Resist composition and method for producing resist pattern

Abstract

To provide a resist composition from which a resist pattern having good LER can be produced.SOLUTION: The resist composition contains: an acid generator containing a salt represented by formula (I); and a resin having an acid-labile group. The resin contains a specific structural unit. [In the formula, R1 represents -O-L1-CO-O-R5, L1 represents an alkanediyl group, and R5 represents a group represented by formula (1a); R2-R4, Rf1 and Rf2 each represent a halogen atom, a fluorinated alkyl group or the like; m2 represents an integer of 0-4, m3 and m4 represent integers of 0-5, s represents an integer of 1-4, and mb represents an integer of 0-4; and Q1 and Q2 each represent an F atom, a perfluoroalkyl group or the like.]SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Patent Document 1 describes a resist composition containing a salt represented by the following formula as an acid generator: It has been done. TIFF2025108447000001.tif3378 Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator: It has been done. TIFF2025108447000002.tif2899 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2014-97074 A [Patent Document 2] JP 2011-006400 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention relates to a resist pattern formed from a resist composition containing the above salt. A resist pattern having good line edge roughness (LER) can be formed by using a resist containing a salt. The objective of the present invention is to provide a drug composition. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF2025108447000003.tif46150[In formula (I), R 1represents -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-. represents. -O- or -CO-. m2 represents any integer from 0 to 4. When m2 is 2 or more, a plurality of Rs may be the same or different from each other. 2 same or different. m3 represents any integer from 0 to 5. When m3 is 2 or more, a plurality of Rs may be the same or different from each other. 3 same or different. m4 represents any integer from 0 to 5. When m4 is 2 or more, a plurality of Rs may be the same or different from each other. 4 same or different. Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents. R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents. z represents any integer from 0 to 6. When z is 2 or more, a plurality of Rs and Rs may be the same or different from each other. 11 and R 12 each other may be the same or different. X 1 is *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (where * is C(R )(R 11 )(R 12 )) or C(Q1 )(Q 2 ) represents the bonding position with). L 2 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a single bond or a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-. Ring W represents an alicyclic hydrocarbon ring having 3 to 36 carbon atoms, and -CH2- contained in the alicyclic hydrocarbon ring may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic hydrocarbon ring may have a substituent. R f1 and R f2 each independently represent a fluorine atom or an alkyl fluoride group having 1 to 6 carbon atoms. s represents any integer from 1 to 10, and when s is 2 or more, a plurality of R f1 and R f2 are each the same or different.] [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). TIFF2025108447000004.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 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 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. aa1 and R aa2 * represents a bond.] TIFF2025108447000005.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, 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 bonded, 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-. X represents an oxygen atom or a sulfur atom. a * represents a bond.] * represents a bond.] [3] X 1 is *-CO-O- or *-O-CO-O- (where * represents the bonding site to C(R 1 )(R 2 )) or C(Q 1 )(Q 2 ))). The salt according to [1] or [2]. [4] Ring W is a ring represented by formula (Ia1-1), a ring represented by formula (Ia1-2) or a formula (Ia1-3). The salt according to any one of [1] to [3]. TIFF2025108447000006.tif2566[In formula (Ia1-1), formula (Ia1-2) and formula (Ia1-3), the -CH2- contained in the ring may be replaced by -O-, -S-, -CO- or -SO2-, and the ring may have a substituent. The bond is at an arbitrary position.] [5] m3 is any integer from 1 to 2, m4 is any integer from 0 to 2, either one of R and R 3 and R 4 is a fluorine atom, an iodine atom or trifluoromethyl . The salt according to 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 -O-L 1 -CO-O-R 5 is, a plurality of R 5 may be the same as or different from each other, and are any of those described in [1] to [4] salts. [7] m2 is 1 or 2, a plurality of R 2 at least one of them is -O-L 1 -CO-O-R 5 is, a plurality of R 5 may be the same as or different from each other, and are any of those described in [1] to [6] salts. [8] An acid generator containing the salt described in any of [1] to [7]. [9] A resist composition containing the acid generator described in [8] and a resin having an acid-labile group.

[10] The resist composition according to [9], 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). In the formulas (a1-1) and (a1-2), TIFF2025108447000007.tif3985 L a1 and L a2 each independently represents -O- or *-O-(CH2) 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 a7is, independently of each other, 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. 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. represents. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1'represents any integer from 0 to 3.

[11] The resin having an acid-labile group contains a structural unit represented by the formula (a2-A) [9] Or the resist composition according to

[10] . TIFF2025108447000008.tif4753 [In the formula (a2-A), R a50 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. represents. R a51 is 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. represents. represents. A a50 is a single bond or * -X a51 -(A a52 -X a52 ) nb - represents, and * represents a bond to the carbon atom to which -R a50 is bonded. represents. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represent -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an integer from 0 to 4. When mb is an integer of 2 or more, the plural R s may be the same as or different from each other.] a51 It further contains a salt that generates an acid with a lower acidity than the acid generated from the

[12] acid generator. The resist composition according to any one of [9] to

[11] .

[13] (1) A step of applying the resist composition according to any one of [9] to

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

Advantages of the Invention

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

Embodiments for Carrying Out the Invention

[0007] In this specification, the “(meth)acrylic monomer” means at least one 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, the “(meth)acrylate” and “(meth)acrylic acid” mean at least one selected from the group consisting of “acrylate and methacrylate” and at least one selected from the group consisting of “acrylic acid and methacrylic acid”, respectively. When a structural unit having “CH2=C(CH3)-CO-” or “CH2=CH-C O-” is exemplified, the structural unit having both groups is similarly exemplified. ​​​It is assumed to be as illustrated. Also, among the groups described in this specification, those that can take both a linear structure and a branched structure may be either. The "combined group" means a group formed by combining two or more of the illustrated groups, and the valences of these groups may be appropriately changed depending on the bonding form. "Derived from" or "induced from" 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. For those that can take both linear and branched structures, either one is acceptable. The "combined group" means a group formed by combining two or more of the illustrated groups, and the valences of these groups may be appropriately changed depending on the bonding form. "Derived from" or "induced from" 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. Let it be assumed to be as illustrated. Also, among the groups described in this specification, those that can take both a linear structure and a branched structure may be either. The "combined group" means a group formed by combining two or more of the illustrated groups, and the valences of these groups may be appropriately changed depending on the bonding form. For those that can take both linear and branched structures, either one is acceptable. The "combined group" means a group formed by combining two or more of the illustrated groups, and the valences of these groups may be appropriately changed depending on the bonding form. "Derived from" or "induced from" 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.

[0008] The present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). Among salts (I), the side with a negative charge may be referred to as "anion (I)", and the side with a positive charge may be referred to as "cation (I)". Among salts (I), the side with a negative charge may be referred to as "anion (I)", and the side with a positive charge may be referred to as "cation (I)". TIFF2025108447000009.tif46150 [In the formula, all symbols have the same meanings as described above.]

[0009] In formula (I), R 1 The alkane diyl group in L 1 constituting includes linear alkane diyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl group, hexane-1,6-diyl group; and branched alkane diyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group. L 1 is preferably an alkane diyl group having 1 to 3 carbon atoms, and more preferably a methylene group. is more preferable.

[0010] R 1 The R that constitutes 5 The acid-labile group of is a group that, when contacted with an acid (e.g., trifluoromethanesulfonic acid), the group represented by R 5 is eliminated to form a carboxy group. Examples of the acid-labile group include a group represented by formula (1a) (hereinafter, sometimes referred to as "acid-labile group (1a" ).), and a group represented by formula (2a) (hereinafter, sometimes referred to as "acid-labile group (2a)"). are preferable. TIFF2025108447000010.tif2056 [In formula (1a), R aa1 , R aa2 and R aa3 each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent , an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or R aa1 and R aa2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. . * represents a bond.] TIFF2025108447000011.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, 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 -C-X a - to which they are bonded, and -CH2- contained in the hydrocarbon group and the heterocyclic group is -O- or - ​It may be replaced with 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, etc. 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 of include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, nonenyl group. R aa1 、R aa2 and R aa3 The alicyclic hydrocarbon group of may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include, for example, decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents a bond.). The number of carbon atoms of the alicyclic hydrocarbon group of aa1 、R aa2 and R aa is preferably 3 to 16, more preferably 3 to 12. TIFF2025108447000012.tif9159R aa1 、R aa2 and R aa3 Examples of the aromatic hydrocarbon group of Examples of the aryl group include a trill group, a biphenyl group, and a phenanthryl group. Aromatic hydrocarbon The number of carbon atoms in the 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 an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the alkenyl group having 2 to 8 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the aromatic hydrocarbon group having 6 to 1 8 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 (an alkylcycloalkyl group or a cycloalkylalkyl group such as a methylcyclohexyl group, a dimethylcyclo hexyl group, a methylnorbornil group, a cyclohexylmethyl group, an adamantylmethyl group, a norbornylethyl group, etc.), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (a p-methylphenyl group, a p-tert-butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl group, etc.). Examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group (a p-cyclohexylphenyl group, a p-adamantylphenyl Examples thereof include aryl-cycloalkyl groups such as a phenyl group and a phenylcyclohexyl group and the like. 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- and so on. and the like. TIFF2025108447000013.tif30140

[0014] Examples of the group represented by formula (1a) include a 1,1,1-trialkyl group (in formula (1a), R , R aa1 , R aa2 and R aa are alkyl groups, preferably a tert-butoxycarbonyl group), a 2-alkyladamantan-2-yl group (in formula (1a), R aa1 , R aa2 and these bonded carbon atoms form an adamantyl group, and R aa3 is an alkyl group), and a 1 -(adamantan-1-yl)-1,1-dialkyl group (in formula (1a), R aa1 and R aa2 are alkyl groups, and R aa3 is an adamantyl group), and the like.

[0015] R aa1' , R aa2' and R aa3' Examples of the hydrocarbon group include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. and the like. The alkyl group and the alicyclic hydrocarbon group are the same as the groups exemplified by R aa1 , R aa2 and R aa are exemplified. . Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like. Examples of the combined group include a group obtained by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, alkylcycloalkyl group or cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-ter t-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-di thylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group and the like. R aa2' and R aa3' are bonded to each other and together with the carbon atom to which they are bonded and X a form a heterocyclic group, -C(R aa1' )(R aa2' )-X a -(R aa3' ) includes the following groups . * represents a bond. TIFF2025108447000014.tif21152R aa1' and R aa2' Among them, at least one is preferably a hydrogen atom.

[0016] Specific examples of the acid-labile group (1a) include the following groups. * represents a bond. TIFF2025108447000015.tif69152

[0017] Specific examples of the acid-labile group (2a) include the following groups. * represents a bond. TIFF2025108447000016.tif64166R 1 The bonding position to the benzene ring of is S + relative to, any of the ortho, meta, or para positions is acceptable, but the para position is preferred.

[0018] R 2 , R 3 and R 4 The fluorinated alkyl group having 1 to 4 carbon atoms for, represents an alkyl group having 1 to 4 carbon atoms with a fluorine atom, and 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 etc. can be mentioned. etc. are mentioned. R 2 , R 3 and R 4 The hydrocarbon group having 1 to 18 carbon atoms for, includes chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these are mentioned. are mentioned. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-b tyl 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 etc. are mentioned. Examples of the alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Examples of cycloalkyl groups include cycloheptyl group, cyclooctyl group, cyclodecyl group, etc. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl group, adamantyl group, norbornil group, etc. Examples of aromatic hydrocarbon groups include phenyl group, naphthyl group, etc.

[0019] Examples of groups formed by combination include a group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (e.g., aromatic hydrocarbon group - alkanediyl group - *, alkyl group - aromatic hydrocarbon group - *), a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (e.g., alicyclic hydrocarbon group - alkanediyl group - *, alkyl group - alicyclic hydrocarbon group - *), and a group formed by combining an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., aromatic hydrocarbon group - alicyclic hydrocarbon group - *, alicyclic hydrocarbon group - aromatic hydrocarbon group - *). * represents the bonding site. Examples of aromatic hydrocarbon group - alkanediyl group - * include aralkyl groups such as benzyl group and phenethyl group. Examples of alkyl group - aromatic hydrocarbon group - * include tolyl group, xylyl group, cumenyl group, etc. Examples of alicyclic hydrocarbon group - alkanediyl group - * include cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 -yl)-1-methylethyl, etc. Examples of alkyl group - alicyclic hydrocarbon group - * include cycloalkyl groups having an alkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, 2-alkyladamantan-2-yl group, etc. Examples of the aromatic hydrocarbon group - alicyclic hydrocarbon group - * include a phenylcyclohexyl group and the like. and the like. Examples of the alicyclic hydrocarbon group - aromatic hydrocarbon group - * include a cyclohexylphenyl group and the like. and the like. In the combination, the alicyclic hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group may be combined in two or more kinds respectively. Also, any of the groups may be bonded to the benzene ring. and the like. Also, any of the groups may be bonded to the benzene ring. and the like. Examples of the group in which -CH2- contained in the hydrocarbon group is replaced by -O- or -CO- include a hydroxy group; a carboxy group; an alkoxy group having 1 to 11 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group; a cycloalkoxy group having 3 to 11 carbon atoms such as a cyclohexyloxy group; a cycloalkylalkoxy group having 4 to 11 carbon atoms such as a cyclohexylmethoxy group; an alkylcarbonyl group having 2 to 12 carbon atoms such as an acetyl group; an alkoxycarbonyl group having 2 to 11 carbon atoms such as a methoxycarbonyl group; an alkylcarbonyloxy group having 2 to 11 carbon atoms such as an acetyloxy group; an alkoxycarbonyloxy group having 2 to 11 carbon atoms such as a butoxycarbonyloxy group; an aromatic hydrocarbon group - carbonyloxy group having 7 to 11 carbon atoms such as a benzoyloxy group. and the like. and the like. and the like. and the like. and the like. and the like. and the like. and the like.

[0020] m2 is preferably any integer from 0 to 2, more preferably 0 or 2. and the like. m3 and m4 are each independently preferably any integer from 0 to 2, more preferably 0 or 1. and the like. 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 (where -CH2- contained in the alkyl group may be replaced by -O- or -CO-). and the like. Good.), -O-L 1 -CO-O-R 5 (L 1 and R 5 have the same sign as described above.) is preferred, and 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 1 -CO-O-R 5 (L 1 and R 5 have the same sign as described above.) is more preferred, and an alkyl group having 1 to 4 carbon atoms or -O-L 1 -CO-O-R 5 (L 1 and R 5 have the same sign as described above.) is even more preferred. When m2 is 1 or 2, at least one of the plurality of R 2 is preferably -O-L 1 -CO-O-R 5 . 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 (wherein -CH2- contained in the alkyl group may be replaced by -O- or -C O-.) or -O-L 1 -CO-O-R 5 (L 1 and R 5 of which have the same sign as described above.) is preferred, a halogen atom, a fluorinated a alkyl group having 1 to 4 carbon atoms or 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 1 -CO-O-R 5 (L 1 and R 5The symbols are the same as described above.) is more preferable, a fluorine atom, an iodine atom, carbon a perfluoroalkyl group having 1 to 4 carbon atoms or, -O-L 1 -CO-O-R 5 (L 1 and R 5 of The symbols are the same as described above.) is even more preferable, a fluorine atom, an iodine atom, trifluoro methyl group or, -O-L 1 -CO-O-R 5 (L 1 and R 5 The symbols are the same as described above.) is even more preferably so. In addition, in formula (I), when there are a plurality of R 5 s, the plurality of R 5 s may be the same as each other or different from each other.

[0021] Examples of the cation of salt (I) include cations represented by the following formula (I-c-1) to formula (I-c-18). etc. TIFF2025108447000017.tif229161

[0022] TIFF2025108447000018.tif207164

[0023] TIFF2025108447000019.tif146163

[0024] Among them, cations represented by formula (I-c-1) to formula (I-c-9), formula (I-c-16), formula (I-c- 19), formula (I-c-20), formula (I-c-25) are preferable, and formula ( I-c-1) to formula (I-c-6), formula (I-c-16), formula (I-c-19), formula (I- c-20), formula (I-c-25) are more preferable, and formula (I-c-1) to formula (I-c-4), formula (I-c-16), formula (I-c-19), formula (I-c-20), The cation represented by the formula (I-c-25) is more preferable, and the 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 the cation represented by the formula (I-c-25) are even more preferable.

[0025] In the formula (I), Q 1 , Q 2 , R 11 and R 12 Examples of the perfluoroalkyl group of include , trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro isopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group, and the like can be mentioned. are mentioned. 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-, *-O-CO- or *-O-CO-O- and more preferably *-CO-O- or *-O-CO-O- (* represents a bond with C(R 11 )(R 12 ) or C(Q 1 )(Q 2 ).).

[0026] Examples of the divalent hydrocarbon group in L 2 include divalent chain hydrocarbon groups such as alkanediyl groups , a monocyclic or polycyclic divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and the like, and a group formed by combining two or more of these groups (for example, a divalent hydrocarbon group formed from an alicyclic hydrocarbon group and an alkanediyl group) may also be used. Among these groups, a group formed by combining two or more of them (for example, a divalent hydrocarbon group formed from an alicyclic hydrocarbon group and an alkanediyl group ) may be used. 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, 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 and other linear alkanediyl groups; and 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, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, and other branched alkanediyl groups. Examples of the monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group include a monocyclic divalent alicyclic saturated hydrocarbon group such as a cyclobutane-1,3-di yl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclo octane-1,5-diyl group and other cycloalkanediyl groups; and a polycyclic divalent alicyclic saturated hydrocarbon group such as a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane- 1,5-diyl group, an adamantane-2,6-diyl group, and the like. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include a norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane- Examples of the hydrogen group include. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a bi Examples of the aromatic hydrocarbon group include an arylene group such as a phenylene group, a phenanthrylene group, etc. . Examples of the group formed by combining two or more types include a group formed by combining an alicyclic saturated hydrocarbon group and an alkanediyl group, and a group formed by combining an aromatic hydrocarbon group and an alkanediyl group. . . Examples of the group formed by combining an alicyclic saturated hydrocarbon group and an alkanediyl group include, for example, - a divalent alicyclic saturated hydrocarbon group - alkanediyl group -, - alkanediyl group - a divalent alicyclic saturated hydrocarbon group - alkanediyl group -, - alkanediyl group - a divalent alicyclic saturated hydrocarbon group - etc. - etc. . Examples of the group formed by combining an aromatic hydrocarbon group and an alkanediyl group include, for example, - a divalent aromatic hydrocarbon group - alkanediyl group -, - alkanediyl group - a divalent aromatic hydrocarbon group - alkanediyl group -, - alkanediyl group - a divalent aromatic hydrocarbon group - etc. . L 2 In the divalent hydrocarbon group having 1 to 28 carbon atoms contained in, -CH2- may be replaced by -O-, -S-, -SO2- or -CO-. L 2 When -CH2- contained in the hydrocarbon group having 1 to 28 carbon atoms of is replaced by -O-, -S-, -SO2 - or -CO-, the carbon number before replacement is taken as the carbon number of the hydrocarbon group .

[0027] L 2 Examples of the substituent that may have include a hydroxy group, a carboxy 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 alkyl group having 2 to 13 carbon atoms an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 2 to 13 carbon atoms An alkoxycarbonyl group, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group combining these may be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, etc. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, a butyryl group, etc. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group, or a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a halogen atom, and most preferably a methyl group.

[0028] ​​​​​​​​​​​​​​It is more preferably a hydrogen atom or a fluorine atom.

[0029] L 2 is a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-; and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and a phenylene group which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is more preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and a phenylene group which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is more preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is more preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is more preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is more preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is more preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is more preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). It is more preferably a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). A group formed by combining with an adamantyl group (provided that - CH2- contained in the alkane diyl group may be replaced by -O- or -CO-. ), or a group formed by combining an alkane diyl group having 1 to 4 carbon atoms with a phenylene group which may have a fluorine atom (provided that -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-. ) is more preferably, and a single bond is even more preferably. -CH2- contained in the alkane diyl group may be replaced by -O- or -CO-. ) is more preferably, and a single bond is even more preferably. It is more preferably, and a single bond is even more preferably.

[0030] The alicyclic hydrocarbon ring having 3 to 36 carbon atoms in ring W may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon ring include cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring and the like. Examples of the polycyclic alicyclic hydrocarbon ring include decahydronaphthalene ring, adamantane ring, norbornane ring, rings as follows and the like. The bonding site is arbitrary. Among them, for example, cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring and the like can be mentioned. Examples of the polycyclic alicyclic hydrocarbon ring include decahydronaphthalene ring, adamantane ring, norbornane ring, rings as follows and the like. The bonding site is arbitrary. Among them, for example, cycloalkane rings such as cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring and the like can be mentioned. Examples of the polycyclic alicyclic hydrocarbon ring include decahydronaphthalene ring, adamantane ring, norbornane ring, rings as follows and the like. The bonding site is arbitrary. Among them, for example, decahydronaphthalene ring, adamantane ring, norbornane ring, rings as follows and the like can be mentioned. The bonding site is arbitrary. Among them, for example, decahydronaphthalene ring, adamantane ring, norbornane ring, rings as follows and the like can be mentioned. The bonding site is arbitrary. TIFF2025108447000020.tif10139 Among them, ring W is preferably a ring represented by formula (Ia1-1), a ring represented by formula (Ia1-2) or a ring represented by formula (Ia1-3). Among them, ring W is preferably a ring represented by formula (Ia1-1), a ring represented by formula (Ia1-2) or a ring represented by formula (Ia1-3). TIFF2025108447000021.tif2566 [In formula (Ia1-1), formula (Ia1-2) and formula (Ia1-3), -CH2- contained in the ring may be replaced by -O-, -S-, -CO- or -SO2-, and the ring may have a substituent. The bond is at an arbitrary position. ] -CH2- contained in the ring may be replaced by -O-, -S-, -CO- or -SO2-, and the ring may have a substituent. The bond is at an arbitrary position. -CH2- contained in the ring may be replaced by -O-, -S-, -CO- or -SO2-, and the ring may have a substituent. The bond is at an arbitrary position.

[0031] Examples of the substituent include a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a group combining these and the like. Examples of the substituent include a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a group combining these and the like. Examples of the substituent include a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a group combining these and the like. 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, a cyclopentyl group, a cyclohexyl group, a methylcyclo hexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isoprop oxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pent oxy group, an n-hexoxy group, and the like. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphe nyl group, and a phenanthryl group. Examples of the combined group include a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, and the like.

[0032] In the above-described ring W, the positions of the bonds of L 2 and the two oxygen atoms can be at any positions. Among them, in the ring represented by formula (Ia1-1), the ring represented by formula (Ia1-2), or the ring represented by formula (Ia1-3), those in which the bond * is at the following positions are preferred. TIFF2025108447000022.tif2165

[0033] R f1 and R f2 Examples of the alkyl fluoride group of include a difluoromethyl group, a trif luoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2, 2-trifluoroethyl group, a perfluoroethyl group, a 1,1,2,2-tetrafluoroprop​​​​ A ropyl group, a 1,1,2,2,3,3-hexafluoropropyl group, a perfluoroethylmethyl group, a 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl group, a per fluoropropyl group, a 1,1,2,2-tetrafluorobutyl group, a 1,1,2,2,3, 3-hexafluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a perfluorobutyl group, a 1,1-bis(trifluoro)methyl-2,2,2-trif luoroethyl group, a 2-(perfluoropropyl)ethyl group, a 1,1,2,2,3,3,4 ,4-octafluoropentyl group, a perfluoropentyl group, a 1,1,2,2,3,3, 4,4,5,5-decafluoropentyl group, a 1,1-bis(trifluoromethyl)-2, 2,3,3,3-pentafluoropropyl group, a perfluoropentyl group, a 2-(perflu orobutyl)ethyl group, a 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, a 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, a perfluoropentylmethyl group and a perfluorohexyl group are exemplified. Among them, a tri fluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonaflu robutyl group and the like are preferable. R f1 and R f2 are each independently preferably a fluorine atom or a fluoroalkyl group having 1 to 3 carbon atoms, and more preferably both are fluorine atoms. s is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, still more preferably an integer of 1 to 4, and is 1 or 2, that is, a ring containing -O-C-O-.

[0034] s is preferably an integer from 1 to 8, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 4, and is 1 or 2, that is, a ring containing -O-C-O-. s is preferably an integer from 1 to 8, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 4, and is 1 or 2, that is, a ring containing -O-C-O-. TIFF2025108447000023.tif1840 is particularly preferably the following base. TIFF2025108447000024.tif2468

[0035] 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-3), formulas (Ia-13) to (Ia-18) are preferred, and anions represented by formulas (Ia-2), (Ia-13) to (Ia-17) are more preferred. TIFF2025108447000025.tif113149

[0036] TIFF2025108447000026.tif227164

[0037] Examples of the salt (I) include the salts described in Table 1. For example, in Table 1, the salt (I-1) is a salt composed of an anion represented by formula (Ia-1) and a cation represented by formula (b2-c-1), and means the salts shown below. TIFF2025108447000027.tif24107

[0038]

Table 1

[0039] <Method for Producing Salt (I)> Salt (I) can be produced by reacting the salt represented by formula (I-a) with the salt represented by formula (I-b) in a solvent. [In the formula, all symbols have the same meanings as described above.] TIFF2025108447000042.tif89163 Examples of the solvent include chloroform, monochlorobenzene, dimethylformamide, aceton itrile, ethyl acetate, water, and the like. The reaction temperature is usually 15°C to 80°C, and the reaction time is usually 0.5 to 24 hours.

[0040] Examples of the salt represented by formula (I-a) include salts represented by the following formula, and they are more easily available from the market. It can be obtained and can also be easily manufactured by known production methods. TIFF2025108447000043.tif92153

[0041] TIFF2025108447000044.tif52133 The salt represented by formula (I-b) includes, for example, the salts represented below, and can be easily obtained from the market and can also be easily manufactured by known production methods. It can be easily obtained and can also be easily manufactured by known production methods. TIFF2025108447000045.tif78158

[0042] <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) may be used alone or in combination of two or more kinds.

[0043] As acid generator (B), either nonionic or ionic may be used. Examples of nonionic acid generators include sulfonate esters (such as 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (such as disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of ionic acid generators include onium salts containing onium cations (such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of anions of onium salts include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, etc. ​

[0044] As the acid generator (B), those described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, U.S. Patent No. 3,779, 778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., compounds that generate an acid upon irradiation can be used. . Also, compounds produced by known methods may be used. The acid generator (B) may be used in combination of two or more.

[0045] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as "acid generator (B1)". However, salt (I) is excluded.) is. TIFF2025108447000046.tif2963[In the formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 2 4 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, - Z1 +represents an organic cation.

[0046] Q b1 and Q b2 Examples of the perfluoroalkyl group represented by Q 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, a perfluorohexyl group, and the like. Q b1 and Q are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0047] L b1 Examples of the divalent saturated hydrocarbon group in L include a linear alkanediyl group, a branched al kanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a group formed by combining two or more of these groups may also be used. Specifically, 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 and the like linear alkanediyl groups; an ethane-1,1-diyl group, a propane-1,1-diyl group, a 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 branched alkanediyl groups such as 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-1,4-diyl group and cyclooctane-1,5-diyl group a monocyclic divalent alicyclic saturated hydrocarbon group, Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like.

[0048] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group is, for example, a group represented by any one of formulas (b1-1) to (b1-3). In addition, the groups represented by the formulae (b1-1) to (b1-3) and their components are also included. In the exemplary groups represented by formulae (b1-4) to (b1-11), * and ** represent bonds. represents a hand, and * represents a bond with -Y.

[0049] TIFF2025108447000047.tif26117[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated -CH2- contained in the hydrocarbon group may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms of and 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 atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms of and 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 atom contained in the saturated hydrocarbon group may be replaced by 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 replaced by a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms of and is 23 or less. * and ** represent bonds, and * represents the bond with Y.

[0050] In the groups represented by formula (b1-1) to formula (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is the saturated When -CH2- is replaced by -O- or -CO-, the number of carbon atoms before replacement is used as the saturated Let the number of carbon atoms in the hydrocarbon group be used. Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L b1 as described above. are mentioned.

[0051] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b7 is 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-. As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by L b1 is replaced with -O- or -CO-, a group represented by formula (b1-1) or formula (b1-3) is preferable. is also acceptable.

[0052] L b1 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by L b1 is replaced with -O- or -CO- include groups represented by formula (b1-1) or formula (b1-3). As the group represented by formula (b1-1), groups represented by formula (b1-4) to formula (b1-8) are mentioned. As the group represented by formula (b1-1), groups represented by formula (b1-4) to formula (b1-8) are respectively mentioned. are mentioned. TIFF2025108447000048.tif48120 [In formula (b1-4), L b8represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be replaced by fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be replaced by 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 hydrogen atoms contained in the divalent saturated hydrocarbon group may be replaced by fluorine atoms or hydroxy groups. 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 the -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be replaced by fluorine atoms or hydroxy groups. ​​​However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. . However, L b16 ~L b18 The total number of carbon atoms 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. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16is 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 a bond with Y. * and ** represent bonds, and * represents a bond with Y.

[0053] Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11). Examples of the group represented by the formula (b1-3) include the groups represented by the formula (b1-9) to the formula (b1-11). TIFF2025108447000049.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 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 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, the total number of carbon atoms of L and L is 23 or less. However, the total number of carbon atoms of L b19 and L b20 is 23 or less. In the formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with 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 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 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 with -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 , L b25 , and L b26 is 21 or less. * and ** represent bonds, and * represents the bond to Y.]

[0054] In addition, in the group represented by formula (b1-9) and the group represented by formula (b1-11), the saturated When the hydrogen atom contained in the hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before replacement shall be 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.

[0055] Examples of the group represented by formula (b1-4) include the following. TIFF2025108447000050.tif17151 (* and ** represent a bond, and * represents a bond to Y.)

[0056] Examples of the group represented by formula (b1-5) include the following. TIFF2025108447000051.tif72149 (* and ** represent a bond, and * represents a bond to Y.)

[0057] Examples of the group represented by formula (b1-6) include the following. TIFF2025108447000052.tif29150 (* and ** represent a bond, and * represents a bond to Y.)

[0058] Examples of the group represented by formula (b1-7) include the following. TIFF2025108447000053.tif63151 (* and ** represent a bond, and * represents a bond to Y.)

[0059] Examples of the group represented by formula (b1-8) include the following. TIFF2025108447000054.tif23150 (* and ** represent a bond, and * represents a bond to Y.)

[0060] Examples of the group represented by formula (b1-2) include the following. TIFF2025108447000055.tif31160 (* and ** represent a bond, and * represents a bond with Y.)

[0061] Examples of the group represented by formula (b1-9) include the following. TIFF2025108447000056.tif44137 (* and ** represent a bond, and * represents a bond with Y.)

[0062] Examples of the group represented by formula (b1-10) include the following. TIFF2025108447000057.tif88159 (* and ** represent a bond, and * represents a bond with Y.)

[0063] Examples of the group represented by formula (b1-11) include the following. TIFF2025108447000058.tif81158 (* and ** represent a bond, and * represents a bond with Y.)

[0064] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11), formula (Y36) to the group represented by 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 more than two. Examples of such a group include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). * represents a bond with L b1 and represents a bond with. TIFF2025108447000059.tif85168 Examples of the alicyclic hydrocarbon group represented by Y preferably include the groups represented by formula (Y1) to formula (Y20), formula ( Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43), and more preferably the groups represented by formula (Y11), formula (Y15), formula (Y16 )、a group represented by formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39), formula (Y40), formula (Y42) or formula (Y43), and 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), etc., the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom preferably has no fluorine atom substituted thereon.

[0065] The substituents of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 1 6 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, -( CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein, R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these. ja represents any integer from 0 to 4. The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O- , -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. ​​It may be replaced. ) etc. are mentioned. Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, and a hydro alkyl group having 1 to 16 carbon atoms which may be substituted with a roxy group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-. ), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O -CO-R b1 group (wherein R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these. ja represents any integer from 0 to 4. The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O-, -S(O)2- or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced with a hydroxy group or a fluorine atom. ) etc. are mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc.

[0066] Examples of the alicyclic hydrocarbon group include, for example, a cyclopentyl group, a cyclohexyl group, a methylcyclo hexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a nor bornyl group, an adamantyl group etc. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples include a methylcyclohexyl group, a dimethylcyclohexyl group etc. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples include a methylcyclohexyl group, a dimethylcyclohexyl group etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably from 3 to 12, more preferably from 3 to 10. It is. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, 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 tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6- ethylphenyl group and the like. Examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group include p-cyclohexylphenyl group, p-adamantylphenyl group and the like. The number of carbon atoms in the aromatic hydrocarbon group is preferably from 6 to 14, more preferably from 6 to 10. It is. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like. The number of carbon atoms in the alkyl group is preferably from 1 to 12, more preferably from 1 to 6, still more preferably from 1 to 4. It is. Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as hydroxymethyl group and hydroxyethyl group. It is. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and naphthylethyl group and the like. It is. Examples of the group in which -CH2- contained in the alkyl group is replaced by -O-, -S(O)2- or -CO- etc. include alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, al kylsulfonyl group and the like. It is. kylsulfonyl group and the like. Examples thereof include a kill carbonyl oxy group or a group combining these groups. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pent yl oxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group. The carbon number of the alkoxy group is preferably 1 to 12 and more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkoxycarbonyl group include, for example, a methoxycarbonyl group, an ethoxycarbonyl yl group, a butoxycarbonyl group and the like. The carbon number of the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylcarbonyl group include, for example, an acetyl group, a propionyl group and a butyryl group and the like. The carbon number of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the alkylcarbonyloxy group include, for example, an acetyloxy group, a propionyloxy group, a butyryloxy group and the like. The carbon number of the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. Examples of the combined group include, for example, a group combining an alkoxy group and an alkyl group, an alkoxy group and an alkoxy group, an alkoxy group and an alkylcarbonyl group, an alkoxy group and an alkylcarbonyloxy group and the like. Examples of the group combining an alkoxy group and an alkyl group include, for example, an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an ethoxymethyl group, etc. and the like. It may be mentioned. The number of carbon atoms of the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group in which an alkoxy group and an alkoxy group are combined include alkoxyalkoxy groups such as methoxymethoxy group, meth oxyethoxy group, ethoxymethoxy group, and ethoxyethoxy group. The number of carbon atoms of the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group in which an alkoxy group and an alkylcarbonyl group are combined include alk oxyalkylcarbonyl groups such as methoxyacetyl group, methoxypropionyl group, ethoxyacetyl group, and ethoxypropionyl group. The number of carbon atoms of the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. There is. Examples of the group in which an alkoxy group and an alkylcarbonyloxy group are combined include alk oxyalkylcarbonyloxy groups such as methoxyacetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, and ethoxy propionyloxy group. The number of carbon atoms 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). There are groups etc. represented by.

[0067] Examples of Y include the following. TIFF2025108447000060.tif160165

[0068] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents and 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 the 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).

[0069] As the anion in the salt represented by formula (B1), anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter, may be referred to as "anion (B1-A-1)" etc. according to the formula number] are preferable, and anions represented by any of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-59) are more preferable.

[0070] TIFF2025108447000061.tif142153

[0071] TIFF2025108447000062.tif75126

[0072] TIFF2025108447000063.tif130157

[0073] TIFF2025108447000064.tif65156

[0074] TIFF2025108447000065.tif110143

[0075] TIFF2025108447000066.tif186165 Here, 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 b2 represent the same meaning as described above. Specific examples of the anion in the salt represented by formula (B1) include those described in JP-A-2010-20 4646.

[0076] Preferred examples of the anion in the salt represented by formula (B1) include anions represented by formula (B1a-1) to formula ( B1a-38), respectively. TIFF2025108447000067.tif126154

[0077] TIFF2025108447000068.tif93139

[0078] TIFF2025108447000069.tif168155

[0079] Among them, formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-1 6), an anion represented by any of Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) to Formula (B1a-3 8) is preferred.

[0080] Z1 + Examples of the organic cation of include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations and organic phosphonium cations and the like. Among these, organic sulfonium cations and organic iodonium cations are preferred, and arylsulfonium cations are more preferred.

[0081] Z + Examples of the organic cation of include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations and organic phosphonium cations 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.) can be mentioned.

[0082] In TIFF2025108447000070.tif47169, 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 atoms contained in the chain hydrocarbon group are hydroxy groups, alkoxy groups having 1 to 12 carbon atoms, or fats having 3 to 12 carbon atoms. ring hydrocarbon group, The hydrogen atoms contained in the chain hydrocarbon group are hydroxy groups, alkoxy groups having 1 to 12 carbon atoms, or fats having 3 to 12 carbon atoms. It may be substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic The hydrogen atom contained in the 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 a halogen atom, a hydroxy group, or an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a perfluoroalkyl group having 1 to 12 carbon atoms or an alk oxy group having 1 to 12 carbon atoms. R b4 and R b5 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- as well. R b7 and R b8 each independently represent a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent any integer from 0 to 5. When m2 is 2 or more, the plurality of R b7 may be the same or different, and when n2 is 2 or more, the plurality of R b8 may be the same or different. R b9 and R b10 each independently 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- as well. R b11represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl oxy group having 1 to 12 carbon atoms. R b11 and R b12 may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent any integer from 0 to 5. q2 and r2 each independently represent any integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, the plurality of R b13 are the same or different, and when p2 is 2 or more, the plurality of R b14 are the same or different, and when q2 is 2 or more, the plurality of R b15 are the same or different, and when r2 is 2 or more, the plurality of R b16 are the same or different, and when s2 is 2 or more, the plurality of R b17 are the same or different, and when t2 is 2 or more, the plurality of Rb18 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. TIFF2025108447000071.tif10158 In particular, the alicyclic hydrocarbon group of R b9 ~R b12 is preferably 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyl adamantan-2-yl group, a 2-isopropyladamantan-2-yl group, a methylnorbornil group, and an isobornyl group. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. The fluoroalkyl group represents an alkyl group having 1 to 12 carbon atoms and having a fluorine atom, and a perfluoro ​ Examples include an oromethyl group, a difluoromethyl group, a trifluoromethyl group, and a perfluorobutyl group. The number of carbon atoms in the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. 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 with 1 to 18 carbon atoms ( 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 etc.), and an aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (p-cyclohe xylphenyl group, a p-adamantylphenyl group, etc.) etc. are mentioned. Note that when the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group with 1 to 18 carbon atoms and an alicyclic hydrocarbon group with 3 to 18 carbon atoms are preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group etc. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include an aralkyl group such as a benzyl group, a phen ethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pent yloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group etc. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group etc. can be obtained. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. and the like. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, a 2-ethylhexylcarbonyloxy group, and the like. R b4 and R b5 which are bonded to each other and together with the sulfur atom to which they are bonded form a ring that can be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated rings. Examples of this ring include rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. Also, rings containing a sulfur atom include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings, and for example, the following rings can be mentioned. * represents a bond. TIFF2025108447000072.tif23143R b9 and R b10 which together form a ring that can be any of monocyclic, polycyclic, aromatic, non-aromatic , saturated, and unsaturated rings. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. For example, a thiolan-1-ium ring (tetrahydrothi ophenium ring), a thian-1-ium ring, a 1,4-oxathian-4-ium ring, etc. can be mentioned. and the like. R b11 and R b12 which together form a ring that can be any of monocyclic, polycyclic, aromatic, non-aromatic It may be either a saturated or unsaturated ring. Examples of this ring include 3-membered rings to 12-membered rings , preferably 3-membered rings to 7-membered rings. Examples include oxocycloheptane rings, oxocyclohexane rings , oxonorbornane rings, oxoadamantane rings, and the like.

[0083] Among cations (b2-1) to (b2-4), preferably, it is cation (b2 -1). Examples of cation (b2-1) include the following cations. TIFF2025108447000073.tif79158

[0084] TIFF2025108447000074.tif110165

[0085] Examples of cation (b2-2) include the following cations. TIFF2025108447000075.tif18150

[0086] Examples of cation (b2-3) include the following cations. TIFF2025108447000076.tif26140

[0087] Examples of cation (b2-4) include the following cations. TIFF2025108447000077.tif127166

[0088] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be combined arbitrarily. As the acid generator (B), preferably, it is represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula ( B1a-19), formula (B1a-22) to formula (B1a-38) And combinations with cation (b2-1), cation (b2-3), or cation (b2-4). Examples thereof include.

[0089] As the acid generator (B), those preferably represented by formula (B1-1) to formula (B1-56) are exemplified. 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) ~formula (B1-14), formula (B1-20) to formula (B1-26), formula (B1-29), formula (B 1-31) to formula (B1-56) are particularly preferred. TIFF2025108447000078.tif62150

[0090] TIFF2025108447000079.tif72164

[0091] TIFF2025108447000080.tif55152

[0092] TIFF2025108447000081.tif87150

[0093] TIFF2025108447000082.tif163153

[0094] TIFF2025108447000083.tif76141

[0095] TIFF2025108447000084.tif158158

[0096] When containing salt (I) and acid generator (B) as the acid generator, the ratio of the content of salt (I) to acid generator (B ) (mass ratio; salt (I): acid generator (B)) is usually 1:99 to 99:1 and preferably 2:98 to 98:2, more preferably 5:95 to 95:5. Preferably, it is 10:90 to 90:10, and particularly preferably 15:85 to 85 :15. In the resist composition of the present invention, the total content 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.

[0097] <Resist composition> The resist composition of the present invention contains an acid generator containing a salt (I) and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). Here, the "acid-labile group" means a group having a leaving group, and when contacted with an acid, the leaving group leaves 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 such as a salt that generates an acid having a lower acidity than the acid generated from the acid generator (hereinafter sometimes referred to as "quencher (C)"), and preferably contains a solvent (hereinafter sometimes referred to as "solvent (E)").

[0098] <Resin (A)> The resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). The resin (A) preferably further contains a structural unit other than the structural unit (a1). As the structural unit other than the structural unit (a1), a structural unit having no acid-labile group ( hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than the structural unit (a1) and the structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4) "), a structural unit having a non-leaving hydrocarbon group described later (hereinafter referred to as "structural unit ( "), etc.). "), etc.). There may be cases such as (a5)), and structural units and the like derived from other monomers known in the art may be mentioned.

[0099] 〈Structural unit (a1)〉 The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)") in some cases). The acid-labile group contained in the resin (A) is preferably a group represented by the formula (1) (hereinafter also referred to as group (1)) and / or a group represented by the formula (2) (hereinafter also referred to as group (2)). TIFF2025108447000085.tif2298 [In the formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms , an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these, or R a1 and R a2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.] TIFF2025108447000086.tif2278 [In the formula (2), R a1’ and R a2’ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 1 2 carbon atoms, 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 the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or - S-. may be replaced by -O- or -S-. X represents an oxygen atom or a sulfur atom. na’ represents 0 or 1. * represents a bond.

[0100] R a1 、R a2 and R a3 Examples of the alkyl group in R , R , and R a1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. a2 Examples of the alkenyl group in R a3 , R , and R include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, a nonenyl group, and the like. . Examples of the alicyclic hydrocarbon group in R a1 , R a2 , and R a3 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). The carbon number of the alicyclic hydrocarbon group in R , R , and R is preferably 3 to 16. Examples of the aromatic hydrocarbon group in R a1 , R a2 , and R a3 include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, and the like. The carbon number of the alicyclic hydrocarbon group is preferably 3 to 16. TIFF2025108447000087.tif10159R a1 Examples of the aromatic hydrocarbon group in R a2 , R a3 , and R include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, and the like. As the combined group, a group combining the above-described alkyl group and alicyclic hydrocarbon group (for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornil group , a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, norborn anyl ethyl group, etc., an alkylcycloalkyl group or a cycloalkylalkyl group such as), a benzyl group, etc., an aralkyl 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 a phenylcyclohexyl group, etc. may be mentioned. Preferably , ma is 0 and na is 1. R a1 and R a2 when bonding to each other to form an alicyclic hydrocarbon group, -C(R a1 )(R a2 )(R a3 ) includes the following groups. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * represents a bond to -O-. TIFF2025108447000088.tif35158

[0101] R a1’ , R a2’ and R a3’ as the hydrocarbon group in, alkyl group, alicyclic carbon hydrocarbon group, aromatic hydrocarbon group, and a group formed by combining these, etc. may be mentioned . The alkyl group and the alicyclic hydrocarbon group are the same as the groups mentioned for R a1 , R a2 and R a3 above. include the following. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. Examples of the combined group include a group obtained by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl group or cycloalkylalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbor nylethyl group), aralkyl group such as benzyl group, aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. Examples of the heterocyclic group formed by R and R a2’ bonding to each other and together with the carbon atom to which they are bonded and X include the following groups. * represents a bond. a3’ It is preferable that at least one of R and R TIFF2025108447000089.tif18124R a1’ is a hydrogen atom. a2’ Preferably, na' is 0. Preferably, na' is 0.

[0102] Examples of the group (1) include the following groups. In formula (1), when R a1 , R a2 and R a3 are alkyl groups, ma = 0, and na = A group represented by 1. As such a group, a tert-butoxycarbonyl group is preferable. In formula (1), R a1 , R a2 together with the carbon atom to which they are attached form an adamantyl group, and R is an alkyl group, ma = 0, and na = 1. a3 A group where ma = 0 and na = 1. In formula (1), R a1 and R a2 are each independently an alkyl group, R a3 is an adamantyl group, ma = 0, and na = 1. A group where ma = 0 and na = 1. Specific examples of the group (1) include the following groups. * represents a bond. TIFF2025108447000090.tif170163

[0103] Specific examples of the group (2) include the following groups. * represents a bond. TIFF2025108447000091.tif68162

[0104] The monomer (a1) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer having an acid-labile group. 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

[0105] can improve the resolution of the resist pattern. 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. can improve the resolution of the resist pattern.

[0106] As the structural unit derived from the (meth)acrylic monomer having the group (1), preferably is the structural unit represented by formula (a1-0) (hereinafter sometimes referred to as the structural unit (a1-0)). ) The structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) .) or the structural unit represented by formula (a1-2) (hereinafter sometimes referred to as structural unit (a1-2)). 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. TIFF2025108447000092.tif46149 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 、L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 - CO-O-, k1 represents an integer from 1 to 7, and * represents a bond with -CO- . R a01 、R a4 and R a5 each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 、R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group formed by combining these . R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group formed by combining these. m1 represents an integer from 0 to 14. n1 represents an integer from 0 to 10. n1' represents an integer of 0 to 3.

[0107] R a01 , R a4 and R a5 is preferably a hydrogen atom or a methyl group, and more preferably It is a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or *-O-(CH2) k01 -C OO- (wherein k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 Alkyl groups, alkenyl groups, alicyclic groups The hydrocarbon group, aromatic hydrocarbon group, and a group obtained by combining these groups are R a1 , R a2 and R a3 Examples of the groups include the same groups as those listed in the above. R a02 , R a03 , and R a04 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. A methyl group or an ethyl group is more preferable, and a methyl group is even more preferable. do. R a6 and R a7 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, it is a methyl group, an ethyl group, an isopropyl group, or a t-butyl group. Preferred is an ethyl group, an isopropyl group or a t-butyl group. R a6 and R a7 The alkenyl group in the formula (I) is preferably an alkenyl group having 2 to 6 carbon atoms. Yes, 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, more preferably 5 to 10. 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, more preferably 6 to 10. The group formed by combining an alkyl group and an alicyclic hydrocarbon group preferably has a total number of carbon atoms of 18 or less when these alkyl group and alicyclic hydrocarbon groups are combined. The group formed by combining an alkyl group and an aromatic hydrocarbon group preferably has a total number of carbon atoms of 18 or less when these alkyl group and aromatic hydrocarbon groups are combined. a02 and R a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group is. 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 is. 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 、isopropyl group, t-butyl group, ethenyl group, phenyl group or naphthyl group, further is preferably an ethyl group, isopropyl group, t-butyl group, ethenyl group or phenyl group is. 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.

[0108] Examples of the structural unit (a1-0) include structural units represented by any of formula (a1-0-1) to formula (a1-0-18) and the methyl group corresponding to R in the structural unit (a1-0) a01 corresponding to me and structural units in which the methyl group is replaced by a hydrogen atom, and the structural unit represented by any of formula (a1-0-1) to formula (a1- 0-10), formula (a1-0-13), and formula (a1-0-14) is preferred. is preferred. TIFF2025108447000093.tif99167

[0109] Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646 . Among them, the structural unit represented by any of formula (a1-1-1) to formula (a1 -1-7) and the structural unit in which the methyl group corresponding to R in the structural unit (a1-1) a4 corresponding to is replaced by a hydrogen atom are preferred, and the structural unit represented by any of formula (a1-1-1) to formula (a1-1-4) is more preferred. TIFF2025108447000094.tif39157

[0110] Examples of the structural unit (a1-2) include structural units represented by any of formula (a1-2-1) to formula (a1-2-12) and the methyl group corresponding to R in the structural unit (a1-2) a5 corresponding to the methyl group is water Examples of the structural unit replaced by a sulfur atom include those represented by formula (a1-2-2), formula (a1-2-5), formula (a1-2-6), and formula (a1-2-10) to formula (a1-2-12). The structural unit represented by any of them is preferable. TIFF2025108447000095.tif75156

[0111] When the resin (A) contains the structural unit (a1-0), the content thereof is usually 5 to 60 mol%, preferably 5 to 50 mol%, more preferably 10 to 40 mol% with respect to 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 of these is usually 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 20 to 85 mol%, still more preferably 25 to 70 mol%, and even more preferably 30 to 70 mol% with respect to all the structural units of the resin (A).

[0112] Examples of the structural unit having the group (2) in the structural unit (a1) include the structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF2025108447000096.tif3854[In 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 alkylcarbonyl group having 2 to 4 carbon atoms, ​​​​​represents an oxy group, an acryloyloxy group or a methacryloyloxy group. A a30 is 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. represents the bonding site with the carbon atom to which -R 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, multiple R s may be the same as or different from each other. a33 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and the -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-. 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 to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and the -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-. are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and the -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-. The halogen atoms in R and R

[0113] R a32 and R a33 include fluorine atoms, chlorine atoms, bromine atoms and the like. are exemplified. R a32 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R includes trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 , 2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pen rufluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, bu tyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro pentyl group, pentyl group, hexyl group and perfluorohexyl group may be mentioned. 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 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. are mentioned. R a33 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, a tert-butoxy group, a pentyloxy group, 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 include a methoxymethyl group, an ethoxyethyl group , a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxy methyl group, 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 a33Examples of the alkoxyalkoxy group include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethyl group or an ethoxyethyl group. 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, even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-. 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, more preferably an acetyl group. R 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 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, 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, even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-. R a33 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, even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group. *-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-. *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-.

[0114] *-X a31 -(A a32 -X a32 ) nc *-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-. a32 *-X-(A-X)- is preferably *-O-, *-CO-O-, *-O-CO-, *-CO-O-A-CO-O-, *-O-CO-A-CO-O-.a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO-, Among them, *-CO-O- and *-CO-OA are the most common. a32 -CO-O- or *- Office Automation a32 -CO-O- is preferred.

[0115] Examples of the alkanediyl group include a methylene group, an ethylene group, and a 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, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and and 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[0116] A a30 is a single bond, *-CO-O- or *-CO-OA a32 -CO-O- Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable.

[0117] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 , R a35 and R a36 The hydrocarbon group in the formula (I) is an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups combining these. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples thereof include a silyl group, a heptyl group, an octyl group and the like. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group includes cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following group (* represents a bonding site) and the like. Examples thereof include. TIFF2025108447000097.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 and the like. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., a cycloalkylalkyl group), an aralkyl group such as a 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 and the like), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexyl phenyl group, p-adamantylphenyl group and the like), an aryl-cycloalkyl group such as a phenylcyclohexyl group and the like. In particular, R Examples of include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group formed by combining these. a36 As, an alkyl group having 1 to 18 carbon atoms includes, 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.

[0118] 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 It is an alicyclic hydrocarbon group, more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group of is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. More preferably, it is 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. R a36 In the alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. R a36 In the aromatic hydrocarbon group, an aromatic ring having an aryloxy group having 6 to 10 carbon atoms is preferable.

[0119] -OC(R a34 )(R a35 )-O-R a36 in the structural unit (a1-4) eliminates upon contact with an acid (for example, p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

[0120] 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, formula ( a32 to a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13), Examples of the structural units are those represented by the formula (a1-4-14). TIFF2025108447000098.tif100167

[0121] When the resin (A) has the structural unit (a1-4), the content thereof is determined based on the total structure of the resin (A). It is preferably 10 to 95 mol %, more preferably 15 to 90 mol %, based on the total of the structural units. More preferably, the content is 20 to 85 mol %, and even more preferably, the content is 20 to 70 mol %. %, and particularly preferably 20 to 60 mol %.

[0122] The structural unit derived from a (meth)acrylic monomer having the group (2) is represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can also be mentioned. can be. TIFF2025108447000099.tif4253 formula (a1-5), R a8 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Represents an acetylene atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 Represents a bond with . L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0123] Examples of the halogen atom include a fluorine atom and a chlorine atom, with a fluorine atom being preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include methyl group and ethyl group , propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoro methyl group and trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. Preferably. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferable that one of them is -O- and the other is -S-. s1 is preferably 1. s1’ is preferably any integer from 0 to 2. Z a1 is preferably a single bond or *-CH2-CO-O-.

[0124] Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among them, the structural units represented by formula (a1-5-1) to formula (a1-5- 4) are preferable, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2 ) is more preferable. ) is more preferable. TIFF2025108447000100.tif31129

[0125] 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% with respect to all the structural units of the resin (A), and even more preferably 5 to 30 mol%. mol% is even more preferable.

[0126] Examples of the structural unit (a1) also include the following structural units. TIFF2025108447000101.tif27161

[0127] When the resin (A) contains structural units such as (a1-3-1) to (a1-3-7) described above , its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, still more preferably 20 to 70 mol% , and particularly preferably 20 to 60 mol%.

[0128] 〈Structural unit(s)〉 The structural unit(s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer(s)"). As the monomer that leads to the structural unit(s), a monomer having no acid-labile group known in the resist field can be used. The structural unit(s) preferably has a hydroxy group or a lactone ring. When a resin having a structural unit having a hydroxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") 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.

[0129] 〈Structural unit (a2)〉 The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention and using a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet light) as the exposure light source , as the structural unit (a2), a structural unit having a phenolic hydroxy group ( a2) 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 arcolic hydroxy group is preferred, and it is more preferable to use the structural unit (a2 -1) described later. As the structural unit (a2), one kind may be included alone, or two or more kinds may be included.

[0130] 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)"). are mentioned. TIFF2025108447000102.tif4450[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. 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. represents. represents. 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 bonded. represents. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represent -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an integer from 0 to 4. When mb is any integer of 2 or more, the plural R may be the same as or different from each other.] a51

[0131] Examples of the halogen atom in R a50 and R a51 include a fluorine atom, a chlorine atom, a bromine atom, etc. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R a50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, 2,2,2 -trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a per fluoro-propyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a per fluoro-butyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropent yl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. Examples of the alkyl group in R a51 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. Examples of the alkoxy group in R a51 include a methoxy group, an ethoxy group, a propoxy group, an iso ​​​​Examples thereof include a 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, even 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, even more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group in 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, more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group in include an acetyl group, a propionyl group, and a butyryl group, etc. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. R a51 Examples of the alkylcarbonyloxy group in 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 a51is 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,

[0132] *-X a51 -(A a52 -X a52 ) nb - is, for example, *-O-, *-CO-O-, *-O-C O-, *-CO-O-A a52 -CO-O-, *-O-CO-A a52 -O-, *-O-A a52 -CO-O-, *-CO-O-A a52 -O-CO-, *-O-CO-A a52 -O-CO-, and the like. Among them, *-CO-O-, *-CO-O-A a52 -CO-O- or *- O-A a52 -CO-O- is preferred.

[0133] 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 a52 is preferably a methylene group or an ethylene group.

[0134] Aa50 is a single bond, *-CO-O- or *-CO-O-A a52 is preferably -CO-O- more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O- even more preferably a single bond or *-CO-O-

[0135] 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 or para position of the benzene ring, more preferably to the para position

[0136] Examples of the structural unit (a2-A) include structural units derived from the monomers described in JP-A-2010-204634 and JP-A-2012- 12577 Examples of the structural unit (a2-A) include the structural units represented by formulas (a2-2-1) to (a2-2-16) and the structural units represented by formulas (a2-2-1) to (a2-2-16) in which the methyl group corresponding to R in the structural unit (a2-A) is replaced by a hydrogen atom. The structural unit (a2-A) is the structural unit represented by formula (a2-2-1) the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-6), the structural unit represented by formula a50 (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3) the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and in the structural units represented by formulas (a2-2-1), (a2-2-3), (a2-2-6), (a2-2-8), (a2-2-12) to (a2-2-14) the methyl group corresponding to R in the structural unit (a2-A) is replaced by a hydrogen atom (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3) the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and in the structural units represented by formulas (a2-2-1), (a2-2-3), (a2-2-6), (a2-2-8), (a2-2-12) to (a2-2-14) the methyl group corresponding to R in the structural unit (a2-A) is replaced by a hydrogen atom (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), the structural unit represented by formula (a2-2-1), the structural unit represented by formula (a2-2-3) the structural unit represented by formula (a2-2-6), the structural unit represented by formula (a2-2-8), the structural units represented by formulas (a2-2-12) to (a2-2-14), and in the structural units represented by formulas (a2-2-1), (a2-2-3), (a2-2-6), (a2-2-8), (a2-2-12) to (a2-2-14) a50 the methyl group corresponding to R in the structural unit (a2-A) is replaced by a hydrogen atom ​It is preferably a structural unit, a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2- 8), a structural unit represented by formulas (a2-2-12) to (a2-2-14) and a structural unit represented by formula (a2-2-3) or a structural unit represented by formula (a2-2-8), a structural unit represented by formulas (a2-2-12) to (a2-2-14), in which the methyl group corresponding to R in the structural unit (a2-A) is more preferably replaced by a hydrogen atom, and in the structural unit represented by formula (a2-2-8) and the structural unit represented by formula (a2-2 -8), it is even more preferably a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced by a hydrogen atom. When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 15 to 65 mol%, and even more preferably 20 to a50 65 mol% with respect to all structural units. The structural unit (a2-A) can be contained in 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 a50 can contain the structural unit (a2-A) in the resin (A). As the structural unit having an alcoholic hydroxy group in the structural unit (a2), the formula ( TIFF2025108447000103.tif63169

[0137] When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, 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 contained in 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 contain the structural unit (a2-A) in the resin (A). As the structural unit having an alcoholic hydroxy group in the structural unit (a2), the formula ( can be used.

[0138] As the structural unit having an alcoholic hydroxy group in the structural unit (a2), the formula ( The structural unit represented by (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") is listed. In formula (a2-1) of TIFF2025108447000104.tif4157, L a3 represents -O- or *-O-(CH2) k2 -CO-O-, k2 represents any integer from 1 to 7. * represents a bond with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group. o1 represents any integer from 0 to 10.

[0139] In formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- wherein (said f1 represents any integer from 1 to 4), and more preferably -O-. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably any integer from 0 to 3, more preferably 0 or 1.

[0140] Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. The structural unit represented by any of formulas (a2-1-1) to (a2-1-6 ) is preferred, the structural unit represented by any of formulas (a2-1-1) to (a2-1-4) is more preferred, and the structural unit represented by formula (a2-1-1) or formula (a2-1- 3) is even more preferred. 3) is even more preferred. TIFF2025108447000105.tif54150

[0141] When the resin (A) contains the structural unit (a2-1), its content is usually 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, still more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol% with respect to all the structural units of the resin (A).

[0142] 〈Structural unit (a3)〉 The lactone ring contained in 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. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ- butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) is exemplified.

[0143] The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). These may be contained alone or in combination of two or more. TIFF2025108447000106.tif53168[In the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4), L a4 、L a5 and L a6 each independently represents a group represented by -O- or *-O-(CH2) k3 - CO-O- (where k3 represents an integer of 1 to 7). L a7 is -O-, *-O-L a8 -O-, *-O-L a8 -CO-O-, *-O-L ​​​​a8 -CO-O-L a9 -CO-O- or *-O-L a8 -O-CO-L a9 represents -O-. That is. 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 may have a halogen atom and represents an alkyl group having 1 to 6 carbon atoms, 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 aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 is 2 or more, a plurality of R a21 , R a22 , R a2 3 and / or R a25 may be the same as or different from each other.

[0144] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon groups in Alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group and the like can be mentioned. R a24 As the halogen atom in, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned. R a24 As the alkyl group in, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, etc. can be mentioned, preferably an alkyl group having 1 to 4 carbon atoms can be mentioned, and more preferably a methyl group or an ethyl group can be mentioned. R a24 As the alkyl group having a halogen atom in, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluoro robutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a per fluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. can be mentioned. L a8 and L a9 As the alkanediyl group in, a methylene group, an ethylene group, a pro pane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pen tane-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 pen tane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group, etc. can be mentioned.

[0145] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably or -O- or, *-O-(CH2) k3 -CO-O- wherein k3 is any integer from 1 to 4, more preferably -O- and, *-O-CH2-CO-O-, still more preferably an oxygen atom. Preferably an oxygen atom. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group or a methyl group. p1, q1 and r1 are each independently preferably any integer from 0 to 2, more preferably 0 or 1.

[0146] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom or a methyl group. 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)’. TIFF2025108447000107.tif4051 (wherein R a24 , L a7 represent the same meaning as above.)

[0147] As the structural unit (a3), the monomer described in JP-A-2010-204646 , monomers described in JP-A No. 2000-122294 and JP-A No. 2012-41274 Structural units derived from the monomers described in the publication are exemplified. As the structural unit (a3), , the 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 said structural units, R in formula (a3-1) to formula ( a3-4) a18 , R a19 , R a20 and R a24 The structural units in which the corresponding methyl groups are replaced by hydrogen atoms are preferred.

[0148] TIFF2025108447000108.tif115165

[0149] When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol%, preferably 10 to 65 mol%, more preferably 10 to 60 mol% with respect to all the structural units of the resin (A). Further, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and still more preferably 10 to 50 mol% with respect to all the structural units of the resin (A). respectively.

[0150] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF2025108447000109.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 fluorine atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO.] R 42 The saturated hydrocarbon group represented by is a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and groups formed by combining these may be mentioned.

[0151] Examples of the chain hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa decyl group, heptadecyl group and octadecyl group. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooct yl group; polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents a bond). TIFF2025108447000110.tif11159 Groups formed by combination include groups formed by combining one or more alkyl groups or one or more alkane di yl groups with one or more alicyclic hydrocarbon groups, and examples include -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -al kane diyl group-alicyclic hydrocarbon group-alkyl group.

[0152] Examples of the structural unit (a4) include at least one structure represented by a group selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula ( a4-3) and formula (a4-4). unit. TIFF2025108447000111.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 perfluoro fluorocycloalkanediyl group having 3 to 12 carbon atoms. R 6 represents a hydrogen atom or a fluorine atom.

[0153] L 4a Examples of the divalent aliphatic saturated hydrocarbon group in L include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group, and branched alkane diyl groups such as an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2- methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group. branched alkane diyl groups. L 3a Examples of the perfluoroalkanediyl group in L include a difluoromethylene group, a perfluoro fluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane -1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane -2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2 ,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1, 5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3, 3-diyl group, a perfluorohexane-1,6-diyl group, a perfluorohexane-2, 2-diyl group, a perfluorohexane-3,3-diyl group, a perfluoroheptane-1, 7-diyl group, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3, 4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1, 8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3, 3-diyl group, perfluorooctane-4,4-diyl group and the like can be mentioned. L 3a The perfluorocycloalkanediyl group in is, perfluorocyclohe xanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanedi yl group, perfluoroadamantanediyl group and the like can be mentioned.

[0154] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond, a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms. is preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0155] 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 can be mentioned. are. TIFF2025108447000112.tif95165

[0156] TIFF2025108447000113.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 a41represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by the 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 group. TIFF2025108447000114.tif1384 [In the formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 each independently represent -O-, -CO-, -CO-O- or -O-CO -. However, the total number of carbon atoms of A a42 , A a43 , A a44 , X a41 and X a42 is 7 or less. ] * represents a bond, and the * on the right side is a bond with -O-CO-R a42 . ]

[0157] R a42 Examples of the saturated hydrocarbon group in include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these. Examples of the chain saturated hydrocarbon group include 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 cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents a bond). Examples of the group formed by the combination of TIFF2025108447000115.tif11159 include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group and the like.

[0158] R a42 Examples of the substituent that R may optionally have include at least one selected from a halogen atom and the group represented by the 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. TIFF2025108447000116.tif965 [In the formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * represents the bond with R. a42 However, in R a42 -X a43 -A a45 when R a42 does not have a halogen atom, A a4 5 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which has at least one halogen atom. ​​​​​。

[0159] A a45 Examples of the aliphatic hydrocarbon 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, a decyl group, a dodecyl group, a penta decyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, etc.; an alkyl group; a monocyclic alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc.; and a polycyclic alicyclic 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 of TIFF2025108447000117.tif11159 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, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -al kanediyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0160] R a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (a-g3). R a42 When 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. A perfluoro Examples of the Ruki group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a per fluoroheptyl group, a perfluorooctyl group, and the like. Examples of the perfluorocyclo alkyl group include a perfluorocyclohexyl group and the like. R a42 When 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, and more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent , the number thereof is preferably 1.

[0161] R a42 When is an aliphatic hydrocarbon having a group represented by the formula (a-g3), R a42 is more preferably a group represented by the formula (a-g2). TIFF2025108447000118.tif879 [In the formula (a-g2), A a46 represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom . X a44 represents **-O-CO- or **-CO-O- (** represents a bond with A a46 ). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom . However, the total number of carbon atoms of A a46 , A a47 and X a44 is 18 or less, and at least one of A a46 and A a47 has at least one halogen atom. * represents a bond to a carbonyl group.

[0162] A a46 The aliphatic hydrocarbon group of A preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. A a47 The aliphatic hydrocarbon group of A preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms. A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0163] The preferred structure of the group represented by formula (a-g2) is the following structure (* is a bond to a carbonyl group ). TIFF2025108447000119.tif13161

[0164] A a41 As the alkanediyl group in A, there are linear alkanediyl groups such as methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, etc.; branched alkanediyl groups such as propane-1,2-diyl group, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned. A a41 As the substituent in the alkanediyl group of A, there are a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. etc. 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.

[0165] A in the group represented by formula (a-g1) a42 , A a43 and A a44 represents a divalent saturated Examples of the 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-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1 ,2-diyl group, and the like. 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.

[0166] In the group represented by formula (a-g1), examples of the group where X a42 is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a bond, and ** is a bond with -O-CO-R a42 . TIFF2025108447000120.tif54162

[0167] Examples of the structural unit represented by formula (a4-1) include the following structural units and the structural units in which the methyl group corresponding to R a41 in the structural unit represented by formula (a4-1) below is replaced by a hydrogen atom. TIFF2025108447000121.tif47144

[0168] TIFF2025108447000122.tif188147

[0169] As the structural unit represented by formula (a4-1), the structural unit represented by formula (a4-2) is preferred. Preferably. TIFF2025108447000123.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 -C H2- 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.]

[0170] The alkanediyl group having 1 to 6 carbon atoms of L 44 is exemplified by the same groups as the alkanediyl groups in A a41 described above. The same groups as those exemplified can be mentioned. R f6 The saturated hydrocarbon group of is exemplified by the same groups as those exemplified by R a42 above. L 44 As the alkanediyl group having 1 to 6 carbon atoms in, an alkanediyl group having 2 to 4 carbon atoms is preferred, and an ethylene group is more preferred.

[0171] As the structural unit represented by formula (a4-2), for example, the structural units represented by formulas (a4-1-1) to (a4 -1-11) can be mentioned respectively. 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 represented by formula (a4-2) and can be mentioned as the structural unit represented by.

[0172] As the structural unit (a4), the structural unit represented by formula (a4-3) can be mentioned. TIFF2025108447000124.tif5771[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. That is. X f12 represents *-O-CO- or *-CO-O- (* represents a bond with A f13 ).) . A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, at least one of A f13 and A f14 has a fluorine atom, and the upper limit of the total number of carbon atoms of L 5 , A f13 and A f14 is 20.]

[0173] L 5 Examples of the alkanediyl group in include the same groups as those exemplified for the alkanediyl group in the divalent saturated hydrocarbon group of A a41 . The alkanediyl group in A Examples of the divalent saturated hydrocarbon group which may have a fluorine atom in include 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, more preferably a perfluoroalkanediyl f13 group. Examples of the divalent aliphatic hydrocarbon group which may have a fluorine atom include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group and a pentanediyl group; a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a per etc. group, a propanediyl group, a butanediyl group and a pentanediyl group; a difluoromethylene group, a perfluoroethylene group, a perfluoropropanediyl group, a per Perfluoroalkanediyl groups such as fluorobutanediyl group and perfluoropentanediyl group, etc. are exemplified. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexanediyl group and perfluorocyclohexanediyl group, etc. Examples of the polycyclic group include adamantanediyl group, norbornanediyl group, perfluoroadamantanediyl group, etc. A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are the same groups as those exemplified by R. a42 Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluoroalkyl groups such as perfluorooctyl group, cyclopropylmethyl group, cyclopropyl group , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornil group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantylmethyl group, etc. are preferable.

[0174] In formula (a4-3), L5 The ethylene group is preferred. A f13 The divalent saturated hydrocarbon group of A preferably includes a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain hydrocarbon group having 2 to 3 carbon atoms. A f14 The saturated hydrocarbon group of A preferably includes a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms. More preferably, it includes a chain hydrocarbon group having 3 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms. Among them, A is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl f14 group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0175] Examples of the structural unit represented by formula (a4-3) include the structural units represented by formula (a4-1'-1) to formula (a 4-1'-11), respectively. The structural unit in which the methyl group corresponding to R in (a4-3) is replaced by a hydrogen atom is also included in the structural units represented by formula (a4-3). f7

[0176] Examples of the structural unit (a4) also include the structural unit represented by formula (a4-4). TIFF2025108447000125.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.

[0177] R f22 The saturated hydrocarbon group of is the same as the saturated hydrocarbon group represented by R a42 and examples include the same. 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. Among them, an alkyl group having 1 to 10 carbon atoms and having a fluorine atom is more preferable, and an alkyl group having 1 to 6 carbon atoms and having a fluorine atom is even more preferable. In formula (a4-4), A

[0178] is preferably -(CH2) f21 -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group. j1 group or a methylene group is more preferable, and a methylene group is even more preferable. Examples of the structural unit represented by formula (a4-4) include the following structural units and the following formulas, where the methyl group corresponding to R in structural unit (a4-4)

[0179] is replaced by a hydrogen atom. In the structural unit represented by formula (a4-4), for example, in the following structural units and the following formulas, the methyl group corresponding to R in structural unit (a4-4) f21 is replaced by a hydrogen atom. Examples of the structural unit include the structural unit in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom. TIFF2025108447000126.tif80148

[0180] 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). %.

[0181] <Structural unit (a5)> The non-leaving hydrocarbon group contained in structural unit (a5) is a linear, branched or cyclic hydrocarbon. Examples of the group having a base include. Among them, the structural unit (a5) has an alicyclic hydrocarbon group and is preferred. Examples of the structural unit (a5) include, for example, a structural unit represented by the formula (a5-1) . TIFF2025108447000127.tif3971 [In the 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 an aliphatic hydrocarbon group 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 -CH2- contained in may be replaced by -O- or -CO-.]

[0182] R 52 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Monocyclic Examples of the alicyclic hydrocarbon group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopent yl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include, for example , an adamantyl group and a norbornyl group, etc. The aliphatic hydrocarbon group having 1 to 8 carbon atoms is, for example, 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 an alkyl group such as 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 The divalent saturated hydrocarbon group in the formula (I) is a divalent chain saturated hydrocarbon group or a divalent fatty acid group. Examples of the hydrocarbon group include cyclic saturated hydrocarbon groups, and preferably divalent chain saturated hydrocarbon groups. Examples of the divalent chain saturated hydrocarbon group include a methylene group, an ethylene group, and a propanediyl group. Examples of the alkyl groups include alkanediyl groups such as dialkyl groups, butanediyl groups, and pentanediyl groups. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the saturated hydrocarbon group include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adatomyl groups. Examples thereof include a manthanediyl group and a norbornanediyl group.

[0183] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula (I) is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * and ** each represent a bond, and * represents a bond to an oxygen atom. TIFF2025108447000128.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 It represents a bond with . ). 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, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. Lx4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, for L x3 and L x4 the total number of carbon atoms 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 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. hydrogen group. However, for L x5 , L x6 and L x7 the total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, for L x8 , L x9 and W x1 the total number of carbon atoms is 15 or less.

[0184] 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 It is a methylene group or an ethylene group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0185] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF2025108447000129.tif23135

[0186] TIFF2025108447000130.tif33116

[0187] Examples of the group represented by the formula (L1-2) include the following divalent groups. TIFF2025108447000131.tif23130

[0188] Examples of the group represented by the formula (L1-3) include the following divalent groups. TIFF2025108447000132.tif15144

[0189] Examples of the group represented by the formula (L1-4) include the following divalent groups. TIFF2025108447000133.tif26114

[0190] L 55 is preferably a single bond or a group represented by the formula (L1-1).

[0191] Examples of the structural unit (a5-1) include the structural units shown below and the structural units in the following structural units ( a5-1) where the methyl group corresponding to R 51 in is replaced by a hydrogen atom. are mentioned. TIFF2025108447000134.tif75150

[0192] 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.

[0193] <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 are preferred. is preferred.

[0194] 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'). TIFF2025108447000136.tif35104[In the formula (II-2-A'), X III3represents 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 substituted by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA - represents a sulfonate group or a carboxylate group. R III3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.]

[0195] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, etc. III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by a8 R Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A A x1 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4- diyl group, etc. A diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl yl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. are mentioned. A X1 perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted in A includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoro isopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert -butyl group, a perfluoropentyl group, a perfluorohexyl group, etc. X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X includes a linear or branched alkane diyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a combination thereof may also be acceptable. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1, 2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1 ,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane- 1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dode cane-1,12-diyl group, etc. of linear alkane diyl groups; a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pent ane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. of branched alkane diyl yl groups; a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohe Ru group; divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. and the like. Examples of the saturated hydrocarbon group in which -CH2- is replaced by -O-, -S- or -CO- include divalent groups represented by formula (X1) to formula (X53). However, the carbon number before the replacement of -CH2- contained in the saturated hydrocarbon group by -O-, -S- or -CO- is 17 or less respectively. In the following formula, * and ** represent bonding sites, and * represents a bond to A and the like. X represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. * represents a bond to A x1 and the like. TIFF2025108447000137.tif145161

[0196] X 3 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 14 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.

[0197] ZA in formula (II-2-A') + is the same as the cation Z1 in the salt represented by formula (B1) + and the like.

[0198] The structural unit represented by formula (II-2-A') is preferably the structural unit represented by formula (II-2-A). and the like. TIFF2025108447000138.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 represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. When z2A is 2 or more, a plurality of R III2 and R III4 may be the same as or different from each other. Q a and Q b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.] R III2 、R III4 、Q a and Q b The perfluoroalkyl groups having 1 to 6 carbon atoms represented by are the same as those of the perfluoroalkyl groups having 1 to 6 carbon atoms represented by the aforementioned Q b1 as described above. are exemplified.

[0199] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). In formula (II-2-A-1), TIFF2025108447000139.tif5577 R III2 、R III3 、R III4 、Q a 、Q b and ZA + have the same meanings as described above . R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents any integer from 0 to 6. X I2represents 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.] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. X I2 Examples of the divalent saturated hydrocarbon group represented by III3 include the same groups as those of the divalent saturated hydrocarbon group represented by X.

[0200] As the structural unit represented by the formula (II-2-A-1), the structural unit represented by the formula (II-2-A-2) is more preferable. In the formula (II-2-A-2), TIFF2025108447000140.tif5287[R R III3 R III5 and ZA + have the same meanings as described above. m and nA each independently represent 1 or 2.]

[0201] Examples of the structural unit represented by the formula (II-2-A') include, for example, the following structural units, and the group corresponding to the methyl group of III3 R is replaced by a hydrogen atom, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, a trifluoromethyl group, etc.) and the structural units described in WO 2012 / 050015. ZA ZA +represents an organic cation. TIFF2025108447000141.tif86163

[0202] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1). It is a structural unit represented by the following formula. TIFF2025108447000142.tif3791[In the formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R II2 and R II3 may combine with each other to form a ring together with the sulfur atom to which they are attached. 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 an alkyl group. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by include a phenylene group and a naphthylene group. R II2 and R II3 Examples of the hydrocarbon group represented by include an alkyl group, an alicyclic hydrocarbon group an aromatic hydrocarbon group, and a group formed by combining these. R II4 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R II4 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by include R a8which may have a halogen atom and is the same as an alkyl group having 1 to 6 carbon atoms include those below. A II1 Examples of the divalent linking group represented by II1 include divalent saturated hydrocarbon groups having 1 to 18 carbon atoms. The -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. Specifically, examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by III3 include those below. -CO-. Specifically, examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by III3 include those below. III3 1 to 1 8 carbon atoms are the same as those below.

[0203] Examples of the structural unit containing the cation in formula (II-1-1) include the structural units represented below and and groups corresponding to the methyl group of R II4 which are replaced by a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc., and structural units obtained by such replacement. include those below. TIFF2025108447000143.tif84130

[0204] A - Examples of the organic anion represented by - include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions, etc. A Examples of the organic anion represented by - include sulfonate anions, sulfonylimide anions, sulfonylmethide anions, carboxylic acid anions, etc. A - The organic anion represented by - is preferably a sulfonate anion, and more preferably an anion contained in the salt represented by the aforementioned formula (B1). is preferably a sulfonate anion, and more preferably an anion contained in the salt represented by the aforementioned formula (B1).

[0205] A - Examples of the sulfonylimide anion represented by - include those below. TIFF2025108447000144.tif36135

[0206] Examples of the sulfonylmethide anion include those below. TIFF2025108447000145.tif29123

[0207] Examples of the carboxylic acid anion include the following. TIFF2025108447000146.tif51152

[0208] Examples of the structural unit represented by formula (II-1-1) include the structural units represented below. and the like. TIFF2025108447000147.tif88149

[0209] When the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% with respect to all the structural units of the resin (A).

[0210] The resin (A) may have a structural unit other than the above-described structural unit, and examples of such a structural unit include structural units well-known in the art.

[0211] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s), that is, a copolymer of the monomer (a1) and the monomer (s). The structural unit (a1) is preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group and a cyclopentyl group), more preferably at least two species, and still more preferably at least two selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably the structural unit (a2-1). Or it is a structural unit (a2-A). The structural unit (a3) is preferably represented by the formula (a3-1). It is at least one selected from the group consisting of a structural unit represented by the formula (a3-2), a structural unit represented by the formula (a3-4), and a structural unit represented by the formula (a3-4). Each structural unit constituting the resin (A) may be used alone or in combination of two or more. Using the monomers that lead to these structural units, it can be produced by a known polymerization method (for example, radical polymerization method). The content of each structural unit of the resin (A) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, even more preferably 3,000 or more), and 50,000 or less (more preferably 30,000 or less, even more preferably 15,000 or less). In this specification, the weight average molecular weight is the value determined by gel permeation chromatography under the conditions described in the examples. The resist composition of the present invention may be used in combination with a resin other than the resin (A). Examples of the resin other than the resin (A) include resins containing the structural unit (a4) or the structural unit (a5) (hereinafter sometimes referred to as resin (X)). Among them, the resin containing the structural unit (a4) is preferable as the resin (X). In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, based on the total of all structural units of the resin (X). Structural units that the resin (X) may further have include the structural unit (a1), the structural unit The resin (X) may further have a structural unit (a2) or a structural unit (a3).

[0212] <Resin other than resin (A)> The resist composition of the present invention may be used in combination with a resin other than the resin (A). Examples of the resin other than the resin (A) include resins containing the structural unit (a4) or the structural unit (a5) (hereinafter sometimes referred to as resin (X)). Among them, the resin containing the structural unit (a4) is preferable as the resin (X). In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 45 mol% or more, based on the total of all structural units of the resin (X). Structural units that the resin (X) may further have include the structural unit (a1), the structural unit The resin (X) may further have a structural unit (a2) or a structural unit (a3). Structural units that the resin (X) may further have include the structural unit (a1), the structural unit Examples include structural units derived from (a2), structural units (a3), and other known monomers. Among them, the resin (X) preferably consists only of the structural unit (a4) and / or the structural unit (a5). Each structural unit constituting the resin (X) may be used alone or in combination of two or more. Using the monomers that induce these structural units, it can be produced by a known polymerization method (for example, radical polymerization method). The content of each structural unit of the resin (X) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,00 0 or more), 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).

[0213] 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), still more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass.

[0214] The content of the resin (A) in the resist composition is preferably 8 0% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, with respect to the solid content of the resist composition. When including resins other than the resin (A), the total content of the resin (A) and resins other than the resin (A) is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, with respect to the solid content of the resist composition. In this specification, ​​​​Here, 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 ratio of the resin thereto can be measured by known analytical means such as liquid chromatography or gas chromatography. The content ratio of the resin to the solid content of the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography. The content ratio of the resin to the solid content of the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography. The content ratio of the resin to the solid content of the resist composition can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0215] <Solvent (E)> The content ratio of the solvent (E) is usually 90% by mass or more and 99.9% by mass or less in the resist composition, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content ratio of the solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography. The content ratio of the solvent (E) is usually 90% by mass or more and 99.9% by mass or less in the resist composition, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content ratio of the solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography. The content ratio of the solvent (E) is usually 90% by mass or more and 99.9% by mass or less in the resist composition, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content ratio of the solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography. The content ratio of the solvent (E) is usually 90% by mass or more and 99.9% by mass or less in the resist composition, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more and 99% by mass or less. The content ratio of the solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0216] Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used.

[0217] <Quencher (C)> Examples of the quencher (C) include basic nitrogen-containing organic compounds and salts that generate an acid having a lower acidity than the acid generated from the acid generator (B). When the resist composition contains the quencher (C), the content of the quencher (C) is based on the solid content of the resist composition. Examples of the quencher (C) include basic nitrogen-containing organic compounds and salts that generate an acid having a lower acidity than the acid generated from the acid generator (B). When the resist composition contains the quencher (C), the content of the quencher (C) is based on the solid content of the resist composition. Examples of the quencher (C) include basic nitrogen-containing organic compounds and salts that generate an acid having a lower acidity than the acid generated from the acid generator (B). When the resist composition contains the quencher (C), the content of the quencher (C) is based on the solid content of the resist composition. Specifically, it is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, still more preferably about 0.1 to 5% by mass, and even more preferably about 0.1 to 3% by mass. As the basic nitrogen-containing organic compound, amines and ammonium salts can be mentioned. As amines, aliphatic amines and aromatic amines can be mentioned. As aliphatic amines, primary amines, secondary amines and tertiary amines can be mentioned. As aromatic amines, 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine,

[0218] octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triiso propylamine, etc. can be mentioned. As ammonium salts, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, tetraheptylammonium chloride, tetraoctylammonium chloride, tetranonylammonium chloride, tetra Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyl diphenylmethane, 4,4'-diamino-3,3'-diethyl diphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-bis(2-pyridyl)ethane, 1,2-bis(4-pyridyl)ethane, 1,2-bis(2-pyridyl)ethene, 1,2-bis(4-pyridyl)ethene, 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned. 4,4'-diamino-3,3'-dimethyl diphenylmethane, 4,4'-diamino-3,3'-diethyl diphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-bis(2-pyridyl)ethane, 1,2-bis(4-pyridyl)ethane, 1,2-bis(2-pyridyl)ethene, 1,2-bis(4-pyridyl)ethene, 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned. 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-bis(2-pyridyl)ethane, 1,2-bis(4-pyridyl)ethane, 1,2-bis(2-pyridyl)ethene, 1,2-bis(4-pyridyl)ethene, 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned. 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned. 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned. 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned. 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned. 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned. 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, bis(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6-diisopropyl aniline is mentioned.

[0219] Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, etc. tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, etc. tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, etc. tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, etc. phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, etc. tetra-n-butylammonium salicylate, choline, etc.

[0220] The acidity of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The acid with a lower acidity than the acid generated from the acid generator (B) The acid dissociation constant of the acid generated from the salt is usually -3 <pKaの塩であり、好 Preferably -1 <pKa<7の塩であり、より好ましくは0<pKa<5の塩である。 As the salt that generates an acid having a weaker acidity than the acid generated by the acid generator (B), there is a salt represented by the following formula: a salt represented by formula (D) described in JP 2015-147926 A (hereinafter, (sometimes referred to as weak acid inner salt (D)) and JP 2012-229206 A , JP 2012-6908 A, JP 2012-72109 A, JP 2011-3 9502 and JP-A 2011-191745. is a salt (carbohydrate) that generates a carboxylic acid having a weaker acidity than the acid generated by the acid generator (B). A salt having a phosphate anion is preferred, and a weak acid inner salt (D) is more preferred. TIFF2025108447000148.tif89165

[0221] Examples of the weak acid inner salt (D) include the following salts. TIFF2025108447000149.tif72165

[0222] <Other Ingredients> The resist composition of the present invention may further contain components other than the above-mentioned components (hereinafter referred to as “other components”) as necessary. (F)) may be contained. There are no particular limitations on other components (F). However, additives known in the resist art, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc., may be used. Agents, dyes, etc. can be used.

[0223] Preparation of Resist Composition The resist composition of the present invention comprises a salt (I), a resin (A), an acid generator (B), and optionally Depending on the resin (A) used, the resin other than the resin (A), the solvent (E), the quencher (C) and its It can be prepared by mixing 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 and the like, and the solubility of the resin in a solvent (E) such as the like. The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. Note that the mixing means is not particularly limited, and stirring and mixing can be used. After mixing the components, it is preferably filtered using a filter with a pore size of about 0.003 to 0.2 μm. After mixing the components, it is preferably filtered using a filter with a pore size of about 0.003 to 0.2 μm.

[0224] <Manufacturing method of resist pattern> The manufacturing method of the resist pattern of the present invention is (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.

[0225] To apply the resist composition onto the substrate, it can be usually performed 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 be usually performed 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 be usually performed 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.

[0226] By drying the applied composition, the solvent is removed to form a composition layer. Drying can be performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake), or by using a decompression device. The heating temperature is 50 to 200 °C. By drying the applied composition, the solvent is removed to form a composition layer. Drying can be performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake), or by using a decompression device. The heating temperature is 50 to 200 °C. By drying the applied composition, the solvent is removed to form a composition layer. Drying can be performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake), or by using a decompression device. The heating temperature is 50 to 200 °C. ​​It is preferably carried out, and the heating time is preferably 10 to 180 seconds. Also, for vacuum drying The pressure during the process is preferably about 1 to 1.0×10 5 Pa.

[0227] The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine as well. As the exposure light source, ultraviolet lasers such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), which emit laser light in the ultraviolet region, lasers from solid laser light sources (such as YAG or semiconductor lasers) whose laser light is wavelength-converted to emit harmonic laser light in the far ultraviolet or vacuum ultraviolet region, electron beams, and those that irradiate extreme ultraviolet light (EUV), etc., various ones can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure" in some cases. During exposure , usually, exposure is carried out through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be carried out by direct drawing without using a mask.

[0228] The composition layer after exposure is heat-treated (so-called post-exposure bake) to promote the deprotection reaction at the acid-labile group. The heating temperature is usually about 50 to 200 °C, preferably about 70 to 150 °C.

[0229] The composition layer after heating is usually developed using a developing solution with a developing device. Examples of the developing method include the dip method, paddle method, spray method, dynamic dispense method, etc. The developing temperature is preferably, for example, 5 to 60 °C, and the developing time is preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as follows A positive resist pattern or a negative resist pattern can be produced.

[0230] When producing a positive resist pattern from the resist composition of the present invention, an alkali developer is used. The alkali developer may be various alkaline aqueous solutions used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxy ethyl)trimethylammonium hydroxide (commonly known as choline) and the like can be mentioned. The alkali developer may contain a surfactant. After development, it is preferable to wash the resist pattern with ultrapure water and then remove the water remaining on the substrate and the pattern.

[0231] When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic-based developer") is used. Examples of the organic solvent contained in the organic-based developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole and the like. In the organic-based developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. Among them, as the organic-based developer, a developer containing butyl acetate and / or 2-heptanone is preferred. In the organic-based developer, the total content of butyl acetate and 2-heptanone is 50% by mass Preferably, the content is 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the components are qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 10%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too.

[0232] It is preferable to wash the resist pattern after development with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and any solvent containing a general organic solvent may be used. Any suitable solvent may be used, preferably an alcohol or ester solvent. After cleaning, it is preferable to remove any rinsing liquid remaining on the substrate and the pattern.

[0233] <Application> The resist composition of the present invention is a resist composition for exposure to a KrF excimer laser, Resist composition for exposure to ximer laser, resist composition for exposure to electron beam (EB) or EU A resist composition for V exposure, particularly a resist composition for electron beam (EB) exposure or EUV exposure The composition is suitable as a resist composition for semiconductor microfabrication. EXAMPLES

[0234] The present invention will be described in more detail with reference to examples. "%" and "parts" are by weight unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analytical 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 ent LC / MSD type). In the following Examples, the value of this molecular ion peak is indicated by "MASS".

[0235] 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 parts of the compound represented by formula (I-1-b). 27 parts were added, and after stirring at 75 °C for 5 hours, it was cooled to 23 °C. To the resulting mixture, 100 parts of chloroform and 45 parts of 5% oxalic acid aqueous solution were added and stirred at 23 °C for 30 minutes and then separated to extract the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added and stirred at 2 3 °C for 30 minutes, then separated to extract the organic layer. This water washing operation was repeated 5 times The obtained organic layer was concentrated to obtain 13.9 parts of the compound represented by formula (I-1-c). 4 parts were obtained. 3.04 parts of the salt represented by formula (I-1-c), 2.72 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. 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 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, stirred at 23 °C for 30 minutes, and then filtered to obtain 4.22 parts of the salt represented by the formula (I-2).

[0236] MASS(ESI(+)Spectrum):M + 485.2 MASS(ESI(-)Spectrum):M - 467.1

[0237] Example 2: Synthesis of the salt represented by the formula (I-13) 3.04 parts of the salt represented by the formula (I-1-c), 2.79 parts of the salt represented by the formula (I-13-d), 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 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, stirred at 23 °C for 30 minutes, and then filtered to obtain 4.09 parts of the salt represented by the formula (I-13).

[0238] MASS(ESI(+)Spectrum):M + 485.2 MASS(ESI(-)Spectrum):M - 481.1

[0239] Example 3: Synthesis of the salt represented by the formula (I-14) 3.04 parts of the salt represented by JPEG2025108447000153.jpg35166 formula (I-1-c), 2.86 parts of the salt represented by formula (I-14-d) 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 and stirred at 23 °C for 30 minutes, then separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue was added 30 parts of tert-butyl methyl ether and stirred at 23 °C for 30 minutes, then filtered to obtain 4.35 parts of the salt represented by formula (I-14).

[0240] MASS(ESI(+)Spectrum): M + 485.2 MASS(ESI(-)Spectrum): M - 497.1

[0241] Example 4: Synthesis of the salt represented by formula (I-42) 10 parts of the salt represented by TIFF2025108447000154.tif42149 formula (I-42-a) and 50 parts of dimethylformamide were mixed and stirred at 2 3 °C for 30 minutes, then 1.48 parts of potassium carbonate and 0.44 parts of potassium iodide were added and the temperature was raised to 75 °C. To the resulting mixture was added 10 .40 parts of the compound represented by formula (I-1-b), and the mixture was stirred at 75 °C for 5 hours and then cooled to 23 °C. To the resulting mixture were added 100 parts of chloroform and 45 parts of 5% oxalic acid aqueous solution, and the mixture was stirred at 23 °C for 30 minutes and then separated to obtain the organic layer. To the obtained organic layer was added 50 parts of ion-exchanged water, and the mixture was stirred at 23 °C for 30 minutes and then separated to obtain the organic layer. This water washing operation was repeated 5 times . By concentrating the obtained organic layer, 12 .89 parts of the compound represented by formula (I-42-c) were obtained. 3.21 parts of the salt represented by JPEG2025108447000155.jpg35166 formula (I-42-c), 2.72 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 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 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, and then filtered to obtain 4.66 parts of the salt represented by formula (I-42).

[0242] MASS(ESI(+)Spectrum):M + 521.2 MASS(ESI(-)Spectrum):M - 467.1

[0243] Example 5: Synthesis of the salt represented by formula (I-62) 10 parts of the salt represented by TIFF2025108447000156.tif42151 formula (I-62-a) and 50 parts of dimethylformamide were mixed and stirred at 2 3 °C for 30 minutes, then 1.22 parts of potassium carbonate and 0.36 part of potassium iodide were added and the temperature was raised to 75 °C. To the obtained mixture, 8. 56 parts of the compound represented by 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% oxalic acid aqueous solution were added and stirred at 23 °C for 30 minutes and then liquid separation was carried out to take out the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added and stirred at 2 3 °C for 30 minutes, and then liquid separation was carried out to take out the organic layer. This water washing operation was repeated 5 times The obtained organic layer was concentrated to obtain 11. 72 parts of the compound represented by formula (I-62-c). 3.69 parts of the salt represented by JPEG2025108447000157.jpg35167 formula (I-62-c), 2.72 parts of the salt represented by formula (I-2-d) parts, 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 to the concentrated residue , 30 parts of tert-butyl methyl ether was added, stirred at 23 °C for 30 minutes, and then filtered to obtain 4.73 parts of the salt represented by formula (I-62).

[0244] MASS(ESI(+)Spectrum): M + 621.2 MASS(ESI(-)Spectrum): M - 467.1

[0245] Example 6: Synthesis of the salt represented by formula (I-302) 10 parts of the salt represented by TIFF2025108447000158.tif42149 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 resulting mixture, 7 .10 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 resulting mixture , 100 parts of chloroform and 45 parts of 5% oxalic acid aqueous solution were added, stirred at 23 °C for 30 minutes , and then separated to obtain the organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added, stirred at 23 °C for 30 minutes, and then separated to obtain the organic layer. This water washing operation was repeated 5 times . By concentrating the obtained organic layer, 1 0.48 part of the compound represented by formula (I-302-c) was obtained. 4.24 parts of the salt represented by JPEG2025108447000159.jpg33166 formula (I-302-c), 2.7 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. The obtained 20 parts of ion-exchanged water was added to the resulting mixture, and the mixture was 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 and stirred at 23 °C for 30 minutes, and then filtered to obtain 4.39 parts of the salt represented by formula (I-302).

[0246] MASS(ESI(+)Spectrum): M + 737.0 MASS(ESI(-)Spectrum): M - 467.1

[0247] Example 7: Synthesis of the salt represented by formula (I-362) 5.19 parts of the salt represented by TIFF2025108447000160.tif56153 formula (I-362-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. 11.27 parts of the compound represented by formula (I-1-b) was added to the obtained mixture and stirred at 75 °C for 5 hours, and then cooled to 23 °C. 100 parts of chloroform and 45 parts of 5% oxalic acid aqueous solution were added to the obtained mixture and 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 and stirred at 23 °C for 30 minutes, and then separated to obtain the organic layer. This water washing operation was repeated 5 times . By concentrating the obtained organic layer, 8.24 parts of the compound represented by formula (I-362-c) was obtained . ​ 4.10 parts of the salt represented by JPEG2025108447000161.jpg43165 formula (I-362-c), 2.7 of the salt represented by formula (I-2-d) 2 parts, 30 parts of chloroform and 15 parts of ethyl acetate were mixed and stirred at 23 °C for 2 hours. The obtained mixture was added with 20 parts of ion-exchanged water, stirred at 23 °C for 30 minutes, and then separated to obtain an 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, followed by filtration to obtain 4.87 parts of the salt represented by formula (I-362).

[0248] MASS(ESI(+)Spectrum): M + 707.3 MASS(ESI(-)Spectrum): M - 467.1

[0249] 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. TIFF2025108447000162.tif4191

[0250] 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 they were mixed so that the molar ratio [monomer (a1-4-2): monomer (a1-1 -3): monomer (a1-2-6)] was 38:24:38, and further, 1.5 mass times of methyl isobutyl ketone was mixed with this monomer mixture based on the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile was used as an initiator ​The lial was added so as to be 7 mol% with respect to the total number of moles of all the monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the mass of the total amount of all the monomers was added to the polymerization reaction solution, and after stirring for 6 hours, liquid separation was carried out. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and by filtration and recovery, a resin A1 (copolymer) having a weight average molecular weight of about 5.3 × 10 was obtained in a yield of 78%. This resin A1 has the following structural units. TIFF2025108447000163.tif29126 3 and Synthesis Example 2 [Synthesis of Resin A2] TIFF2025108447000163.tif29126

[0251] As monomers, monomer (a1-4-2) and monomer (a1-2-6) were used, and their molar ratio [monomer (a1-4-2): monomer (a1-2-6)] was 38:62 and they were mixed so as to be in this ratio. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all the monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% with respect to the total number of moles of all the monomers, and polymerization was carried out by heating this at 85 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, and after stirring for 6 hours, liquid separation was carried out. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and by filtration and recovery, a resin A2 (copolymer) having a weight average molecular weight of about 5.4 × 10 was obtained in a yield of 89%. This resin A2 has the following structural units. and was added, and after stirring for 6 hours, liquid separation was carried out. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin, and by filtration and recovery, a resin A2 (copolymer) having a weight average molecular weight of about 5.4 × 10 was obtained in a yield of 89%. This resin A2 has the following structural units. 3 and has the following structural units. TIFF2025108447000164.tif2887

[0252] <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.

[0253]

Table 2

[0254] <Resin> A1, A2: Resin A1, Resin A2 <Salt (I)> I-2: Salt represented by formula (I-2) I-13: Salt represented by formula (I-13) I-14: Salt represented by formula (I-14) 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: TIFF2025108447000166.tif3378IX-2: TIFF2025108447000167.tif2899<Quencher (C)> C1: Synthesized by the method described in JP-A-2011-39502 TIFF2025108447000168.tif4356<Solvent> 400 parts of propylene glycol monomethyl ether acetate 100 parts of propylene glycol monomethyl ether 5 parts of γ-butyrolactone

[0255] (Electron Beam Exposure Evaluation of Resist Composition) A 6-inch silicon wafer was placed on a direct hot plate and treated with hexamethyldisilazane ​It was treated at 90 °C for 60 seconds using . On this silicon wafer, a resist composition was spin-coated so that the film thickness of the composition layer became 0.04 μm. Then, it was pre-baked 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 line and space pattern was directly drawn by changing the exposure dose stepwise using an electron beam lithography machine ["HL-800D 50 keV" manufactured by Hitachi, Ltd.]. After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 2 on a hot plate, and further paddle development was performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern. The obtained resist pattern (line and space pattern) was observed with a scanning electron microscope, and the exposure dose at which the line width and space width of the 60 nm line and space pattern became 1:1 was defined as the effective sensitivity. Line Edge Roughness Evaluation (LER): The fluctuation width of the unevenness on the side surface of the resist pattern manufactured with the effective sensitivity was measured with a scanning electron microscope to obtain the line edge roughness. The results are shown in Table 3. Compared with Comparative Compositions 1 and 2, the standard deviation in Compositions 1 to 8 was small, and the line edge roughness (LER) evaluation was good.

[0256]

[0257]

Table 3

Industrial Applicability

[0258] The resist composition containing the salt of the present invention has good line edge roughness (LER).​​​​​​​​​​​ To obtain a resist pattern suitable for semiconductor microfabrication and extremely useful industrially. It is useful.

Claims

1. An acid generator containing a salt represented by formula (I), and a resin having an acid-labile group, wherein the resin having an acid-labile group is a resist composition containing a structural unit represented by formula (a2-A). [In formula (I), R １ represents -O-L １ -CO-O-R ５ and 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 wherein -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- or *-O-CO-O- (where * represents C(R １1 )(R １2 ), or C(Q 1 )(Q 2 ).). L ２ represents a single bond. Ring W represents a cyclohexane ring or an adamantane ring. R f1 and R f2 each independently represents a fluorine atom or a C1-6 fluoroalkyl group. s represents an integer of any one of 1 to 4, and when s is 2 or more, a plurality of Rs f1 and R f2 are each the same or different.] 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 any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.]

2. X in formula (I) 1 is *-CO-O- or *-O-CO-O- (where * is a bonding site with C(R １ )(R ２ ), or C(Q １ )(Q ２ ).). The resist composition according to claim 1

3. In formula (I), m3 is any integer from 1 to 2, m4 is any integer from 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. In formula (I), m3 is any integer from 1 to 2, m4 is any integer from 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 is the resist composition according to claim 1 or 2, which may be the same as or different from each other.

5. In formula (I), 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 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, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ａ６ and R ａ７ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1' represents any integer from 0 to 3. ]

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, comprising the steps.

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