Resist composition and method for producing resist pattern

Abstract

To provide a resist composition from which a resist pattern having good CD uniformity can be produced.SOLUTION: The resist composition contains: an acid generator containing a salt represented by formula (I); and a resin containing a structural unit having an acid-labile group and a structural unit represented by formula (a2-A). [In the formula (I), R1 represents -O-L1-CO-O-R5, L1 represents an alkanediyl group, and R5 represents a group of formula (1a); and Q1 and Q2 each represent an F atom or a perfluoroalkyl group.]SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resist composition and a method for producing a resist pattern.

Background Art

[0002] Patent Document 1 describes a resist composition containing a salt represented by the following formula as an acid generator. It is described. TIFF2025108554000001.tif2979 Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator. It is described. TIFF2025108554000002.tif2989 Patent Document 3 describes a resist composition containing a salt represented by the following formula as an acid generator. It is described. TIFF2025108554000003.tif3692

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention provides a resist composition that forms a resist pattern having better CD uniformity (CDU) than a resist pattern formed from a resist composition containing the above salt. This is the problem.

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF2025108554000004.tif46116[In formula (I), R 1 represents -O-L 1 -CO-O-R 5 represents. L 1 represents an alkanediyl group having 1 to 6 carbon atoms. R 5 represents an acid-labile group. R 2 , R 3 and R 4 each independently represents a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the hydrocarbon group may be replaced by -O- or -CO-. m2 represents any integer from 0 to 4, and when m2 is 2 or more, a plurality of R 2 may be the same or different from each other. m3 represents any integer from 0 to 5, and when m3 is 2 or more, a plurality of R 3 may be the same or different from each other. m4 represents any integer from 0 to 5, and when m4 is 2 or more, a plurality of R 4 may be the same or different from each other. Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. z represents any integer from 0 to 6, and when z is 2 or more, a plurality of R 11 and R 12 may be It may be the same or different even if it is the same. X 1 is *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (provided that *, C(R 11 )(R 12 ) or C(Q 1 )(Q 2 ) represents the bonding position with.). A 1 represents a group formed by combining a saturated cyclic hydrocarbon group and an alkanediyl group, and the total number of carbon atoms of the saturated cyclic hydrocarbon group and the alkanediyl group is 4 to 36. Both the saturated cyclic hydrocarbon group and the alkanediyl group may have substituents, and -CH2- contained in the saturated cyclic hydrocarbon group and the alkanediyl group may be replaced by -O-, -S-, -C O- or -SO2-. R 13 represents a cyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2- . [2]R 5 is the salt according to [1], which is a group represented by the formula (1a) or a group represented by the formula (2a). TIFF2025108554000005.tif2056 [In the formula (1a), R aa1 , R aa2 and R aa3 each independently represent an alkyl group having 1 to 8 carbon atoms which may have substituents, an alkenyl group having 2 to 8 carbon atoms which may have substituents, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have substituents, or R and R are bonded to each other, or R aa1 and R aa2 are bonded to each other. together with the carbon atom to which they are attached to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms . * represents a bond.] TIFF2025108554000006.tif2059[In formula (2a), R aa1’ and R aa2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 1 2 carbon atoms, and R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other to form, together with the -C-X a - to which they are attached, a heterocyclic group having 3 to 20 carbon atoms, and the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or - S-. S-. X a represents an oxygen atom or a sulfur atom. * represents a bond.] [3]A 1 is *-L 2 -CO-O-(L 2 represents a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms or a group formed by combining a cyclic hydrocarbon group having 3 to 18 carbon atoms and an alkanediyl group having 1 to 4 carbon atoms, and the -CH2- contained in the saturated cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and the -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. * represents the bond to X 1 .) or *-L 21 -W 1 -L 22 -CO-O-L 23 -(W 1 1 represents a divalent saturated cyclic hydrocarbon group which may have a substituent, and the -CH2- contained in the saturated cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2- and may be replaced by -O-, -S-, -CO- or -SO2-. 。L 21 、L 22 and L 23 each independently represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. * represents the bonding site with X The salt described in [1] or [2]. * is the bonding site with X 1 The salt described in [1] or [2]. salt. [4] L 2 and W 1 are a group represented by the following formula (L 2 -1), formula (L 2 -2), formula (L 2 -3) or formula (L 2 -4) (* represents a bond). The salt described in [3]. TIFF2025108554000007.tif3096[5] X 1 is -CO-O-. The salt described in any one of [1] to [4]. [6] m3 is any integer from 1 to 2, m4 is any integer from 0 to 2, R 3 and R 4 either one of them is a fluorine atom, an iodine atom or trifluoromethyl The salt described in any one of [1] to [5]. [7] m3 is any integer from 1 to 2, m4 is any integer from 0 to 2, R 3 and R 4 either one of them is -O-L 1 -CO-O-R 5 and a plurality of R 5 may be the same as or different from each other. The salt described in any one of [1] to [5]. salt. [8] m2 is 1 or 2, at least one of a plurality of R 2 is -O-L 1 -CO-O-R 5and a plurality of R 5 may be the same as or different from each other, and are any one of [1] to [7] described salts. An acid generator containing the salt described in any one of [9][1] to [8].[[]END]]

[10] A resist composition containing the acid generator described in [9] and a resin having an acid-labile group .

[11] The resist composition according to

[10] , wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1 -2). resist composition. TIFF2025108554000008.tif49107 [In the formula (a1-1) and the formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -CO-O -, k1 represents an integer of any one of 1 to 7, and * represents a bond with -CO. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an 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 any one of 0 to 14. n1 represents an integer of any one of 0 to 10. n1'represents an integer of any one of 0 to 3.]

[12] The resist composition according to

[0010] or

[11] , wherein the resin having an acid-labile group contains a structural unit represented by the formula (a2-A). TIFF2025108554000009.tif5259 [In the formula (a2-A), R a50 ​represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. represents 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. represents 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. represents 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. represents an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or * -X a51 -(A a52 -X a52 ) nb - and * represents a bond to the carbon atom to which -R a50 is bonded. represents a bond to the carbon atom to which -R 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 an integer of 2 or more, a plurality of R may be the same as or different from each other. a51 Further containing a salt that generates an acid having a lower acidity than the acid generated from the

[13] acid generator. The resist composition according to any one of

[10] to

[12] .

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

[10] to

[13] onto a substrate. step, (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 steps.​

Advantages of the Invention

[0006] By using the resist composition containing the salt 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 “(meth)acrylic monomer” means at least one selected from the group consisting of a monomer having a structure of “CH2=CH-CO-” and a monomer having a structure of “CH2=C(CH3)-CO-”. Similarly, “(meth)acrylate” and “(meth)acrylic acid” mean at least one selected from the group consisting of “at least one selected from the group consisting of acrylate and methacrylate” and “at least one selected from the group consisting of acrylic acid and methacrylic acid”, respectively. When a structural unit having a structure of “CH2=C(CH3)-CO-” or “CH2=CH-CO-” is exemplified, a structural unit having both groups is similarly exemplified. Also, among the groups described in this specification, those that can take both a linear structure and a branched structure may be either of them. The “combined group” means a group in which two or more of the exemplified groups are bonded, and the valences of those groups may be appropriately changed depending on the bonding form “Derived from” or “derived” refers to the fact that the polymerizable C=C bond contained in the molecule becomes a -C-C- group by polymerization. When stereoisomers exist, all stereoisomers are included. When a structural unit having a structure of “CH2=C(CH3)-CO-” or “CH2=CH-CO-” is exemplified, a structural unit having both groups is similarly exemplified. Also, among the groups described in this specification, those that can take both a linear structure and a branched structure may be either of them. The “combined group” means a group in which two or more of the exemplified groups are bonded, and the valences of those groups may be appropriately changed depending on the bonding form “Derived from” or “derived” refers to the fact that the polymerizable C=C bond contained in the molecule becomes a -C-C- group by polymerization. When stereoisomers exist, all stereoisomers are included. stereoisomers are included.

[0008] The present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as “salt (I)”). Among salts (I), the side having a negative charge is “anion (I)”, and the side having a positive charge is “cation” may be referred to as "on (I)". TIFF2025108554000010.tif46116 [wherein all the symbols have the same meanings as described above.]

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

[0010] R 1 The acid-labile group in R 5 means a group that forms a carboxy group by elimination of the group represented by R upon contact with an acid (e.g., trifluoromethanesulfonic acid). 5 Examples of the acid-labile group include a group represented by formula (1a) (hereinafter, sometimes referred to as "acid-labile group (1a" ).), a group represented by formula (2a) (hereinafter, sometimes referred to as "acid-labile group (2a)"). are preferred. TIFF2025108554000011.tif2056 [In formula (1a), R aa1 , R aa2 and R aa3each independently may have a substituent an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or R and R aa1 and R aa2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded . * represents a bond.] TIFF2025108554000012.tif2059[In formula (2a), R aa1’ and R aa2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 1 2 carbon atoms, R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the -C-X a - to which they are bonded, and -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or - S-. X a represents an oxygen atom or a sulfur atom. * represents a bond.]

[0011] R aa1 、R aa2 and R aa3 Examples of the alkyl group of include methyl group, ethyl group, propyl group, n -butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like. The number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 3 . R aa1 、R aa2 and R aa3 ​Examples of the alkenyl group include ethenyl group, propenyl group, isoprop ropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hex enyl group, heptenyl group, octynyl group, isooctynyl group, nonenyl group. R aa1 、R aa2 and R aa3 's alicyclic hydrocarbon groups may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cyclohept tyl group, cyclooctyl group, etc. Examples of the polycyclic alicyclic hydrocarbon group include, for example, decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents a bond). etc. R aa1 、R aa2 and R aa 's alicyclic hydrocarbon group The number of carbon atoms is preferably 3 to 16, more preferably 3 to 12. TIFF2025108554000013.tif9159R aa1 、R aa2 and R aa3 Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anth ryl group, biphenyl group, phenanthryl group, etc. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10.

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

[0013] R aa1 and R aa2 When they are bonded to each other to form an alicyclic hydrocarbon group, examples of -C(R aa1 )( R aa2 )(R aa3 ) include the following groups. The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms, more preferably 3 to 12 carbon atoms. * represents a bond to -O-. Examples thereof include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Examples thereof include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alicyclic hydrocarbon group having 3 to 20 carbon atoms. TIFF2025108554000014.tif31145

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

[0015] Examples of the hydrocarbon groups of R aa1' , R aa2' , and R aa3' include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups. Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those exemplified for R aa1 , R aa2 , and R aa . Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, etc. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., an alkylcycloalkyl group or a cycloalkylalkyl group), an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (a p-methylphenyl group, a p-ter group), etc. ​t-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-di ethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as phenylcyclohexyl group, etc. may be mentioned. R aa2' and R aa3' are bonded to each other and together with the carbon atom to which they are bonded and X a form a heterocyclic group, -C(R aa1' )(R aa2' )-X a -(R aa3' ) includes the following groups may be mentioned. * represents a bond. TIFF2025108554000015.tif22152R aa1' and R aa2' Of these, at least one is preferably a hydrogen atom.

[0016] Specific examples of the acid-labile group (1a) include the following groups. * represents a bond. TIFF2025108554000016.tif69152

[0017] Specific examples of the acid-labile group (2a) include the following groups. * represents a bond. TIFF2025108554000017.tif68167R 1 The bonding position of to the benzene ring of S + may be any of ortho, meta, and para positions with respect to but is preferably the para position.

[0018] R 2 R 3 and R 4 The C1-C4 fluorinated alkyl group of and is a carbon having a fluorine atom ​Represents an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms (trifluoro methyl 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 and the like. R 2 、R 3 and R 4 The hydrocarbon groups having 1 to 18 carbon atoms include chain-like carbonized hydrogen groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-but yl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group and the like. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as 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, norbornil group and the like. Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group and the like.

[0019] Examples of the group formed by combination include a group formed by combining an aromatic hydrocarbon group and a chain-like hydrocarbon group (for example, aromatic hydrocarbon group - alkane diyl group - *, alkyl group - aromatic An aromatic hydrocarbon group-*), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example , an alicyclic hydrocarbon group-alkanediyl group-*, an alkyl group-alicyclic hydrocarbon group-*), an aro matic hydrocarbon group and a group combining an alicyclic hydrocarbon group (for example, an aromatic hydrocarbon group-al icyclic hydrocarbon group-*, an alicyclic hydrocarbon group-aromatic hydrocarbon group-*). * represents a bond ing site. Examples of the aromatic hydrocarbon group-alkanediyl group-* include aralkyl groups such as a benzyl group and a phenethyl group. Examples of the alkyl group-aromatic hydrocarbon group-* include a tolyl group, a xylyl group, and a cumenyl group. Examples of the alicyclic hydrocarbon group-alkanediyl group-* include cycloalkylalkyl groups such as a cyclohexylmethyl group, a cyclo hexylethyl group, a 1-(adamantan-1-yl)methyl group, and a 1-(adamantan-1 -yl)-1-methylethyl. Examples of the alkyl group-alicyclic hydrocarbon group-* include cycloalkyl groups having an alkyl group such as a methylcyclohexyl group, a dimethylcyclo hexyl 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 of the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the chain hydrocarbon group may be combined. Also, any of the groups may be bonded to the benzene ring. Examples of the group in which -CH2- contained in the hydrocarbon group is replaced by -O- or -CO- include Hydroxy group; carboxy group; alkoxy groups having 1 to 11 carbon atoms such as methoxy group, ethoxy group, butoxy group; cycloalkoxy groups having 3 to 11 carbon atoms such as cyclohexyloxy group; cycloalkylalkoxy groups having 4 to 11 carbon atoms such as cyclohexylmethoxy group; alkylcarbonyl groups having 2 to 12 carbon atoms such as acetyl group; alkoxycarbonyl groups having 2 to 11 carbon atoms such as methoxycarbonyl group; alkylcarbonyloxy groups having 2 to 11 carbon atoms such as acetyloxy group; alkoxycarbonyloxy groups having 2 to 11 carbon atoms such as butoxycarbonyloxy group; aromatic hydrocarbon group-carbonyl oxy groups having 7 to 11 carbon atoms such as benzoyloxy group etc. may be mentioned.

[0020] m2 is preferably any integer from 0 to 2, more preferably 0 or 2. m3 and m4 are each independently preferably any integer from 0 to 2, more preferably 0 or 1. R 2 is a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-). ), -O-L -CO-O-R 5 (the symbols of L 1 and R 5 are the same as above). 1 is preferably, and more preferably an alkyl group having 1 to 4 carbon atoms (wherein -CH2- contained in the alkyl group may be replaced by -O- - or -CO-), or -O-L -CO-O-R 5 (the symbols of L 1 and R are the same as above), and still more preferably an alkyl group having 1 to 4 carbon atoms or 5 -O-L ​1 -CO-O-R 5 (L 1 and R 5 have the same symbols as described above.) is more preferred. When m2 is 1 or 2, at least one of the plurality of R 2 is -O-L 1 -CO-O-R 5 is preferably. R 3 and R 4 are each independently a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 6 carbon atoms (the -CH2- contained in the alkyl group may be replaced by -O- or -C O-).), -O-L 1 -CO-O-R 5 (L 1 and R 5 symbols are the same as described above.) is preferably, a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms (the -CH2- contained in the alkyl group may be replaced by -O- or -CO-).), -O-L 1 -CO-O-R 5 (L 1 and R 5 of symbols are the same as described above.) is more preferably, a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is even more preferred. Furthermore, when m3 is any integer from 1 to 2 and m4 is an integer from 0 to 2, R 3 and and R 4 either one of them is a fluorine atom, an iodine atom, a trifluoromethyl group or - - O-L 1 -CO-O-R 5 (L 1 and R 5 symbols are the same as described above.) is even more preferred. In formula (I), when there are a plurality of Rs 5 if present, the plurality of Rs 5 may be the same as or different from each other from each other.

[0021] Examples of the cation of salt (I) include cations represented by the following formulae (I-c-1) to (I-c-26). etc. TIFF2025108554000018.tif82157

[0022] TIFF2025108554000019.tif212163

[0023] TIFF2025108554000020.tif235160

[0024] Among them, cations represented by formulae (I-c-1) to (I-c-9), formula (I-c-16), formula (I-c- 19), formula (I-c-20), and formula (I-c-25) are preferred, and cations represented by formulae ( I-c-1) to (I-c-6), formula (I-c-16), formula (I-c-19), formula (I- c-20), and formula (I-c-25) are more preferred, and cations represented by formula (I-c-1) to (I-c-4), formula (I-c-16), formula (I-c-19), formula (I-c-20), formula (I-c-25) are even more preferred, and cations represented by formula (I-c-1), formula (I- c-3), formula (I-c-4), formula (I-c-16), formula (I-c-19), formula (I-c- 20), and formula (I-c-25) are even more preferably.

[0025] In formula (I), Q 1 and Q 2 and R 11 and R 12 Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoro Isopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group and the like can be mentioned. Hereof. Q 1 And Q 2 Are each independently preferably a trifluoromethyl group or a fluorine atom And more preferably a fluorine atom. R 11 And R 12 Are each independently preferably a hydrogen atom or a fluorine atom. z is preferably 0 or 1. X 1 Is preferably *-CO-O- or *-O-CO-O-, and more preferably *-CO-O -(where * represents a bond with C(R 11 )(R 12 ) or C(Q 1 )(Q 2 ).). Represents a bond.).

[0026] A 1 Represents a group formed by combining a saturated cyclic hydrocarbon group and an alkanediyl group. As the saturated cyclic hydrocarbon group, any of monocyclic, polycyclic and spiro ring may be used. For example , The following groups can be mentioned. The bond can be at any position. TIFF2025108554000021.tif41166

[0027] A 1 The saturated cyclic hydrocarbon group contained in A preferably has 3 to 35 carbon atoms, and more preferably Has 3 to 34 carbon atoms, still more preferably has 3 to 18 carbon atoms , And still more preferably has 3 to 16 carbon atoms. A 1 The saturated cyclic hydrocarbon group contained in A may be one or more. As the saturated cyclic hydrocarbon group Then, for example, a monocyclic saturated cyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a polycyclic saturated 1 cyclic hydrocarbon group such as a norbornyl group, a group represented by the following formula (A -1), a group represented by the formula (A 1 -2), a group represented by the formula (A 1 -3), etc. are more preferable, and a cyclohexyl group, a group represented by the following formula (A -1), 1 a group represented by the following formula (A -2) or a group represented by the formula (A 1 -3) is even more 1 preferable, and a group represented by the following formula (A -1), a group represented by the following formula (A 1 -2) or a group represented by the formula ( 1 A A 1 -3) is even more preferably a group represented by the following formula (A 1 -2), and it is even more preferable that it is a group represented by the following formula (A -2). The bond can be at any position. TIFF2025108554000022.tif2966

[0028] In the saturated cyclic hydrocarbon group, -CH2- contained in the saturated cyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-. When -C H2- contained in the saturated cyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated cyclic hydrocarbon group. Examples of the group in which -C H2- contained in the saturated cyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include the following groups. The bond can be at any position. Among them, the following groups are preferable. TIFF2025108554000023.tif74150 Among them, the following groups are preferable. TIFF2025108554000024.tif19132

[0029] Examples of the alkanediyl group 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 , a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,1 2-diyl group, and other linear alkanediyl groups; 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, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, and other branched alkanediyl groups.

[0030] The -CH2- contained in the alkanediyl group may be replaced by -O-, -S-, -CO- or -SO2- . When the -CH2- contained in the alkanediyl group is replaced by -O-, -S-, -CO- or -SO2- , the number of carbon atoms before replacement is taken as the number of carbon atoms of the alkanediyl group. Examples of the group in which the -CH2- contained in the alkanediyl group is replaced by -O- or -CO- include a carbonyloxy group (a group in which -CH2-CH2- contained in the ethylene group is replaced by -O-CO-), an alkanediyl-oxy group (a group in which -CH2- contained in the alkanediyl group is replaced by -O-), an alkanediyl-oxycarbonyl group (a group in which -CH2-CH2- contained in the alkanediyl group is replaced by -O-CO-), an alkanediyl A carbonyl group (a group in which -CH2- contained in an alkanediyl group is replaced by -CO-), an alkanediylcarbonyloxy group (a group in which -CH2-CH2- contained in an alkanediyl group is replaced by -CO-O-), etc. may be mentioned. ) - is replaced by -CO-O-), etc. may be mentioned. Examples of the alkanediyl group include a methyleneoxy group, an ethyleneoxy group, a propylene oxy group, a butyleneoxy group, a pentanediyl group, a hexanediyl group, an oct anediyl group, a 2-ethylhexanediyl group, a nonanediyl group, a dec anediyl group, an undecanediyl group, etc. may be mentioned. The alkanediyl oxycarbonyl group, the alkanediylcarbonyl group and the alkanediyl carbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkanediyl group or alkanediyl oxy group. Examples of the alkanediyl oxycarbonyl group include a methyleneoxycarbonyl group, an ethylene oxycarbonyl group, a butyleneoxycarbonyl group, etc., examples of the alkanediylcarbonyl group include an ethylenecarbonyl group, a propylenecarbonyl group and a butylenecarbonyl group, etc., and examples of the alkanediylcarbonyloxy group include an ethylenecarbonylo xy group, a propylenecarbonyloxy group, a butylenecarbonyloxy group, etc. may be mentioned.

[0031] The total number of carbon atoms of the saturated cyclic hydrocarbon group and the alkanediyl group is 4 to 36, preferably 4 to 34, more preferably 6 to 32, and still more preferably 8 to 30. Further, these saturated cyclic hydrocarbon groups and alkanediyl groups may each have a substituent.

[0032] A 1A group formed by combining a saturated cyclic hydrocarbon group and an alkanediyl group, in the alkan diyl group, -CH2- contained therein is preferably replaced by -O-, -S-, -CO- or -SO2- . In this case, one -CH2- may be replaced, but those in which two or more -CH2- are replaced are preferred. For example, those replaced by one -O-, -S-, -CO- or -SO2-, those replaced by two -O-, -S- or -CO-, those replaced by one or more -O- or -S- and one or more -CO- or -SO2- and the like can be mentioned. Specifically, -O-, -CO-, -O-CO-, -CO-O- , -O-CO-O- and the like can be mentioned. Among them, -O-CO-, -CO-O-, -O-C O-O- are preferred. For example, when A is *-L 1 -CO-O-, *-L 2 -O-CO-, *-L 2 -O-CO 2 -O-, *-L -O-CO 21 -W 1 -L 22 -CO-O-L 23 -, *-L 21 -W 1 -L 22 - O-CO-L 23 - or *-L 21 -W 1 -L 22 -O-CO-O-L 23 -. Here, * represents the bonding site with X . 1 Here, L represents a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms or a group formed by combining a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms and an alkanediyl group having 1 to 4 carbon atoms, and -CH2- contained in the saturated cyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- 2 . In the hydrocarbon group, -CH2- contained therein is preferably replaced by -O-, -S-, -CO- or -SO2- Alternatively, -CH2- contained in the alkandiyl group may be replaced with -O- or -CO-. L 2 Examples of the saturated cyclic hydrocarbon group and the alkandiyl group in include the same groups as those exemplified above. L 2 is preferably a polycyclic divalent saturated cyclic hydrocarbon group having 6 to 12 carbon atoms (the saturated cyclic hydrocarbon group may have a substituent, and -CH2- contained in the saturated cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-). More preferably, it is a polycyclic divalent saturated alicyclic hydrocarbon group having 7 to 11 carbon atoms (the -CH2- contained in the saturated alicyclic hydrocarbon group may be replaced with -O- or -CO-). Even more preferably, it is a group represented by the following formula (L 2 -1), a group represented by the formula (L 2 -2), a group represented by the formula (L 2 - 3), or a group represented by the formula (L 2 -4), and even more preferably, it is a group represented by the formula ( L 2 -2). TIFF2025108554000025.tif3096 Also, W 1 represents a divalent saturated cyclic hydrocarbon group, which may have a substituent, and -CH2- contained in the saturated cyclic hydrocarbon group may be replaced with -O-, -S-, -C O- or -SO2-. L O-. L 21 L 22 and L 23 each independently represent a single bond or an alkandiyl group having 1 to 4 carbon atoms, and -CH2- contained in the alkandiyl group may be replaced with -O- or -CO-. In this case, the saturated cyclic hydrocarbon group in W and L 1 in ​21 , L 22 and L 23 The alkandiyl group in Examples thereof include the same groups as those exemplified above. W 1 is a polycyclic divalent saturated cyclic hydrocarbon group having 6 to 12 carbon atoms (the saturated cyclic hydrocarbon group may have a substituent, and -CH2- contained in the saturated cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). Preferably,[[]] a polycyclic divalent saturated alicyclic hydrocarbon group having 7 to 11 carbon atoms (the -CH2- contained in the saturated alicyclic hydrocarbon group may be replaced by -O- or -CO-). More preferably,[[]] the group represented by the above formula (L 2 -1), the group represented by the formula (L 2 -2), the group represented by the formula (L 2 -[[]] 3), or the group represented by the formula (L 2 -4). Even more preferably, it is the group represented by the formula([[]] L 2 -2). Even more preferably, it is the group represented by the formula (L 21 , L 22 and L 23 are each independently , a single bond or an alkandiyl group having 1 to 3 carbon atoms (the -CH2 - contained in the alkandiyl group may be replaced by -O- or -CO-). Preferably,[[]] Among them, A 1 is *-L 2 -CO-O- or *-L 21 -W 1 -L 22 -CO-O- L 23 -. Preferably, it is *-L 2 -CO-O-. More preferably, it is *-L

[0033] A 1 The saturated cyclic hydrocarbon group and the alkandiyl group in may have one or more substituents It may be. A 1 As substituents that the saturated cyclic hydrocarbon group and the alkanediyl group in may have include a halogen atom, a hydroxy group, a cyano group, a carboxy 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, a carbon alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, a carbon alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a group formed by combining these. etc. can be mentioned.

[0034] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. etc. can be mentioned. Examples of the alkyl group having 1 to 12 carbon atoms 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 nonyl group, a decyl group, an undecyl group and a dodecyl group etc. can be mentioned. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a but oxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexy loxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group etc. can be mentioned. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy carbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexy loxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, an undecy loxycarbonyl group, and a dodecyloxycarbonyl group etc. can be mentioned. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propio nyloxy group, and a butyryloxy group. Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.

[0035] Examples of the combined group include a group formed by combining an alkoxy group having 1 to 12 carbon atoms and an alkyl group having 1 to 12 carbon atoms, a group formed by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group formed by combining an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, a group formed by combining an alkoxy group having 1 to 12 carbon atoms and an alkylcarbonyl group having 2 to 13 carbon atoms, a group formed by combining an alkoxy group having 1 to 12 carbon atoms and an alkylcarbonyloxy group having 2 to 13 carbon atoms, a group formed by combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the like. Examples of the group formed by combining an alkoxy group having 1 to 12 carbon atoms and an alkyl group having 1 to 12 carbon atoms include alkoxyalkyl groups having 2 to 24 carbon atoms such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and an ethoxymethyl group. Examples of the group formed by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms include hydroxyalkyl groups having 1 to 12 carbon atoms such as a hydroxymethyl group and a A group combining an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms Examples thereof include alkoxyalkoxy groups having 2 to 24 carbon atoms such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group. Examples of a group combining an alkoxy group having 1 to 12 carbon atoms and an alkylcarbonyl group having 2 to 13 carbon atoms include alkoxyalkylcarbonyl groups having 3 to 25 carbon atoms such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, and an ethoxypropionyl group. Examples of a group combining an alkoxy group having 1 to 12 carbon atoms and an alkylcarbonyloxy group having 2 to 13 carbon atoms include alkoxyalkylcarbonyloxy groups having 2 to 24 carbon atoms such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, and an ethoxypropionyloxy group. Examples of a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include aralkyl groups having 7 to 22 carbon atoms such as a benzyl group.

[0036] The substituent is preferably a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylcarbonyloxy group having 2 to 1 3 carbon atoms, an alkoxyalkyl group having 2 to 24 carbon atoms, an alkoxyalkoxy group having 2 to 24 carbon atoms, or a cyano group, and more preferably a halogen atom, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0037] A 1 ​​​​Examples of the group include the following. * and ** represent bonds, and * represents a bond with X 1 bond with represents a bond. TIFF2025108554000026.tif116165

[0038] R 13 The cyclic hydrocarbon group of R may be monocyclic, polycyclic or spiro, and may be saturated or unsaturated, and examples include alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of the alicyclic hydrocarbon group include the groups shown below. The bond can be at any position. TIFF2025108554000027.tif41166 Specifically, monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, etc., and polycyclic cycloalkyl groups such as norbornyl group and adamantyl group are included. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, phenanthryl group, etc. The number of carbon atoms in the cyclic hydrocarbon group is preferably 3 to 18 and more preferably 3 to 16. R 13 When -CH2- contained in the cyclic hydrocarbon group of R is replaced by -O-, -S-, -CO- or -SO 2-, the number of carbon atoms before replacement is taken as the total number of carbon atoms of the cyclic hydrocarbon group. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2 - include the following groups, etc. The bond can be at any position. TIFF2025108554000028.tif74150

[0039] R​​​​13 The alicyclic hydrocarbon group in and the -CH2- contained in the alicyclic hydrocarbon group being -O- As the group replaced by -S-, -SO2- or -CO-, it is preferably a group represented by formulas (Y1) to (Y41) and more preferably a group represented by any of formula (Y1) to formula (Y20), formula (Y26), formula (Y 27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43), and even more preferably a group represented by formula (Y3), formula (Y4), formula (Y11), formula (Y15) , formula (Y18), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y3 1), formula (Y39), formula (Y40), formula (Y42) or formula (Y43). Even more preferably. TIFF2025108554000029.tif85168

[0040] R 13 The cyclic hydrocarbon group of R has 3 to 24 carbon atoms in total 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 16 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 iodine. Examples of the alkyl group having 1 to 12 carbon atoms 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 nonyl group, a decyl group, an undecyl group and a dodecyl group. Examples of the alkyl group having 1 to 12 carbon atoms 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 nonyl group, a decyl group, an undecyl group, a dodecyl 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-ethylhexy loxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. 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, and a butoxycarbonyl group. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alicyclic hydrocarbon group having 3 to 16 carbon atoms may be either monocyclic or polycyclic. Examples thereof include the groups shown below. ** represents a bond to an aromatic hydrocarbon group. TIFF2025108554000030.tif16157 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.

[0041] R 13 Examples of the combined groups in the substituent of R include a group combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms, a group combining an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, and a group combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms. ​Examples of the group formed by combining a hydroxy group and an alkyl group having 1 to 12 carbon atoms include hydroxy alkyl groups having 1 to 12 carbon atoms such as a methyl group and a hydroxyethyl group, etc. are included. Examples of the group formed by combining an alkoxy group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms include alkoxyalkoxy groups having 2 to 24 carbon atoms such as an ethoxyethoxy group, etc. are included. Examples of the group formed by combining an alkyl group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms include aralkyl groups having 7 to 22 carbon atoms such as a benzyl group, etc.

[0042] R 13 The substituent that R has is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, a hydroxy group or a halogen atom, and more preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a fluorine atom.

[0043] R 13 The cyclic hydrocarbon group of R (the cyclic hydrocarbon group may have a substituent, and -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-) is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms that may have a substituent (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 18 carbon atoms that may have a substituent, and more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms that may have an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a fluorine atom (wherein -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-). ​​​​​​​​​It may be replaced). Specifically, preferably, an alkyl group having 1 to 4 carbon atoms is a cyclopentyl group having, a cyclohexyl group having an alkyl group having 1 to 4 carbon atoms, a carbon number an adamantyl group having 1 to 4 alkyl groups, a hydroxyadamantyl group, an adamantano ne group, an adamantanlactone ring group or a norbornanelactone ring group, more preferably an adamantyl group having an alkyl group having 1 to 4 carbon atoms, a hydroxyadamantyl group or an adamantanone group.

[0044] Examples of the anion (I) include anions represented by the following formulas (Ia-1) to (Ia-20). Among them, anions represented by formulas (Ia-1) to (Ia-12), formula (Ia-18 ), and formula (Ia-19) are preferred, and anions represented by formula (Ia-1), formula (Ia-2) ), formulas (Ia-8) to (Ia-12), and formula (Ia-19) are more preferred. TIFF2025108554000031.tif185141

[0045] TIFF2025108554000032.tif162149

[0046] Examples of the salt (I) include the salts listed in Table 1. For example, in Table 1, the salt (I-1) is a salt formed from an anion represented by formula (Ia-1) and a cation represented by formula (b2-c-1), and means the salt shown below. TIFF2025108554000033.tif24110

[0047]

Table 1

[0048] <Method for producing salt (I)> Salt (I) can be produced by reacting the salt represented by formula (I-a) and the salt represented by formula (I-b) in a solvent. TIFF2025108554000047.tif86148 [In the formula, all the symbols have the same meanings as described above.] 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.

[0049] Examples of the salt represented by formula (I-a) include salts represented by the following formula, etc., which can be easily obtained from the market and can also be easily produced by known production methods. TIFF2025108554000048.tif145159

[0050] Examples of the salt represented by formula (I-b) include salts represented by the following, etc., which can be easily obtained from the market and can also be easily produced by known production methods. TIFF2025108554000049.tif24133

[0051] <Acid generator> The acid generator of the present invention is an acid generator containing salt (I). It may contain one kind of salt (I) or may contain two or more kinds of salt (I). In addition to salt (I), the acid generator of the present invention may contain an acid generator known in the resist field (hereinafter sometimes referred to as "acid generator (B)"). Acid generator (B) can be used alone or in combination with other components. ​​​​Alternatively, two or more of them may be used in combination.

[0052] The acid generator (B) may be either a nonionic or ionic acid generator. Biocides include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, etc.). sulfonates, oximesulfonates, N-sulfonyloxyimides, sulfonyloxyketones ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g. disulfone, ketone Examples of ionic acid generators include oni Onium salts containing ion cations (e.g. diazonium salts, phosphonium salts, sulfonium salts) The anion of the onium salt is typically a sulfonate anion. ion, sulfonylimide anion, sulfonylmethide anion, etc.

[0053] Examples of the acid generator (B) include those described in JP-A-63-26653 and JP-A-55-164824. JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate an acid when exposed to radiation, such as those described in US Pat. No. 5,312,712, can be used. In addition, a compound produced by a known method may be used. The acid generator (B) may be a compound containing two or more kinds of compounds. They may also be used in combination.

[0054] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)", except for salt (I).) It is. TIFF2025108554000050.tif2963[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and the 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 the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, - S(O)2- or -CO-. Z1 + represents an organic cation.]

[0055] Q b1 and Q b2 Examples of the perfluoroalkyl group represented by include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluoro butyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoro pentyl group, and a perfluorohexyl group. Q b1 and Q b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0056] L b1 Examples of the divalent saturated hydrocarbon group in include a linear alkanediyl group, a branched al kanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and these groups It may also be a group formed by combining two or more of them. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4 -diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1 ,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1 ,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane- 1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17- diyl group, etc., linear alkanediyl groups; 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, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc., branched alkanediyl groups; a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohex ane-1,4-diyl group, a cyclooctane-1,5-diyl group, etc., cycloalkanediyl groups which are monocyclic divalent alicyclic saturated hydrocarbon groups; a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane- 1,5-diyl group, an adamantane-2,6-diyl group, etc., polycyclic divalent alicyclic saturated carbon hydrogen groups and the like can be mentioned.

[0057] L b1 In the divalent saturated hydrocarbon group represented by, when -CH2- contained therein is replaced by -O- or -CO-, examples of the group include those represented by any of formula (b1-1) to formula (b1-3) and are represented by Examples of the group include. In the groups represented by formula (b1-1) to formula (b1-3) and their specific examples, formula (b1-4) to formula (b1-11), * and ** represent bonding hands, and * represents a bonding hand with -Y. In the groups represented by formula (b1-4) to formula (b1-11) which are specific examples, * and ** represent bonding hands, and * represents a bonding hand with -Y. In the groups represented by formula (b1-4) to formula (b1-11) which are specific examples, * and ** represent bonding hands, and * represents a bonding hand with -Y.

[0058] TIFF2025108554000051.tif26117 [In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L and L b2 and L b3 is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, the total number of carbon atoms of L and L b4 and L b5 is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. The hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the 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 replaced with -O- or -CO-. However, b6 the total number of carbon atoms of b7 L and L is 23 or less. * and ** represent bonds, and * represents a bond with Y.]

[0059] In the groups represented by formula (b1-1) to formula (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include the same groups as the divalent saturated hydrocarbon group of L. b1 are mentioned.

[0060] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be 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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b7is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups , and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO- .

[0061] L b1 As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO-, a group represented by formula (b1-1) or formula (b1-3) is preferable. As the group represented by formula (b1-1), groups represented by formulas (b1-4) to (b1-8) are exemplified. In formula (b1-4), L TIFF2025108554000052.tif48120represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon L b8 group may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L 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, the total number of carbon atoms of L b9 and L b10 is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the divalent saturated The hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. . However, the total number of carbon atoms of L b11 and L b12 is 21 or less. In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. . However, the total number of carbon atoms of L b13 to L b15 is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. . However, the total number of carbon atoms of L b16 to L b18 is 19 or less. 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. Lb10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. * and ** represent bonds, and * represents the bond to Y.]

[0062] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11), respectively. are as follows. TIFF2025108554000053.tif23139[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 in the saturated hydrocarbon group may be substituted with fluorine atoms. L b20represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total number of carbon atoms of L b19 and L b20 is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L 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 a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total number of carbon atoms of L b21 , L b22 and L b23 is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with 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 the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. The -CH2- contained in the alkylcarbonyloxy group may be replaced by -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total number of carbon atoms of L , L , and L b24 is 21 or less. b25 and L b26 * and ** represent bonds, and * represents a bond to Y.]

[0063] In addition, in the group represented by the formula (b1-9) to the group represented by the formula (b1-11), when the hydrogen atoms contained in the saturated hydrocarbon group are substituted with an alkylcarbonyloxy group, the number of carbon atoms before substitution is taken as the number of carbon atoms of the saturated hydrocarbon group. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

[0064] Examples of the group represented by the formula (b1-4) include the following. TIFF2025108554000054.tif17151(* and ** represent bonds, and * represents a bond to Y.)

[0065] Examples of the group represented by the formula (b1-5) include the following. TIFF2025108554000055.tif72149(* and ** represent bonds, and * represents a bond to Y.)

[0066] Examples of the group represented by formula (b1-6) include the following. TIFF2025108554000056.tif29150 (* and ** represent bonds, and * represents the bond to Y.)

[0067] Examples of the group represented by formula (b1-7) include the following. TIFF2025108554000057.tif63151 (* and ** represent bonds, and * represents the bond to Y.)

[0068] Examples of the group represented by formula (b1-8) include the following. TIFF2025108554000058.tif23150 (* and ** represent bonds, and * represents the bond to Y.)

[0069] Examples of the group represented by formula (b1-2) include the following. TIFF2025108554000059.tif31160 (* and ** represent bonds, and * represents the bond to Y.)

[0070] Examples of the group represented by formula (b1-9) include the following. TIFF2025108554000060.tif44137 (* and ** represent bonds, and * represents the bond to Y.)

[0071] Examples of the group represented by formula (b1-10) include the following. TIFF2025108554000061.tif88159 (* and ** represent bonds, and * represents the bond to Y.)

[0072] Examples of the group represented by formula (b1-11) include the following. TIFF2025108554000062.tif81158 (* and ** represent bonds, and * represents the bond to Y.)

[0073] Examples of the alicyclic hydrocarbon group represented by Y include 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-, -S(O)2- or - CO-, the number thereof may be one or two or more. Examples of such groups include groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). * represents a bond to L b1 and represents a bond to L. TIFF2025108554000063.tif85168 Examples of the alicyclic hydrocarbon group represented by Y preferably include groups represented by formula (Y1) to formula (Y20), formula ( Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43), more preferably a group represented by any of formula (Y11), formula (Y15), formula (Y16 ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39), 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 having an oxygen atom such as formula (Y28) to formula (Y35), formula (Y39), formula (Y 40), formula (Y42) or formula (Y43), the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. In addition, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom preferably has no fluorine atom substituted thereon.

[0074] ​​The substituent of the methyl group represented by Y is a halogen atom, a hydroxyl group, a methyl group having 3 to 1 carbon atoms, 6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -( CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, represents an aromatic hydrocarbon group having a molecular weight of from 0 to 18 or a combination thereof; The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group represents an integer of -O- , -S(O)2- or -CO-, and the alkyl group, the alicyclic carbon atom, The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group is replaced with a hydroxyl group or a fluorine atom. It may be replaced.) The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxyl group, an alkyl group having 1 to 16 carbon atoms which may be substituted with an alkoxy group (the alkyl group -CH2- may be replaced by -O- or -CO-.) A cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, Glycidyloxy group, -(CH2) ja -CO-OR b1 Group or -(CH2) ja -O -CO-R b1 group (in the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an aliphatic group having 3 to 16 carbon atoms. A cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. ja represents an integer of 0 to 4. The alkyl group and the alicyclic hydrocarbon group The -CH2- may be replaced by -O-, -S(O)2- or -CO-, and the hydrogen atoms 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. Examples thereof include) etc.

[0075] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group and a dimethylcyclohexyl group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group and the like. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group. Examples of the aromatic hydrocarbon group having a chain hydrocarbon group include a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6- ethylphenyl group and the like. Examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group include a p-cyclohexylphenyl group, a p-adamantylphenyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, A methyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group , a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and the like. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkyl group substituted with a hydroxy group include a hydroxymethyl group and a hydroxy alkyl group such as a hydroxyethyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylme thyl group, a naphthylethyl group and the like. Examples of the group in which -CH2- contained in the alkyl group is replaced with -O-, -S(O)2- or -CO- etc. include an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an al kylcarbonyloxy group or a group combining these. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pen tyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group and the like. The number of carbon atoms in the alkoxy group is preferably 1 to 12 and more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkoxycarbonyl group include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and the like. The number of carbon atoms 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, for example, an acetyl group, a propionyl group and a butyryl group and the like. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably Preferably, it is 2 to 6, more preferably 2 to 4. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the combined group include a group formed by combining an alkoxy group and an alkyl group, an alkoxy group and an alkoxy group, an alkoxy group and an alkylcarbonyl group, a group formed by combining an alkoxy group and an alkylcarbonyloxy group, and the like. Examples of the group formed by combining an alkoxy group and an alkyl group include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an ethoxymethyl group and the like. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and 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, an ethoxyethoxy group and the like. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group formed by combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, an ethoxypropionyl group and the like. The number of carbon atoms in the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include methoxy cetoxy group, methoxypropyonyloxy group, ethoxyacetyloxy group, ethoxy propyonyloxy group and other alkoxyalkylcarbonyloxy groups. The carbon number of the alk oxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S(O)2- or -CO- etc. include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43).

[0076] Examples of Y include the following. TIFF2025108554000064.tif160165

[0077] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have substituents, even more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have substituents, even more preferably an adamantyl group which may have substituents, and -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).

[0078] Examples of the anion in the salt represented by formula (B1) include formula (B1-A-1) to formula (B1- ​​​​​An anion represented by (A-59) [hereinafter, “anion (B1-A-1)” etc. according to the formula number may be mentioned.], is 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-5 9) is more preferable.

[0079] TIFF2025108554000065.tif142153

[0080] TIFF2025108554000066.tif75126

[0081] TIFF2025108554000067.tif130157

[0082] TIFF2025108554000068.tif65156

[0083] TIFF2025108554000069.tif110143

[0084] TIFF2025108554000070.tif186166Here, R i2 ~R i7 are, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms , preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these , more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms group. Q b1 and Q b2represents the same meaning as described above. As the anion in the salt represented by formula (B1), specifically, those described in JP-A-2010-20 No. 4646 can be mentioned.

[0085] As the anion in the salt represented by formula (B1), preferably, the anions represented by formula (B1a-1) to formula ( B1a-38) can be mentioned respectively. TIFF2025108554000071.tif126154

[0086] TIFF2025108554000072.tif93139

[0087] TIFF2025108554000073.tif168155

[0088] Among them, the anions represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula ( B1a-1 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) to formula (

[0089] Z1 + As the organic cation of , organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations and organic phosphonium cations etc. can be mentioned. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred.

[0090] Z + As the organic cation of , organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations and ​Examples thereof include 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.

[0091] TIFF2025108554000074.tif46167 In 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. 18 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 represents an aliphatic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5. When m2 is 2 or more, a plurality of Rs b7 may be the same or different, and when n2 is 2 or more, a plurality of Rs may be the same or different. b8 R b9 and R b10 each independently represent 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 combine with each other to form a ring together with the sulfur atom to which they are attached, 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 alkylcarbonyl oxy group having 1 to 12 carbon atoms. R b11 and R b12 may combine with each other to form a ring including the -CH-CO- to which they are attached, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18 each independently represent a halogen atom, a hydroxy group, an aliphatic group having 1 to 12 carbon atoms represents an aliphatic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, a plurality of R b13 are the same or different, and when p2 is 2 or more, a plurality of R b14 are the same or different, and when q2 is 2 or more, a plurality of R b15 are the same or different, and r2 When is 2 or more, a plurality of R b16 are the same or different, and when s2 is 2 or more, a plurality of R b17 are the same or different, and when t2 is 2 or more, a plurality of R b18 are the same or different. The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include 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 an alkyl group such as a 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups. TIFF2025108554000075.tif10158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group of is preferably a C3-C18 alicyclic hydrocarbon group, more preferably is a C4-C12 alicyclic hydrocarbon group. Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include methylcyclohe xyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyl adamantan-2-yl group, 2-isopropyladamantan-2-yl group, methylnorborn yl group, isobornyl group, etc. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms and having a fluorine atom, and fluoro methyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl, etc. are exemplified The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, phenanthryl group, etc. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms ( tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert -butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group etc.), and an aromatic hydrocarbon group having an alicyclic hydrocarbon group having 3 to 18 carbon atoms (p-cyclohe xylphenyl group, p-adamantylphenyl group, etc.) etc. are exemplified. Note that the aromatic hydrocarbon When the hydrogen group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. As the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group, a p-methoxyphenyl group and the like can be mentioned. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, and naphthylethyl group. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and dodecyloxy group. Examples of the alkylcarbonyl group include acetyl group, propionyl group, and butyryl group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. Examples of the alkylcarbonyloxy group include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, and 2-ethylhexylcarbonyloxy group. The ring formed by R and R bonding to each other together with the sulfur atom to which they are bonded may be a monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated ring. This ring includes rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. R b4 and R b5 and together with the sulfur atom to which they are attached form a ring which may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. This ring may be any of rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. ​​​​​​​​​​​​ The ring containing a sulfur atom includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. For example, the following rings can be mentioned. * represents a bond. TIFF2025108554000076.tif23143R b9 and R b10 The ring formed by combining with is monocyclic, polycyclic, aromatic, non-aromatic, either a saturated or unsaturated ring. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. For example, thiolan-1-ium ring (tetrahydrothi ophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring, etc. can be mentioned. R b11 and R b12 The ring formed by combining with is monocyclic, polycyclic, aromatic, non-aromatic, either a saturated or unsaturated ring. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring oxonorbornane ring, oxoadamantane ring, etc. can be mentioned.

[0092] Among cations (b2-1) to (b2-4), preferably, it is cation (b2 -1). Examples of cation (b2-1) include the following cations. TIFF2025108554000077.tif117169

[0093] TIFF2025108554000078.tif72165

[0094] Examples of cation (b2-2) include the following cations. TIFF2025108554000079.tif18150

[0095] Examples of the cation (b2-3) include the following cations. TIFF2025108554000080.tif26140

[0096] Examples of the cation (b2-4) include the following cations. TIFF2025108554000081.tif62166

[0097] TIFF2025108554000082.tif69157 The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), preferably, any of the anions represented by formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula ( B1a-19), formula (B1a-22) to formula (B1a-38) and a combination with the cation (b2-1), the cation (b2-3) or the cation (b2-4) is mentioned.

[0098] As the acid generator (B), preferably, those represented by formula (B1-1) to formula (B1-56) are mentioned. Among them, those containing an arylsulfonium cation are preferred. 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 (B 1-31) to formula (B1-56) are particularly preferred. TIFF2025108554000083.tif62150

[0099] TIFF2025108554000084.tif131164

[0100] TIFF2025108554000085.tif87150 ​​

[0101] TIFF2025108554000086.tif163153

[0102] TIFF2025108554000087.tif76141

[0103] TIFF2025108554000088.tif158158

[0104] When containing salt (I) and acid generator (B) as the acid generator, the content ratio (mass ratio; salt (I): acid generator (B)) of salt (I) and acid generator (B ) is usually 1:99 to 99:1 and preferably 2:98 to 98:2, more preferably 5:95 to 95:5 and even more preferably 10:90 to 90:10, particularly preferably 15:85 to 85 :15. In the resist composition of the present invention, the total content rate of the acid generator is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin (A) described later.

[0105] <Resist composition> The resist composition of the present invention contains an acid generator containing salt (I) and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). Here, the "acid-labile group" has a leaving group, and when contacted with an acid, the leaving group leaves, and the structural unit is converted into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). The resist composition of the present invention preferably contains a quencher (hereinafter sometimes referred to as "quencher (C)") such as a salt that generates an acid having a lower acidity than the acid generated from the acid generator, and preferably contains a solvent (hereinafter sometimes referred to as "solvent (E)").

[0106] <Resin (A)> Resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). Resin (A) preferably further contains a structural unit other than structural unit (a1). Examples of the structural unit other than 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 structural unit (a1) and 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 a structural unit derived from other monomers known in the art, etc.).

[0107] 〈Structural unit (a1)〉 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 Resin (A) is preferably a group represented by formula (1) (hereinafter also referred to as group (1)) and / or a group represented by formula (2) (hereinafter also referred to as group (2)). TIFF2025108554000089.tif2298[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a combination thereof, or R a1 and R a2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond. TIFF2025108554000090.tif2278 [In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 1 2 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and 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. * represents a bond.

[0108] R a1 , R a2 and R a3 Examples of the alkyl group in 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. a1 R a2 Examples of the alkenyl group in a3 include an ethenyl group, a propenyl group, an iso propenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a he xenyl group, a heptenyl group, an octynyl group, an isooctynyl group, a nonenyl group. R a1 Examples of the alicyclic hydrocarbon group in a2 include both monocyclic and polycyclic a3 ones. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cyclo heptyl group, a cyclooctyl group, etc. Examples of the polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cyclo Examples of the hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). R a1 , R a2 and R a3 The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms. TIFF2025108554000091.tif10159R a1 , R a2 and R a3 Examples of the aromatic hydrocarbon group in R , R Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, an alkylcycloalkyl group or cycloalkylalkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group , a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbor nylethyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (a p-methylphenyl group, a p -tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, 2, 6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group , etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, etc. Preferably , ma is 0 and na is 1. R a1 and R a2 When R a1 and R a2 and R a3) Examples include the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents a bond to -O-. TIFF2025108554000092.tif35158

[0109] R a1’ 、R a2’ and R a3’ Examples of the hydrocarbon group in include alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and groups formed by combining these, etc. are included. The alkyl group and alicyclic hydrocarbon group are the same as the groups a1 mentioned for R a2 , R a3 . are included. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, alkylcycloalkyl group or cycloalkylalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group , cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbor nylethyl group, etc.), aralkyl group such as benzyl group, aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group , etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. R a2’ and R a3’When they are bonded to each other and together with the carbon atom to which they are bonded and X form a heterocyclic ring, -C(R )(R a1' )(R a2' )-X-R a3' includes the following groups . * represents a bond. TIFF2025108554000093.tif18124R a1’ and R a2’ , at least one of which is preferably a hydrogen atom. na’ is preferably 0.

[0110] Examples of group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 are alkyl groups, ma = 0, and na = 1. As such a group, a tert-butoxycarbonyl group is preferred. In formula (1), R a1 , R a2 together with the carbon atom to which they are bonded form an adamantyl group, R is an alkyl group, ma = 0, and na = 1. a3 In formula (1), R and R a1 are each independently an alkyl group, R a2 is an adamantyl group, ma = 0, and na = 1. a3 adam yl group, ma = 0, and na = 1. Specific examples of group (1) include the following groups. * represents a bond. TIFF2025108554000094.tif170163

[0111] Specific examples of group (2) include the following groups. * represents a bond. TIFF2025108554000095.tif68162

[0112] 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. Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are preferably included. Using a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group in the resist composition can improve the resolution of the resist pattern.

[0113] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are preferably included. Using a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group in the resist composition can improve the resolution of the resist pattern. As the structural unit derived from the (meth)acrylic monomer having group (1), preferably, a structural unit represented by formula (a1-0) (hereinafter, may be referred to as structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter, may be referred to as structural unit (a1-1)), or a structural unit represented by formula (a1-2) (hereinafter, may be referred to as structural unit (a1-2)) is included. More preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used alone or in combination of two or more. In formulas (a1-0), (a1-1) and (a1-2), L, L and L each independently represent -O- or *-O-(CH2)-CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-.

[0114] As the structural unit derived from the (meth)acrylic monomer having group (1), preferably, a structural unit represented by formula (a1-0) (hereinafter, may be referred to as structural unit (a1-0)), a structural unit represented by formula (a1-1) (hereinafter, may be referred to as structural unit (a1-1)), or a structural unit represented by formula (a1-2) (hereinafter, may be referred to as structural unit (a1-2)) is included. More preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used alone or in combination of two or more. In formulas (a1-0), (a1-1) and (a1-2), L, L and L each independently represent -O- or *-O-(CH2)-CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. In formulas (a1-0), (a1-1) and (a1-2), L, L and L each independently represent -O- or *-O-(CH2)-CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. More preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used alone or in combination of two or more. In formulas (a1-0), (a1-1) and (a1-2), L, L and L each independently represent -O- or *-O-(CH2)-CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. In formulas (a1-0), (a1-1) and (a1-2), L, L and L each independently represent -O- or *-O-(CH2)-CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. In formulas (a1-0), (a1-1) and (a1-2), L, L and L each independently represent -O- or *-O-(CH2)-CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. L a01 L a1 L a2 Each independently represents -O- or *-O-(CH2)-CO-O-. k1 - k1 represents an integer of 1 to 7, and * represents a bond to -CO-. In formulas (a1-0), (a1-1) and (a1-2), L, L and L each independently represent -O- or *-O-(CH2)-CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. R a01 R a4 R a5represents 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 are each independently 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 are each independently 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 any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3.

[0115] R a01 , R a4 and R a5 are preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 , L a1 and L a2 are preferably an oxygen atom or *-O-(CH2) k01 -C O-O- (wherein k01 is preferably any integer from 1 to 4, more preferably 1. ), more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 The alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and the group formed by combining these in R of formula (1), a1 R a2 and Ra3 Groups similar to the groups listed above can be mentioned. R a02 、R a03 、and R a04 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms and more preferably a methyl group or an ethyl group, and still more preferably a methyl group. is. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms and more preferably a methyl group, an ethyl group, an isopropyl group or a t-butyl group, and still more preferably an ethyl group, an isopropyl group or a t-butyl group. R a6 and R a7 The alkenyl group in is preferably an alkenyl group having 2 to 6 carbon atoms and more preferably an ethenyl group, a propenyl group, an isopropenyl group or a butenyl group. is. R a02 、R a03 、R a04 、R a6 、and R a7 The number of carbon atoms of the alicyclic hydrocarbon group of is preferably 5 to 12, and more preferably 5 to 10. R a02 、R a03 、R a04 、R a6 、and R a7 The number of carbon atoms of the aromatic hydrocarbon group of is preferably 6 to 12, and more preferably 6 to 10. The group combining an alkyl group and an alicyclic hydrocarbon group preferably has a total number of carbon atoms combining these alkyl groups and alicyclic hydrocarbon groups of 18 or less. The group combining an alkyl group and an aromatic hydrocarbon group preferably has a total number of carbon atoms combining these alkyl groups and aromatic hydrocarbon groups of 18 or less. R a02 and Ra03 is 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.

[0116] Examples of the structural unit (a1-0) include structural units represented by any of formula (a1-0-1) to formula (a1-0-18) and structural units in which the methyl group corresponding to R in the structural unit (a1-0) a01 is replaced by a hydrogen atom, and structural units represented by any of formula (a1-0-1) to formula (a1- 0-10), formula (a1-0-13), and formula (a1-0-14) are preferred. TIFF2025108554000097.tif100167

[0117] ​​​​​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 formulas (a1-1-1) to (a1-1-7) and the structural units in which the methyl group corresponding to R in the structural unit (a1-1) is replaced by a hydrogen atom are preferred, and the structural units represented by any of formulas (a1-1-1) to (a1-1-4) are more preferred. Among them, the structural units represented by any of formulas (a1-1-1) to (a1-1-7) and the structural units in which the methyl group corresponding to R in the structural unit (a1-1) is replaced by a hydrogen atom are preferred, and the structural units represented by any of formulas (a1-1-1) to (a1-1-4) are more preferred. a4 Among them, the structural units represented by any of formulas (a1-1-1) to (a1-1-7) and the structural units in which the methyl group corresponding to R in the structural unit (a1-1) is replaced by a hydrogen atom are preferred, and the structural units represented by any of formulas (a1-1-1) to (a1-1-4) are more preferred. Among them, the structural units represented by any of formulas (a1-1-1) to (a1-1-7) and the structural units in which the methyl group corresponding to R in the structural unit (a1-1) is replaced by a hydrogen atom are preferred, and the structural units represented by any of formulas (a1-1-1) to (a1-1-4) are more preferred. TIFF2025108554000098.tif39156

[0118] Examples of the structural unit (a1-2) include structural units represented by any of formulas (a1-2-1) to (a1-2-12) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) is replaced by a hydrogen atom. The structural units represented by any of formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-12) are preferred. a5 Examples of the structural unit (a1-2) include structural units represented by any of formulas (a1-2-1) to (a1-2-12) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) is replaced by a hydrogen atom. The structural units represented by any of formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-12) are preferred. Examples of the structural unit (a1-2) include structural units represented by any of formulas (a1-2-1) to (a1-2-12) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) is replaced by a hydrogen atom. The structural units represented by any of formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-12) are preferred. Examples of the structural unit (a1-2) include structural units represented by any of formulas (a1-2-1) to (a1-2-12) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) is replaced by a hydrogen atom. The structural units represented by any of formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-12) are preferred. Examples of the structural unit (a1-2) include structural units represented by any of formulas (a1-2-1) to (a1-2-12) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) is replaced by a hydrogen atom. The structural units represented by any of formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-12) are preferred. TIFF2025108554000099.tif75156

[0119] When the resin (A) contains the structural unit (a1-0), the content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol% based on all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-0), the content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol% based on all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-0), the content is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol% based on all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 85 mol%, still more preferably 25 to 70 mol%, even more preferably 30 to 70 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 90 mol%, more preferably 20 to 85 mol%, still more preferably 25 to 70 mol%, even more preferably 30 to 70 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 90 mol%, more preferably 20 to 85 mol%, still more preferably 25 to 70 mol%, even more preferably 30 to 70 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 90 mol%, more preferably 20 to 85 mol%, still more preferably 25 to 70 mol%, even more preferably 30 to 70 mol% based on all the structural units of the resin (A).

[0120] As the structural unit having a base (2) in the structural unit (a1), there is a structural unit represented by the formula (a1-4) (hereinafter, may be referred to as "structural unit (a1-4)"). TIFF2025108554000100.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, plural R may be the same as or different from each other. a33 R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R​​​​​​​a36 are bonded to each other and together with the -C-O- to which they are bonded, form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.]

[0121] R a32 and R a33 Examples of the halogen atom in include fluorine atom, chlorine atom, bromine atom and the like R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, per fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, but yl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro pentyl group, pentyl group, hexyl group and perfluorohexyl group. R a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a33 Examples of the alkyl group in include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group R a33 Examples of the alkoxy group in include methoxy group, ethoxy group, propoxy group, iso propoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy​​​​​ Examples thereof include a Si group and a hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a33 Examples of the alkoxyalkyl group in R include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxy methyl 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 R include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxy methoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxy methoxy 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 R 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 R include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a33is 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, 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, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group or an ethoxyethoxy group, and even more preferably a fluorine atom, an iodine atom,

[0122] *-X a31 -(A a32 -X a32 ) nc -Examples of *-O- include *-O-, *-CO-O-, *-O-C O-, *-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-, Among them, *-CO-O-, *-CO-O-A a32 -CO-O- or *- O-A a32 -CO-O- is preferred.

[0123] 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 and the like. A a32 is preferably a methylene group or an ethylene group.

[0124] Aa30 is a single bond, *-CO-O- or *-CO-O-A a32 -CO-O- is preferred, and a single bond, *-CO-O- or *-CO-O-CH2-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred.

[0125] 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 hex yl group, a heptyl group, an octyl group, etc. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group Examples include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group etc. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group an adamantyl group, a norbornyl group, and the following group (* represents the bonding site). etc. are included. TIFF2025108554000101.tif10151 Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, etc. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbor an alkylcycloalkyl group or cycloalkylalkyl group such as a nilylethyl group), benzyl an aralkyl group such as a group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group such as a p-cyclohexylphenyl group, a p-adamantylphenyl group etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, etc. are mentioned. In particular , R a36 as, 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 is mentioned.

[0126] 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, more preferably a methyl group or an ethyl group. R a36 's hydrocarbon group 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 to form, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 1 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. In R a36 the alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. In R a36 the aromatic hydrocarbon group preferably has an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0127] -OC(R a34 )(R a35 )-O-R a36 is eliminated upon contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 is preferably bonded to the o-position or p-position of the benzene ring, more preferably to the p-position. Preferably, it is bonded to the p-position, more preferably to the p-position.

[0128] Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, the structural units represented by formula (a1-4-1) to formula (a1 -4-18) and the structural units in which the hydrogen atom corresponding to R in the structural unit (a1-4) is replaced by a methyl group are included. More preferably, the structural units represented by formula ( a32 a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13), formula (a1-4-14) are included. a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13), formula (a1-4-14) are included. TIFF2025108554000102.tif100166

[0129] When the resin (A) has the structural unit (a1-4), its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol% with respect to the total of all the structural units of the resin (A), still more preferably 20 to 85 mol% and even more preferably 20 to 70 mol% and particularly preferably 20 to 60 mol%.

[0130] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) include the formula (a1 The structural unit represented by (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)") is also included. It can be mentioned. In formula (a1-5) of TIFF2025108554000103.tif4253, R a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Z a1 represents a single bond or *-(CH2) h3 -CO-L 54 -, h3 represents any integer from 1 to 4 and * represents a bond with L 51 It represents a bond with. L 51 L 52 L 53 and L 54 each independently represents -O- or -S-. s1 represents any integer from 1 to 3. s1' represents any integer from 0 to 3.

[0131] 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 fluoro methyl group and a trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. is preferred. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferred that one is -O- and the other is -S-. s1 is preferably 1. s1' is preferably any integer from 0 to 2. Z a1is preferably a single bond or *-CH2-CO-O-.

[0132] 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. TIFF2025108554000104.tif31129

[0133] 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% with respect to all the structural units of the resin (A).

[0134] Examples of the structural unit (a1) also include the following structural units. TIFF2025108554000105.tif27161

[0135] When the resin (A) contains structural units such as the above (a1-3-1) to (a1-3-7), its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, and even more preferably 20 to 70 mol% with respect to all the structural units of the resin (A). Even more preferably, it is 20 to 60 mol%.

[0136] <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. ​​​As the structural unit(s), it is preferable to have a hydroxy group or a lactone ring. Hydro A structural unit having a xy 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)") is used in the resist composition of the present invention, The resolution of the resist pattern and the adhesion to the substrate can be improved. 〈Structural unit (a2)〉 The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.

[0137] When producing a resist pattern from the resist composition of the present invention, when using high-energy rays such as KrF excimer laser (248 nm), electron beam or EUV (extreme ultraviolet light) as the exposure light source, As the structural unit (a2), a structural unit (a2) having a phenolic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-A) described later. Also, When using an ArF excimer laser (193 nm) or the like, as the structural unit (a2), a structural unit (a2) having an alcoholic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-1) described later. As the structural unit (a2), one kind may be contained alone, or two or more kinds may be contained. Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). In [formula (a2-A), R

[0138] a50 a50 a50 TIFF2025108554000106.tif4551[In formula (a2-A), R a50represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or *-X a51 -(A a52 -X a52 ) nb -, where * represents the bond to the carbon atom to which -R a50 is attached. A a52 represents a C1-C6 alkanediyl group. X a51 and X a52 each independently represent -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is an integer of 2 or more, the plural R a51 may be the same as or different from each other.

[0139] 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 C1-C6 alkyl group 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 ​A ruoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, per fluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropent yl group, a pentyl group, a hexyl group, and a perfluorohexyl group may be mentioned. 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 still more preferably a hydrogen atom or a methyl group. R a51 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. R a51 Examples of the alkoxy group in include a methoxy group, an ethoxy group, a propoxy group, an iso propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group. R a51 Examples of the alkoxyalkyl group in include a methoxymethyl group, an ethoxyethyl group , a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxy methyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group. R a51Examples of the alkoxyalkoxy group include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group. Examples of the alkylcarbonyl group in R include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. Examples of the alkylcarbonyloxy group in R include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group. R 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. *-X R a51 Examples of the alkylcarbonyl group in R include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. R 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. Examples of the alkylcarbonyloxy group in R include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group. R a51 Examples of the alkylcarbonyloxy group in R include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group. R 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. Examples of *-X-(A-X)- include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-. R a51 R 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. Examples of *-X-(A-X)- include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-. *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-. *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-. *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-.

[0140] *-X a51 -(A a52 -X a52 ) nb Examples of *-X-(A-X)- include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-. *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-. a52 *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-.a52 -O-, *-O-A a52 -CO-O-, *-CO-O-A a52 -O-CO-, *-O-CO-A a52 -O-CO-, are exemplified. Among them, *-CO-O-, *-CO-O-A a52 -CO-O- or *- O-A a52 -CO-O- is preferred.

[0141] 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, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group and the like. A a52 is preferably a methylene group or an ethylene group.

[0142] A a50 is a single bond, *-CO-O- or *-CO-O-A a52 -CO-O- is preferred, and a single bond, *-CO-O- or *-CO-O-CH2-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred.

[0143] mb is preferably 0, 1 or 2, more preferably 0 or 1, and even more 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.

[0144] Examples of the structural unit (a2-A) include JP-A-2010-204634 and JP-A-2012- Examples include structural units derived from the monomers described in Japanese Patent No. 12577. Examples of the structural unit (a2-A) include those represented by Formula (a2-2-1) to Formula (a2-2-16) and, in the structural units represented by Formula (a2-2-1) to Formula (a2-2-16), structural units in which the methyl group corresponding to R a50 in the structural unit (a2-A) is replaced with a hydrogen atom. 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), Formula (a2-2-8), structural units represented by Formula (a2-2-12) to Formula (a2-2-14) and, in the structural units represented by Formula (a2-2-1) to 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 Formula (a2-2-12) to Formula (a2-2-14), structural units in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom. Preferably, the structural unit is a structural unit represented by Formula (a2-2-3), a structural unit represented by Formula (a2-2 -8), structural units represented by Formula (a2-2-12) to Formula (a2-2-14), and, in the structural units represented by Formula (a2-2-3) or Formula (a2-2-8), structural units represented by Formula (a2-2-12) to Formula (a2-2-14), structural units in which the methyl group corresponding to R a50 in the structural unit (a2-A) is replaced with a hydrogen atom. More preferably, the structural unit is a structural unit represented by Formula (a2-2-8) and, in the structural unit represented by Formula (a2- 2-8), structural units in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom. Even more preferably, the structural unit is a structural unit represented by Formula (a2-2-8) and, in the structural unit represented by Formula (a2- 2-8), structural units in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom. Still more preferably, the structural unit is a structural unit represented by Formula (a2-2-8) and, in the structural unit represented by Formula (a2- 2-8), structural units in which the methyl group corresponding to R a50 in the structural unit (a2-A) is replaced with a hydrogen atom. Even still more preferably, the structural unit is a structural unit represented by Formula (a2-2-8) and, in the structural unit represented by Formula (a2- 2-8), structural units in which the methyl group corresponding to R in the structural unit (a2-A) corresponds to a50 and It is more preferable that the methyl group is replaced by a hydrogen atom. TIFF2025108554000107.tif64170

[0145] Content rate of structural unit (a2-A) when it is contained in resin (A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol% with respect to all 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-toluene sulfonic acid. Also , after polymerizing using acetoxystyrene or the like, treating with an alkali such as tetramethylammonium hydroxide can incorporate the structural unit (a2-A) into the resin (A).

[0146] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula ( a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). TIFF2025108554000108.tif4157In the formula (a2-1), L a3 represents -O- or *-O-(CH2) k2 -CO-O-, k2 represents an integer of 1 to 7. * represents a bond to -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represent a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer of 0 to 10.

[0147] ​​ In formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- and (wherein f1 represents any integer from 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 any integer from 0 to 3, more preferably 0 or 1.

[0148] Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. Structural units represented by any of formulas (a2-1-1) to (a2-1-6 ) are preferred, structural units represented by any of formulas (a2-1-1) to (a2-1-4) are more preferred, and structural units represented by formula (a2-1-1) or formula (a2-1- 3) are even more preferred. 3) are even more preferred. TIFF2025108554000109.tif54150

[0149] 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 1 to 20 mol%, and even more preferably 1 to 10 mol% based on all the structural units of the resin (A). 1 to 10 mol% based on all the structural units of the resin (A).

[0150] 〈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 a condensed ring of a monocyclic lactone ring and another ring A fused ring may be used. Preferably, a γ-butyrolactone ring, an adamantanone lactone ring, or a bridged ring containing a γ -butyrolactone ring structure (for example, the structural unit represented by the following formula (a3-2)) is exemplified.

[0151] 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 two or more of them may be contained. TIFF2025108554000110.tif52167[In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 、L a5 and L a6 each independently represents -O- or *-O-(CH2) k3 - CO-O- (where k3 represents an integer from 1 to 7). L a7 represents -O-, *-O-L a8 -O-, *-O-L a8 -CO-O-, *-O-L a8 -CO-O-L a9 -CO-O- or *-O-L a8 -O-CO-L a9 -O-. means. 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 a carbon atom; Represents an aliphatic hydrocarbon group having 1 to 4 prime numbers. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 may be the same or different.]

[0152] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in propyl, isopropyl, butyl, sec-butyl and tert-butyl groups Examples of alkyl groups include the following. R a24 The halogen atom in the formula (I) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Atoms include: R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Of these, preferred is an alkyl group having 1 to 4 carbon atoms, and more preferred is a methyl group. or an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro luorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, per fluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like can be mentioned. L a8 and L a9 As the alkanediyl group in, methylene group, ethylene group, pro pane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pen tane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen tane-1,4-diyl group and 2-methylbutane-1,4-diyl group and the like can be mentioned.

[0153] In formula (a3-1) to formula (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 any of the groups, 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 me thyl group. p1, q1 and r1 are each independently preferably an integer from 0 to 2, more preferably 0 or 1.

[0154] In formula (a3-4), R a24is 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 any integer from 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)’. TIFF2025108554000111.tif4051(wherein R a24 , L a7 represent the same meaning as described above.)

[0155] Examples of the structural unit (a3) include monomers described in JP-A-2010-204646, monomers described in JP-A-2000-122294, and structural units derived from monomers described in JP-A-2012-41274 No. Gazette. Examples of the structural unit (a3) include structural units represented by formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-1 2), and in the above structural units, R in formula (a3-1) to formula ( a3-4), R a3-4), R a18 , R a19 , R a20 and R a24 and structural units in which the methyl group corresponding to is replaced by a hydrogen atom are preferred.

[0156] TIFF2025108554000112.tif115165

[0157] When the resin (A) contains the structural unit (a3), the total content of the structural unit (a3) is the total content of all structural units of the resin (A). The amount is usually 5 to 70 mol %, preferably 10 to 65 mol %, more preferably Or, it is 10 to 60 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit The content of the units (a3-4) is 5 to 60 moles per total structural units of the resin (A). % by mole, more preferably 5 to 50 mol %, and further preferably 10 to 50 mol %.

[0158] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025108554000113.tif3066[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, The -CH2- contained in the group may be replaced with -O- or -CO. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain hydrocarbon group and a monocyclic or polycyclic alicyclic hydrocarbon group. groups, as well as groups formed by combining these groups.

[0159] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexa Examples of the cycloaliphatic carbons include decyl, heptadecyl and octadecyl groups. The hydrogen group includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and Cycloalkyl groups such as a tert-butyl group; decahydronaphthyl group, adamantyl group, norbornyl group And polycyclic alicyclic hydrocarbon groups such as the following groups (* represents a bond). TIFF2025108554000114.tif11159Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanedi yl groups with one or more alicyclic hydrocarbon groups, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -al kanediyl group-alicyclic hydrocarbon group-alkyl group, etc. are mentioned.

[0160] Examples of the structural unit (a4) include at least one structural unit selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula( a4-3) and formula (a4-4). TIFF2025108554000115.tif4652[In formula (a4-0), R 5 represents a hydrogen atom or a methyl group. L 4a represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms. L 3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perflu luorocycloalkanediyl group having 3 to 12 carbon atoms. R 6 represents a hydrogen atom or a fluorine atom.]

[0161] Examples of the divalent aliphatic saturated hydrocarbon group in L 4a include linear alkanediyl groups such as methylene group, ethylene group, prop ane-1,3-diyl group, butane-1,4-diyl group, etc., eth ane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2- ​Branches such as methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group include branched alkanediyl groups. L 3a Examples of the perfluoroalkanediyl group in L include difluoromethylene group, per fluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane -1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane -2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2 ,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1, 5-diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3, 3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2, 2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1, 7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3, 4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1, 8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3, L 3a Examples of the perfluorocycloalkanediyl group in L include perfluorocyclohexanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanedi yl group, perfluoroadamantanediyl group and the like.

[0162] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group. L3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0163] As the structural unit (a4-0), the following structural units and the structural units in the following structural units ( a4-0) where the methyl group corresponding to R 5 is replaced by a hydrogen atom are included. TIFF2025108554000116.tif95165

[0164] TIFF2025108554000117.tif4466 [In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g 1). However, at least one of A a41 and R a42 has a halogen atom (preferably a fluorine atom) as a substituent. TIFF2025108554000118.tif1384 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 ​​Each independently represents -O-, -CO-, -CO-O- or -O-CO -. However, the total number of carbon atoms in A a42 , A a43 , A a44 , X a41 and X a42 is 7 or less.]] * represents a bond, and the * on the right is a bond with -O-CO-R a42 .]

[0165] 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, etc. Examples of the chain saturated 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 he xadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cy cloheptyl group, a cyclooctyl group; a polycyclic alicyclic saturated hydrocarbon group such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). Examples of the group formed by the combination in TIFF2025108554000119.tif11159 include a group formed by combining one or more alkyl groups or one or more alkanedi yl groups with one or more alicyclic saturated hydrocarbon groups, and examples include -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, etc.

[0166] R a42Examples of the substituent that may be possessed include at least one selected from a halogen atom and a group represented by formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom. In formula (a-g3), TIFF2025108554000120.tif965X represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. a43 A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * represents a bond to R. a42 However, in R a42 -X a43 -A a45 when R a42 does not have a halogen atom, A a4 5 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which has at least one halogen atom. Examples of the aliphatic hydrocarbon group in A

[0167] include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl a45 group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a penta decyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group; monocyclic alicyclic hydrocarbon groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following group (* represents a bond). Examples of the group formed by the combination include one or more alkyl groups or one or more alkanedi TIFF2025108554000121.tif11159 ​​Groups formed by combining an iyl group and one or more alicyclic hydrocarbon groups include -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -al kanediyl group-alicyclic hydrocarbon group-alkyl group, etc.

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

[0169] R a42 ​​​​When it is an aliphatic hydrocarbon having a group represented by the formula (a-g3), R a42 is, further preferably a group represented by the formula (a-g2). TIFF2025108554000122.tif879[In the formula (a-g2), A a46 represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom and represents. X a44 represents **-O-CO- or **-CO-O- (** represents a bond with A a46 and represents a bond ). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom . However, the total number of carbon atoms of A a46 , A a47 and X a44 is 18 or less, and at least one of A a46 and A a47 has at least one halogen atom. * represents a bond with a carbonyl group. * represents a bond with a carbonyl group.]

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

[0171] A preferred structure of the group represented by the formula (a-g2) is the following structure (* is a bond with a carbonyl group ). TIFF2025108554000123.tif13161

[0172] A a41Examples of the alkanediyl group 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, a hexane-1 ,6-diyl group; and branched alkanediyl groups such as a propane-1,2-diyl group, a butane-1 ,3-diyl group, a 2-methylpropane-1,2-diyl group, a 1-methylbutane-1,4- diyl group, a 2-methylbutane-1,4-diyl group. A a41 Examples of the substituent in the alkanediyl group of A 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.

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

[0174] In the group represented by formula (a-g1), X a42 is -O-, -CO-, -CO-O- or -O-CO-. Examples of the group include the following groups. In the following examples, * and ** each represent a bond, and ** is a bond with -O-CO-R a42 . TIFF2025108554000124.tif54162

[0175] Examples of the structural unit represented by formula (a4-1) include the following structural units and the methyl group corresponding to R in the structural unit represented by formula (a4-1) below in the structural unit represented by formula (a4-1) being replaced by a hydrogen atom. a41 TIFF2025108554000125.tif47144

[0176] TIFF2025108554000126.tif186147

[0177] As the structural unit represented by formula (a4-1), the structural unit represented by formula (a4-2) is preferred. TIFF2025108554000127.tif4365[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 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.]

[0178] L44 The C1-C6 alkanediyl group is the same as the one exemplified by the alkanediyl group in A a41 and examples thereof include groups similar to those exemplified. R f6 The saturated hydrocarbon group of is the same as the group exemplified by R a42 and examples thereof include groups similar to those exemplified. L 44 As the C1-C6 alkanediyl group in, a C2-C4 alkanediyl group is preferred, and an ethylene group is more preferred.

[0179] Examples of the structural unit represented by formula (a4-2) include, for example, the structural units represented by formula (a4-1-1) to formula (a4 -1-11). In the structural unit (a4-2), R f5 The structural unit in which the methyl group corresponding to is replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-2).

[0180] Examples of the structural unit (a4) include the structural unit represented by formula (a4-3). TIFF2025108554000128.tif5771 [In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents a C1-C6 alkanediyl group. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. X f12 represents *-O-CO- or *-CO-O- (* represents the bond with A f13 ).) A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, at least one of A f13 and A f14 has a fluorine atom, and L 5, A f13 and A f14 The upper limit of the total carbon number of is 20.]

[0181] L 5 As the alkanediyl group in, A a41 the alkanediyl group in the divalent saturated hydrocarbon group of is exemplified by the same groups as those listed. A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in is preferably a divalent aliphatic saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. As the divalent aliphatic hydrocarbon group which may have a fluorine atom, there are alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoro butanediyl group and perfluoropentanediyl group, etc. are listed. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. As the monocyclic group, there are cyclohexanediyl group and perfluorocyclohexane diyl group, etc. As the polycyclic group, there are adamantanediyl group, norbornane diyl group, perfluoroadamantanediyl group, etc. are listed. The divalent saturated hydrocarbon group and the divalent saturated hydrocarbon group which may have a fluorine atom of A are exemplified by the same groups as those exemplified by R . Among them, trifluoromethyl group, difluoromethyl group, etc. A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom of are the same groups as those a42 exemplified by R . Among them, trifluoromethyl group, difluoromethyl A t-butyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group , a perfluorohexyl group, a heptyl group, a perfluoroheptyl group, an octyl group and a per fluoro octyl group and other alkyl fluoride groups, a cyclopropylmethyl group, a cyclopropyl group , a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group, a perfluorocyclohe xyl group, an adamantyl group, an adamantylmethyl group, an adamantyldimethyl group, a norbor nyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamant ylmethyl group and the like are preferred.

[0182] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group of is preferably 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 is even more preferred. A f14 The saturated hydrocarbon group of is preferably a group containing a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms , and more preferably a group containing a chain hydrocarbon group having 3 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 1 0. Among them, A f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably cyclopropylmethyl is a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably cyclopropylmethyl a base, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or an adamantyl group.

[0183] Examples of the structural unit represented by formula (a4-3) include structural units represented by formulas (a4-1’-1) to (a 4-1’-11), respectively. In the structural unit (a4-3), the methyl group corresponding to R f7 is replaced by a hydrogen atom, and the resulting structural unit is also included in the structural units represented by formula (a4-3).

[0184] Examples of the structural unit (a4) also include the structural unit represented by formula (a4-4). TIFF2025108554000129.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -, or -(CH2) j4 - CO-O-(CH2) j5 -. j1 to j5 each independently represent an integer from 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom. ]

[0185] Examples of the saturated hydrocarbon group of R f22 are the same as the saturated hydrocarbon group represented by R a42 . R f22 is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms and having a fluorine atom.

[0186] In formula (a4-4), A f21 is preferably -(CH2) j1 -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group.

[0187] Examples of the structural unit represented by formula (a4-4) include the following structural units and the following formulas In the structural units represented, the methyl group corresponding to R in structural unit (a4-4) f21 is replaced by a hydrogen atom to give the structural units. TIFF2025108554000130.tif80148

[0188] When resin (A) has structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol% based on all the structural units of resin (A). % is even more preferable.

[0189] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group in structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Among them, structural unit (a5) preferably has a group having an alicyclic hydrocarbon group group. Examples of structural unit (a5) include the structural unit represented by formula (a5-1) . TIFF2025108554000131.tif3971[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- contained therein may be replaced by -O- or -CO-.

[0190] R 52 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Monocyclic Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopen tyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include , an adamantyl group, a norbornyl group, and the like. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, an iso propyl 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 and the like . R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group. L 55 Examples of the divalent saturated hydrocarbon group in 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 an alkanediyl group 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 a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an ada Examples thereof include a mantandiyl group and a norbornandiyl group.

[0191] L 55 In the divalent saturated hydrocarbon group represented by L, the -CH2- contained therein is replaced by -O- or -CO-. The resulting groups include, for example, the groups represented by Formula (L1-1) to Formula (L1-4). In the following formulas, * and ** each represent a bond, and * represents a bond to an oxygen atom. In Formula (L1-1), TIFF2025108554000132.tif18165In Formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents a bond to L). x1 (. L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, the total number of carbon atoms of L x1 and L x2 is 16 or less. In Formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, the total number of carbon atoms of L x3 and L x4 is 17 or less. In Formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. (. However, 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 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, the total number of carbon atoms in x8 L x9 L x1 and W is 15 or less.

[0192] 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. Wx1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0193] Examples of the group represented by formula (L1-1) include the following divalent groups. TIFF2025108554000133.tif23135

[0194] TIFF2025108554000134.tif33116

[0195] Examples of the group represented by formula (L1-2) include the following divalent groups. TIFF2025108554000135.tif23130

[0196] Examples of the group represented by formula (L1-3) include the following divalent groups. TIFF2025108554000136.tif15144

[0197] Examples of the group represented by formula (L1-4) include the following divalent groups. TIFF2025108554000137.tif26114

[0198] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0199] Examples of the structural unit (a5-1) include the following structural units and the structural units in the following structural units ( a5-1) where the methyl group corresponding to R 51 is replaced by a hydrogen atom. are included. TIFF2025108554000138.tif75150

[0200] 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). 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). % is even more preferred.

[0201] <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 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 is preferred. 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). Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and 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 is preferred. Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and 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 is preferred. Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and 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 is preferred.

[0202] The structural unit having a sulfonate group or a carboxylate group in the side chain is preferably a structural unit represented by the formula (II-2-A'). The structural unit having a sulfonate group or a carboxylate group in the side chain is preferably a structural unit represented by the formula (II-2-A'). TIFF2025108554000140.tif35104[In the formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be replaced by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be replaced by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be replaced by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA -represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a carbon atom having 1 Represents an alkyl group of 1 to 6. Z.A. + represents an organic cation.

[0203] R III3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples include an uran atom. R III3 The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom is represented by the formula: R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by the formula: Examples include the following. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Examples of the aryl group include pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group. do. A X1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Isopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert -butyl group, perfluoropentyl group, perfluorohexyl group, and the like. XIII3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations thereof may be used. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane- 1,12-diyl group and other linear alkanediyl groups; 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 and other branched alkanediyl groups; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane- 1,4-diyl group, cyclooctane-1,5-diyl group and other cycloalkanediyl groups; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- 1,5-diyl group, adamantane-2,6-diyl group and other divalent polycyclic alicyclic saturated hydrocarbon groups and the like. 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 carbon number before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less, respectively. In the following formula, * and ** represent bonding sites, * represents a bond to A x1 and. TIFF2025108554000141.tif145161

[0204] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0205] ZA in formula (II-2-A’) + is the cation Z1 in the salt represented by formula (B1) + and the like can be mentioned.

[0206] The structural unit represented by formula (II-2-A’) is preferably the structural unit represented by formula (II-2-A) as follows. TIFF2025108554000142.tif38109[In formula (II-2-A), R III3 、X III3 and ZA + have the same meanings as described above. z2A represents any integer from 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, and 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 bEach independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R III2 、R III4 、Q a and Q b Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by are the same as those of the perfluoroalkyl group having 1 to 6 carbon atoms represented by the aforementioned Q b1 .

[0207] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF2025108554000143.tif5577[In formula (II-2-A-1), R III2 、R III3 、R III4 、Q a 、Q b and ZA + represent 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, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom or a hydroxy group.] 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 III5 , 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 III3 are the same as those of the divalent saturated hydrocarbon group.

[0208] As the structural unit represented by formula (II-2-A-1), the structural unit represented by formula (II-2-A-2) is more preferable. TIFF2025108554000144.tif5287 [In formula (II-2-A-2), R III3 and R III5 and ZA + have the same meanings as described above. m and nA each independently represent 1 or 2.]

[0209] Examples of the structural unit represented by formula (II-2-A’) include, for example, the following structural units, where the group corresponding to the methyl group of R III3 is replaced with a hydrogen atom, a halogen atom (e.g., a fluorine atom), or an alkyl group having 1 to 6 carbon atoms that may have a halogen atom (e.g., a trifluoromethyl group, etc. ), and the structural units described in International Publication No. 2012 / 050015. ZA represents an organic cation. + TIFF2025108554000145.tif86163

[0210] The structural unit having a sulfonio group and an organic anion in the side chain is preferably the structural unit represented by formula (II-1-1). TIFF2025108554000146.tif3791 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3Each independently represents a hydrocarbon group having 1 to 18 carbon atoms, R II2 and R II3 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. It may be. 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. It represents. A - represents an organic anion.] R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by include a phenylene group and a naphthylene group and the like. 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 and the like. R II4 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom and the like. R II4 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 The same ones are included. They are mentioned. A II1 Examples of the divalent linking group represented by include, for example, a divalent saturated carbonized hydrogen group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S-, or It may be replaced by -CO-. Specifically, X III3 The same ones as the divalent saturated hydrocarbon group having 1 to 1 8 carbon atoms represented by are included.

[0211] Examples of the structural unit containing the cation in formula (II-1-1) include the structural units represented below and and RII4 Groups corresponding to the methyl group include structural units in which the methyl group is replaced with a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. Examples thereof include structural units in which the methyl group is replaced with a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. TIFF2025108554000147.tif84130

[0212] A - Examples of the organic anion represented by A include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, and carboxylate anions. Examples of the organic anion represented by A include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, and carboxylate anions. - The organic anion represented by A is preferably a sulfonate anion, and more preferably an anion contained in the salt represented by the aforementioned formula (B1). The organic anion represented by A is preferably a sulfonate anion, and more preferably an anion contained in the salt represented by the aforementioned formula (B1).

[0213] A - Examples of the sulfonylimide anion represented by A include the following. TIFF2025108554000148.tif36135

[0214] Examples of the sulfonylmethide anion include the following. TIFF2025108554000149.tif29123

[0215] Examples of the carboxylate anion include the following. TIFF2025108554000150.tif51152

[0216] Examples of the structural unit represented by the formula (II-1-1) include structural units represented by the following. Examples thereof include structural units represented by the following. TIFF2025108554000151.tif88149

[0217] When the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 20 mol% with respect to all the structural units of the resin (A), and more preferably 2 to It is 15 mol%, more preferably 3 to 10 mol%.

[0218] 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.

[0219] Resin (A) is preferably a resin composed of structural unit (a1) and structural unit (s), that is, a copolymer of monomer (a1) and monomer (s). Structural unit (a1) is preferably at least one selected from the group consisting of structural unit (a1-0), structural unit (a1-1) and structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two kinds, and still more preferably at least two kinds selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). Structural unit (s) is preferably at least one selected from the group consisting of structural unit (a2) and structural unit (a3). Structural unit (a2) is preferably structural unit (a2-1) or structural unit (a2-A). Structural unit (a3) is preferably at least one selected from the group consisting of the structural unit represented by formula (a3-1), the structural unit represented by formula (a3-2) and the structural unit represented by formula (a3-4). Each structural unit constituting resin (A) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using the monomers leading to these structural units. The content of each structural unit of resin (A) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,5​​​​​​​​​​​​​ 0 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 ,000 or less, more preferably 15,000 or less). In this specification, the weight average molecular weight is the value determined by the conditions described in the examples by gel permeation chromatography .

[0220] <Resin other than resin (A)> The resist composition of the present invention may be used in combination with a resin other than resin (A). Examples of the resin other than resin (A) include resins containing structural unit (a4) or structural unit (a5) (hereinafter sometimes referred to as resin (X)). Among them, a resin containing structural unit (a4) is preferred as resin (X). In resin (X), the content of structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more with respect to the total of all structural units of resin (X), and even more preferably 45 mol% or more . Examples of the structural units that resin (X) may further have include structural unit (a1), structural unit (a2), structural unit (a3), and structural units derived from other known monomers . Among them, resin (X) is preferably a resin composed of only structural unit (a4) and / or structural unit (a5). Each structural unit constituting resin (X) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using the monomers that induce these structural units . The content of each structural unit of resin (X) can be adjusted by the amount of monomers used in the polymerization . The weight average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,00 ​​is 0 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that of the resin (A).

[0221] When the resist composition of the present invention contains the resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the resin (A), even more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass.

[0222] The content rate of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, relative to the solid content of the resist composition. When the resist composition contains a resin other than the resin (A), the total content rate of the resin (A) and the resin other than the resin (A) is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, relative to the solid content of the resist composition. In this specification, "the solid content of the resist composition" means the total of the components excluding the solvent (E) described later from the total amount of the resist composition. The solid content of the resist composition and the content rate of the resin with respect to this can be measured by known analysis means such as liquid chromatography or gas chromatography.

[0223] <Solvent (E)> The content rate of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, more preferably 94% by mass or more and 99% by mass or less. The content rate of the solvent (E) can be measured by, for example, liquid chromatography or gas chromatography. This can be measured by known analytical means such as chromatography.

[0224] The solvent (E) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0225] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound and an acid generator (B). The resist composition may be a salt that generates an acid having a weaker acidity than the acid that generates the quencher. When (C) is contained, the content of the quencher (C) is based on the solid content of the resist composition. Generally, the content is about 0.01 to 15% by mass, and preferably about 0.01 to 10% by mass. It is more preferable that the content is about 0.1 to 5 mass %, and further preferably about 0.1 to 3 It is even more preferable that the content is about % by mass. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary Amines include secondary amines and tertiary amines.

[0226] Amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylamine, Ruaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylani line, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine , octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylam ine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine , methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibut ylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohe xylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triiso propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenedia mine, 4,4’-diamino-1,2-diphenylethane, 4,4’-diamino-3,3’ -dimethyl diphenylmethane, 4,4’-diamino-3,3’-diethyldiphenylmeth ane, 2,2’-methylenebisaniline, imidazole, 4-methylimidazole, pyridi ne, 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridi yl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide ide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are exem plified, preferably diisopropyl aniline is exemplified, more preferably 2,6-diiso propyl aniline is exemplified.

[0227] Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopro pylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimeth ylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylamm onium hydroxide, tetra-n-butylammonium salicylate, and choline, etc. are exem plified.

[0228] The acidity of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is a salt with an acid dissociation constant of the acid generated from the salt usually -3 < pKa, preferably a salt of -1 < pKa < 7, more preferably a salt of 0 < pKa < 5. Examples of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) include the salts represented by the following formula, the salts represented by formula (D) described in JP-A-2015-147926 (hereinafter, " sometimes referred to as "weak acid intramolecular salt (D)".") and the salts described in JP-A-2012-229206 JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745 are exemplified. Preferably ​ is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B), and more preferably, it is an intramolecular salt (D) of a weak acid. (A salt having a carboxylate anion). TIFF2025108554000152.tif89165

[0229] Examples of the intramolecular salt (D) of a weak acid include the following salts. TIFF2025108554000153.tif72165

[0230] 〈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.

[0231] 〈Preparation of resist composition〉 The resist composition of the present invention can be prepared by mixing the salt (I), the resin (A), and the acid generator (B), and, if necessary, a resin other than the resin (A) used, 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.

[0232] ​​​​​​​​​​<Method for Manufacturing a Resist Pattern> The method for manufacturing a resist pattern of the present invention comprises: (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.

[0233] To apply the resist composition onto the substrate, it can usually be carried out by using an apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be cleaned, or an antireflection film or the like may be formed on the substrate. By using an apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be cleaned, or an antireflection film or the like may be formed on the substrate. To apply the resist composition onto the substrate, it can usually be carried out by using an apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. Before applying the resist composition, the substrate may be cleaned, or an antireflection film or the like may be formed on the substrate. or the like.

[0234] By drying the applied composition, the solvent is removed to form a composition layer. Drying can be carried out, for example, by evaporating the solvent using a heating apparatus such as a hot plate (so-called prebaking), or by using a decompression apparatus. The heating temperature is preferably 50 to 200 °C, and the heating time is preferably 10 to 180 seconds. Also, the pressure during decompression drying is preferably about 1 to 1.0×10 Pa. Pa. Pa. Pa. 5 Pa.

[0235] The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, those that emit laser light in the ultraviolet region such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and an F2 excimer laser (wavelength 157 nm), or laser light from a solid laser light source (such as a YAG or semiconductor laser) can be used. can be used. can be used. Those that emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region by wavelength conversion, electron beams, extreme ultraviolet light (EUV), etc., 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.

[0236] The composition layer after exposure is heat-treated (so-called post-exposure bake) to promote the deprotection reaction in the acid-labile group. The heating temperature is usually about 50 to 200 °C, preferably about 70 to 150 °C.

[0237] The composition layer after heating is usually developed using a developing solution with a developing device. As the developing method , dipping method, paddle method, spraying method, dynamic dispensing method, etc. can be mentioned. 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.

[0238] When manufacturing a positive resist pattern from the resist composition of the present invention, an alkaline developing solution is used as the developing solution. The alkaline developing solution may be various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide and (2-hydroxy ethyl)trimethylammonium hydroxide (commonly known as choline), etc. can be mentioned. The alkaline developing solution may contain a surfactant. ​After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and the pattern is preferably removed.

[0239] When producing a negative resist pattern from the resist composition of the present invention, as the developer a developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. Examples of the organic solvent contained in the organic developer include ketone solvents such as 2 - hexanone and 2 - heptanone; glycol ether esters 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, and the like. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among them, as the organic developer, a developer containing butyl acetate and / or 2 - heptanone is preferred. In the organic developer, the total content of butyl acetate and 2 - heptanone is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially only butyl acetate and / or 2 - heptanone. The organic developer may contain a surfactant. Also, the organic developer may contain a trace amount of water. During development, development may be stopped by replacing with a solvent of a different type from the organic developer. It is also possible.

[0240] It is preferable to wash the developed resist pattern with a rinse solution. As the rinse solution, There is no particular limitation 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.

[0241] <Use> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, an ArF excimer laser exposure resist composition, an electron beam (EB) exposure resist composition, or an EUV exposure resist composition, particularly an electron beam (EB) exposure resist composition or an EUV exposure resist composition, and is useful for semiconductor microfabrication. <Examples>

[0242] The present invention will be further specifically described 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 1100 type, MASS is Agilent LC / MSD type). The following In the examples, the value of this molecular ion peak is indicated by "MASS".

[0243] Example 1: Synthesis of the salt represented by formula (I-2) 10 parts of the salt represented by formula (I-1-a) and 50 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes, then 1.60 parts of potassium carbonate and 0.48 parts of potassium iodide were added and the temperature was raised to 75 °C. To the resulting mixture, 11. 27 parts of the compound represented by formula (I-1-b) were added, and the mixture was stirred at 75 °C for 5 hours and then cooled to 23 °C. To the resulting mixture, 100 parts of chloroform and 45 parts of 5% aqueous oxalic acid solution were added and stirred at 23 °C for 30 minutes, then the layers were separated and the organic layer was taken out. To the obtained organic layer, 50 parts of ion-exchanged water were added and stirred at 2 3 °C for 30 minutes, then the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times times. By concentrating the obtained organic layer, 13.9 4 parts of the compound represented by formula (I-1-c) were obtained. TIFF2025108554000155.tif35164 3.04 parts of the salt represented by formula (I-1-c), 3.06 parts of the salt represented by formula (I-2-d) , 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23 °C for 2 hours. To the resulting mixture, 20 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes, then the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 30 parts of tert-butyl methyl ether were added and stirred at 23 °C for 30 minutes, then filtered to obtain 4.15 parts of the salt represented by formula (I-2).

[0244] MASS(ESI(+)Spectrum):M + 485.2 MASS(ESI(-)Spectrum): M - 517.1

[0245] Example 2: Synthesis of the salt represented by formula (I-1) 3.04 parts of the salt represented by formula (I-1-c) and 2.99 parts of the salt represented by formula (I-1-d) in TIFF2025108554000156.tif35164 , 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. The resulting mixture was added with 20 parts of ion-exchanged water, stirred at 23°C for 30 minutes, and then separated to obtain the organic layer . This water-washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the concentrated residue, stirred at 23°C for 30 minutes, and then filtered to obtain 4.15 parts of the salt represented by formula (I-1).

[0246] MASS(ESI(+)Spectrum): M + 485.2 MASS(ESI(-)Spectrum): M - 503.1

[0247] Example 3: Synthesis of the salt represented by formula (I-21) 10.65 parts of the salt represented by formula (I-21-a) and 50 parts of dimethylformamide in TIFF2025108554000157.tif49147 were mixed and stirred at 23°C for 30 minutes. Then, 1.60 parts of potassium carbonate and 0.48 parts of potassium iodide were added, and the temperature was raised to 75°C. To the obtained mixture, 11.27 parts of the compound represented by formula (I-1-b) was added, stirred at 75°C for 5 hours, and then cooled to 23°C. To the obtained mixture , 100 parts of chloroform and 45 parts of 5% aqueous oxalic acid solution were added, stirred at 23°C for 30 minutes , and then separated to obtain the organic layer. 50 parts of ion-exchanged water was added to the obtained organic layer . Added thereto, and after stirring at 23 °C for 30 minutes, liquid separation was performed to extract the organic layer. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 11.89 parts of the compound represented by the formula (I-21-c) was obtained. 3.17 parts of the salt represented by the formula (I-21-c), 2.99 parts of the salt represented by the formula (I-1-d), 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 liquid separation was performed to extract the organic layer. This washing operation with water was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred at 23 °C for 30 minutes, and then filtered to obtain 4.01 parts of the salt represented by the formula (I-21).

[0248] MASS(ESI(+)Spectrum):M + 513.3 MASS(ESI(-)Spectrum):M - 503.1

[0249] Example 4: Synthesis of the salt represented by the formula (I-42) 10 parts of the salt represented by the formula (I-42-a) and 50 parts of dimethylformamide were mixed and stirred at 23 °C for 30 minutes, and then 1.48 parts of potassium carbonate and 0.44 part of potassium iodide were added, and the temperature was raised to 75 °C. To the obtained mixture, 10.40 parts of the compound represented by the formula (I-1-b) was added, and after stirring at 75 °C for 5 hours, it was cooled to 23 °C. To the obtained mixture, 100 parts of chloroform and 45 parts of 5% aqueous oxalic acid solution were added and stirred at 23 °C for 30 minutes, and then liquid separation was performed to extract the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated to obtain compound 12 represented by formula (I-42-c). It sold .89 copies. TIFF2025108554000160.tif35164 3.21 parts of a salt represented by formula (I-42-c), 3.06 parts of a salt represented by formula (I-2-d) 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23°C for 2 hours. To the mixture, 20 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, and then the liquid was separated to obtain an organic phase. The organic layer was taken out. This water washing procedure was repeated five times. The obtained organic layer was concentrated to give a concentrated residue. 30 parts of tert-butyl methyl ether was added, and the mixture was stirred at 23°C for 30 minutes and then filtered. As a result, 4.56 parts of the salt represented by the formula (I-42) was obtained.

[0250] MASS(ESI(+)Spectrum):M + 521.2 MASS(ESI(-)Spectrum):M - 517.1

[0251] Example 5: Synthesis of a salt represented by formula (I-62) TIFF2025108554000161.tif41151 10 parts of the salt represented by formula (I-62-a) and 50 parts of dimethylformamide were mixed, and 2 After stirring at 3°C for 30 minutes, 1.22 parts of potassium carbonate and 0.36 parts of potassium iodide were added. The mixture was heated to 75°C. Compound 8. represented by formula (I-1-b) was added to the resulting mixture. 56 parts of the ethyl alcohol was added, and the mixture was stirred at 75°C for 5 hours, and then cooled to 23°C. 100 parts of chloroform and 45 parts of 5% aqueous oxalic acid solution were added and stirred at 23° C. for 30 minutes. Then, the organic layer was separated and separated. 50 parts of ion-exchanged water was added to the obtained organic layer, and After stirring at 3°C for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 72 parts of Compound 11 represented by the formula (I-62-c) was obtained. 72 parts were obtained. 3.69 parts of the salt represented by the formula (I-62-c), 3.06 parts of the salt represented by the formula (I-2-d), 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 and the organic layer was taken out. This washing operation with water was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes and then filtered to obtain 4.88 parts of the salt represented by the formula (I-62). 3.69 parts of the salt represented by the formula (I-62-c), 3.06 parts of the salt represented by the formula (I-2-d), 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 and the organic layer was taken out. This washing operation with water was repeated 5 times. 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 and the organic layer was taken out. This washing operation with water was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes and then filtered to obtain 4.88 parts of the salt represented by the formula (I-62). To the concentrated residue, 30 parts of tert-butyl methyl ether was added, stirred at 23°C for 30 minutes, and then filtered. Thereby, 4.88 parts of the salt represented by the formula (I-62) was obtained.

[0252] MASS(ESI(+)Spectrum):M + 621.2 MASS(ESI(-)Spectrum):M - 517.1

[0253] Example 6: Synthesis of the salt represented by the formula (I-302) 10 parts of the salt represented by the formula (I-302-a) and 50 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 1.01 parts of potassium carbonate and 0.30 parts of potassium iodide were added, and the temperature was raised to 75°C. To the obtained mixture, 7.10 parts of the compound represented by the formula (I-1-b) was added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. To the obtained mixture, 100 parts of chloroform and 45 parts of 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, and then the layers were separated and the organic layer was taken out. To the obtained organic layer, 50 parts of ion-exchanged water was added. 10 parts of the salt represented by the formula (I-302-a) and 50 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Then, 1.01 parts of potassium carbonate and 0.30 parts of potassium iodide were added, and the temperature was raised to 75°C. To the obtained mixture, 7.10 parts of the compound represented by the formula (I-1-b) was added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. To the obtained mixture, 7.10 parts of the compound represented by the formula (I-1-b) was added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. To the obtained mixture, 100 parts of chloroform and 45 parts of 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, and then the layers were separated and the organic layer was taken out. To the obtained organic layer, 50 parts of ion-exchanged water was added. After stirring at 23°C for 30 minutes, liquid separation was performed to obtain the organic layer. This water washing operation was repeated 5 times. By concentrating the obtained organic layer, 0.48 part of Compound 1 represented by the formula (I-302-c) was obtained. 4.24 parts of the salt represented by the formula (I-302-c), 3.06 parts of the salt represented by the formula (I-2-d), 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, then liquid separation was performed to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred at 23°C for 30 minutes, then filtered to obtain 4.89 parts of the salt represented by the formula (I-302). After stirring at 23°C for 30 minutes, liquid separation was performed to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred at 23°C for 30 minutes, then filtered to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23°C for 30 minutes, then filtered to obtain 4.89 parts of the salt represented by the formula (I-302).

[0254] MASS(ESI(+)Spectrum):M + 737.0 MASS(ESI(-)Spectrum):M - 517.1

[0255] Example 7: Synthesis of the salt represented by the formula (I-362) 5.19 parts of the salt represented by the formula (I-362-a) and 50 parts of dimethylformamide were mixed, stirred at 23°C for 30 minutes, then 1.60 parts of potassium carbonate and 0.48 part of potassium iodide were added, and the temperature was raised to 75°C. To the obtained mixture, 11.27 parts of the compound represented by the formula (I-1-b) was added, stirred at 75°C for 5 hours, then cooled to 23°C. To the obtained mixture, 100 parts of chloroform and 45 parts of 5% oxalic acid aqueous solution were added and stirred at 23°C for 30 minutes, then liquid separation was performed to obtain the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, then liquid separation was performed to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 100 parts of chloroform and 45 parts of 5% oxalic acid aqueous solution were added and stirred at 23°C for 30 minutes, then liquid separation was performed to obtain the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, then liquid separation was performed to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 100 parts of chloroform and 45 parts of 5% oxalic acid aqueous solution were added and stirred at 23°C for 30 minutes, then liquid separation was performed to obtain the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, then liquid separation was performed to obtain the organic layer. Added thereto, and after stirring at 23 °C for 30 minutes, liquid separation was carried out to take out the organic layer. This washing operation with water was repeated 5 times. By concentrating the obtained organic layer, 8.24 parts of the compound represented by the formula (I-362-c) was obtained. 4.10 parts of the salt represented by the formula (I-362-c), 3.06 parts of the salt represented by the formula (I-2-d), 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 liquid separation was carried out to take out the organic layer. This washing operation with water was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23 °C for 30 minutes, and then filtered to obtain 4.89 parts of the salt represented by the formula (I-362).

[0256] MASS(ESI(+)Spectrum):M + 707.3 MASS(ESI(-)Spectrum):M - 517.1

[0257] 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. TIFF2025108554000167.tif4192

[0258] 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 their molar ratio [monomer (a1-4-2): monomer (a1-1-3): monomer (a1-2-6)] was mixed so as to be in a ratio of 38:24:38. Furthermore, 1.5 times the mass of methyl was added to this monomer mixture relative to the total mass of all the monomers. Isobutyl ketone was mixed. To the resulting mixture, azobisisobutyronitrile was added in an amount of 7 mol% relative to the total number of moles of all the monomers. This was heated at 85 °C for about 5 hours to carry out polymerization. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) at 2.0 times the mass of the total monomer amount was added to the polymerization reaction solution. After stirring for 6 hours, liquid separation was performed. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered to obtain resin A1 (copolymer) having a weight average molecular weight of about 5.3×10 in a yield of 78%. This resin A1 has the following structural units. TIFF2025108554000168.tif29126 3 Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) were used and mixed so that their molar ratio [monomer (a1-4-2): monomer (a1-2-6)] was 38:62. TIFF2025108554000168.tif29126

[0259] Furthermore, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all the monomers. To the resulting mixture, azobisisobutyronitrile was added in an amount of 7 mol% relative to the total number of moles of all the monomers. This was heated at 85 °C for about 5 hours to carry out polymerization. Thereafter, an aqueous solution of p-toluenesulfonic acid (2 .5 wt%) at 2.0 times the mass of the total monomer amount was added to the polymerization reaction solution. After stirring for 6 hours, liquid separation was performed. The obtained organic layer was poured into a large amount of n- heptane to precipitate the resin, which was then filtered and recovered to obtain a resin having a weight average molecular weight of about 5.4 by pouring the obtained organic layer into a large amount of n-heptane to precipitate the resin and then filtering and recovering it. Furthermore, 1.5 times the mass of methyl isobutyl ketone was added to this monomer mixture relative to the total mass of all the monomers. .5 wt%) was added, and after stirring for 6 hours, liquid separation was performed. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered to obtain a resin having a weight average molecular weight of about 5.4 ×10 3 The resin A2 (copolymer) represented by the following structure was obtained in a yield of 89%. It has the following units. TIFF2025108554000169.tif2887

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

[0261]

Table 2

[0262] <Resin> A1, A2: Resin A1, Resin A2 <Salt (I)> I-1: Salt represented by formula (I-1) I-2: Salt represented by formula (I-2) I-21: Salt represented by formula (I-21) I-42: Salt represented by formula (I-42) I-62: Salt represented by formula (I-62) I-302: Salt represented by formula (I-302) I-362: Salt represented by formula (I-362) <Acid Generator> IX-1: TIFF2025108554000171.tif3082IX-2: TIFF2025108554000172.tif3093IX-3: TIFF2025108554000173.tif4296<Quencher (C)> C1: Synthesized by the method described in JP-A-2011-39502 400 parts of propylene glycol monomethyl ether acetate ​100 parts of propylene glycol monomethyl ether 5 parts of γ-butyrolactone

[0263] (Electron beam exposure evaluation of the 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 prebaked for 60 seconds at the temperature shown in the "PB" column of Table 2 on a direct hot plate to form a composition layer. On the composition layer formed on the wafer a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn using an electron beam lithography machine ["ELS-F1 25 125 keV" manufactured by Elionix, Inc.] with the exposure dose changed stepwise After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 2 on a hot plate and then paddle development was carried out for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern

[0264] 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

[0265] (CD uniformity (CDU) evaluation) At the 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 average hole diameter of the pattern formed with a hole diameter of 17 nm within the same wafer was measured at 400 locations and the standard deviation was calculated with this as the population The results are shown in Table 3. The numerical values in the table indicate the standard deviation (nm) ​​

[0266]

Table 3

Industrial Applicability

[0267] The resist composition containing the salt of the present invention can obtain a resist pattern with good CD uniformity (CDU), and thus is suitable for fine processing of semiconductors and extremely useful industrially. Therefore, it is suitable for semiconductor microfabrication and extremely useful industrially.

Claims

1. An acid generator containing a salt represented by formula (I), a resin containing a structural unit having an acid-labile group and a structural unit represented by formula (a2-A). [In formula (I), R １ represents -O-L １ -CO-O-R ５ and represents. L １ represents an alkanediyl group having 1 to 6 carbon atoms. R ５ represents an acid-labile group which is a group represented by the formula (1a). R ２ , R ３ and R ４ each independently represents a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, a hydrocarbon group having 1 to 18 carbon atoms or -O-L １ -CO-O-R ５ , and the -CH 2 - in the hydrocarbon group may be replaced by -O- or -CO-. m2 represents any integer from 0 to 4, and when m2 is 2 or more, the plurality of Rs ２ may be the same as or different from each other. m3 represents any integer from 0 to 5, and when m3 is 2 or more, the plurality of Rs ３ may be the same as or different from each other. m4 represents any integer from 0 to 5, and when m4 is 2 or more, the plurality of Rs ４ may be the same as or different from each other. Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R １１ and R １２ each independently represents a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. z represents 0 or 1. X 1 represents a bonding position with *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (where * is C(R １1 )(R １2 ), or C(Q 1 )(Q 2 ).). A １ represents *-L ２ -CO-O-, and L ２ represents a group represented by the following formula (L ２ -1), formula (L ２ -2), formula (L ２ -3) or formula (L ２ -4) (where * represents a bond). R １３ represents an adamantyl group, a hydroxyadamantyl group or an adamantanone group which may have an alkyl group having 1 to 4 carbon atoms.] [In formula (1a), R aa3 represents an alkyl group having 1 to 8 carbon atoms, and R aa1 and R aa2 are bonded to each other to form a cyclopentyl group, a cyclohexyl group or an adamantyl group together with the carbon atom to which they are bonded. * represents a bond. ] [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a50 represents a single bond or *-X a51 -(A a52 -X a52 ) nｂ -, where * represents a bond with the carbon atom to which -R a50 is attached. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 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.]

2. X １ The resist composition according to claim 1, wherein X is *-CO-O-.

3. m3 is an integer of 1 to 2, m4 is an integer of 0 to 2, R ３ and R ４ The resist composition according to claim 1 or 2, wherein either one of them is a fluorine atom, an iodine atom, or trifluoromethyl.

4. m3 is an integer of 1 to 2, m4 is an integer of 0 to 2, R ３ and R ４ One of them is -O-L １ -CO-O-R ５ is A plurality of Rs ５ The resist composition according to any one of claims 1 to 3, which may be the same as or different from each other.

5. m2 is 1 or 2, A plurality of Rs ２ At least one of which is -O-L １ -CO-O-R ５ and is A plurality of Rs ５ The resist composition according to any one of claims 1 to 4, which may be the same as or different from each other.

6. The resist composition according to any one of claims 1 to 5, wherein the resin having an acid-labile group contains at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). [In formula (a1-1) and formula (a1-2), L ａ１ and L ａ２ each independently represents -O- or *-O-(CH ２ ) ｋ１ -CO-O-, k1 represents any integer from 1 to 7, and * represents a bond with -CO-. R ａ４ and R ａ５ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ａ６ and R ａ７ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these groups. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. ]

7. The resist composition according to any one of claims 1 to 6, further containing a salt that generates an acid having a lower acidity than the acid generated from the acid generator.

8. (1) A step of applying the resist composition according to any one of claims 1 to 7 onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern including these steps.

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