 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.

[0044] In the case of a combined group, groups having 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 an adamantylphenyl group and the like. In the combination, two or more alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined with each other. Further, any of these groups may be bonded to L B in any manner. Examples of the group in which -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include, in addition to the groups described above, a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyloxy 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-carbonyloxy group include aromatic hydrocarbon group-carbonyloxy 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. Further, the number may be one or two or more.

[0045] 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, the same groups as those described above can be mentioned. R A The hydrocarbon group in R may have one substituent or a plurality of substituents.

[0046] R A The hydrocarbon group in R is preferably 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-). More 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-).

[0047] 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 each be combined with two or more kinds. Also, any group may be bonded to L B and may be bonded thereto.

[0048] 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 alicyclic 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 (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-), or, is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms, more preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-). As the alicyclic hydrocarbon group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, the following groups (the bonding site is at an arbitrary position) are preferable, and as the aromatic hydrocarbon group, a phenyl group and a naphthyl group are preferable. TIFF0007716900000027.tif1897

[0049] Examples of the carboxylate anion in the carboxylate represented by the formula (I) include the carboxylate anions described below. TIFF0007716900000028.tif141165

[0050] TIFF0007716900000029.tif236168

[0051] TIFF0007716900000030.tif71168

[0052] TIFF0007716900000031.tif155165

[0053] TIFF0007716900000032.tif173159

[0054] Specific examples of the carboxylate (I) include salts formed by arbitrarily combining the above-mentioned cations and anions. Specific examples of the salt (I) are shown in the following table. TIFF0007716900000033.tif27114

[0055] 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).

Table 1

[0056] Among them, as the carboxylate (I), a salt formed by combining an anion represented by any one of the formulas (I-a-1) to (I-a-5), (I-a-10) to (I-a-21), and (I-a-57) to (I-a-66) with a cation represented by any one of the formulas (I-c-1) to (I-c-52) is preferred. Specifically, carboxylates (I-1) to (I-5), carboxylates (I-10) to (I-21), carboxylates (I-57) to (I-66), carboxylates (I-96) to (I-100), carboxylates (I-105) to (I-116), carboxylates (I-152) to (I-161), carboxylates (I-191) to (I-195), carboxylates (I-200) to (I-211), carboxylates (I-247) to (I-256), carboxylates (I-286) to (I-290), carboxylates (I-295) to (I-306), carboxylates (I-342) to (I-351), carboxylates (I-381) to (I-385), carboxylates (I-390) to (I-401), carboxylates (I-437) to (I-446), carboxylates (I-476) to (I-480), carboxylates (I-485) to (I-496), carboxylates (I-532) to (I-541), carboxylates (I-571) to (I-575), carboxylates (I-580) to (I-591), carboxylates (I-627) to (I-636), carboxylates (I-666) to (I-670), carboxylates (I-675) to (I-686), carboxylates (I-722) to (I-731), carboxylates (I-761) to (I-765), carboxylates (I-770) to (I-781), carboxylates (I-817) to (I-826), carboxylates (I-856) to (I-860), carboxylates (I-865) to (I-876), carboxylates (I-912) to (I-921).Carboxylate (I-951) to Carboxylate (I-955), Carboxylate (I-960) to Carboxylate (I-971), Carboxylate (I-1007) to Carboxylate (I-1016), Carboxylate (I-1046) to Carboxylate (I-1050), Carboxylate (I-1055) to Carboxylate (I-1066), Carboxylate (I-1102) to Carboxylate (I-1111), Carboxylate (I-1141) to Carboxylate (I-1145), Carboxylate (I-1150) to Carboxylate (I-1161), Carboxylate (I-1197) to Carboxylate (I-1206), Carboxylate (I-1236) to Carboxylate (I-1240), Carboxylate (I-1245) to Carboxylate (I-1256), Carboxylate (I-1292) to Carboxylate (I-1301), Carboxylate (I-1331) to Carboxylate (I-1335), Carboxylate (I-1340) to Carboxylate (I-1351), Carboxylate (I-1387) to Carboxylate (I-1396), Carboxylate (I-1426) to Carboxylate (I-1430), Carboxylate (I-1435) to Carboxylate (I-1446), Carboxylate (I-1482) to Carboxylate (I-1491), Carboxylate (I-1521) to Carboxylate (I-1525), Carboxylate (I-1530) to Carboxylate (I-1541), Carboxylate (I-1577) to Carboxylate (I-1586), Carboxylate (I-1616) to Carboxylate (I-1620), Carboxylate (I-1625) to Carboxylate (I-1636), Carboxylate (I-1672) to Carboxylate (I-1681), Carboxylate (I-1711) to Carboxylate (I-1715), Carboxylate (I-1720) to Carboxylate (I-1731), Carboxylate (I-1767) to Carboxylate (I-1776), Carboxylate (I-1806) to Carboxylate (I-1810), Carboxylate (I-1815) to Carboxylate (I-1826), Carboxylate (I-1862) to Carboxylate (I-1871), Carboxylate (I-1901) to Carboxylate (I-1905), Carboxylate (I-1910) to Carboxylate (I-1921), Carboxylate (I-1957) to Carboxylate (I-1966)Carboxylate (I-1996) to Carboxylate (I-2000), Carboxylate (I-2005) to Carboxylate (I-2016), Carboxylate (I-2052) to Carboxylate (I-2061), Carboxylate (I-2091) to Carboxylate (I-2095), Carboxylate (I-2100) to Carboxylate (I-2111), Carboxylate (I-2147) to Carboxylate (I-2156), Carboxylate (I-2186) to Carboxylate (I-2190), Carboxylate (I-2195) to Carboxylate (I-2206), Carboxylate (I-2242) to Carboxylate (I-2251), Carboxylate (I-2281) to Carboxylate (I-2285), Carboxylate (I-2290) to Carboxylate (I-2301), Carboxylate (I-2337) to Carboxylate (I-2346), Carboxylate (I-2376) to Carboxylate (I-2380), Carboxylate (I-2385) to Carboxylate (I-2396), Carboxylate (I-2432) to Carboxylate (I-2441), Carboxylate (I-2471) to Carboxylate (I-2475), Carboxylate (I-2480) to Carboxylate (I-2491), Carboxylate (I-2527) to Carboxylate (I-2536), Carboxylate (I-2566) to Carboxylate (I-2570), Carboxylate (I-2575) to Carboxylate (I-2586), Carboxylate (I-2622) to Carboxylate (I-2631), Carboxylate (I-2661) to Carboxylate (I-2665), Carboxylate (I-2670) to Carboxylate (I-2681), Carboxylate (I-2717) to Carboxylate (I-2726), Carboxylate (I-2756) to Carboxylate (I-2760), Carboxylate (I-2765) to Carboxylate (I-2776), Carboxylate (I-2812) to Carboxylate (I-2821), Carboxylate (I-2851) to Carboxylate (I-2855), Carboxylate (I-2860) to Carboxylate (I-2871), Carboxylate (I-2907) to Carboxylate (I-2916), Carboxylate (I-2946) to Carboxylate (I-2950), Carboxylate (I-2955) to Carboxylate (I-2966), Carboxylate (I-3002) to Carboxylate (I-3011)Carboxylate (I-3041) to Carboxylate (I-3045), Carboxylate (I-3050) to Carboxylate (I-3061), Carboxylate (I-3097) to Carboxylate (I-3106), Carboxylate (I-3136) to Carboxylate (I-3140), Carboxylate (I-3145) to Carboxylate (I-3156), Carboxylate (I-3192) to Carboxylate (I-3201), Carboxylate (I-3231) to Carboxylate (I-3235), Carboxylate (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-36'67) 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), Carboxylate (I-3801) to Carboxylate (I-3805), Carboxylate (I-3810) to Carboxylate (I-3821), Carboxylate (I-3857) to Carboxylate (I-3866), Carboxylate (I-3896) to Carboxylate (I-3900), Carboxylate (I-3905) to Carboxylate (I-3916), Carboxylate (I-3952) to Carboxylate (I-3961), Carboxylate (I-3991) to Carboxylate (I-3995), Carboxylate (I-4000) to Carboxylate (I-4011), Carboxylate (I-4047) to Carboxylate (I-4056)Carboxylate (I-4086) to Carboxylate (I-4090), Carboxylate (I-4095) to Carboxylate (I-4106), Carboxylate (I-4142) to Carboxylate (I-4151), Carboxylate (I-4181) to Carboxylate (I-4185), Carboxylate (I-4190) to Carboxylate (I-4201), Carboxylate (I-4237) to Carboxylate (I-4246), Carboxylate (I-4276) to Carboxylate (I-4280), Carboxylate (I-4285) to Carboxylate (I-4296), Carboxylate (I-4332) to Carboxylate (I-4341), Carboxylate (I-4371) to Carboxylate (I-4375), Carboxylate (I-4380) to Carboxylate (I-4391), Carboxylate (I-4427) to Carboxylate (I-4436), Carboxylate (I-4466) to Carboxylate (I-4470), Carboxylate (I-4475) to Carboxylate (I-4486), Carboxylate (I-4522) to Carboxylate (I-4531), Carboxylate (I-4561) to Carboxylate (I-4565), Carboxylate (I-4570) to Carboxylate (I-4581), Carboxylate (I-4617) to Carboxylate (I-4626), Carboxylate (I-4656) to Carboxylate (I-4660), Carboxylate (I-4665) to Carboxylate (I-4676), Carboxylate (I-4712) to Carboxylate (I-4721), Carboxylate (I-4751) to Carboxylate (I-4755), Carboxylate (I-4760) to Carboxylate (I-4771), Carboxylate (I-4807) to Carboxylate (I-4816), Carboxylate (I-4846) to Carboxylate (I-4850), Carboxylate (I-4855) to Carboxylate (I-4866), Carboxylate (I-4902) to Carboxylate (I-4911) are preferred.

[0057] <Method for Producing Carboxylate (I)> Carboxylate (I) can be produced by reacting a salt represented by formula (I-a) and a salt represented by formula (I-b) in a solvent. TIFF0007716900000036.tif91164 [wherein all symbols have the same meanings as defined above.] R A , R B and R C each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or R A , R B and R C may combine to form an aromatic ring. D represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.] Examples of solvents used in this reaction include chloroform, acetonitrile, and ion-exchanged water. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0058] The salt represented by formula (Ib) can be synthesized with reference to the methods described in JP-A Nos. 2011-39502 and 2014-88367, and examples thereof include salts represented by the following formulas. TIFF0007716900000037.tif133164

[0059] In the salt (Ia), R 1 , R 2 and R 3 But, -OL 1 -CO-OR 10 The salt represented by formula (I-a1) can be produced by reacting a salt represented by formula (Ic) with a compound represented by formula (Id) in a solvent in the presence of a base catalyst. TIFF0007716900000038.tif85162 [wherein all symbols have the same meanings as defined above.] Examples of the base include potassium carbonate, potassium iodide, pyridine, and triethylamine. Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, acetonitrile, ethyl acetate, and water. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0060] Examples of the compound represented by formula (I-d) include the compounds represented below, and they can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007716900000039.tif13162

[0061] The salt represented by formula (I-c) can be produced by reacting the salt represented by formula (I-e), the compound represented by formula (I-f1), the compound represented by formula (I-f2), and the compound represented by formula (I-f3) in a solvent in the presence of a catalyst. TIFF0007716900000040.tif83145[In the formula, all the symbols have the same meanings as described above.] Examples of the catalyst include potassium carbonate and sodium hydride. Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, and water. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours.

[0062] Examples of the salt represented by formula (I-e) include the salts represented by the following formula, and they can be easily obtained from the market. TIFF0007716900000041.tif35163

[0063] Examples of the compound represented by formula (I-f1), the compound represented by formula (I-f2), and the compound represented by formula (I-f3) include the compounds represented below, and they can be easily obtained from the market. TIFF0007716900000042.tif20104

[0064] The salt represented by formula (I-c) can also be produced by reacting the salt represented by formula (I-e), the compound represented by formula (I-f4), the compound represented by formula (I-f5), and the compound represented by formula (I-f6) in a solvent in the presence of potassium carbonate and then subjecting the reaction product to acid treatment. TIFF0007716900000043.tif170159[wherein all the symbols have the same meanings as described above respectively. R ac represents an acid-labile group.] Examples of the solvent include chloroform, monochlorobenzene, acetonitrile, water and the like. The reaction temperature is usually from 15°C to 100°C, and the reaction time is usually from 0.5 to 24 hours. Examples of the acid include p-toluenesulfonic acid, hydrochloric acid and the like.

[0065] Examples of the compound represented by formula (I-f4), the compound represented by formula (I-f5) and the compound represented by formula (I-f6) include the compounds represented below and the like, and they can be easily obtained from the market. TIFF0007716900000044.tif78146

[0066] In salt (I-a), R 1 , R 2 and R 3 being -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. TIFF0007716900000045.tif83164[wherein all the symbols have the same meanings as described above respectively.] 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 from 15°C to 80°C, and the reaction time is usually from 0.5 to 24 hours.

[0067] Examples of the compound represented by formula (I-d2) include the compounds represented below and the like, and they can be easily obtained from the market, and can also be easily produced by known production methods. TIFF0007716900000046.tif18135

[0068] 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. TIFF0007716900000047.tif81160[Wherein 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 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-d3) include the compounds represented below, which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007716900000048.tif14129

[0070] In salt (I-a), R 1 , R 2 and R 3 are -O-CO-O-R 10 The salt represented by formula (I-a4) 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 carbonyldiimidazole. TIFF0007716900000049.tif73165[Wherein 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 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0071] [Carboxylic Acid Generator] The carboxylic acid generator of the present invention is an acid generator containing a carboxylic acid salt (I). The carboxylic acid salt (I) of the present invention can act as an acid generator in a resist composition. When the carboxylic acid salt (I) is used as an acid generator in a resist composition, the acid generator may contain only one type of carboxylic acid salt (I) or two or more types of carboxylic acid salts (I). Furthermore, as will be described later, the acid generator of the present invention may further contain an acid generator other than the carboxylate (I) that is known in the resist field (hereinafter, sometimes referred to as "acid generator (B)") and / or a carboxylic acid generator other than the carboxylate (I) that is known in the resist field. The acid generator (B) may be used alone or in combination of two or more kinds. When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the ratio of the content of the carboxylic acid salt (I) to the content of the acid generator (B) or the like (mass ratio; carboxylic acid salt (I):acid generator (B)) or the like is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, and even more preferably 5:95 to 95:5.

[0072] [Resist Composition] The resist composition contains a carboxylic acid generator containing the carboxylic acid salt (I) of the present invention, an acid generator (B) other than the carboxylic acid salt (I), and a resin having an acid labile group (hereinafter sometimes referred to as "resin (A)"). Here, the "acid labile group" refers to a group that has a leaving group and that is eliminated upon contact with an acid to form a hydrophilic group (e.g., a hydroxy group or a carboxy group). The resist composition may further contain 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 of the carboxylate (I) is preferably 0.1% by mass or more and 35% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, and still more preferably 1% by mass or more and 25% by mass or less, based on the solid content of the resist composition.

[0073] <Acid generator (B)> As the acid generator (B), either a nonionic or ionic one may be used. Examples of the nonionic acid generator include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of the ionic acid generator include onium salts containing an onium cation (e.g., diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include sulfonic acid anion, sulfonylimide anion, sulfonylmethide anion, etc.

[0074] As the acid generator (B), compounds that generate an acid by radiation described in, for example, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Also, compounds produced by known methods may be used. The acid generator (B) may be used in combination of two or more.

[0075] The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007716900000050.tif2962[In the formula (B1), Q b1 and Q b2Each 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.

[0076] 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, and a perfluorohexyl group. Q b1 and Q b2 Each is preferably independently a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0077] 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. Specifically, linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, and heptadecane-1,17-diyl group; Branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; Monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. may be mentioned.

[0078] L b1 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by L 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.

[0079] TIFF0007716900000051.tif22101[In formula (b1-1), L b2represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0080] In the groups represented by formulae (b1-1) to (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 Examples of the divalent saturated hydrocarbon group include the same as the divalent saturated hydrocarbon group.

[0081] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the divalent saturated hydrocarbon group may be substituted with -O- or -CO-.

[0082] L b1 As the divalent saturated hydrocarbon group represented by the formula (b1-1) or (b1-3), in which one --CH.sub.2-- contained in the group is replaced by --O-- or --CO--, a group represented by the formula (b1-1) or (b1-3) is preferred.

[0083] Examples of the group represented by formula (b1-1) include groups represented by formulas (b1-4) to (b1-8). TIFF0007716900000052.tif48120[In formula (b1-4), L b8represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b9 L b10 and In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b11 L b12 and 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 the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b13 L b15 to In formula (b1-8), L b16represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. However, L b16 ~L b18 The total number of carbon atoms of is 19 or less.]

[0084] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and 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, and 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 b18is 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.

[0085] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11), respectively. TIFF0007716900000053.tif23140[In the formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b20 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, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, L b19 and L b20 have a total carbon number of 23 or less. In the formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, L b21 , L b22 and Lb23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group, or an alkylcarbonyloxy group. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0086] In addition, in the groups represented by formulae (b1-9) to (b1-11), when a hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group.

[0087] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, and an adamantylcarbonyloxy group.

[0088] Examples of the group represented by formula (b1-4) include the following. TIFF0007716900000054.tif16154

[0089] Examples of the group represented by formula (b1-5) include the following. TIFF0007716900000055.tif68152

[0090] Examples of the group represented by formula (b1-6) include the following. TIFF0007716900000056.tif32164

[0091] Examples of the group represented by formula (b1-7) include the following. TIFF0007716900000057.tif57146

[0092] Examples of the group represented by formula (b1-8) include the following. TIFF0007716900000058.tif23150

[0093] Examples of the group represented by formula (b1-2) include the following. TIFF0007716900000059.tif31161

[0094] Examples of the group represented by formula (b1-9) include the following. TIFF0007716900000060.tif44137

[0095] Examples of the group represented by formula (b1-10) include the following. TIFF0007716900000061.tif92165

[0096] Examples of the group represented by formula (b1-11) include the following. TIFF0007716900000062.tif84164

[0097] 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). * is L b1represents the bonding position with

[0098]

[0099] 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 even more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43).When the alicyclic hydrocarbon group represented by Y is a spiro ring such as formula (Y28) to formula (Y35), formula (Y39), formula (Y40), formula (Y42), formula (Y43), etc., the alkanediyl group between two oxygen atoms preferably has one or more fluorine atoms. 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. 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-, -S(O)2- or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.) and the like 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-, -S(O)2- 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.

[0100] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, 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 thereof include aromatic hydrocarbon groups having a chain hydrocarbon group with 1 to 18 carbon atoms (such as 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 aromatic hydrocarbon groups having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as 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 9, still 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, alkylsulfonyl 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, still more preferably 1 to 4. Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The number of carbon atoms in the alkylsulfonyl 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, and a butoxycarbonyl group. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and even 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, and a group formed by combining an alkoxy group and an alkylcarbonyloxy group. 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, and an ethoxymethyl group. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even 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, and an ethoxyethoxy group. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, and an ethoxypropionyl group. The number of carbon atoms of the alkoxyalkylcarbonyl group is preferably from 3 to 13, more preferably from 3 to 7, and still more preferably from 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, and an ethoxypropionyloxy group. The number of carbon atoms of the alkoxyalkylcarbonyloxy group is preferably from 3 to 13, more preferably from 3 to 7, and still 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).

[0101] Examples of Y include the following. TIFF0007716900000064.tif103165

[0102] TIFF0007716900000065.tif64161

[0103] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, still more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, even more preferably an alicyclic hydrocarbon group substituted with a hydroxy group, and still even more preferably an adamantyl group which may have a substituent. The -CH2- constituting the alicyclic hydrocarbon group or adamantyl group may be replaced by -CO-, -S(O)2- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by formula (Y42), formula (Y100) to formula (Y114), and particularly preferably a hydroxyadamantyl group or an oxoadamantyl group, or a group containing these.

[0104] As the anion in the salt represented by formula (B1), anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter, may be referred to as "anion (B1-A-1)" etc. according to the formula number] are preferable, and an anion represented by any of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-59) is more preferable.

[0105] TIFF0007716900000066.tif74143

[0106] TIFF0007716900000067.tif115156

[0107] TIFF0007716900000068.tif87146

[0108] TIFF0007716900000069.tif160156

[0109] TIFF0007716900000070.tif165161

[0110] 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 A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 represent the same meaning as described above. Specific examples of the anion in the salt represented by the formula (B1) include the anions described in JP-A-2010-204646.

[0111] Preferred anions in the salt represented by the formula (B1) include the anions represented by the formulas (B1a-1) to (B1a-38), respectively. TIFF0007716900000071.tif206152

[0112] TIFF0007716900000072.tif165155

[0113] Among them, anions represented by any of the formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-19), and (B1a-22) to (B1a-38) are preferred.

[0114] Z1 +Examples of the organic cation include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, organic phosphonium cations, and the like. 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 exemplified. TIFF0007716900000073.tif47165In formula (b2-1) to formula (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the hydrogen atom contained in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b7 and R b8 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of any of 0 to 5. When m2 is 2 or more, a plurality of R b7 may be the same or different, and when n2 is 2 or more, a plurality of Rb8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the chain hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent any integer from 0 to 5. q2 and r2 each independently represent any integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, the plurality of R b13 are the same or different, and when p2 is 2 or more, the plurality of R b14are the same or different, and when q2 is 2 or more, a plurality of Rs b15 are the same or different, and when r2 is 2 or more, a plurality of Rs b16 are the same or different, and when s2 is 2 or more, a plurality of Rs b17 are the same or different, and when t2 is 2 or more, a plurality of Rs b18 are the same or different. The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. In particular, the chain hydrocarbon group of R b9 ~R b12 is preferably 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, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups. TIFF0007716900000074.tif10159 In particular, the alicyclic hydrocarbon group of R b9 ~R b12 is preferably 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 with a fluorine atom, and examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl, etc. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, phenanthryl group, etc. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and aromatic hydrocarbon groups having a chain hydrocarbon group with 1 to 18 carbon atoms (such as tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and aromatic hydrocarbon groups having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as p-cyclohexylphenyl group, p-adamantylphenyl group, etc.) can be mentioned. In addition, when the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group with 1 to 18 carbon atoms and an alicyclic hydrocarbon group with 3 to 18 carbon atoms are preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include 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, naphthylethyl group, etc. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, dodecyloxy group, etc. Examples of the alkylcarbonyl group include acetyl group, propionyl group, butyryl group, etc. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom, etc. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group. R b4 and R b5 The ring formed by R and R being bonded to each other together with the sulfur atom to which they are bonded may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated ring. Examples of this ring include rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. Further, examples of the ring containing a sulfur atom include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples thereof include the following rings. * represents a bonding position. TIFF0007716900000075.tif23144R b9 and R b10 The ring formed by R and R together may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated ring. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples thereof include a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, a 1,4-oxathian-4-ium ring, and the like. R b11 and R b12 The ring formed by R and R together may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated ring. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples thereof include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, an oxoadamantane ring, and the like.

[0115] Among the cations (b2-1) to (b2-4), the cation (b2-1) is preferred. Examples of the cation (b2-1) include the following cations. TIFF0007716900000076.tif79158

[0116] TIFF0007716900000077.tif109165

[0117] Examples of the cation (b2-2) include the following cations and the like. TIFF0007716900000078.tif18150

[0118] Examples of the cation (b2-3) include the following cations and the like. TIFF0007716900000079.tif25122

[0119] Examples of the cation (b2-4) include the following cations and the like. TIFF0007716900000080.tif127166

[0120] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. Preferred examples of the acid generator (B) include a combination of an anion represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19), formula (B1a-22) to formula (B1a-38) and the cation (b2-1), the cation (b2-3) or the cation (b2-4).

[0121] Preferred examples of the acid generator (B) include those represented by formula (B1-1) to formula (B1-56), among which those containing an arylsulfonium cation are preferred, 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 preferred. TIFF0007716900000081.tif98161

[0122] TIFF0007716900000082.tif152164

[0123] TIFF0007716900000083.tif92158

[0124] TIFF0007716900000084.tif130161

[0125] TIFF0007716900000085.tif99130

[0126] TIFF0007716900000086.tif92158

[0127] In the resist composition of the present invention, the content of the acid generator (B) is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, still more preferably 3 parts by mass or more and 35 parts by mass or less, based on 100 parts by mass of the resin (A). The resist composition of the present invention may contain one kind of the acid generator (B) alone or a plurality of kinds thereof.

[0128] <Resin (A)> The resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). The resin (A) preferably further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than the structural unit (a1) and the structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)")), a structural unit having a non-leaving hydrocarbon group described later (hereinafter sometimes referred to as "structural unit (a5)"), and structural units derived from other monomers known in the art.

[0129] 〈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)). TIFF0007716900000087.tif2397[In the formula (1), R a1 、R a2 and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, or R a1 and R a2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bonding position.] TIFF0007716900000088.tif2379[In the formula (2), R a1’ and R a2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X represents an oxygen atom or a sulfur atom. na’ represents 0 or 1. * represents a bond.]

[0130] Examples of the alkyl group for R a1 、R a2 and R a3 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc. Examples of the hydrocarbon group for R a1 、R a2 and R a3Examples of the alkenyl group in [the compound] include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, and nonenyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in [the compound], R a1 , R a2 and R a3 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following group (* represents a bond): etc. The number of carbon atoms of the alicyclic hydrocarbon group of R TIFF0007716900000089.tif10159R a1 , R a2 and R a3 Examples of the aromatic hydrocarbon group in [the compound], R include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl group or cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, etc. Preferably, ma is 0 and na is 1. R a1 and R a2 When R a1 and R a2 are bonded to each other to form an alicyclic hydrocarbon group, -C(R a3) includes the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents the bonding position with -O-. TIFF0007716900000090.tif31135

[0131] R a1’ , R a2’ and R a3’ Examples of the hydrocarbon group in 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 represented by R a1 , R a2 and R a3 Examples of the groups include the same as those listed in the above. 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-mentioned alkyl group with an 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 (such as 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, or a 2-methyl-6-ethylphenyl group), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (such as a p-cyclohexylphenyl group or a p-adamantylphenyl group), and an alicyclic hydrocarbon group having an aromatic hydrocarbon group (such as a phenylcyclohexyl group). R a2’ and R a3’ When they are bonded to each other to form a heterocyclic group together with the carbon atoms to which they are bonded and X, -C(R a1’ )(R a2’ )-XR a3’ Examples of the group include the following: * represents the bonding position. TIFF0007716900000091.tif21142R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0132] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 are alkyl groups, ma = 0, and na = 1. As such a group, a tert-butoxycarbonyl group is preferable. In formula (1), R a1 , R a2 together with the carbon atom to which they are attached form an adamantyl group, R a3 is an alkyl group, ma = 0, and na = 1. In formula (1), R a1 and R a2 are each independently an alkyl group, R a3 is an adamantyl group, ma = 0, and na = 1. Specific examples of the group (1) include the following groups. * represents a bond. TIFF0007716900000092.tif154163

[0133] Specific examples of the group (2) include the following groups. * represents a bonding position. TIFF0007716900000093.tif68162

[0134] 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.

[0135] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are preferable. If a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

[0136] As a structural unit derived from a (meth)acrylic monomer having a group (1), there may be mentioned a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as the structural unit (a1-0)), a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as the structural unit (a1-1)), or a structural unit represented by the formula (a1-2) (hereinafter sometimes referred to as the structural unit (a1-2)). Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more. TIFF0007716900000094.tif42139[In the formula (a1-0), the formula (a1-1), and the formula (a1-2), L a01 、L a1 and L a2 each independently represents -O- or * -O-(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.]

[0137] 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), and more preferably an oxygen atom. R a02 , R a03 and R a04 Examples of the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and groups combining these in R a1 ~R a3 are the same groups as those exemplified 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 groups combining these in R a1 , R a2 and R a3 are the same groups as those exemplified 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 still more preferably a methyl group. R a6 and R a7 The alkyl group in R R a02 , R a03 and R a04The number of carbon atoms in the alicyclic hydrocarbon group is preferably 5 to 12, more preferably 5 to 10. R a02 and R a03 and R a04 and R a6 and R a7 The number of carbon atoms in the aromatic hydrocarbon group of and R is preferably 6 to 12, more preferably 6 to 10. For the group combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms of these combined alkyl group and alicyclic hydrocarbon group is 18 or less. For the group combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms of these combined alkyl group and aromatic hydrocarbon group is 18 or less. R a02 and R a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7 are preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group. m1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1' is preferably 0 or 1.

[0138] Examples of the structural unit (a1-0) include structural units represented by any of Formula (a1-0-1) to Formula (a1-0-18) and R in the structural unit (a1-0)a01 Examples of the structural unit in which the methyl group corresponding to 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 the structural units are preferred. TIFF0007716900000095.tif99159

[0139] 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 Preferably, the methyl group corresponding to is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group, and more preferably, the structural units are represented by any of formula (a1-1-1) to formula (a1-1-4). TIFF0007716900000096.tif39167

[0140] Examples of the structural unit (a1-2) include structural units represented by any of formula (a1-2-1) to formula (a1-2-14) and the structural unit (a1-2) in which the methyl group corresponding to R a5 is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group, and the 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 (a1-2-14) are preferred. TIFF0007716900000097.tif67163

[0141] When the resin (A) contains the structural unit (a1-0), the content thereof is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol% based on all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol%, preferably 15 to 85 mol%, more preferably 15 to 80 mol%, still more preferably 20 to 80 mol%, and even more preferably 20 to 75 mol% based on all the structural units of the resin (A).

[0142] 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)"). TIFF0007716900000098.tif3954[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 the -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.]

[0143] R a32 and R a33 Examples of the halogen atom in R R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R R a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a33 Examples of the alkyl group in R R a33 Examples of the alkoxy group in R Ra33 Examples of the alkoxyalkyl group in a33 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 a33 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 a33 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 a33 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.

[0144] *-X a31 -(A a32 -X a32 ) nc- includes, among others, *-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 these, *-CO-O-, *-CO-O-A a32 -CO-O- or *-O-A a32 -CO-O- is preferred.

[0145] 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.

[0146] 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-.

[0147] 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). Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like.TIFF0007716900000099.tif10151 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 thereof 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 groups.

[0148] 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 groups, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. R a36The alkyl group and alicyclic hydrocarbon group in [it] are preferably unsubstituted. R a36 The aromatic hydrocarbon group in [it] preferably has an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.

[0149] -OC(R a34 )(R a35 )-O-R a36 in the structural unit (a1-4) eliminates upon contact with an acid (for example, p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 preferably binds to the o-position or p-position of the benzene ring, and more preferably binds to the p-position.

[0150] 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 the formulas (a1-4-1) to (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 the formulas (a1-4-1) to (a1-4-5), the formula (a1-4-10), the formula (a1-4-13), and the 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% with respect to the total of all the structural units of the resin (A).

[0151] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) also include the structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007716900000101.tif4354In the 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 represents 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.

[0152] 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-.

[0153] 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 preferred, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferred. 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).

[0154] 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).

[0155] 〈Structural unit (s)〉 The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer (s)"). As the monomer that leads to the structural unit (s), a monomer having no acid-labile group known in the resist field can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. By using a resin having a structural unit having a hydroxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0156] 〈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, if a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet) is used as an exposure light source, the structural unit (a2) preferably has a phenolic hydroxy group, and more preferably the structural unit (a2-A) described below. Furthermore, if an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) preferably has an alcoholic hydroxy group, and more preferably the structural unit (a2-1) described below. The structural unit (a2) may contain one type alone or two or more types.

[0157] In the structural unit (a2), the structural unit having a phenolic hydroxy group includes a structural unit represented by formula (a2-A) (hereinafter, sometimes referred to as "structural unit (a2-A)"). TIFF0007716900000104.tif4349[In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - represents -R a50 represents the bond position with the carbon atom to which it is bonded. A a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.]

[0158] R a50 and R a51 Examples of the halogen atom in R include a fluorine atom, a chlorine atom, and a bromine atom. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a51 Examples of the alkyl group in R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a51 Examples of the alkoxy group in R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a51Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a51 Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, 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.

[0159] *-X a51 -(A a52 -X a52 ) nb- includes, among others, *-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 these, *-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 preferably a single bond, *-CO-O- or *-CO-O-A a52 -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-. 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.

[0160] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577. Examples of the structural unit (a2-A) include the structural units represented by formula (a2-2-1) to formula (a2-2-16), and R in the structural unit (a2-A) in the structural units represented by formula (a2-2-1) to formula (a2-2-16). a50Examples of the structural unit in which the methyl group corresponding to [[ID=]] is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. The structural unit (a2-A) is a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), structural units represented by formulas (a2-2-12) to (a2-2-14), and in the structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), 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), a structural unit represented by formula (a2-2-8), structural units represented by formulas (a2-2-12) to (a2-2-14), and in the structural unit represented by formula (a2-2-3) or a structural unit represented by formula (a2-2-8), 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 and then treating with an alkali such as tetramethylammonium hydroxide, the structural unit (a2-A) can be incorporated into the resin (A).

[0161] 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 TIFF0007716900000106.tif3957 L a3 represents -O- or * -O-(CH2) k2 -CO-O-, k2 represents an integer of any one of 1 to 7. * represents the bonding position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group or a hydroxy group. o1 represents an integer of any one of 0 to 10.

[0162] 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.

[0163] Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. The structural unit represented by any of formulas (a2-1-1) to (a2-1-6) is preferable, the structural unit represented by any of formulas (a2-1-1) to (a2-1-4) is more preferable, and the structural unit represented by formula (a2-1-1) or formula (a2-1-3) is even more preferable. When the 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 even more preferably 2 to 10 mol% based on all the structural units of the resin (A).

[0164] <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. Preferably, 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)) can be mentioned. The structural unit (a3) is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3), or formula (a3-4). These may be contained alone or in combination of two or more. TIFF0007716900000108.tif53165[In formulas (a3-1), (a3-2), (a3-3), and (a3-4), L a4 , L a5 and L a6 each independently represents a group represented by -O- or *-O-(CH2) k3 -CO-O- (where k3 represents an integer of 1 to 7). L a7 is -O-, *-O-L a8 -O-, *-O-L a8 -CO-O-, *-O-L a8 -CO-O-La9 -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.

[0165] R a21 、R a22 、R a23 and R a25 Examples of the aliphatic hydrocarbon group in R a24Examples of the halogen atom in [compound name] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R a24 Examples of the alkyl group in [compound name] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group, etc. Preferably, an alkyl group having 1 to 4 carbon atoms is exemplified, and more preferably, a methyl group or an ethyl group is exemplified. R a24 Examples of the alkyl group having a halogen atom in [compound name] 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.

[0166] L a8 and L a9 Examples of the alkanediyl group in [compound name] and [compound name] 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.

[0167] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably -O- or, *-O-(CH2) k3 -CO-O- where k3 is an integer from 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.

[0168] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and still more preferably a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group, or a methyl group. L a7 is preferably -O- or *-O-L a8 -CO-O-, more preferably -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably an integer of 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)'. TIFF0007716900000109.tif4151 (wherein R a24 , L a7 represent the same meaning as above.)

[0169] 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).

[0170] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007716900000111.tif3165[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having a fluorine atom and having 1 to 24 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.] R 42 Examples of the saturated hydrocarbon group represented by include a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these.

[0171] 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 TIFF0007716900000112.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, and the like.

[0172] 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). TIFF0007716900000113.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.]

[0173] 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.

[0174] L 3aExamples of the perfluoroalkanediyl group in [reference] 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 [reference] include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

[0175] 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.

[0176] Examples of the structural unit (a4-0) include the structural units shown below and the structural units in the following structural units where the methyl group corresponding to R in the structural unit (a4-0) is replaced by a hydrogen atom. 5a are included. TIFF0007716900000114.tif95165

[0177] TIFF0007716900000115.tif4764In 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 them has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007716900000116.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 . ]

[0178] Examples of the saturated hydrocarbon group in R a42 include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

[0179] 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 TIFF0007716900000117.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.

[0180] 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. TIFF0007716900000118.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. ​

[0181] A a45 Examples of the aliphatic hydrocarbon group in [context not clear] include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents the bonding position). TIFF0007716900000119.tif11160

[0182] R a42 R is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3). R a42 When R is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group and perfluorooctyl group. Examples of the perfluorocycloalkyl group include perfluorocyclohexyl group. R a42 When R is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the carbon atoms contained in the group represented by the formula (a-g3), the total carbon number of R a42 is preferably 15 or less, more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent, the number thereof is preferably 1.

[0183] Ra42 When it is a saturated hydrocarbon group having a group represented by the formula (a-g3), R a42 is more preferably a group represented by the formula (a-g2). TIFF0007716900000120.tif874[In the formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents **-O-CO- or **-CO-O- (** represents the bonding 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.]

[0184] A a46 The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3. A a47 The number of carbon atoms of the aliphatic hydrocarbon group is preferably 4 to 15, more preferably 5 to 12, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0185] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is the bonding position with the carbonyl group). TIFF0007716900000121.tif13161

[0186] A a41Examples of the alkanediyl group in [compound name] include linear alkanediyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl; and branched alkanediyl groups such as propane-1,2-diyl, butane-1,3-diyl, 2-methylpropane-1,2-diyl, 1-methylbutane-1,4-diyl, and 2-methylbutane-1,4-diyl. A a41 Examples of the substituent in the alkanediyl group represented by [compound name] 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 even more preferably an ethylene group.

[0187] A in the group represented by formula (a-g1) a42 、A a43 and A a44 Examples of the divalent saturated hydrocarbon group represented by [compound name] include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic hydrocarbon groups, and groups formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specifically, examples include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, 1-methylpropane-1,3-diyl, 2-methylpropane-1,3-diyl, and 2-methylpropane-1,2-diyl. A a42 、A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by [compound name] include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. s is preferably 0.

[0188] In the group represented by formula (a-g1), examples of the group in which X a42 is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a bonding position, and ** is -O-CO-Ra42 is a bonding site with TIFF0007716900000122.tif48153

[0189] Examples of the structural unit represented by formula (a4-1) include the following structural units and the structural units represented by formula (a4-1) in the following structural units, where the methyl group corresponding to R a41 is replaced by a hydrogen atom. TIFF0007716900000123.tif100142

[0190] TIFF0007716900000124.tif123141

[0191] As the structural unit represented by formula (a4-1), the structural unit represented by formula (a4-2) is preferred. TIFF0007716900000125.tif3251[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and the -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 carbon number of L 44 and R f6 is 21.]

[0192] The alkanediyl group of L 44 is exemplified by the same groups as those exemplified by A a41 R f6 The saturated hydrocarbon group of a42 is exemplified by the same groups as those exemplified by R L 44 As the alkanediyl group in

[0193] ​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 in which is replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-2).

[0194] TIFF0007716900000126.tif5164[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. X f12 represents *-O-CO- or *-CO-O- (* represents the bonding position 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.]

[0195] 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; perfluoro alkane diyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropane diyl group, perfluorobutane diyl group and perfluoropentane diyl group, etc. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexane diyl group and perfluorocyclohexane diyl group, etc. Examples of the polycyclic group include adamantane diyl group, norbornane diyl group, perfluoroadamantane diyl group, etc.

[0196] A f14 Examples of the saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom in 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, etc. are preferred.

[0197] 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 preferably represents a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0198] Examples of the structural unit represented by the formula (a4-3) include structural units represented by the formulas (a4-1'-1) to (a4-1'-11), respectively. The methyl group corresponding to R f7 in the structural unit (a4-3) replaced by a hydrogen atom is also included in the structural units represented by the formula (a4-3).

[0199] Examples of the structural unit (a4) also include the structural unit represented by the formula (a4-4). TIFF0007716900000127.tif4163[In the formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 - or -(CH2) j4 -CO-O-(CH2) j5 -. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom.]

[0200] R f22 The saturated hydrocarbon group of is R a42Examples thereof include the same saturated hydrocarbon groups represented by R f22 R is preferably an alkyl group having 1 to 10 carbon atoms or an alicyclic hydrocarbon group having 1 to 10 carbon atoms, each having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and 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.

[0201] Examples of the structural unit represented by formula (a4-4) include structural units represented by the following structural units and the following formulas, in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom. f21 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).

[0202] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group of the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably has a group having an alicyclic hydrocarbon group. Examples of the structural unit (a5) include a structural unit represented by formula (a5-1). TIFF0007716900000129.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-.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] Examples of the group represented by formula (L1-1) include, for example, the following divalent groups. TIFF0007716900000131.tif54134

[0208] Examples of the group represented by formula (L1-2) include the following divalent groups. TIFF0007716900000132.tif24131

[0209] Examples of the group represented by formula (L1-3) include the following divalent groups. TIFF0007716900000133.tif15145

[0210] Examples of the group represented by formula (L1-4) include the following divalent groups. TIFF0007716900000134.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0211] Examples of the structural unit (a5-1) include the following structural units and the structural units in the following structural units where the methyl group corresponding to R in the structural unit (a5-1) is replaced by a hydrogen atom. 51 and the structural units in which the methyl group corresponding to R in the structural unit (a5-1) is replaced by a hydrogen atom. TIFF0007716900000135.tif110150 When the resin (A) has the structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 3 to 15 mol% based on all the structural units of the resin (A). 〈Structural unit (a6)〉 The structural unit (a6) is a structural unit having a -SO2- group, and preferably has a -SO2- group in the side chain. The structural unit having a -SO2- group may have a linear structure having a -SO2- group, a branched structure having a -SO2- group, or a cyclic structure (monocyclic and polycyclic structures) having a -SO2- group. Preferably, it is a structural unit having a cyclic structure having a -SO2- group, and more preferably, it is a structural unit having a cyclic structure (sultone ring) containing -SO2-O-.

[0212] Examples of the sultone ring include the following formula (T 1 -1), formula (T1 -2), formula (T 1 -3) and formula (T 1 -4). The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. The polycyclic sultone ring means a bridged ring containing -SO2-O- as an atomic group constituting the ring, and formulas (T 1 -1) and formula (T 1 -2). The sultone ring may further contain a heteroatom in addition to -SO2-O- as an atomic group constituting the ring, like the ring represented by formula (T 1 -2). Examples of the heteroatom include an oxygen atom, a sulfur atom or a nitrogen atom, preferably an oxygen atom. TIFF0007716900000136.tif3087

[0213] The sultone ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyl group having 2 to 4 carbon atoms, etc.

[0214] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and a decyl group. Preferably, it is an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group and a triiodomethyl group. Preferably, a trifluoromethyl group is mentioned. Examples of the alkyl group having a hydroxy group include hydroxyalkyl groups such as hydroxymethyl group and 2-hydroxyethyl group. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group. Examples of the aryl group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl group. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and naphthylethyl group. Examples of the alkoxycarbonyl group include groups in which an alkoxy group such as methoxycarbonyl group and ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or less carbon atoms, more preferably methoxycarbonyl group. Examples of the alkylcarbonyl group include acetyl group, propionyl group and butyryl group.

[0215] From the viewpoint of easy production of the monomer leading to the structural unit (a6), a sultone ring having no substituent is preferred. As the sultone ring, a ring represented by the following formula (T1') is preferred. TIFF0007716900000137.tif3072[In the formula (T1'), X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. The bonding site is at an arbitrary position.] X 11 is preferably an oxygen atom or a methylene group, more preferably a methylene group. R 41 Examples of R

[0216] As the sultone ring, a ring represented by the formula (T1) is more preferable. TIFF0007716900000138.tif3049[In the formula (T1), R 8 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. m represents any integer from 0 to 9. When m is 2 or more, a plurality of R 8 may be the same or different. The bonding site is at an arbitrary position.]

[0217] R 8 is the same as R 41 and the like can be mentioned. ma in the formula (T1') and m in the formula (T1) are preferably 0 or 1, more preferably 0.

[0218] Examples of the ring represented by formula (T1’) and the ring represented by formula (T1) include the following rings. The bonding site can be at any position. TIFF0007716900000139.tif52160

[0219] The structural unit having a sultone ring preferably has the following group. * in the following group represents the bonding site. TIFF0007716900000140.tif50161

[0220] The structural unit having a -SO2- group preferably further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group, and the like. Among them, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer.

[0221] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007716900000141.tif4956[In formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. A xx represents an oxygen atom, -N(R c )- or a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -N(R d )-. X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. R c and R d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0222] R x Examples of the halogen atom of R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R x Examples of the alkyl group of R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and an n-hexyl group, etc. Preferably it is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. R x Examples of the alkyl group having a halogen atom of R include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group and a triiodomethyl group, etc. R x is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

[0223] A xExamples of the divalent saturated hydrocarbon group include linear alkanediyl groups, branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of two or more of these groups may also be used. Specific examples include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, and propane-2,2-diyl group; branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group; monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and cyclooctane-1,5-diyl group; polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0224] R 41 、X 11 and ma are the same as those in formula (T1'). Examples of the sultone ring include those described above, and among them, those with specific bonding positions are preferred.

[0225] Examples of the structural unit (a6) include the following structural units. TIFF0007716900000142.tif100159

[0226] Among them, the structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8) and formula (a6-12) are preferable, and the structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferable. When the resin (A) has the structural unit (a6), its content is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and even more preferably 3 to 30 mol% based on all the structural units of the resin (A).

[0227] <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 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.

[0228] The structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007716900000143.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA- represents a sulfonate group or a carboxylate group. R III3 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.

[0229] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R 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 alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted on A include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, and the like. X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations thereof. Specifically, linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group; branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. may be mentioned. Examples of those in which -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- include divalent groups represented by formula (X1) to formula (X53). However, the number of carbon atoms before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less respectively. In the following formulae, * and ** represent a bond, and * represents a bond to A x1 and represents a bond to A. TIFF0007716900000144.tif145161

[0230] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0231] ZA in formula (II-2-A’) + is the same as the cation Z1 in the acid generator (B1). + Examples thereof include the same ones.

[0232] The structural unit represented by formula (II-2-A’) is preferably the structural unit represented by formula (II-2-A). TIFF0007716900000145.tif38109 [In formula (II-2-A), R III3 , X III3 and ZA + represent the same meanings as described above. z2A represents any integer from 0 to 6. R III2 and R III4 each independently represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. When z2A is 2 or more, a plurality of R III2 and R III4 may be the same as or different from each other. Q a and Q b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R III2 , R III4 , Q a and Q b Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by b1 are the same as those of the perfluoroalkyl group having 1 to 6 carbon atoms represented by the aforementioned Q.

[0233] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF0007716900000146.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Qb and ZA + represents the same meaning as described above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents any integer from 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, wherein -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom or a hydroxy group. R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. X I2 Examples of the divalent saturated hydrocarbon group represented by X include those similar to the divalent saturated hydrocarbon group represented by X III3 represented by.

[0234] 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. TIFF0007716900000147.tif5288 [In the formula (II-2-A-2), R III3 R III5 and ZA + represent the same meaning as described above. mA and nA each independently represent 1 or 2.

[0235] 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 wherein the hydrogen atom, a halogen atom (for example, a fluorine atom) or a halogen atom may have a C1-C6 alkyl group (e.g., trifluoromethyl group, etc.) which may be replaced by a group having a structure unit and WO 2012 / 050015 described. ZA+ represents an organic cation. TIFF0007716900000148.tif87163

[0236] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1). TIFF0007716900000149.tif3791[In the formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R II2 and R II3 may combine with each other to form a ring together with the sulfur atom to which they are attached. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A - represents an organic anion.] R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R include a phenylene group and a naphthylene group. R II2 and R II3 Examples of the hydrocarbon group represented by include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. R II4 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R II4 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 A II1 ​Examples of the divalent linking group represented by include divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. Specifically, X III3 Examples thereof include the same divalent saturated hydrocarbon groups having 1 to 18 carbon atoms represented by .

[0237] Examples of the structural unit containing the cation in formula (II-1-1) include the structural unit represented by the following and a structural unit in which a group corresponding to the methyl group of R II4 is replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group or the like, and the like. TIFF0007716900000150.tif85130

[0238] A - Examples of the organic anion represented by include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions and the like. A - The organic anion represented by is preferably a sulfonate anion, and more preferably an anion contained in the salt represented by the aforementioned formula (B1).

[0239] A - Examples of the sulfonylimide anion represented by include the following. TIFF0007716J900000151.tif36134 Examples of the sulfonylmethide anion include the following. TIFF0007716900000152.tif29123 Examples of the carboxylic acid anion include the following. TIFF0007716900000153.tif41155

[0240] Examples of the structural unit represented by formula (II-1-1) include the structural unit represented by the following and the like. In the case where the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% based on all the structural units of the resin (A).

[0241] The resin (A) may have structural units other than the above-mentioned structural units, and examples of such structural units include structural units well-known in the art.

[0242] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s). The structural unit (a1) is preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two kinds, and still more preferably the structural unit (a1-1) and / or the structural unit (a1-2). The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-A) or a structural unit represented by the formula (a2-1). The structural unit (a3) is preferably at least one selected from the group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a structural unit represented by the formula (a3-4).

[0243] Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using monomers that lead to these structural units. The content of each structural unit of the resin (A) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, even more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, even more preferably 15,000 or less). In this specification, the weight average molecular weight is a value determined by gel permeation chromatography under the conditions described in the Examples.

[0244] <Resins other than Resin (A)> The resist composition of the present invention may contain a resin other than the resin (A) in combination. Examples of resins other than resin (A) include resins containing the structural unit (a4) or the structural unit (a5) (hereinafter, sometimes referred to as resin (X)). As the resin (X), a resin containing the structural unit (a4) is particularly preferred. 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 structural units in the resin (X). Examples of structural units that the resin (X) may further have include the structural unit (a2), the structural unit (a3), and structural units derived from other known monomers. Among these, the resin (X) is preferably a resin consisting only of the structural unit (a4) and / or the structural unit (a5), and more preferably a resin consisting only of the structural unit (a4). The structural units constituting the resin (X) may be used singly or in combination of two or more, and can be produced by a known polymerization method (e.g., radical polymerization) using monomers that derive these structural units. The content of each structural unit in the resin (X) can be adjusted by the amount of monomer used in the polymerization. The weight average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight average molecular weight of resin (X) is the same as that for resin (A). When the resist composition contains resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass, based on 100 parts by mass of resin (A).

[0245] The content ratio of 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 resin (A), the total content ratio of resin (A) and the resin other than 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 ratio of the resin thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0246] <Solvent (E)> The content ratio of solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, more preferably 94% by mass or more and 99% by mass or less. The content ratio of solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography. Examples of solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of solvent (E) may be used alone, or two or more kinds may be used.

[0247] <Quencher (C)> The quencher (C) is a salt that generates an acid with a lower acidity than the acid generated from the basic nitrogen-containing organic compound or the acid generator (B) (however, carboxylic acid salts represented by the 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, still more preferably about 0.1 to 5% by mass, and even more preferably about 0.1 to 3% by mass based on the solid content of the resist composition. Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of the amines include aliphatic amines and aromatic amines. Examples of the aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4'-dipyridylsulfide, 4,4'-dipyridyldisulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Aromatic amines such as diisopropylaniline are preferable, and 2,6-diisopropylaniline is more preferable. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, and the like.

[0248] 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). TIFF0007716900000155.tif94163

[0249] Examples of the weak acid inner salt (D) include the following salts. TIFF0007716900000156.tif72165

[0250] 〈Other components〉 The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes referred to as "other components (F)"). There are no particular limitations on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used.

[0251] 〈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.

[0252] 〈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 carried out by a commonly used apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers and organic substrates such as already formed resist films. Before applying the resist composition, the substrate may be cleaned, 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. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake), or by using a decompression device. The heating temperature is preferably 50 to 200 °C, and the heating time is preferably 10 to 180 seconds. Also, the pressure during vacuum drying is preferably about 1 to 1.0×10 5 Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), those that convert laser light from a solid laser light source (YAG or semiconductor laser, etc.) into harmonic laser light in the far ultraviolet region or vacuum ultraviolet region and emit it, electron beams, those that irradiate extreme ultraviolet light (EUV), etc., various ones can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure". During exposure, usually, exposure is performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The exposed composition layer is heat-treated (so-called post-exposure bake) to promote the deprotection reaction in the acid-labile group. The heating temperature is usually about 50 to 200 °C, preferably about70 to 150 °C. Chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating. Also, before development, the steps of coating, drying, exposing, and heating the resist composition may be repeated on the exposed composition layer. The heated composition layer is usually developed using a developing solution with a developing device. Examples of the developing method include the dip method, paddle method, spray method, dynamic dispense method, etc. The developing temperature is preferably, for example, 5 to 60 °C, and the developing time is preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as follows, a positive resist pattern or a negative resist pattern can be manufactured. When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline), etc. may be mentioned. The alkaline developer may contain a surfactant. After development, it is preferable to wash the resist pattern with ultrapure water and then remove the water remaining on the substrate and the pattern. When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic-based developer") is used as the developer. Examples of the organic solvent contained in the organic-based developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole, etc. In the organic-based developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among them, as the organic-based developer, a developer containing butyl acetate and / or 2-heptanone is preferable. In the organic-based developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2-heptanone. The organic-based developer may contain a surfactant. Also, the organic-based developer may contain a small amount of water. During development, development may be stopped by substituting with a solvent of a different type from the organic-based developer. It is preferable to wash the developed resist pattern with a rinse solution. The rinse solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After washing, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

[0253] <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

[0254] 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”.

[0255] 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 liquid separation was carried out to take out 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 liquid separation was carried out to take out 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 liquid separation was carried out to take out 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 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 obtained mixture, 0.53 part of the compound represented by formula (I-2-g) was added, and the mixture was stirred at 75 °C for 5 hours and then cooled to 23 °C. To the obtained 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 take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then the layers were separated to take out the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.28 parts of the salt represented by formula (I-2-h) was obtained. 0.96 part of the salt represented by formula (I-2-h), 0.47 part of the salt represented by formula (I-2-i), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23 °C for 2 hours. To the obtained mixture, 20 parts of ion-exchanged water was 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, 1.15 parts of the salt represented by formula (I-2) was obtained. MASS(ESI(+)Spectrum):M + 563.2 MASS(ESI(-)Spectrum):M - 193.1

[0256] Example 2: Synthesis of the salt represented by formula (I-4) 0.98 part of the salt represented by formula (I-2-h), 0.70 part of the salt represented by formula (I-4-i), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23 °C for 2 hours. To the obtained mixture, 20 parts of ion-exchanged water was 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, 1.39 parts of the salt represented by formula (I-4) was obtained. MASS(ESI(+)Spectrum):M+ 563.2 MASS(ESI(-)Spectrum):M - 337.1

[0257] Example 3: Synthesis of the salt represented by formula (I-5) 0.96 part of the salt represented by formula (I-2-h), 0.38 part of the salt represented by formula (I-5-i), 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, and 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, 1.02 parts of the salt represented by formula (I-5) was obtained. MASS(ESI(+)Spectrum):M + 563.2 MASS(ESI(-)Spectrum):M - 137.0

[0258] 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 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 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 2.26 parts of the salt represented by formula (I-2474-f). 1.24 parts of the salt represented by TIFF0007716900000164.tif48149 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 obtained mixture, 1.07 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 obtained 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, 1.88 parts of the salt represented by formula (I-2474-b) were obtained. 1.43 parts of the salt represented by TIFF0007716900000165.tif110156 formula (I-2474-b), 0.70 part of the salt represented by formula (I-4-i), 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23 °C for 2 hours. To the obtained 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, 1.67 parts of the salt represented by formula (I-2474) were obtained. MASS(ESI(+)Spectrum):M + 863.4 MASS(ESI(-)Spectrum):M - 337.1

[0259] Example 5: Synthesis of the salt represented by formula (I-479) 0.95 parts of the compound represented by TIFF0007716900000166 in the 90164th formula (I-2-d) and 20 parts of tetrahydrofuran were mixed, stirred at 23 °C for 30 minutes, then cooled to 5 °C, and 0.14 parts of sodium hydride was added. To the resulting mixture, 2.60 parts of the salt represented by the formula (I-479-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, stirred at 23 °C for 30 minutes, then 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, stirred at 23 °C for 30 minutes, then the supernatant was removed and concentrated to obtain 2.11 parts of the salt represented by the formula (I-479-f). 1.27 parts of the salt represented by TIFF0007716900000167 in the 34150th formula (I-479-f) and 30 parts of dimethylformamide were mixed, stirred at 23 °C for 30 minutes, then 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added, and the temperature was raised to 75 °C. To the resulting mixture, 0.53 parts of the compound represented by the formula (I-2-g) was added, 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% oxalic acid aqueous solution were added, stirred at 23 °C for 30 minutes, then separated, and the organic layer was taken out. To the obtained organic layer, 20 parts of ion-exchanged water was added, stirred at 23 °C for 30 minutes, then separated, and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.37 parts of the salt represented by the formula (I-479-g) was obtained. 1.17 parts of the salt represented by TIFF0007716900000168 in the 70160th formula (I-479-g), 0.70 parts of the salt represented by the formula (I-4-i), 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, stirred at 23 °C for 30 minutes, then separated, and the organic layer was taken out. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 1.44 parts of the salt represented by the formula (I-479) was obtained. MASS(ESI(+)Spectrum):M + 699.2 MASS(ESI(-)Spectrum):M - 337.1

[0260] Example 6: Synthesis of the salt represented by formula (I-3234) 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, 2.64 parts of the salt represented by formula (I-3234-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, 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 the mixture was 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-3234-f). 1.53 parts of the salt represented by formula (I-3234-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, 1.07 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, and the organic layer was taken out. 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, and the organic layer was taken out. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 2.03 parts of the salt represented by formula (I-3234-b) was obtained. 1.64 parts of the salt represented by formula (I-3234-h), 0.70 parts of the salt represented by formula (I-4-i), 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, followed by liquid separation to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated to obtain 1.99 parts of the salt represented by formula (I-3234). MASS(ESI(+)Spectrum):M + 989.3 MASS(ESI(-)Spectrum):M - 337.1

[0261] Example 7: Synthesis of the salt represented by formula (I-1999) 0.95 parts of the salt represented by formula (I-2-f) and 30 parts of chloroform were mixed and stirred at 23 °C for 30 minutes. To the resulting mixed solution, 0.38 parts of the compound represented by formula (I-1999-a) was added, and further stirred at 50 °C for 2 hours. To the resulting mixed solution, 0.35 parts of the compound represented by formula (I-1999-b) was added, and further stirred at 50 °C for 3 hours and then cooled to 23 °C. To the resulting mixture, 15 parts of 5% aqueous oxalic acid solution was added and stirred at 23 °C for 30 minutes, followed by liquid separation to obtain the organic layer. 15 parts of ion-exchanged water was added to the obtained organic layer and stirred at 23 °C for 30 minutes, followed by liquid separation to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether was added to the concentrated residue, stirred at 23 °C for 30 minutes, the supernatant was removed, and concentrated to obtain 1.26 parts of the salt represented by formula (I-1999-h). 0.94 parts of the salt represented by TIFF0007716900000173 (I-1999-h), 0.70 parts of the salt represented by formula (I-4-i), 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, followed by liquid separation to obtain the organic layer. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 1.28 parts of the salt represented by formula (I-1999) was obtained. MASS(ESI(+)Spectrum):M + 549.2 MASS(ESI(-)Spectrum):M - 337.1

[0262] Synthesis of Resin The compounds (monomers) used for the synthesis of resin (A) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-3)" etc. according to their formula numbers. TIFF0007716900000174.tif46154

[0263] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) were used and mixed so that their molar ratio [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6)] was 38:24:38. Further, to this monomer mixture, 1.5 mass times of methyl isobutyl ketone was mixed with respect to the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, to the polymerization reaction solution, a 2.5 wt% aqueous solution of p-toluenesulfonic acid 2.0 mass times the total mass of all monomers was added, stirred for 6 hours, and then liquid-separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered, whereby the weight average molecular weight was about 5.3×10 3Resin A1 (copolymer) was obtained in a yield of 78%. This resin A1 has the following structural units. TIFF0007716900000175.tif28125

[0264] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) were used and mixed so that the molar ratio [monomer (a1-4-2): monomer (a1-2-6)] was 38:62. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the resulting mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the mass with respect to the total mass of the total monomer amount was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered, whereby a resin A2 (copolymer) having a weight average molecular weight of about 5.4×10 3 was obtained in a yield of 89%. This resin A2 has the following structural units. TIFF0007716900000176.tif2887

[0265] Synthesis Example 3 [Synthesis of Resin A3] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (aa1-4-2) were used and mixed so that the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2)] was 20:35:3:15:27. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, with respect to the total monomer amount, and these were heated at 73 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the mass with respect to the total mass of the total monomer amount was added to the polymerization reaction solution, stirred for 12 hours, and then separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, whereby resin A3 having a weight average molecular weight of about 5.3×10 3 was obtained at a yield of 63%. This resin A3 has the following structural units. TIFF0007716900000177.tif37154

[0266] Synthesis Example 4 [Synthesis of Resin A4] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a1-4-13) were used, and their molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13)] was mixed at a ratio of 20:35:3:15:27. Further, to this monomer mixture, methyl isobutyl ketone 1.5 times the total mass of all monomers was mixed. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total amount of all monomers, and these were heated at 73 °C for about 5 hours. Then, to the polymerization reaction solution, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the total mass of the total amount of all monomers was added, stirred for 12 hours, and then separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was filtered and recovered to obtain resin A4 having a weight average molecular weight of about 5.1×10 3 and the resin A4 was obtained in a yield of 61%. This resin A4 has the following structural units. TIFF0007716900000178.tif38154

[0267] <Preparation of Resist Composition> As shown in Table 2, the following components were mixed, and the obtained mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

Table 2

[0268] <Resin> A1~A4: Resin A1~Resin A4 <Acid Generator (B)> B1-25: Salt represented by formula (B1-25); synthesized by the method described in JP-A-2011-126869 TIFF0007716900000180.tif2667<Carboxylate (I)> I-2: Salt represented by formula (I-2) I-4: Salt represented by formula (I-4) I-5: Salt represented by formula (I-5) I-479: Salt represented by formula (I-479) I-1999: Salt represented by formula (I-1999) I-2474: Salt represented by formula (I-2474) I-3234: Salt represented by formula (I-3234) <Quencher (C)> IX-1 IX-2 IX-3 IX-4 TIFF0007716900000181.tif60162 <Solvent> 400 parts of propylene glycol monomethyl ether acetate 100 parts of propylene glycol monomethyl ether 5 parts of γ-butyrolactone

[0269] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 °C for 60 seconds. The resist composition was spin-coated on this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, it was pre-baked on a direct hot plate at the temperature shown in the "PB" column of Table 2 for 60 seconds to form a composition layer. A contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn on the composition layer formed on the wafer using an electron beam lithography machine ["ELS-F125 125 keV" manufactured by Elionix, Inc.] while changing the exposure dose stepwise. After exposure, post-exposure baking was performed on a hot plate at the temperature shown in the "PEB" column of Table 2 for 60 seconds, and further paddle development was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 60 seconds to obtain a resist pattern.

[0270] In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was defined as the effective sensitivity.

[0271] <CD Uniformity (CDU) Evaluation> In terms of effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. Using as the population the measurement of the average hole diameter of the patterns formed with a hole diameter of 17 nm at 400 locations within the same wafer, the standard deviation was obtained. The results are shown in Table 3. The numerical values in the table indicate the standard deviation (nm).

Table 3

[0272] (Electron Beam Exposure Evaluation of Resist Composition: Organic Solvent Development) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 °C for 60 seconds. The resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Thereafter, it was pre-baked on a direct hot plate at the temperature shown in the "PB" column of Table 2 for 60 seconds to form the composition layer. Using an electron beam lithography machine ["ELS-F125 125 keV" manufactured by Elionix, Inc.], a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn on the composition layer formed on the wafer while changing the exposure dose stepwise. After exposure, post-exposure baking was performed on a hot plate at the temperature shown in the "PEB" column of Table 2 for 60 seconds. Next, the composition layer on this silicon wafer was developed at 23 °C for 20 seconds by the dynamic dispense method using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the developer to obtain a resist pattern.

[0273] In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was taken as the effective sensitivity.

[0274] <CD Uniformity (CDU) Evaluation> In terms of effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was obtained using as the population the average hole diameters of the patterns formed with a hole diameter of 17 nm measured at 400 locations within the same wafer. The results are shown in Table 4. The numerical values in the table indicate the standard deviation (nm).

Table 4

Industrial Applicability

[0275] The carboxylate salt of the present invention and the resist composition containing the carboxylate salt have good CD uniformity (CDU) and are useful for semiconductor microfabrication.

Claims

1. The carboxylate salt represented by formula (I). [In formula (I), R １ , R ２ and R ３ each independently represents -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 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-, -S-, -CO- or -SO ２ -. R １０ represents an acid-stable hydrocarbon group represented by the formula (3a). X １ , X ２ and X ３ each independently represents an oxygen atom or a sulfur atom. m1 represents any integer from 1 to 5, and when m1 is 2 or more, the groups within multiple parentheses may be the same or different from each other. m2 represents any integer from 0 to 5, and when m2 is 2 or more, the groups within multiple parentheses may be the same or different from each other. m3 represents any integer from 0 to 5, and 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, the plurality of Rs １０ may be the same as or different from each other. m4 represents any integer from 0 to 4, and when m4 is 2 or more, the plurality of Rs ４ may be the same as or different from each other. m5 represents any integer from 0 to 4. When m5 is 2 or more, the plurality of Rs ５ may be the same as or different from each other. 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, the 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 (3a), R1a and R2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, or R1a and R2a are bonded to each other to form a hydrocarbon ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms. R3a represents a hydrogen atom, or R1a, R2a, and R3a are bonded to each other to form a hydrocarbon ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms. * represents a bond. ]

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

3. R １ , R ２ and R ３ is -O-CO-O-R １０ or -O-L １ -CO-O-R １０ The carboxylate according to claim 1 or 2, wherein

4. The carboxylate salt according to any one of Claims 1 to 3, wherein m1 is 1 or 2, and m2 and m3 are each 0 or 1.

5. The carboxylate salt according to any one of Claims 1 to 4, wherein when m2 is 0, m8 is 1, when m3 is 0, m9 is 1, and when m2 and m3 are 0, m8 and m9 are 1.

6. When m2 is 0, the bonding position of R ８ is in the p-position relative to the bonding position of S ＋ and when m3 is 0, the bonding position of R ９ is in the p-position relative to the bonding position of S ＋ The carboxylate according to claim 5.

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

8. 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 - contained in the alicyclic 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 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 7.

9. X ０ The carboxylate according to any one of claims 1 to 8, wherein X is 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.

10. X ０ The carboxylate according to any one of claims 1 to 8, 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 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 － . ]

11. A carboxylic acid generator containing the carboxylate salt according to any one of Claims 1 to 10.

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

13. The resist composition according to Claim 12, 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 an 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. ]

14. The resist composition according to Claim 12 or 13, wherein the resin having an acid-labile group contains a structural unit represented by formula (a2-A). [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a50 represents a single bond or *-X a51 -(A a52 -X a52 ) nｂ -, where * represents a bond with the carbon atom to which -R a50 is attached. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.]

15. (1) A step of applying the resist composition according to any one of claims 12 to 14 on a substrate; (2) A step of drying the applied composition to form a composition layer; (3) A step of exposing the composition layer; (4) A step of heating the exposed composition layer; and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern including the above steps.

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