Resist composition and method for producing resist pattern

Abstract

To provide a resist composition from which a resist pattern can be produced with good line edge roughness.SOLUTION: The resist composition contains: a carboxylic acid generator containing a salt represented by formula (I); and a resin containing a structural unit having an acid-labile group and a structural unit represented by formula (a2-A). [In the formula (I), R1a and R1b each represent a hydrogen atom or an acid-labile group.]SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Patent Document 1 describes a resin containing a carboxylate represented by the following formula as a carboxylate generator. Dist compositions are described. TIFF2025041750000001.tif2439 Patent Document 2 describes a laser printer that contains a carboxylate represented by the following formula as a carboxylate generator. Dist compositions are described. TIFF2025041750000002.tif2543 Patent Document 3 describes a salt represented by the following formula: TIFF2025041750000003.tif1764 Patent Document 4 describes a salt represented by the following formula: TIFF2025041750000004.tif1372 Patent Document 5 describes a salt represented by the following formula: TIFF2025041750000005.tif1780 Patent Document 6 describes salts represented by the following formulas. TIFF2025041750000006.tif21141 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2011-39502 A [Patent Document 2] JP 2014-88367 A [Patent Document 3] Japanese Patent Application Publication No. 08-160620 [Patent Document 4] Japanese Patent Application Publication No. 09-124533 [Patent Document 5] JP 2000-147772 A [Patent Document 6] International Patent Application WO99 / 48945 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention relates to a resist pattern formed using a resist composition containing the above-mentioned carboxylate. Cu has a better resist pattern with better line edge roughness (LER) than ZnO. The present invention provides a bon acid salt. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A carboxylate represented by formula (I). TIFF2025041750000007.tif33119 [In formula (I), R 1a represents a hydrogen atom or an acid labile group. R 2 is a halogen atom, a fluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. The fluorinated alkyl group and the -CH 2 - is -O- or It may be replaced by -CO-. R 3 is a halogen atom, a fluoroalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, Group or -L 11' -OR 1b The fluorinated alkyl group and the alkyl group each contain -C H 2 - may be replaced by -O- or -CO-. L 11 and L 11' each independently represents an alkanediyl group having 1 to 6 carbon atoms, -CH contained in the candiyl group 2 - may be replaced by -O- or -CO-. R1b represents a hydrogen atom or an acid labile group. m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R 2 are the same They may be the same or different. m3 represents an integer of 0 to 5, and when m3 is 2 or more, a plurality of R 3 are the same They may be the same or different. X 0 represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by .] [2] R 1a and R 1b each independently represents a group represented by the formula (R1-1) or the formula (R1- 2) The carboxylate according to [1], wherein the carboxylate is a group represented by the formula (1). TIFF2025041750000008.tif1981[In formula (R1-1), R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 8 carbon atoms; R represents a group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof; 4 and R 5 are bonded to each other and to the carbon atoms to which they are bonded, forming non-aromatic carbon atoms having 3 to 20 carbon atoms. Forms a hydrogen ring. m represents 0 or 1. * denotes a binding site.] TIFF2025041750000009.tif2181[In formula (R1-2), R 7 and R 8 each independently represents a hydrogen atom or a C1-12 represents a hydrocarbon group, R 9 represents a hydrocarbon group having 1 to 20 carbon atoms, or R 8 and R 9 are mutually The carbon atom and X to which they are attached X and together with the above, form a heterocycle having 3 to 20 carbon atoms, The hydrocarbon group and the heterocyclic ring each contain -CH 2 - may be replaced by -O- or -S- good. X X represents an oxygen atom or a sulfur atom. n represents 0 or 1. * denotes a binding site.] [3]X 0 an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that the aliphatic -CH contained in aliphatic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Place The carboxylate according to [1] or [2], wherein [4]X 0 is an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxyl group (the -CH contained in alicyclic hydrocarbon group 2 - may be replaced by -O- or -CO-. ) or a group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are combined (the alicyclic hydrocarbon group and -CH contained in the chain hydrocarbon group 2 - is replaced by -O- or -CO- The alicyclic hydrocarbon group and the chain hydrocarbon group may each be a fluorine atom or a hydroxyl group. The carboxylate according to any one of [1] to [3], wherein [5] A carboxylic acid generator comprising the carboxylate according to any one of [1] to [4]. [6] The carboxylic acid generator according to [5], an acid generator other than the carboxylic acid generator, and an acid labile A resist composition comprising a resin having a functional group. [7] The resin having an acid labile group is a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1- 2) is a resin containing at least one selected from the group consisting of structural units represented by the formula (6). The resist composition described above. TIFF2025041750000010.tif46102 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or *-O-(CH 2 ) k1 -CO-O- In the formula, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 18 carbon atoms, represents a hydrocarbon group of the formula: m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. [8] The resin having an acid labile group further contains a structural unit represented by formula (a2-A): The resist composition according to item [6] or [7]. TIFF2025041750000011.tif4247[In formula (a2-A), R a50 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: R a51 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or * -X a51 -(Aa52 -X a52 ) nb - stands for -R. a50 is combined Indicates the bond position with respect to the carbon atom. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, R in Numbers a51 may be the same or different.] [9] (1) A process for applying the resist composition according to any one of [6] to [8] onto a substrate. About (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A method for producing a resist pattern, comprising the step of developing the composition layer after heating. Effect of the Invention

[0006] By using a resist composition using the carboxylate of the present invention, it is possible to obtain a good line area. It is possible to produce resist patterns with low edge roughness (LER). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In this specification, the term "(meth)acrylic monomer" refers to a compound represented by "CH 2 =CH-CO-" Monomers having the structure "CH 2 =C(CH 3 Monomers with the structure "-CO-" Similarly, "(meth)acrylate" and "(Meth)acrylic acid" refers to a compound selected from the group consisting of acrylate and methacrylate. "At least one selected from the group consisting of acrylic acid and methacrylic acid" and "at least one selected from the group consisting of acrylic acid and methacrylic acid "CH" means "at least one type". 2 =C(CH 3 )-CO-" or "CH 2 =CH-C When a structural unit having "O-" is exemplified, structural units having both groups are also included. In addition, in the groups described in this specification, straight chain structures and branched structures are For those which can have both structures, either one is acceptable. The valence of the groups may vary depending on the bond type. "Derived from" or "derived from" refers to a polymerizable C=C This means that the bond is polymerized to become a -CC- group. When stereoisomers exist, all Includes stereoisomers. In this specification, the term "solid content of a resist composition" refers to the fraction of the total amount of the resist composition that is This refers to the total of all components excluding the solvent (E) described below.

[0008] [Salt represented by formula (I)] The present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "carboxylate (I)"). Regarding. In the carboxylate (I), the side with the negative charge is called the "anion (I)" and the side with the positive charge is called the "anion (I)". The side is sometimes referred to as "cation (I)". TIFF2025041750000012.tif33119 [wherein all symbols have the same meanings as defined above.]

[0009] R 1a and R 1b The acid labile group is a group that, when it comes into contact with an acid, is eliminated and becomes a hydroxyl group. means a group which forms Examples of the acid labile group include a group represented by the formula (R1-1) (hereinafter sometimes referred to as “acid labile group”). A group represented by the formula (R1-1) (hereinafter, sometimes referred to as "stable group (R1-2)") and a group represented by the formula (R1-2) (hereinafter, sometimes referred to as "stable group (R1-3)") These are referred to as "acid labile groups (R1-2)". TIFF2025041750000013.tif1983[In formula (R1-1), R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 8 carbon atoms; R represents a group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof; 4 and R 5 are bonded to each other and to the carbon atoms to which they are bonded, forming non-aromatic carbon atoms having 3 to 20 carbon atoms. Forms a hydrogen ring. m represents 0 or 1. * denotes a binding site.] TIFF2025041750000014.tif2389[In formula (R1-2), R 7 and R 8 each independently represents a hydrogen atom or a C1-12 represents a hydrocarbon group, R 9 represents a hydrocarbon group having 1 to 20 carbon atoms, or R 8 and R 9 are mutually The carbon atom and X to which they are attached X and together with the above, form a heterocycle having 3 to 20 carbon atoms, The hydrocarbon group and the heterocyclic ring each contain -CH 2 - may be replaced by -O- or -S- good. X X represents an oxygen atom or a sulfur atom. n represents 0 or 1. * denotes a binding site.]

[0010] R 4 , R 5 and R 6Examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, a propyl group, n-Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. Some examples include: R 4 , R 5 and R 6 The alicyclic hydrocarbon group represented by the formula (I) may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, cycloalkyl groups such as butyl and cyclooctyl groups. Examples of the alkyl group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and The following groups (* represents a bond): 4 , R 5 and R 6 of alicyclic hydrocarbon groups The number of carbon atoms is preferably 3 to 16. TIFF2025041750000015.tif10150

[0011] Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexane. xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group , adamantylmethyl group, and norbornylethyl group.

[0012] R 4 and R 5 When they are bonded to each other to form a non-aromatic hydrocarbon ring, -C(R 4 )(R 5 ) (R 6 The non-aromatic hydrocarbon ring preferably has 3 carbon atoms. ~12. * represents a bond to -O-. TIFF2025041750000016.tif30139

[0013] R7 , R 8 and R 9 The hydrocarbon group may be an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or the like. Hydrogen groups and groups formed by combining these groups are included. Examples of the alkyl group and the alicyclic hydrocarbon group include the same as those mentioned above. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group and the like. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl group), aralkyl group (e.g., benzyl group), alkyl group Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group) , xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6 -ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl phenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group (phenyl cyclohexyl group, etc. R 8 and R 9 are bonded to each other and the carbon atom to which they are bonded and X X Forms a heterocyclic ring together with If you want to use -C(R 7 )(R 8 )-X X -R 9 Examples of the alkyl group include the following. * indicates a bond. represent. TIFF2025041750000017.tif18130R 7 and R 8 At least one of these is preferably a hydrogen atom. R 1a and R 1b is preferably an acid labile group.

[0014] Specific examples of the acid labile group (R1-1) include the following groups. * represents a bond. . TIFF2025041750000018.tif41147

[0015] Specific examples of the acid labile group (R1-2) include the following groups. * represents a bond. . TIFF2025041750000019.tif76149

[0016] R 2 and R 3 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. etc. R 2 and R 3 Examples of the fluorinated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a difluoromethyl group, Fluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1, 2,2-Tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentane Perfluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octyl Trifluorobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5- Examples of the fluorinated alkyl group include a nonafluoropentyl group and a perfluorohexyl group. The fluorinated alkyl group preferably has 1-4 carbon atoms, and more preferably has 1-3 carbon atoms. R 2 and R 3 Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, and a propyl group. , isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group The alkyl group may be an alkyl group such as a phenyl group, an octyl group, or a nonyl group. Preferably, it is 1 to 9, more preferably 1 to 6, and further preferably 1 to 4. R 2 and R 3 and -CH contained in the alkyl group 2 - is -O When the fluorinated alkyl group is replaced by - or -CO-, the number of carbon atoms before the replacement is and the total number of carbon atoms in the alkyl group. R 2 and R 3 The -CH 2 - is replaced with -O- or -CO- The replaced groups are hydroxy groups (-CH 2 - is placed in -O- substituted group), carboxy group (-CH contained in ethyl group 2 -CH 2 -But -O-CO- ), alkoxy group (groups replaced by -CH at any position in the alkyl group) 2 -but , -O- substituted), alkoxycarbonyl group (any group contained in an alkyl group Position -CH 2 -CH 2 - is replaced by -O-CO-), alkylcarbonyl group ( -CH at any position in the alkyl group 2 - is replaced by -CO-), alkylcarbonyloxy group (-CH at any position in the alkyl group) 2 -CH 2 -but,- CO-O- replaced groups). R 2 and R 3 The -CH group contained in the fluoroalkyl group represented by 2 - is -O- or -CO- The group substituted with is a fluorinated alkoxy group (any group contained in a fluorinated alkyl group). Position -CH 2 - is replaced by -O-), fluorinated alkoxycarbonyl group (fluorinated Any -CH position in the alkyl group 2 -CH 2 - is replaced by -O-CO- Fluoroalkylcarbonyl group (a group containing -C at any position in the fluorinated alkyl group) H 2 - is replaced by -CO-), fluorinated alkylcarbonyloxy group (fluorinated alkyl -CH at any position in the alkyl group 2 -CH 2 - is replaced by -CO-O- ) etc. The alkoxy group includes an alkoxy group having 1 to 11 carbon atoms, such as a methoxy group, an ethoxy group, or an alkoxy group having 1 to 11 carbon atoms. oxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group oxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, etc. Examples include: The alkoxycarbonyl group includes an alkoxycarbonyl group having 2 to 11 carbon atoms. For example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and and butoxycarbonyl groups. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 12 carbon atoms. Examples include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyloxy group is an alkylcarbonyloxy group having 3 to 12 carbon atoms. Examples of the aryloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, and a propylcarbonyloxy group. Examples include a carbonyloxy group and a butylcarbonyloxy group. Fluorinated alkoxy groups, fluorinated alkoxycarbonyl groups, fluorinated alkylcarbonyl groups, and The fluorinated alkylcarbonyloxy group is, for example, a fluorinated alkylcarbonyloxy group having 1 to 5 carbon atoms. fluorinated alkoxycarbonyl groups having 2 to 5 carbon atoms, fluorinated alkyl groups having 2 to 6 carbon atoms Examples of the fluorinated alkyl group include a fluoroalkyl group having 2 to 5 carbon atoms. One or more hydrogen atoms of the indicated groups may be replaced with fluorine atoms. R 2 represents a fluorine atom, a fluorinated alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. (The fluoroalkyl group and the —CH 2 - is -O- or -CO- It is preferable that the aryl group is aryl, which may be replaced by aryl. R 3 is a fluorine atom, a fluoroalkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 6 carbon atoms ( The fluorinated alkyl group and the —CH 2 - is replaced by -O- or -CO-. (may be replaced) or -L 11' -OR 1b It is preferable that the group is represented by - L 11' -OR 1b It is more preferable that the group is a group represented by the following formula: R 2 -L 11 -OR 1a The group may be the same as the group represented by Good. Also, R 2 -L 11 -O-(CO-O)mC(R 4 )(R 5 )(R 6 ) or -L 11 -O-(CO-O)nC(R 7 )(R 8 )-X 1 -R 9 may be the same group as may be also possible. Also, R 3 -L 11 -OR 1a The group represented by the formula (I) may be the same as the group represented by the formula (I), or may be a different group. Also, R 3 -L 11 -O-(CO-O)mC(R 4 )(R 5 )(R 6 ) or -L 11 -O-(CO-O)nC(R 7 )(R 8 )-X X -R 9 may be the same group as It may be a group represented by the formula: m2 is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. It is more preferable that the number of sigma-doped indices is 1, and it is even more preferable that the number of sigma-doped indices is 0. m3 is preferably an integer of 0 to 4, and more preferably an integer of 0 to 3. It is more preferable that the number of sigma-doped aryl groups is 1, and it is even more preferable that the number of sigma-doped aryl groups is 1.

[0017] L 11 and L 11' The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane group, 1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, Straight-chain alkanediyl groups such as san-1,6-diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group 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 and branched alkanediyl groups such as 2-methylbutane-1,4-diyl group. The alkanediyl group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. L 11 and L 11' The alkanediyl group represented by -CH 2 - is -O- or -CO When it is replaced by -, the number of carbon atoms before the replacement is regarded as the total number of carbon atoms of the alkanediyl group. Also, L 11 and L 11' The alkanediyl group represented by the formula Included -CH 2 - is replaced by -O-), carboxy group (containing an ethyl group Ru-CH 2 -CH 2 - is replaced by -O-CO-), alkoxy group (alkyl group -CH at any position included in 2 - is replaced by -O-), alkoxycarbonyl (-CH at any position in the alkyl group) 2 -CH 2 - is replaced by -O-CO- alkylcarbonyl group (a group in which -CH 2 -but , -CO- substituted), alkylcarbonyloxy group (alkyl group -CH at any position 2 -CH 2 - is replaced by -CO-O-), alkanediyloxy An oxy group (-CH at any position in an alkanediyl group) 2 - is replaced by -O- alkanediyloxycarbonyl group (any position contained in the alkanediyl group) -CH 2 -CH 2 - is replaced by -O-CO-), alkanediylcarbonyl group (-CH at any position in the alkanediyl group) 2 - is replaced by -CO- ), an alkanediylcarbonyloxy group (an alkanediyl group having - at any position therein); CH 2 -CH 2 - may be replaced with -CO-O-. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. etc. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the alkyl group include a propoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. etc. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, and an ethylcarbonyloxy group. Examples include a carbonyloxy group and a propylcarbonyloxy group. Examples of the alkanediyloxy group include a methyleneoxy group, an ethyleneoxy group, a propanediyloxy group, and a propyleneoxy group. propanediyloxy group, butanediyloxy group, pentanediyloxy group, etc. . Examples of the alkanediyloxycarbonyl group include a methyleneoxycarbonyl group, Ethyleneoxycarbonyl group, propanediyloxycarbonyl group, butanediyloxy Examples thereof include a carbonyl group. Examples of the alkanediylcarbonyl group include a methylenecarbonyl group and an ethylenecarbonyl group. bonyl group, propanediylcarbonyl group, butanediylcarbonyl group, pentanediylcarbonyl group Examples include a carbonyl group. Examples of the alkanediylcarbonyloxy group include a methylenecarbonyloxy group, Ethylenecarbonyloxy group, propanediylcarbonyloxy group, butanediylcarbonyloxy group Examples thereof include a nyloxy group. L 11 and L 11' Examples of the alkanediyl group include an alkanediyl group having 1 to 4 carbon atoms. -CH 2 - may be replaced by -O- or -CO-. It is preferably an alkanediyl group having 1 to 4 carbon atoms, and more preferably a linear alkyl group having 1 to 4 carbon atoms. More preferably, it is an alkanediyl group represented by the formula: Even more preferably it is a propanediyl group. -L 11 -OR 1a The bonding position of to the benzene ring is I + For оth, mth, or pth Although either may be used, the p-position is preferred. R 2 and R 3 The bonding position of to the benzene ring is I + For either о-th, m-th, or p-th Good. Especially R 3 I + For -L 11 -OR 1a It is preferable that the bond is at the same position as I wish. R 1a is preferably an acid labile group, R 3 -L 11' -OR 1b It is preferable to be R 1b More preferably, is an acid labile group.

[0018] Examples of the cation (I) include the following cations: TIFF2025041750000020.tif230165

[0019] In formula (I), X 0 The hydrocarbon group represented by the formula (I) is an aliphatic hydrocarbon group (alkyl chain hydrocarbon groups such as alkyl, alkenyl, and alkynyl groups, and alicyclic hydrocarbon groups), aromatic carbons, Aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof are also included. -CH contained in the base group 2 - is -O-, -S-, -CO- or -SO 2 -Replaced by This is also fine. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The alkyl group preferably has 1 to 18 carbon atoms, and more preferably has 1 to 18 carbon atoms. It is preferably 1 to 12, more preferably 1 to 9, and even more preferably 1 to 6. and even more preferably 1 to 4. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, and a butenyl group. isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples of such groups include an octynyl group, an isooctynyl group, and a nonenyl group. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, Examples thereof include a nonynyl group. -CH contained in chain hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -Placed The replaced groups are hydroxy groups (-CH 2 - is placed in -O- substituted group), carboxy group (-CH 2 -CH 2 -But-O-CO - substituted), alkoxy group (-CH at any position in the alkyl group) 2 - is replaced by -O-), alkoxycarbonyl group (any group contained in an alkyl group -CH position 2 -CH 2 - is replaced by -O-CO-), alkylcarbonyl group (-CH at any position in the alkyl group) 2- is replaced by -CO-), Alkylcarbonyloxy group (-CH at any position in the alkyl group) 2 -CH 2 -but, -CO-O- substituted group), alkylthio group (any position in the alkyl group) -CH 2 - is replaced with -S-. Alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyl The oxy group is, for example, an alkoxy group having 1 to 17 carbon atoms, an alkoxy group having 2 to 17 carbon atoms, alkylcarbonyl groups having 2 to 18 carbon atoms and alkylcarbonyl groups having 2 to 17 carbon atoms. Examples of the alkylthio group include a carbonyloxy group, and examples of the alkylthio group include the same groups as those described above. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and an alkylthio group having a number of 1 to 17. Examples thereof include a ruthio group. The substitution in the alkenyl group and the alkynyl group is the same as that in the alkyl group described above. In the examples of substitutions, a carbon-carbon double bond or a carbon-carbon triple bond at any position is It is sufficient if it includes the above. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spirocyclic groups, and may be saturated or unsaturated. The alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclobutyl group, or a cyclopropyl group. Cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group group, monocyclic cycloalkyl groups such as cyclododecyl group, norbornyl group, adamantyl group, etc. Examples of the polycyclic cycloalkyl group include the polycyclic cycloalkyl groups represented by the formula: Alicyclic hydrocarbon groups and -CH contained in alicyclic hydrocarbon groups 2 -, -O-, -S-, - CO- or -SO 2 Specific examples of the group substituted with - include the following groups. The binding site can be at any position. TIFF2025041750000021.tif129164Alicyclic hydrocarbon group or -CH contained in an alicyclic hydrocarbon group 2 -, -O-, -S-, - CO- or -SO 2 The group substituted with - includes groups represented by formulae (y1) to (y71). are preferred, and the formulae (y1) to (y20), (y26), (y27), (y30), A group represented by any one of formula (y31) and formula (y39) to formula (y71) is more preferable, and the formula (y3), (y4), formula (y9), formula (y11), formula (y14), formula (y15), formula (y 16), formula (y20), formula (y26), formula (y27), formula (y30), formula (y31), formula (y39), formula (y40), formula (y42), formula (y43), formula (y49)~formula (y58) More preferred are groups represented by the formulae (y62) to (y71). The number is preferably 3 to 36, more preferably 3 to 24, and further preferably 3 〜18, and more preferably 3~16.

[0020] Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, Examples of aromatic hydrocarbon groups include aryl groups such as phenanthryl and binaphthyl groups. The prime number is preferably 6 to 36, more preferably 6 to 24, and even more preferably It is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. be. In the case of a combination of groups, the above groups each having a different valence (such as an alkanediyl group, ... cycloalkanetriyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group A cycloalkyl group, a cycloalkanetetrayl group, etc. may be included.

[0021] The combined groups are: A group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (the chain hydrocarbon group and the alicyclic Hydrocarbon groups in the formula -CH 2 - is -O-, -S-, -CO- or -SO 2 -Replaced with (You may know), A group that combines a chain hydrocarbon group and an aromatic hydrocarbon group (the chain hydrocarbon group -CH 2 - is -O-, -S-, -CO- or -SO 2 -), and Beauty A group that combines an alicyclic hydrocarbon group with an aromatic hydrocarbon group (including the alicyclic hydrocarbon group) Reru-CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by Represents. In addition, in the combination, alicyclic hydrocarbon groups, chain hydrocarbon groups and aromatic hydrocarbon groups may be used in combination of two or more of each. Specifically, the combined groups are Alicyclic hydrocarbon groups such as adamantylmethylene groups and cyclohexylmethylene groups - Chain carbonization Hydrogen group -*, (alicyclic hydrocarbon group) 2 -Acyclic hydrocarbon group-* (the acyclic hydrocarbon group and the fatty acid -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Place may be replaced), Chain hydrocarbon groups such as methyladamantyl group, dimethyladamantyl group, etc. - Alicyclic hydrocarbons Group -*, (chain hydrocarbon group) 2 -alicyclic hydrocarbon group-* (the chain hydrocarbon group and the alicyclic -CH contained in the hydrocarbon group 2- is -O-, -S-, -CO- or -SO 2 -Replaced by (It may be possible to Aromatic hydrocarbon groups such as tolyl and xylyl groups - Aromatic hydrocarbon groups - * (Aromatic hydrocarbon groups Included in -CH 2 - is -O-, -S-, -CO- or -SO 2 Even if it is replaced with - good), Methylcyclohexylmethylene group and other chain hydrocarbon groups - alicyclic hydrocarbon groups - chain hydrocarbon groups Basic group -*, (chain hydrocarbon group) 2 -Alicyclic hydrocarbon group-Acyclic hydrocarbon group-*, (Acyclic carbon Hydrogen group-alicyclic hydrocarbon group) 2 - Acyclic hydrocarbon groups -* (The acyclic hydrocarbon groups and the alicyclic -CH contained in hydrogen radical 2 - is -O-, -S-, -CO- or -SO 2 -Replaced by (may be Aromatic hydrocarbon groups such as benzyl groups - Chain hydrocarbon groups -* (The chain hydrocarbon groups include -CH 2 - is -O-, -S-, -CO- or -SO 2 -), Aromatic hydrocarbon groups such as tolylmethyl groups - Aromatic hydrocarbon groups - Aromatic hydrocarbon groups - Aromatic hydrocarbon groups -* (The above -CH contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -Replaced by (It may be possible to Methyladamantane methylene adamantyl group, di(methyladamantane methylene)adamantyl group Manthyl group or other open chain hydrocarbon groups - alicyclic hydrocarbon groups - open chain hydrocarbon groups - alicyclic hydrocarbon groups -*, (open chain hydrocarbon group-alicyclic hydrocarbon group-open chain hydrocarbon group) 2 -Alicyclic hydrocarbon group- *, (chain hydrocarbon group - alicyclic hydrocarbon group) 2-Acyclic hydrocarbon groups-Alicyclic hydrocarbon groups-* , (chain hydrocarbon group) 2 -Alicyclic hydrocarbon group-Acyclic hydrocarbon group-Alicyclic hydrocarbon group-*( -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group 2 - is -O-, -S-, - CO- or -SO 2 -), Alicyclic hydrocarbon group-Acyclic hydrocarbon group-Acyclic hydrocarbon group-Acyclic hydrocarbon group-*, (alicyclic Formula: Hydrocarbon group 2 -Open chain hydrocarbon group-Alicyclic hydrocarbon group-Open chain hydrocarbon group-*, (Alicyclic Hydrocarbon group - Acyclic hydrocarbon group 2 -Alicyclic hydrocarbon group-Acyclic hydrocarbon group-*, (alicyclic carbon Hydrocarbon group-Linear hydrocarbon group-Alicyclic hydrocarbon group) 2 - Acyclic hydrocarbon group -* (The acyclic hydrocarbon group The -CH group contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or - SO 2 -), Acyclic hydrocarbon group - alicyclic hydrocarbon group - acyclic hydrocarbon group - alicyclic hydrocarbon group - acyclic hydrocarbon group Basic group -*, (chain hydrocarbon group) 2 -Alicyclic hydrocarbon group -Open chain hydrocarbon group -Alicyclic hydrocarbon Group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group) 2 -Acyclic hydrocarbon group- Alicyclic hydrocarbon group-open chain hydrocarbon group-*, (open chain hydrocarbon group-alicyclic hydrocarbon group-open chain Hydrogen radical) 2 -Alicyclic hydrocarbon group-Acyclic hydrocarbon group-*, (Acyclic hydrocarbon group-Alicyclic Hydrogen group - linear hydrocarbon group - alicyclic hydrocarbon group) 2 -A chain hydrocarbon group-* (the chain hydrocarbon group group and the -CH 2 - is -O-, -S-, -CO- or -S O2 -), Here, * indicates the bond position to the carbon atom of the carbonyl group.

[0022] X 0 The -CH 2 - is -O-, -S-, -CO- or -S O 2 When it is replaced with -, the number of carbon atoms before the replacement is counted as the total number of carbon atoms in the hydrocarbon group. Also, X 0 When a substituent is bonded to a hydrocarbon group represented by the formula: The total number of carbon atoms in the hydride groups.

[0023] X 0 The hydrocarbon group represented by the following formula may have one or more substituents. The substituents include halogen atoms, cyano groups, hydroxy groups, and alkyl groups having 1 to 12 carbon atoms. group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, Alkylcarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a combination thereof Examples of the group include a group obtained by combining the Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Of these, a fluorine atom is preferable. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl Examples of the alkyl group include an aryl group and a nonyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a bromine group, and a butyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group etc. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms is the above-mentioned alkyl or alkoxy group. The aryl group represents a group having a carbonyl group or a carbonyloxy group bonded to the aryl group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy carbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 13 carbon atoms. Examples of the aryl group include an acetyl group, a propionyl group, and a butyryl group, and the like. The alkylcarbonyloxy group of 3 is an acetyloxy group, a propionyloxy group, butyryloxy group and the like. Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** represents X 0 represents the bonding position with TIFF2025041750000022.tif17162The aromatic hydrocarbon group having 6 to 10 carbon atoms is an aryl group such as a phenyl group or a naphthyl group. Examples include: The combined group is a combination of a hydroxyl group and an alkyl group having 1 to 12 carbon atoms. a group in which an alkyl group having 1 to 12 carbon atoms is combined with an aromatic hydrocarbon group having 6 to 10 carbon atoms; a group consisting of an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms; and the like. Examples of the group combining a hydroxyl group and an alkyl group having 1 to 12 carbon atoms include hydroxyl Examples of the hydroxyalkyl group include a methyl group and a hydroxyethyl group, each of which has 1 to 12 carbon atoms. do. A group formed by combining an alkyl group having 1 to 12 carbon atoms with an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the alkyl group include aralkyl groups having 7 to 22 carbon atoms, such as benzyl groups, tolyl groups, and xylyl groups. Examples of the alkylaryl groups include alkylaryl groups having 7 to 22 prime numbers. A combination of an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the group include a cyclohexylphenyl group.

[0024] X 0 The hydrocarbon group represented by the formula (I) is preferably a hydrocarbon group having 1 to 7 carbon atoms, which may have a substituent. 2 aliphatic hydrocarbon group (-CH contained in the aliphatic hydrocarbon group) 2 - is -O-, -S-, -CO- or -SO 2 - may be substituted.) an aromatic hydrocarbon group represented by formula (aa) or a group represented by formula (bb) , More preferably, it is an alicyclic hydrocarbon group which may have a hydroxy group or a fluorine atom ( The -CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -To ), a group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are combined ( The -CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -To The -CH 2 - is -O- or -CO -, and the alicyclic hydrocarbon group and the chain hydrocarbon group are each independently selected from the group consisting of a fluorine atom, or a hydroxy group.) an aromatic hydrocarbon group, a group represented by formula (aa) or a group represented by formula (bb), More preferably, *-alicyclic hydrocarbon group (-CH contained in the alicyclic hydrocarbon group)2 - is -O-, -S-, -CO- or -SO 2 -, and the alicyclic carbon The hydrogen group may have a hydroxyl group or a fluorine atom. * is -COO - Carbon atom of ), *-alicyclic hydrocarbon group-chain hydrocarbon group (represents the bonding position with the alicyclic hydrocarbon group) Included -CH 2 - is -O-, -S-, -CO- or -SO 2 - It's okay if it's replaced by The -CH group contained in the chain hydrocarbon group 2 - is replaced by -O- or -CO- The alicyclic hydrocarbon group and the chain hydrocarbon group may each have a fluorine atom or a hydroxyl group. * is -COO - ), *-chain hydrocarbon group- Cyclic hydrocarbon groups (-CH contained in the chain hydrocarbon groups) 2 - is replaced with -O- or -CO- may be replaced, and the -CH 2 - is -O-, -S-, - CO- or -SO 2 - may be substituted, and the chain hydrocarbon group and the alicyclic hydrocarbon group may be substituted with -. The radical may have a fluorine atom or a hydroxyl group. * is -COO - Bonding with the carbon atom of ), an aromatic hydrocarbon group which may have a fluorine atom or a hydroxyl group, A group represented by formula (aa) or a group represented by formula (bb), More preferably, the polycyclic alicyclic hydrocarbon group is Included -CH 2 - is -O-, -S-, -CO- or -SO 2 - It's okay if it's replaced by The polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. -COO - ), *-Polycyclic alicyclic hydrocarbon group-chain carbon Hydrogen group (-CH contained in the polycyclic alicyclic hydrocarbon group) 2 - is -O-, -S-, -CO -OR-SO 2 - may be replaced by -, and -CH 2 -teeth, The polycyclic alicyclic hydrocarbon group and the chain The hydrocarbon group may have a fluorine atom or a hydroxyl group. * represents -COO - Carbon atom of ), *-a chain hydrocarbon group-a polycyclic alicyclic hydrocarbon group (represents the bond position with the chain hydrocarbon group). -CH contained in the base group 2 - may be replaced by -O- or -CO-, and the polycyclic -CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -To The chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group may be substituted with fluorine. may have a -COO atom or a hydroxyl group. - It represents the bond position with the carbon atom of an aromatic hydrocarbon group which may have a fluorine atom or a hydroxyl group; or a group represented by formula (bb): Particularly preferred are an adamantanone group, a hydroxyadamantyl group, and a combination of an adamantyl group and an adamantanyl group. A group combining an alkyl group (the —CH 2 - is -O- or -CO - may be substituted.), a group represented by formula (Y30F), It is a phenyl group, a group represented by formula (aa) or a group represented by formula (bb). In the above groups, the alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably It is preferably 3 to 24, more preferably 3 to 18, and even more preferably 3 to 1 The number of carbon atoms in the chain hydrocarbon group is preferably 6, and more preferably 3 to 12. is 1 to 18, more preferably 1 to 12, even more preferably 1 to 9, More preferably, it is 1 to 6, and even more preferably, it is 1 to 4. The number of carbon atoms is preferably 6 to 36, more preferably 6 to 24, and further preferably Preferably, it is 6 to 18, more preferably 6 to 14, and even more preferably 6 to 1 The value is 0. TIFF2025041750000023.tif26127[In formula (aa), X a and X b each independently represents -O- or -S-. X 1 represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by . X 2 represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by . * indicates the bonding position with the carbon atom of the carbonyl group. [In formula (bb), L A represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom. L B represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, -CH 2 - is -O-, -S-, -CO- or -SO2 - may be replaced by . R A represents a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by . * indicates the bonding position with the carbon atom of the carbonyl group.

[0025] X a and X b are preferably the same atom, and more preferably are both oxygen atoms. It is.

[0026] X 1 and X 2 The hydrocarbon group represented by the formula (I) is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or Examples of the hydrocarbon group include a group obtained by combining two or more of these. In addition, the -CH contained in these hydrocarbon groups may be 2 - is -O-, -S-, - CO- or -SO 2 Here, the number of carbon atoms in the hydrocarbon group may be This refers to the number of carbon atoms in an unsubstituted hydrocarbon group that does not have any substituents.

[0027] X 1 The aliphatic hydrocarbon group may be a chain hydrocarbon group such as an alkanetriyl group, an alicyclic hydrocarbon group, etc. Hydrogen groups or combinations thereof. Specific examples of the alkanetriyl group include a methine group, an ethanetriyl group, a propanetriyl group, and a cyclohexyl group. Triyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl yl group, octanetriyl group, nonanetriyl group, decanetriyl group, undecanetriyl group Examples of the alkyl group include a cycloalkyl group and a dodecanetriyl group.

[0028] The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutanetriyl group, a cyclopentanetriyl group, and a cyclopentanetriyl group. Examples of the alkyl group include a cyclohexyl group, a cyclohexanetriyl group, and a cyclooctanetriyl group. Examples of the polycyclic alicyclic hydrocarbon group include a norbornane triyl group, a norbornane triyl group, group, adamantanetriyl group, and the like. Examples of the aromatic hydrocarbon group include a benzenetriyl group, a naphthalenetriyl group, an anthracene group, and Examples of the aryl group include phenyltriyl group. In the case of a combination of groups, the above groups each having a different valence (alkyl group, alkanediyl group, etc.) aryl group, alkanetetrayl group, cycloalkyl group, cycloalkanediyl group, cycloalkanediyl group, cantetrayl group, etc.) may be included.

[0029] X 1 The hydrocarbon group represented by the formula (I) has 1 to 24 carbon atoms and further has one or more substituents. The substituent may be a hydroxy group, a halogen atom, a cyano group, a carbon number Alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, alkoxy groups having 2 to 13 carbon atoms alkylcarbonyl group having 2 to 13 carbon atoms, alkylcarbonyl group having 2 to 13 carbon atoms nyloxy group, alicyclic hydrocarbon group having 3 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 10 carbon atoms Or a group combining these may be mentioned. Halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and the like Examples of the group combining these include the same groups as above.

[0030] X1 The hydrocarbon group represented by the formula (I) is an alkane group having 1 to 6 carbon atoms which may have a substituent. It is preferably an aryl group or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. Alkanetriyl groups having 1 to 6 carbon atoms, represented by formulas (w1-1) to (w1-11), More preferably, it is an alkanetriyl group having 1 to 6 carbon atoms, a group represented by the formula (w1-1): a polycyclic hydrocarbon group such as a group represented by formula (w1-3) or a group represented by formula (w1-2) or a monocyclic hydrocarbon group such as a group represented by formula (w1-6): It is. TIFF2025041750000024.tif48131[Formula (w1-1) to formula (w1-11), The ring may be a hydroxyl group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or a an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, Alkylcarbonyl group, alkylcarbonyloxy group having 2 to 13 carbon atoms, alkylcarbonyloxy group having 3 to 12 carbon atoms an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a combination thereof It may have. * indicates the bond position.]

[0031] X 2 The number of carbon atoms in the hydrocarbon group represented by the formula (I) is preferably 2 to 48, and more preferably 4 to 48. It is more preferable that the ratio is 6 to 44, and further preferably 8 to 40. It is more preferable that the ratio is 10 to 38, and even more preferable that the ratio is 10 to 38.

[0032] X 2 The substituents which the hydrocarbon group may have in the formula (I) include a halogen atom, a cyano group, , a hydroxy group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyloxy groups having 3 to 13 carbon atoms, alicyclic hydrocarbon groups having 3 to 12 carbon atoms, 10 aromatic hydrocarbon groups or combinations thereof. Halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and Examples of the group combining the above include the same groups as above. X 2 The hydrocarbon group having 1 to 48 carbon atoms represented by the formula (I) has one or more substituents. It may be possible.

[0033] X 2 The hydrocarbon group in the formula (I) is a straight-chain or branched chain hydrocarbon group (e.g., arylene). candiyl group, etc.), monocyclic or polycyclic alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Two or more of these groups may be combined. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 linear alkanediyl groups such as octane-1,7-diyl group and octane-1,8-diyl group; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group 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 Monocyclic cycloalkanediyl group, such as cyclohexene-1,4-diyl group, cyclooctane-1,5-diyl group, etc. a monocyclic alicyclic hydrocarbon group which is an yl group; Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic cycloalkanediyl groups such as 1,5-diyl group and adamantane-2,6-diyl group a polycyclic alicyclic hydrocarbon group, Phenylene group, naphthylene group, biphenylene group, anthrylene group, phenanthrylene group and aromatic hydrocarbon groups such as a binaphthylene group. In the case of a combination of groups, the above groups each having a different valence (alkyl group, alkanetri group, etc.) yl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cyclo An alkanetetrayl group may be included. Examples of the combined group include a group that combines a chain hydrocarbon group and an alicyclic hydrocarbon group; Groups that combine a hydrocarbon group and an aromatic hydrocarbon group, and alicyclic hydrocarbon groups and aromatic hydrocarbon groups Specifically, a group in which one or more alicyclic hydrocarbon groups are combined with a chain hydrocarbon group can be mentioned. A group in which - is bonded (for example, -chain hydrocarbon group-alicyclic hydrocarbon group, -chain hydrocarbon group-(alicyclic Cyclic hydrocarbon group) 2 etc.), groups in which one or more chain hydrocarbon groups are bonded to an alicyclic hydrocarbon group (e.g. For example, -alicyclic hydrocarbon group-chain hydrocarbon group, -alicyclic hydrocarbon group-(chain hydrocarbon group) 2 etc.), groups in which one or more alicyclic hydrocarbon groups and a chain hydrocarbon group are bonded to a chain hydrocarbon group (e.g. For example, -chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group, -chain hydrocarbon group-(alicyclic Cyclic Hydrocarbon Group - Chain Hydrocarbon Group 2 etc.)

[0034] X 2As the hydrocarbon group in A chain hydrocarbon group having 2 to 18 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-, and the chain hydrocarbon group may have a substituent. stomach.), Alicyclic hydrocarbon groups having 3 to 18 carbon atoms (-CH contained in the alicyclic hydrocarbon groups) 2 -teeth,- O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a substituent.) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Place (which may have a substituent) It is preferable that A chain hydrocarbon group having 4 to 18 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-, and the chain hydrocarbon group may have a substituent. ) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (the alicyclic -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Place (which may have a substituent) It is more preferable that A chain hydrocarbon group having 6 to 14 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-, and the chain hydrocarbon group may have a substituent. ) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 14 carbon atoms (the alicyclic -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Place (which may have a substituent) It is even more preferable that

[0035] Specifically, X 2 As the hydrocarbon group in An alkanediyl group having 2 to 18 carbon atoms (the —CH 2 -teeth,- The alkanediyl group may be substituted with -O- or -CO-. ) Alicyclic hydrocarbon groups having 3 to 18 carbon atoms (-CH contained in the alicyclic hydrocarbon groups) 2 -teeth,- O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a substituent. An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- ) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms ( The -CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -To and (which may have a substituent), teeth An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- may be replaced by -O- or -CO-; and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. An alkyl group having 1 to 12 carbon atoms (including —CH 2 - is -O- or -CO - may be replaced by -.) (the group may have a substituent). It is preferred that An alkanediyl group having 4 to 18 carbon atoms (the —CH 2 -teeth,- The alkanediyl group may be substituted with -O- or -CO-. ) An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- ) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms ( The -CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -To and (which may have a substituent), teeth An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- may be replaced by -O- or -CO-; and an alicyclic hydrocarbon group having 3 to 16 carbon atoms. An alkyl group having 1 to 12 carbon atoms (including —CH 2 - is -O- or -CO - may be replaced by -.) (the group may have a substituent). It is more preferable that An alkanediyl group having 6 to 14 carbon atoms (the —CH 2 -teeth,- The alkanediyl group may be substituted with -O- or -CO-. ) An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- may be replaced by -O- or -CO-.) and an adamantanediyl group (the adamantane -CH contained in the phenyl group 2 - may be replaced by -O- or -CO-. (The group may have a substituent.) Or An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- may be replaced by -O- or -CO-.) and an adamantanediyl group and a C1-C1 2 alkyl group (-CH 2 - is replaced by -O- or -CO- and (the group may have a substituent). Even more preferred.

[0036] Specifically, X 2 is the formula (X 2 -1), a group represented by the formula (X 2 -2), a group represented by the formula ( X 2 -3) or a group represented by the formula (X 2 -4) is preferred. TIFF2025041750000025.tif34157[In the formula, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x each independently represents an alkyl group having 1 to 6 carbon atoms; a group, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group combining two or more of these groups. The alkyl group and the alicyclic hydrocarbon group each have a -CH 2 - is -O-, -S-, - CO- or -SO 2 The alkyl group and the alicyclic hydrocarbon group may be substituted with -. may have a substituent. * is X a and X b represents the bond position with The combined group is a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined one by one. The group may be a combination of two or more of either one or two or more of both. The combined carbon number of the groups is 39 or less, preferably 37 or less.

[0037] Among them, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable. Group (-CH contained in the alkyl group 2 - may be replaced by -O- or -CO-. The alkyl group may have a substituent.) Group (the -CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 The alicyclic hydrocarbon group may be substituted with -, and the alicyclic hydrocarbon group may have a substituent. is an alkyl group having 1 to 6 carbon atoms (-CH 2 - is -O- or -CO - may be substituted.) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (the alicyclic hydrocarbon -CH contained in the base group 2 - is -O-, -S-, -CO- or -SO 2 -Replaced by and a group which may have a substituent. Preferred are a methoxy group and an adamantyl group (the —CH 2 -teeth,- The adamantyl group may be substituted with -O- or -CO-, and the adamantyl group has a substituent. ) or an alkyl group having 1 to 6 carbon atoms (the —CH 2 - is -O - or -CO- may be substituted.) and an adamantyl group (the The group may have a substituent.

[0038] In formula (bb), L A and L B As the alkanediyl group having 1 to 6 carbon atoms, For example, a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, linear alkanediyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, etc. propane-1,2-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methyl Branched alkanediyl groups such as butane-1,4-diyl group and 2-methylbutane-1,4-diyl group The number of carbon atoms in the alkanediyl group is preferably 1 to 4, and more preferably 1 to 4. Preferably it is 1 to 3. Examples of the alkanediyl group which may have a fluorine atom include a difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group, and and perfluoroalkanediyl groups such as perfluoropentanediyl group. The alkanediyl group contains -CH 2 - is replaced by -O- or -CO-. In this case, the number of carbon atoms before substitution is the total number of carbon atoms in the alkanediyl group. , hydroxyl group (-CH contained in methyl group) 2 - is replaced by -O-), carboxyl group (-CH contained in ethyl group) 2 -CH 2 - is replaced by -O-CO- , an alkoxy group (an alkyl group having -CH 2 - is replaced by -O- alkoxycarbonyl group (a group in which -CH 2 -C H 2 - is replaced by -O-CO-), alkylcarbonyl group (a group containing Any position of -CH 2 - is replaced by -CO-), alkylcarbonyloxy An oxy group (-CH at any position in an alkyl group) 2 -CH 2 - is replaced by -CO-O- substituted groups), alkanediyloxy groups (alkanediyl groups each containing - at any position); CH 2 - is replaced by -O-), alkanediyloxycarbonyl group (alkane -CH at any position in the diyl group 2 -CH 2 - is replaced by -O-CO- ), an alkanediylcarbonyl group (-CH 2 - is replaced by -CO-), alkanediylcarbonyloxy group (alkanediyl -CH at any position in the 2 -CH 2 - is replaced by -CO-O- It may have. Examples of the alkanediyloxy group include a methyleneoxy group, an ethyleneoxy group, a propanediyloxy group, and a propyleneoxy group. propanediyloxy group, butanediyloxy group, pentanediyloxy group, etc. . Examples of the alkanediyloxycarbonyl group include a methyleneoxycarbonyl group, Ethyleneoxycarbonyl group, propanediyloxycarbonyl group, butanediyloxy Examples thereof include a carbonyl group. Examples of the alkanediylcarbonyl group include a methylenecarbonyl group and an ethylenecarbonyl group. bonyl group, propanediylcarbonyl group, butanediylcarbonyl group, pentanediylcarbonyl group Examples include a carbonyl group. Examples of the alkanediylcarbonyloxy group include a methylenecarbonyloxy group, Ethylenecarbonyloxy group, propanediylcarbonyloxy group, butanediylcarbonyloxy group Examples thereof include a nyloxy group.

[0039] L A is an alkanediyl group having 1 to 4 carbon atoms which may have a fluorine atom. It is preferably an alkanediyl group having 1 to 3 carbon atoms and containing a fluorine atom. stomach. L B is a single bond or an alkanediyl group having 1 to 3 carbon atoms (the alkanediyl group -CH 2 - may be replaced by -O- or -CO-, A single bond, a methylene group or an ethylene group is more preferred.

[0040] R A The hydrocarbon group in the above is an aliphatic hydrocarbon group (alkyl group, alkenyl group, Aromatic hydrocarbon groups and the like, Examples of the groups include groups formed by combining The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, Examples of the alkyl group include an n-undecyl group and an n-dodecyl group. The number of carbon atoms in the alkyl group is preferably It is 1 to 18, more preferably 1 to 12, even more preferably 1 to 9, and even more preferably It is more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, and a butenyl group. isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples of such groups include an octynyl group, an isooctynyl group, and a nonenyl group. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, Examples thereof include a nonynyl group. -CH contained in chain hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -Placed The substituted groups include hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbo groups, etc. Examples of the alkyl group include an alkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, and an alkylthio group. can be done. Alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyl Examples of the oxy group and alkylthio group include an alkoxy group having 1 to 17 carbon atoms, Alkoxycarbonyl groups having 2 to 17 carbon atoms, alkylcarbonyl groups having 2 to 18 carbon atoms, an alkylcarbonyloxy group having from 1 to 17 carbon atoms and an alkylthio group having from 1 to 17 carbon atoms, Examples of the groups include the same groups as those mentioned above.

[0041] The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spiro rings, and may be saturated or The monocyclic alicyclic hydrocarbon group may be, for example, cyclopropyl. group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo Monocyclic cycloalkyl groups such as octyl, cyclononyl, cyclodecyl, and cyclododecyl groups Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl. Examples of polycyclic cycloalkyl groups include polycyclic cycloalkyl groups such as adamantyl group and norbornyl group. Alicyclic hydrocarbon groups and -CH contained in alicyclic hydrocarbon groups 2 -, -O-, -S-, - CO- or -SO 2 Specific examples of the group substituted with - include the groups represented by the above formulae (y1) to (y7 The alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms. It is more preferably 3 to 24, even more preferably 3 to 18, and even more preferably It is preferably 3 to 16, and even more preferably 3 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, Examples of aromatic hydrocarbon groups include aryl groups such as phenanthryl and binaphthyl groups. The prime number is preferably 6 to 36, more preferably 6 to 24, and even more preferably It is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. be.

[0042] In the case of a combination of groups, the above groups each having a different valence (such as an alkanediyl group, ... cycloalkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) Good too. The group formed by the combination is an aromatic hydrocarbon group and a chain hydrocarbon group. A group that combines (for example, aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic aromatic hydrocarbon group-*), groups combining alicyclic and chain hydrocarbon groups (e.g. , alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), aromatic A group that combines an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., an aromatic hydrocarbon group-alicyclic Cyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). Represents the binding site. Aromatic hydrocarbon groups - alkanediyl groups -* include aryl groups such as benzyl and phenethyl groups. Examples include ralkyl groups. Examples of alkyl groups - aromatic hydrocarbon groups -* include tolyl groups, xylyl groups, and cumenyl groups. Some examples include: Alicyclic hydrocarbon groups - alkanediyl groups - * include cyclohexylmethyl groups, cyclohexylmethyl groups, Hexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 -1-methylethyl, and the like. Examples of alkyl groups - alicyclic hydrocarbon groups -* include methylcyclohexyl, dimethylcyclohexyl, cyclohexyl group, 2-alkyladamantan-2-yl group, etc. Examples of the alkyl groups include alkyl groups. Examples of aromatic hydrocarbon groups - alicyclic hydrocarbon groups -* include phenyladamantyl groups. can be done. Alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include adamantylphenyl groups, etc. can be done. In addition, in the combination, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups are In addition, any of the groups L may be a combination of two or more. B It may be bound to stomach.

[0043] -CH contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -Replaced with In addition to the above groups, the groups that can be substituted include cycloalkoxy groups, cycloalkylalkoxy groups, and the like. group, alkoxycarbonyloxy group, aromatic hydrocarbon group-carbonyloxy group, Groups formed by combining two or more of these groups are also included. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms. Examples of the cycloalkylalkoxy group include a cyclohexyloxy group. and cycloalkylalkoxy groups having a carbon number of 4 to 17, such as cyclohexylmethoxy. The alkoxycarbonyloxy group includes an alkoxy group having 2 to 16 carbon atoms. Examples of the aryloxy group include butoxycarbonyloxy groups. The aromatic hydrocarbon group-carbonyloxy group is an aromatic hydrocarbon group having 7 to 17 carbon atoms. Examples of the group include a carbonyloxy group, such as a benzoyloxy group. -CH contained in the hydrocarbon group 2 -, -O-, -S-, -SO 2 - or -CO- In the case where the carbon atom is replaced by another carbon atom, the number of carbon atoms before the replacement is regarded as the total number of carbon atoms of the hydrocarbon group. may be one or may be two or more.

[0044] R A The substituents which the hydrocarbon group may have include halogen atoms, cyano groups, carbon atoms, An alkyl group having a number of 1 to 12 (the —CH 2 - is -O-, -S-, -C O- or -SO 2 - may be substituted). Examples of the halogen atom include the same groups as those mentioned above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those mentioned above. -CH in the alkyl group 2 Examples of the group in which - is replaced by -O- or -CO- include: Hydroxy group, carboxy group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group Examples of the alkyl group include an aryl group and an alkylcarbonyloxy group. Alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups and alkylcarbonyl groups The alkoxy group may be an alkoxy group having 1 to 11 carbon atoms, an alkoxy group having 2 to 11 carbon atoms, carboxyl group, alkylcarbonyl group having 2 to 12 carbon atoms, alkylcarbonyl group having 2 to 11 carbon atoms Examples of the alkyl group include an aryloxy group, and examples of the alkyl group include the same groups as those mentioned above. R A The hydrocarbon group in may have one or more substituents.

[0045] R A The hydrocarbon group in the formula (I) is an alkyl group having 1 to 12 carbon atoms which may have a substituent. (However, the —CH 2 - is -O-, -S-, -CO- or -SO 2 - or a cyclic hydrocarbon having 3 to 18 carbon atoms which may have a substituent. group (provided that the -CH 2 - is -O-, -S-, -CO- or - SO 2 - may be substituted.) is preferable, and a fluorine atom, a hydroxyl atom, A cyclic hydrocarbon group having 3 to 18 carbon atoms, which may have a group or an alkyl group having 1 to 6 carbon atoms (provided that , the -CH contained in the cyclic hydrocarbon group2 - is -O-, -S-, -CO- or -SO 2 -To It is more preferable that

[0046] Examples of the cyclic hydrocarbon group include monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms and A cyclic hydrocarbon group such as an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination of these groups etc. The alicyclic hydrocarbon group, aromatic hydrocarbon group, and combined group are the same as those described above. Some examples include: In the combination, two or more types of alicyclic hydrocarbon groups and two or more types of aromatic hydrocarbon groups may be used. The above may be combined. B may be bound to

[0047] A cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group is a fluorine atom, a hydroxyl group or may have an alkyl group having 1 to 6 carbon atoms, and the -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by . A fluorine atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Alicyclic hydrocarbon groups of 8 (-CH contained in the alicyclic hydrocarbon groups) 2 - is -O-, -S-, -CO- or -SO 2 -), or A compound having 6 to 1 carbon atoms, which may have a fluorine atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms. 8 is preferably an aromatic hydrocarbon group, A fluorine atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Alicyclic hydrocarbon groups of 8 (-CH contained in the alicyclic hydrocarbon groups) 2 - is -O- or -CO - (which may be replaced by -) is more preferred. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, Cyclohexyl group, norbornyl group, adamantyl group, the following groups (binding site is arbitrary position) The aromatic hydrocarbon group is preferably a phenyl group or a naphthyl group. TIFF2025041750000026.tif1897

[0048] The anion in the carboxylate represented by formula (I) may be any of the anions listed below. Examples include: TIFF2025041750000027.tif97163

[0049] TIFF2025041750000028.tif118141

[0050] TIFF2025041750000029.tif126141

[0051] TIFF2025041750000030.tif123154

[0052] TIFF2025041750000031.tif115153

[0053] TIFF2025041750000032.tif138157

[0054] TIFF2025041750000033.tif96151

[0055] TIFF2025041750000034.tif152150

[0056] Specific examples of the carboxylate (I) include carboxylates having any combination of the above cations and anions. Specific examples of the carboxylate (I) are shown in the table below. In the table below, each symbol represents the symbol attached to the structure representing the above-mentioned anion or cation. For example, the carboxylate (I-1) is a compound having an anion represented by the formula (Ia-1) and an anion represented by the formula (I -c-1) is a salt formed with a cation represented by the following formula: TIFF2025041750000035.tif1796 [Table 1] TIFF2025041750000037.tif223153 TIFF2025041750000038.tif223153 TIFF2025041750000039.tif223153 TIFF2025041750000040.tif223153 TIFF2025041750000041.tif223153 TIFF2025041750000042.tif223153 TIFF2025041750000043.tif223153 TIFF2025041750000044.tif223153 TIFF2025041750000045.tif223153 TIFF2025041750000046.tif223153 TIFF2025041750000047.tif223153 TIFF2025041750000048.tif223153 TIFF2025041750000049.tif223153 TIFF2025041750000050.tif223153 TIFF2025041750000051.tif223153 TIFF2025041750000052.tif223153 TIFF2025041750000053.tif223153 TIFF2025041750000054.tif223153 TIFF2025041750000055.tif223153 TIFF2025041750000056.tif223153 TIFF2025041750000057.tif223153 TIFF2025041750000058.tif223153 TIFF2025041750000059.tif223153 TIFF2025041750000060.tif67145

[0057] Among them, the carboxylate (I) is preferably carboxylate (I-1) to carboxylate (I -5), Carboxylate (I-55)~Carboxylate (I-59), Carboxylate (I-1 09)~Carboxylic Acid Salts (I-113), Carboxylic Acid Salts (I-163)~Carboxylic Acid Salts (I -167), Carboxylic Acid Salts (I-217) ~ Carboxylic Acid Salts (I-221), Carboxylic Acid Salts (I-271)~Carboxylic Acid Salt (I-275), Carboxylic Acid Salt (I-325)~Carvone Salts (I-329), Carboxylate (I-379)~Carboxylate (I-383), Carboxylic acid salt (I-433) ~ Carboxylic acid salt (I-437), Carboxylic acid salt (I-487) ~ Carboxylic Acid Salts (I-491), Carboxylic Acid Salts (I-541) ~ Carboxylic Acid Salts (I-545 ), Carboxylic Acid Salts (I-595) ~ Carboxylic Acid Salts (I-599), Carboxylic Acid Salts (I-6 49)~Carboxylic acid salt (I-653), Carboxylic acid salt (I-703)~Carboxylic acid salt (I -707), Carboxylic Acid Salts (I-757) ~ Carboxylic Acid Salts (I-761), Carboxylic Acid Salts (I-811)~Carboxylic Acid Salt (I-815), Carboxylic Acid Salt (I-865)~Carvone Acid salt (I-869), carboxylate (I-919) to carboxylate (I-923) are preferred. It is.

[0058] <Method for producing carboxylate (I)> The carboxylate (I) is a salt represented by the formula (Ia) and a compound represented by the formula (Ib) and in a solvent in the presence of a base. TIFF2025041750000061.tif45147 [wherein all symbols have the same meanings as defined above.] Bases include triethylamine, pyridine, dimethylaminopyridine, and potassium carbonate. , potassium iodide, etc. Examples of solvents include chloroform, acetonitrile, and dimethylformamide. do. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours. .

[0059] The compound represented by formula (Ib) includes the compound represented by the following formula, which is commercially available. can be more easily obtained. TIFF2025041750000062.tif1382

[0060] The salt represented by formula (Ia) can be prepared by subjecting the salt represented by formula (Ic) to a deprotection reaction with a base in a solvent. It can be produced by reacting TIFF2025041750000063.tif44158 [wherein all symbols have the same meanings as above. Rf is a fluorine atom having 1 to 4 carbon atoms. represents a halogenated alkyl group. The base includes tetramethylammonium hydroxide and the like. Solvents include chloroform, acetonitrile, dimethylformamide, tetrahydrofuran, Franc, for example. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours. .

[0061] The salt represented by formula (Ic) is a salt represented by formula (Id) and a salt represented by formula (Ie) The compound can be produced by reacting the compound with a salt in a solvent. TIFF2025041750000064.tif54164 [wherein all symbols have the same meaning as defined above. X represents a chlorine atom, a bromine atom or an iodine atom. R A , R B and R C each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or R A , R B and R C may combine together to form an aromatic ring. D is a hydrogen atom or a carbon atom represents a hydrocarbon group having a molecular weight of from 1 to 12. Solvents for this reaction include chloroform, acetonitrile, ion-exchanged water, etc. Can be obtained. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0062] The salt represented by formula (Ie) is disclosed in JP 2011-39502 A and JP 2014-888 A. The salts can be synthesized by referring to the method described in the publication of US Pat. No. 367, and include salts represented by the following formula: Examples include: TIFF2025041750000065.tif100163

[0063] The salt represented by formula (Id) is a compound represented by formula (If) and a compound represented by formula (Ig). The compound can be produced by reacting the compound to be treated with the compound in a solvent in the presence of a catalyst. TIFF2025041750000066.tif43140 [wherein all symbols have the same meanings as defined above.] Catalysts include potassium peroxymonosulfate (Oxone®), sulfuric acid, p-toluenesulfonyl ether, and toluene. enesulfonic acid and the like. Examples of the solvent include chloroform, monochlorobenzene, and acetonitrile. The reaction temperature is usually from 0° C. to 80° C., and the reaction time is usually from 0.5 to 24 hours.

[0064] The compound represented by formula (If) includes the compound represented by the following formula, and is commercially available. It is more readily available and can be easily produced by known methods. . TIFF2025041750000067.tif37122

[0065] The compound represented by formula (Ig) includes the compound represented by the following formula, and is commercially available. can be more easily obtained. TIFF2025041750000068.tif1417

[0066] The salt represented by the following formula (I-d1) is a compound represented by the formula (Ih) and potassium iodate. The reaction is carried out in a solvent in the presence of sulfuric acid catalyst, and then mixed with sodium bromide. It can be manufactured as follows. TIFF2025041750000069.tif43137 [wherein all symbols have the same meanings as defined above.] Solvents include acetic acid, acetic anhydride, chloroform, monochlorobenzene, and acetonitrile. etc. The reaction temperature is usually from 0° C. to 80° C., and the reaction time is usually from 0.5 to 24 hours.

[0067] The compound represented by formula (Ih) includes the compound represented by the following formula, and is commercially available. It is more readily available and can be easily produced by known methods. . TIFF2025041750000070.tif16139

[0068] [Carboxylic Acid Generator] The carboxylic acid generator of the present invention is an acid generator containing a carboxylate (I). The carboxylate (I) can act as an acid generator in a resist composition. When the carboxylate (I) is used as an acid generator in the resist composition, may contain only one type or two or more types of carboxylates (I). The carboxylic acid generator of the present invention is a carboxylic acid generator known in the resist field other than the carboxylate (I). In this case, the carboxylate (I) and the salt other than the carboxylate (I) may be included. The ratio (mass ratio) of the content to the carboxylate is usually 1:99 to 100:0, preferably 1: :99 to 99:1, more preferably 2:98 to 98:2, and even more preferably 5:95 to 9 It's 5:5. In addition, the resist composition of the present invention contains a carboxylate (I) as described below. The acid generator (B) may be an acid generator known in the resist field other than the carboxylic acid generator. The acid generator (B) may be used alone or in combination. Two or more species may be used in combination. When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the carboxylic acid salt (I) The ratio of the content of the carboxylate (I) to the content of the acid generator (B) (mass ratio; carboxylate (I):acid generator (B), etc.) is , usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:9 The ratio is preferably 8 to 98:2, and more preferably 5:95 to 95:5.

[0069] [Resist Composition] The resist composition comprises a carboxylic acid generator containing the carboxylate (I) of the present invention and a carboxylate. The acid generator (B) is a resin having an acid labile group (hereinafter referred to as "resin (A)"). In this context, the term "acid labile group" refers to a group that has a leaving group and is labile when exposed to an acid. The leaving group is eliminated by the reaction to form a hydrophilic group (e.g., a hydroxyl group or a carboxyl group). It means a group. The resist composition further contains a quencher (hereinafter sometimes referred to as “quencher (C)”). The composition may contain a binder (which may be referred to hereinafter as "solvent (E)") and / or a solvent (which may be referred to hereinafter as "solvent (E)").

[0070] <Acid Generator (B)> The acid generator (B) may be either a nonionic or ionic acid generator. Biocides include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, etc.). sulfonates, oximesulfonates, N-sulfonyloxyimides, sulfonyloxyketones ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g. disulfone, ketone Examples of ionic acid generators include oni Onium salts containing ion cations (e.g. diazonium salts, phosphonium salts, sulfonium salts) The anion of the onium salt is typically a sulfonate anion. ion, sulfonylimide anion, sulfonylmethide anion, etc.

[0071] Examples of the acid generator (B) include those described in JP-A-63-26653 and JP-A-55-164824. JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate an acid when exposed to radiation, such as those described in US Pat. No. 5,312,712, can be used. In addition, a compound produced by a known method may be used. The acid generator (B) may be a compound containing two or more kinds of compounds. They may also be used in combination.

[0072] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)"). TIFF2025041750000071.tif2962[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms; It represents a aryl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CH 2 - may be replaced by -O- or -CO-, and is included in the saturated hydrocarbon group. The hydrogen atom may be substituted by a fluorine atom or a hydroxy group. Y is a methyl group which may have a substituent or a methyl group having 3 to 2 carbon atoms which may have a substituent. 4, and the -CH 2 -, -O-, - S(O) 2 It may be replaced by - or -CO-. Z1 + represents an organic cation.

[0073] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) is a trifluoromethyl group, a perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a perfluorohexyl group and a perfluorohexyl group. Q b1 and Q b2 are each independently a fluorine atom or a trifluoromethyl group. It is preferable that both are fluorine atoms.

[0074] L b1 The divalent saturated hydrocarbon group in the formula (I) is a straight-chain alkanediyl group, a branched alkanediyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A group formed by combining two or more of these may also be used. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- Linear alkanediyl groups such as diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group 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.

[0075] L b1 -CH contained in a divalent saturated hydrocarbon group represented by 2 - is replaced by -O- or -CO-. The replaced group is, for example, a group represented by any one of formulas (b1-1) to (b1-3). In addition, the formulae (b1-1) to (b1-3) and specific examples thereof, such as the formula ( In the groups represented by formulae (b1-4) to (b1-11), * and ** represent bonding positions, and * represents -Represents the bonding position with Y.

[0076] TIFF2025041750000072.tif26117[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxy groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0077] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group -CH 2 When - is replaced by -O- or -CO-, the number of carbon atoms before the replacement is The number of carbon atoms in the hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 The divalent saturated hydrocarbon groups are the same as those of the above. do.

[0078] L b2 is preferably a single bond. Lb3 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, The hydrogen atoms contained in the radicals 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, The hydrogen atoms contained in the hydride 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, A hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The divalent saturated hydrocarbon group contains -CH 2 - is replaced by -O- or -CO- Good too. L 1 -CH contained in a divalent saturated hydrocarbon group represented by 2 - is replaced by -O- or -CO- The substituted group is preferably a group represented by formula (b1-1) or formula (b1-3).

[0079] The group represented by formula (b1-1) is preferably any of the groups represented by formulas (b1-4) to (b1-8). Examples of such groups include those mentioned above. TIFF2025041750000073.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, -CH 2 - 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, The hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b11 and L b12 The total number of carbon atoms 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, -CH contained in hydrogen radical 2 - 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, The hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. 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, Included -CH 2 - 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, The hydrogen atom contained in the hydride group may be substituted with 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 is preferred. 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 is preferred. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms is preferred.

[0080] The group represented by formula (b1-3) is represented by formulas (b1-9) to (b1-11), Examples of the groups include those represented by the following formula: TIFF2025041750000074.tif23139[In formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The alkylcarbonyloxy group may be substituted. 2 - is -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The alkylcarbonyloxy group may be substituted. 2 - is -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, A hydrogen atom contained in the 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, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The alkylcarbonyloxy group may be substituted. 2 - is -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0081] In addition, in the groups represented by formulae (b1-9) to (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group.

[0082] The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0083] Examples of the group represented by formula (b1-4) include the following. TIFF2025041750000075.tif15139

[0084] Examples of the group represented by formula (b1-5) include the following. TIFF2025041750000076.tif59138

[0085] Examples of the group represented by formula (b1-6) include the following. TIFF2025041750000077.tif29164

[0086] Examples of the group represented by formula (b1-7) include the following. TIFF2025041750000078.tif57139

[0087] Examples of the group represented by formula (b1-8) include the following. TIFF2025041750000079.tif21133

[0088] Examples of the group represented by formula (b1-2) include the following. TIFF2025041750000080.tif27141

[0089] Examples of the group represented by formula (b1-9) include the following. TIFF2025041750000081.tif37125

[0090] Examples of the group represented by formula (b1-10) include the following. TIFF2025041750000082.tif86154

[0091] Examples of the group represented by formula (b1-11) include the following. TIFF2025041750000083.tif51151

[0092] TIFF2025041750000084.tif30145

[0093] The alicyclic hydrocarbon group represented by Y includes those represented by the formulae (Y1) to (Y11) and (Y36) to (Y38). Examples of the group include a group represented by the formula (Y38). -CH contained in the alicyclic hydrocarbon group represented by Y 2 - is -O-, -S(O) 2 -or-C When the group is replaced by O-, the number of the O- may be one or more. Examples of the groups represented by the formulae (Y12) to (Y35) and (Y39) to (Y43) include groups represented by the formulae (Y12) to (Y35) and (Y39) to (Y43). * is L b1 represents the binding site with TIFF2025041750000085.tif82167

[0094] The alicyclic hydrocarbon group represented by Y is preferably a group represented by the formula (Y1) to the formula (Y20), Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43) and more preferably a group represented by formula (Y11), formula (Y15), or formula (Y16) ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39), a group represented by the formula (Y40), the formula (Y42) or the formula (Y43), and more preferably Or formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula ( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) It is a group represented by the following formula: The alicyclic hydrocarbon group represented by Y is represented by the formula (Y28) to the formula (Y35), the formula (Y39) to the formula (Y 40), or a spiro ring containing an oxygen atom, such as formula (Y42) or formula (Y43), The alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. In addition, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

[0095] The substituent of the methyl group represented by Y is a halogen atom, a hydroxyl group, a methyl group having 3 to 1 carbon atoms, 6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -( CH 2 ) ja -CO-OR b1 Group or -(CH 2 ) ja -O-CO-R b1 group (in the formula, R b1 Charcoal Alkyl groups having 1 to 16 carbon atoms, alicyclic hydrocarbon groups having 3 to 16 carbon atoms, aromatic groups having 6 to 18 carbon atoms represents an aromatic hydrocarbon group or a combination thereof; and ja represents an integer of 0 to 4. The -CH groups contained in the alkyl groups and alicyclic hydrocarbon groups 2 -, -O-, -SO 2 -also may be replaced by -CO-, and the alkyl group, the alicyclic hydrocarbon group and the aromatic The hydrogen atoms contained in the hydrocarbon group may be replaced by hydroxy groups or fluorine atoms. ) etc. The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxyl group, an alkyl group having 1 to 16 carbon atoms which may be substituted with an alkoxy group (the alkyl group -CH 2 - may be replaced by -O- or -CO-.) A cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, Glycidyloxy group, -(CH 2 ) ja -CO-ORb1 Group or -(CH 2 ) ja -O-CO- R b1 group (in the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon having 3 to 16 carbon atoms represents a group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. The alkyl group and the alicyclic hydrocarbon group each represent an integer of any one of the following: 2 -, -O-, -SO 2 The alkyl group, the fatty acid, The hydrogen atoms contained in the cyclic hydrocarbon group and the aromatic hydrocarbon group are substituted with hydroxyl groups or fluorine groups. The atom may be substituted.

[0096] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexane group, and a cyclohexane group. Cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, Examples of the alicyclic hydrocarbon group include a carboxyl group and an adamantyl group. Examples of the cyclohexyl group include a methylcyclohexyl group and a dimethylcyclohexyl group. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 10 carbon atoms. do. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and the like. Examples of the aromatic hydrocarbon group include aryl groups such as an alkyl group and an aryl group such as a phenyl group and a phenanthryl group. It may have a fluorine atom or an alicyclic hydrocarbon group, and may have a chain hydrocarbon group having 1 to 18 carbon atoms. The aromatic hydrocarbon groups are tolyl, xylyl, cumenyl, mesityl, p- Ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2 phenyl group, etc., which have an alicyclic hydrocarbon group having 3 to 18 carbon atoms. The aromatic hydrocarbon group is p-cyclohexylphenyl, p-adamantylphenyl. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 14. Preferably 6 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromoalkyl 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 The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 It is preferably from 1 to 6, and more preferably from 1 to 4. Examples of alkyl groups substituted with hydroxy groups include hydroxymethyl groups, hydroxy Examples of such groups include hydroxyalkyl groups such as an ethyl group. The aralkyl group includes a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and the like. Examples of the alkyl group include ethyl and naphthylethyl groups. -CH in the alkyl group 2 - is -O-, -S(O) 2 - or -CO- etc. Examples of the group include an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkyl Examples of the alkyl group include a aryloxy group, a carboxyloxy group, and a combination thereof. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy group. The number of carbon atoms of the alkoxy group is preferably 1 to 12. It is preferably 1 to 6, and more preferably 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group is preferably Preferably, it is 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably It is preferably 2-6, and more preferably 2-4. Examples of the alkylcarbonyloxy group include an acetyloxy group and a propionyloxy group. The number of carbon atoms of the alkylcarbonyloxy group is preferably Preferably, it is 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. Examples of the combined group include a group in which an alkoxy group and an alkyl group are combined, a group combining an alkoxy group and an alkoxy group; and a group combining an alkoxy group and an alkylcarbonyloxy group. Some examples include: Examples of the group consisting of an alkoxy group and an alkyl group include a methoxymethyl group, Alkoxyalkyl groups such as methoxyethyl, ethoxyethyl, and ethoxymethyl groups; The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, and more preferably The number is preferably 2 to 6, and more preferably 2 to 4. Examples of the combination of an alkoxy group and an alkoxy group include a methoxymethoxy group, a meth alkoxyalkoxy groups such as oxyethoxy group, ethoxymethoxy group, and ethoxyethoxy group; The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, and more preferably It is preferably 2 to 6, and more preferably 2 to 4. Examples of a group that combines an alkoxy group and an alkylcarbonyl group include methoxyacetyl. Alkoxy groups such as methoxypropionyl groups, ethoxyacetyl groups, and ethoxypropionyl groups. The number of carbon atoms in the alkoxyalkylcarbonyl group is Preferably, it is 3 to 13, more preferably 3 to 7, and further preferably 3 to 5. be. Examples of the combination of an alkoxy group and an alkylcarbonyloxy group include methoxy groups. Cetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, ethoxy Examples of such groups include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the koxyalkylcarbonyloxy group is preferably 3 to 13, and more preferably The number is preferably 3 to 7, and more preferably 3 to 5. -CH contained in alicyclic hydrocarbon group 2 - is -O-, -S(O) 2 - or -CO- etc. The replaced groups are represented by formulae (Y12) to (Y35) and formulae (Y39) to (Y43). Examples of such groups include those mentioned above.

[0097] Y includes the following: TIFF2025041750000086.tif140165

[0098] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent. and more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. More preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. An adamantyl group which may have a substituent is even more preferred. -CH group or adamantyl group 2 - is -CO-, -S(O) 2 - or -CO- Y is preferably an adamantyl group, a hydroxyadamantyl group, adamantyl group, oxoadamantyl group, or a group represented by the following formula: TIFF2025041750000087.tif75159

[0099] The anion in the salt represented by formula (B1) is represented by the formulas (B1-A-1) to (B1- A-59) (hereinafter, "anion (B1-A-1), etc." according to the formula number) Formula (B1-A-1) to Formula (B1-A-4), Formula (B1 -A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 9) is more preferable.

[0100] TIFF2025041750000088.tif111143

[0101] TIFF2025041750000089.tif128167

[0102] TIFF2025041750000090.tif93145

[0103] TIFF2025041750000091.tif137140

[0104] TIFF2025041750000092.tif123167

[0105] TIFF2025041750000093.tif61126 Here R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably Preferably, the alkyl group has 1 to 4 carbon atoms, the alicyclic hydrocarbon group has 5 to 12 carbon atoms, or a combination thereof. A group formed by combining these groups, more preferably a methyl group, an ethyl group, or a cyclohexyl group. or an adamantyl group. A4 is a single bond or an alkanediyl group having 1 to 4 carbon atoms . Q b1 and Q b2 has the same meaning as above. Specific examples of the anion in the salt represented by formula (B1) include those described in JP-A-2010-20 Examples of the anions include those described in US Pat. No. 4,646.

[0106] Preferred anions in the salt represented by formula (B1) include those represented by formulae (B1a-1) to (B1a-2) B1a-38) are examples of anions represented by the formula: TIFF2025041750000094.tif222158

[0107] TIFF2025041750000095.tif167155

[0108] Among them, the compounds represented by formulae (B1a-1) to (B1a-3) and (B1a-7) to (B1a- 16), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a- 38) is preferably an anion represented by any one of the following:

[0109] Z1 + Examples of the organic cation include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations and Among these, organic sulfonium cations are Preferred are iodonium and organic iodonium cations, and more preferred are arylsulfonium cations. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter In some cases, they are referred to as "cation (b2-1)" depending on the formula number. TIFF2025041750000096.tif47166In equations (b2-1) to (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, It represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the chain hydrocarbon group The hydrogen atoms contained in the alkyl group are hydroxyl groups, alkoxy groups having 1 to 12 carbon atoms, and fatty acids having 3 to 12 carbon atoms. The alicyclic group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms, aliphatic hydrocarbon groups having 1 to 18 carbon atoms, may be substituted with an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group is replaced by a halogen atom, a hydroxyl group, or a C1 It may be substituted with up to 12 alkoxy groups. R b4 and R b5 are bonded together to form a ring with the sulfur atom to which they are attached The ring may contain -CH 2 - may be replaced by -O-, -S- or -CO- good. R b7 and R b8 each independently represents a hydroxyl group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms; Or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5. When m2 is 2 or more, multiple R b7 may be the same or different, and when n2 is 2 or more, R in Numbers b8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or a chain hydrocarbon group having 3 to 4 carbon atoms, Represents 36 alicyclic hydrocarbon groups. R b9 and R b10 are bonded together to form a ring with the sulfur atom to which they are attached The ring may contain -CH 2 - is replaced by -O-, -S- or -CO- Good too. R b11 is a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, It represents a hydrogen group 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 It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the chain hydrocarbon group are It may be substituted with an aromatic hydrocarbon group having a prime number of 6 to 18, and the aromatic hydrocarbon group The hydrogen atom is preferably an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group. R b11 and R b12 means that they are bonded together to form a ring including the -CH-CO- to which they are attached. The ring may have -CH 2 - is replaced by -O-, -S- or -CO-. It is also possible. R b13 ~R b18each independently represents a hydroxyl group or 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 an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14 are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, r2 When is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 teeth Identical or different, when t2 is 2 or more, multiple R b18 are the same or different. The aliphatic hydrocarbon group refers to 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, and a butyl group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and An example of the alkyl group is 2-ethylhexyl. In particular, R b9 ~R b12 The chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the hydrogen group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. cycloalkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl and adamantyl groups. , norbornyl group, and the following groups. TIFF2025041750000097.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms. Examples of alicyclic hydrocarbon groups in which hydrogen atoms are replaced by aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl, dimethylcyclohexyl, 2-methyladamantan-2-yl, 2-ethyl 2-Isopropyladamantan-2-yl group, methylnor Examples of the alkyl group include a bornyl group and an isobornyl group. In the alicyclic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably Preferably, it is 20 or less. The aromatic hydrocarbon group includes a phenyl group, a biphenylyl group, a naphthyl group, a phenanthryl group, The aromatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group. The aromatic hydrocarbon group may have a hydrogen group and may have a chain hydrocarbon group, such as a tolyl group. , xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butyl Examples of the phenyl group include a phenyl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. and an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p -adamantylphenyl group, etc. In addition, the aromatic hydrocarbon group may be a chain hydrocarbon group. In the case where an alicyclic hydrocarbon group is contained, it is preferably a chain hydrocarbon group having 1 to 18 carbon atoms and a chain hydrocarbon group having 3 to 4 carbon atoms. Alicyclic hydrocarbon groups of 18 are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples thereof include the aryl group. Examples of the chain hydrocarbon group in which a hydrogen atom is replaced by an aromatic hydrocarbon group include a benzyl group, a phenoxy group, and the like. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples of such groups include aralkyl groups. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be done. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. The alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, and an ethyl Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group Si group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples thereof include an oxy group and a 2-ethylhexylcarbonyloxy group. R b4 and R b5 and form a ring together with the sulfur atom to which they are attached: The ring may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated. The ring may be one having 3 to 18 carbon atoms, and preferably one having 4 to 18 carbon atoms. The ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples of the ring include the following rings, where * represents the bond position. TIFF2025041750000098.tif23144R b9 and R b10The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. The ring may be either a saturated or unsaturated ring. Examples of the ring include a 3-membered ring to a 12-membered ring. Preferably, it is a 3- to 7-membered ring. For example, a thiolane-1-ium ring (tetrahydrothio ophenium ring), thian-1-ium ring, 1,4-oxathiane-4-ium ring, etc. Can be obtained. R b11 and R b12 The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. The ring may be either a saturated or unsaturated ring. Examples of the ring include a 3-membered ring to a 12-membered ring. and preferably a 3- to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring , oxonorbornane ring, oxoadamantane ring, etc.

[0110] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2025041750000099.tif79158

[0111] TIFF2025041750000100.tif74143

[0112] Examples of the cation (b2-2) include the following cations. TIFF2025041750000101.tif18127

[0113] Examples of the cation (b2-3) include the following cations. TIFF2025041750000102.tif26139

[0114] Examples of the cation (b2-4) include the following cations. TIFF2025041750000103.tif85169

[0115] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation. The acid generator (B) is preferably a compound represented by the formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), an aniline represented by any one of formulas (B1a-22) to (B1a-38) A combination of on and the cation (b2-1) or the cation (b2-3) is also included.

[0116] The acid generator (B) is preferably a compound represented by formula (B1-1) to formula (B1-56), Among them, those containing an arylsulfonium cation are preferred. Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B Those represented by formulas (B1-31) to (B1-56) are particularly preferred. TIFF2025041750000104.tif119149

[0117] JPEG2025041750000105.jpg77147

[0118] JPEG2025041750000106.jpg147147

[0119] JPEG2025041750000107.jpg61154

[0120] TIFF2025041750000108.tif60166

[0121] TIFF2025041750000109.tif92157

[0122] In the resist composition of the present invention, the content of the carboxylate (I) in the resist composition is The solid content is preferably 0.1% by mass or more and 35% by mass or less, and more preferably 0.5% by mass or more and 30% by mass or less. % by mass or less is more preferable, and 1% by mass or more and 25% by mass or less is even more preferable. In addition, when an acid generator (B) or the like is contained, the carboxylate (I) and the acid generator (B) or the like The total content is preferably 1 part by mass or more (more preferably At least 3 parts by mass), preferably at most 55 parts by mass (more preferably at most 50 parts by mass, and even more preferably at most 55 parts by mass). Preferably, the content is 45 parts by mass or less.

[0123] <Resin (A)> Resin (A) contains a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). The resin (A) may further contain a structural unit other than the structural unit (a1). As the structural unit other than the structural unit (a1), a structural unit not having an acid labile group ( (hereinafter sometimes referred to as "structural unit (s)"), structural unit (a1) and structural unit (s) other than (for example, a structural unit having a halogen atom described later (hereinafter referred to as "structural unit (a4) "), a structural unit having a non-leaving hydrocarbon group described below (hereinafter referred to as a "structural unit ( a5) and other structural units derived from monomers known in the art etc.

[0124] <Structural unit (a1)> The structural unit (a1) is a monomer having an acid labile group (hereinafter referred to as "monomer (a1)"). In some cases, The acid labile group contained in the resin (A) is a group represented by formula (1) (hereinafter, also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF2025041750000110.tif2397[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, R represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms or a combination thereof; a1 and R a2 are bonded to each other and form, together with the carbon atom to which they are bonded, an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Form. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * indicates the bond position.] TIFF2025041750000111.tif2379[In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a C1-12 represents a hydrocarbon group, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. and the —CH 2 - is replaced by -O- or -S- It is also possible. X represents an oxygen atom or a sulfur atom. na′ represents 0 or 1. * denotes a binding site.]

[0125] R a1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, Examples of the alkyl group include a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , Ra2 and R a3 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, cycloalkyl groups such as butyl and cyclooctyl groups. Examples of the alkyl group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group ( * indicates a binding site.) etc. a1 , R a2 and R a3 The carbon of the alicyclic hydrocarbon group The number is preferably 3 to 16. TIFF2025041750000112.tif10150 Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexane. xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group , adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. do. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form a non-aromatic hydrocarbon ring, -C(R a1 )(R a2 )(R a3 The non-aromatic hydrocarbon ring is preferably a carbon ring. The numbers are 3 to 12. * indicates the bonding site with -O-. TIFF2025041750000113.tif30139

[0126] R a1’ , R a2’ and R a3’ The hydrocarbon group in the formula (I) is an alkyl group, an alicyclic hydrocarbon group, groups, aromatic hydrocarbon groups, and groups formed by combining these groups. . The alkyl group and the alicyclic hydrocarbon group are R a1 , R a2 and R a3 The same groups as those listed in Can be obtained. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl p-adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. Examples include aryl-cycloalkyl groups. R a2’ and R a3’ are bonded to each other to form a heterocyclic ring together with the carbon atom to which they are bonded and X. When forming, -C(R a1’ )(R a2’ )-XR a3’ Examples of the ring include the following: * indicates a binding site. TIFF2025041750000114.tif19130R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0127] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and na=1 The group is preferably a tert-butoxycarbonyl group. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamantane. Forming a ethyl group, R a3 is an alkyl group, ma=0, and na=1. In formula (1), R a1 and R a2 are each independently an alkyl group; R a3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following groups: * represents a binding site. TIFF2025041750000115.tif73158

[0128] Specific examples of the group (2) include the following groups. * represents the bonding position. TIFF2025041750000116.tif66153

[0129] The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond. More preferably, it is a (meth)acrylic monomer having an acid labile group.

[0130] Of the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of such a bulky structure include those having an alicyclic hydrocarbon group. A resin (A) having a structural unit derived from a monomer (a1) having the above structure is used in a resist composition. This can improve the resolution of the resist pattern.

[0131] As a structural unit derived from a (meth)acrylic monomer having a group (1), 0) (hereinafter, may be referred to as structural unit (a1-0)), -1) (hereinafter, may be referred to as structural unit (a1-1)) or a1-2) (hereinafter, may be referred to as structural unit (a1-2)). Preferably, the structural unit (a1-1) is selected from the group consisting of the structural unit (a1-2) These may be used alone or in combination of two or more. They may be used in combination. TIFF2025041750000117.tif42143 [In the formula (a1-0), the formula (a1-1) and the formula (a1-2), L a01 , L a1 and L a2 each independently represents -O- or * -O-(CH 2 ) k1 -CO-O k1 represents an integer of 1 to 7, and * represents the bonding position with -CO-. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups or combinations thereof. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 18 carbon atoms, or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0132] R a01 , R a4 and R a5 is preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or -O-(CH 2 ) k01 -CO-O- (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 The alkyl group, alicyclic hydrocarbon group and As a group formed by combining these, R in formula (1) a1 , R a2 and R a3 The same groups as those listed in can be. 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 More preferably, it is a methyl group, an ethyl group, or an isopropyl group, and even more preferably, it is an ethyl group. Or an isopropyl group. R a02 , R a03 and R a04 The alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms. More preferably, it is 5 to 10. The group consisting of a combination of an alkyl group and an alicyclic hydrocarbon group is It is preferred that the total number of carbon atoms in combination with the group is 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl It is a phenyl group or an ethyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms. is preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. be. R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl group, an ethyl group, or an isopropyl group, and more preferably an ethyl group or an isopropyl group. It is. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0133] Examples of the structural unit (a1-0) include those represented by the formulae (a1-0-1) to (a1-0-12): and R in the structural unit (a1-0) a01 Methionine equivalent The structural units represented by the formulae (a1-0-1) to (a1-0- -10) is preferred. TIFF2025041750000118.tif66158

[0134] Examples of the structural unit (a1-1) include those described in JP-A-2010-204646. Among them, structural units derived from the monomers of formula (a1-1-1) to formula (a1-1-2) are included. -1-4) and R in the structural unit (a1-1) a4 Equivalent to The structural units represented by the formulas (a1-1-1) to (a1-1-2) are preferably those in which the methyl group is replaced by a hydrogen atom. A structural unit represented by any one of a1-1-4) is more preferable. TIFF2025041750000119.tif44114

[0135] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to (a1-2-6). The structural unit represented by the formula (a1-2) is R a5 The methyl group corresponding to The structural units represented by the formula (a1-2-2), the formula (a1-2-5) and the formula A structural unit represented by any one of (a1-2-6) is preferred. TIFF2025041750000120.tif36161

[0136] When the resin (A) contains the structural unit (a1-0), the content of the structural unit (a1-0) is determined based on the total amount of the structural units of the resin (A). The amount is usually 5 to 60 mol %, preferably 5 to 50 mol %, more preferably The content is usually 10 to 40 mol %. When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), The total content of these units is usually 10 to 95 mol % based on the total structural units of the resin (A). The content is preferably 15 to 85 mol %, more preferably 15 to 80 mol %, and further preferably Preferably, it is 20 to 80 mol %, and even more preferably, it is 20 to 75 mol %.

[0137] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of the structural unit include a structural unit (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF2025041750000121.tif3867[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1-6 alkyl group which may have a halogen atom represents an alkyl group represented by the formula: R a33is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of R a33 are mutual may be the same or different. 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 combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH group contained in the divalent hydrocarbon group 2 - is replaced by -O- or -S- That's fine.]

[0138] R a32 and R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the alkyl group include propyl, butyl, pentyl and hexyl groups. An alkyl group having 1 to 4 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even more preferred. R a32 and R a33 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl. group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoro Ethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoro 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, Examples of the alkyl group include an alkyl group, a hexyl group, and a perfluorohexyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, Among them, alkoxy groups having 1 to 4 carbon atoms are particularly preferred. A methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. . Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Examples thereof include a thyloxy group. 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 include a silyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aryl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, The following groups (* indicates a bonding site): Some examples include: TIFF2025041750000122.tif10151 Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples of the aryl group include a phenanthryl group and the like. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl p-adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36 As for the carbon number 1-18, an alkyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Examples of the groups include groups formed by combining these.

[0139] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. is more preferred, and a methoxy group is even more preferred. la is preferably 0 or 1, and more preferably 0. R a34 is preferably a hydrogen atom. R a35 is preferably an alkyl group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms, more preferably More preferably, it is a methyl group or an ethyl group. R a36The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is an alkyl group having 1 to 18 carbon atoms, a group having 3 to 1 R is an alicyclic hydrocarbon group having 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. a36 Archi The R alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 Aromatic carbonization in The hydrogen group is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0140] -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid) and is eliminated to form a hydroxyl group. Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers represented by the formula (a1-4-1) to (a1-4-2) are preferably included. -4-12) and R in the structural unit (a1-4) a32 In accordance with A structural unit in which the hydrogen atom in the aryl group is replaced by a methyl group is preferable. Structural units represented by formulas (a1-4-1) to (a1-4-5) and (a1-4-10), respectively Examples include: TIFF2025041750000123.tif68157When the resin (A) has the structural unit (a1-4), the content of the structural unit (a1-4) is determined based on the total structure of the resin (A). It is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, based on the total of the structural units. It is more preferable that the content is 10 to 40 mol %.

[0141] 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. TIFF2025041750000124.tif4354 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 *-(CH 2 ) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 represents the bonding position 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.

[0142] 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 a methyl group, an ethyl group, Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group Examples of the alkyl group include the ethyl group and the trifluoromethyl group. In formula (a1-5), R a8 is a hydrogen atom, a methyl group, or a trifluoromethyl group. preferable. L 51 is preferably an oxygen atom. L 52 and L 53 Of these, it is preferred that one is -O- and the other is -S-. It is preferable that s1 is 1. s1' is preferably an integer of 0 to 2. Z a1 is a single bond or -CH 2 -CO-O- is preferred.

[0143] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers represented by the formula (a1-5-1) to the formula (a1-5- 4), and the structural units represented by the formula (a1-5-1) or the formula (a1-5-2) are preferred. ) is more preferred. TIFF2025041750000125.tif34138When resin (A) has structural units (a1-5), the content of the structural units is determined based on the total structure of resin (A). The content of the copolymer is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0144] Examples of the structural unit (a1) include a structural unit represented by the formula (a1-0X) (hereinafter, This is sometimes called the structural unit (a1-0X). TIFF2025041750000126.tif3961[In formula (a1-0X), R x1 represents a hydrogen atom or a methyl group. R x2 and R x3 each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms. Ar x1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms.]

[0145] R x2 and R x3 The saturated hydrocarbon group includes an alkyl group, an alicyclic hydrocarbon group, and and the like. The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. do. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and a monocyclic alicyclic hydrocarbon group Examples of the aryl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples include: Ar x1 Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, and the like. Examples of the aryl groups include aryl groups having 6 to 36 carbon atoms. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 1 8, and more preferably a phenyl group. Ar x1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a phenyl It is preferably a nyl group or a naphthyl group, and more preferably a phenyl group. R x1 , R x2 and R x3 are each preferably independently a methyl group or an ethyl group. , and more preferably a methyl group.

[0146] The structural unit (a1-0X) may be any of the structural units and structural units (a1-0X) shown below. R in x1 Examples of compounds in which the methyl group corresponding to the structure is replaced with a hydrogen atom include The position (a1-0X) is the structural unit (a1-0X-1) to the structural unit (a1-0X-3). It is preferred. TIFF2025041750000127.tif34161 When resin (A) has a structural unit (a1-0X), the content of the structural unit (a1-0X) in resin (A) is It is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, based on the total monomers in the copolymer. It is more preferable that the content is 10 to 40 mol %, and further more preferable that the content is 10 to 40 mol %. The resin (A) may contain two or more types of the structural unit (a1-0X).

[0147] Further, examples of the structural unit (a1) include the following structural units. TIFF2025041750000128.tif27161When resin (A) contains the above structural unit, its content is based on the total structural units of resin (A). The content is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %. More preferred.

[0148] Structural unit(s) The structural unit (s) is a monomer that does not have an acid labile group (hereinafter referred to as "monomer (s)"). The monomer from which the structural unit (s) is derived is an acid-inhibiting monomer known in the resist field. Monomers that do not have stabilizing groups can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. A structural unit having an oxy group and no acid labile group (hereinafter referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid labile group (hereinafter referred to as "structural unit" When a resin having the structural unit (a3) ​​is used in the resist composition of the present invention, For example, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0149] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may be a carboxylic hydroxy group. When a resist pattern is produced from the resist composition of the present invention, the exposure light source is KrF Using high energy rays such as excimer laser (248 nm), electron beam or EUV (extreme ultraviolet light) In this case, the structural unit (a2) is a structural unit having a phenolic hydroxy group ( a2) is preferred, and it is more preferred to use the structural unit (a2-A) described below. When using an ArF excimer laser (193 nm) or the like, the structural unit (a2) is The structural unit (a2) having an alcoholic hydroxy group is preferred, and the structural unit (a2) described below is It is more preferable to use the structural unit (a2) alone. It may contain two or more kinds.

[0150] In the structural unit (a2), the structural unit having a phenolic hydroxy group is represented by the formula (a 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") is can be done. TIFF2025041750000129.tif4349[In 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 an alkyl group. R a51 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - stands for -R. a50 Combined represents the bond position with the carbon atom. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, R in Numbers a51 may be the same or different.]

[0151] R a50 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. can be. R a50 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom is, for example, tri Fluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2 -Trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoroethyl group 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluoropropyl group, Fluorobutyl 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 Examples of the alkyl group include ethyl, pentyl, hexyl and perfluorohexyl groups. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or is more preferably an ethyl group, and further preferably a hydrogen atom or a methyl group. R a51 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. can be done. R a51 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an iso Examples of the group include a propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group or an ethoxy group is more preferred. A toxyl group is more preferred. R a51 The alkylcarbonyl group in the formula (I) is an acetyl group, a propionyl group, or a butyl group. Examples of the alkyl group include an aryl group. R a51 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, Examples of the alkyl groups include an alkyloxy group and a butyryloxy group. R a51 is preferably a methyl group.

[0152] *-X a51 -(A a52 -X a52 ) nb - includes *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, Among them, *-CO-O- and *-CO-OA are the most common. a52 -CO-O- or *- Office Automation a52 -CO-O- is preferred. 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 a52 is preferably a methylene group or an ethylene group. A a50 is a single bond, *-CO-O- or *-CO-OA a52-CO-O- Preferred are single bonds, *-CO-O- or *-CO-O-CH 2 -CO-O- A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable. mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the ortho or para position of the benzene ring, and more preferably to the para position. It is more preferred to bind to

[0153] Examples of the structural unit (a2-A) include those described in JP-A-2010-204634 and JP-A-2012- Examples of structural units include those derived from monomers described in US Pat. No. 5,12577. The structural unit (a2-A) is represented by the formulas (a2-2-1) to (a2-2-6). In the structural units and the structural units represented by formulae (a2-2-1) to (a2-2-6), R in structural unit (a2-A) a50 The structural unit in which the methyl group corresponding to The structural unit (a2-A) is a structural unit represented by the formula (a2-2-1), A structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6) and a structural unit represented by formula ( a2-2-1), a structural unit represented by formula (a2-2-3) or a structural unit represented by formula (a In the structural unit represented by (a2-A), R a50 Equivalent to It is preferable that the structural unit is a structural unit in which a methyl group is replaced with a hydrogen atom. TIFF2025041750000130.tif42166Content of structural unit (a2-A) when structural unit (a2-A) is contained in resin (A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, based on all structural units. % by mole, more preferably 15 to 65 mol %, and even more preferably 20 to 65 mol %. 65 mol %, and particularly preferably 25 to 55 mol %. The structural unit (a2-A) can be prepared, for example, by polymerization of the structural unit (a1-4) followed by p-toluenesulfonyl chloride. It can be incorporated into the resin (A) by treating it with an acid such as benzenesulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating the resin with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0154] In the structural unit (a2), the structural unit having an alcoholic hydroxy group is represented by the formula ( a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") Some examples include: TIFF2025041750000131.tif4260 formula (a2-1), L a3 is -O- or * -O-(CH 2 ) k2 represents -CO-O-, k2 represents an integer of any one of 1 to 7. * represents the bonding position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer of 0 to 10.

[0155] In formula (a2-1), L a3 is preferably -O-, -O-(CH 2 ) f1 -CO-O- (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0156] Examples of the structural unit (a2-1) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a2-1-1) to formula (a2-1-6) are included. ), and the structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) is preferred. A structural unit represented by any one of the formulas (a2-1-1) or (a2-1- The structural unit represented by 3) is more preferred. TIFF2025041750000132.tif54150 When the resin (A) contains the structural unit (a2-1), the content of the structural unit (a2-1) is determined based on the total amount of the structural units of the resin (A). The amount is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably It is preferably 1 to 35 mol %, more preferably 1 to 20 mol %, and even more preferably The content is usually 1 to 10 mol %.

[0157] <Structural unit (a3)> The lactone ring contained in the structural unit (a3) ​​is a β-propiolactone ring, a γ-butyrolactone ring, or It may be a monocyclic ring such as a lactone ring or a δ-valerolactone ring, or a condensation ring of a monocyclic lactone ring with another ring. It may be a γ-butyrolactone ring, an adamantane lactone ring, or a γ -Bridged ring containing a butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) Examples include: The structural unit (a3) ​​is preferably represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or a structural unit represented by formula (a3-4). One of these may be contained alone, Two or more types may be contained. TIFF2025041750000133.tif52165 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH 2 ) k3 -CO-O -(k3 represents an integer of 1 to 7). L a7 , -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -C OOL a9 -CO-O- or *-OL a8 -O-CO-L a9 Represents -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or Represents a halogen atom. X a3 is -CH 2 - 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 group having 1 to 10 carbon atoms; 4 represents an aliphatic hydrocarbon group. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a23 and / or R a25 may be the same or different.]

[0158] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in propyl, isopropyl, butyl, sec-butyl and tert-butyl groups Examples of alkyl groups include the following. R a24 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine atoms. Children are mentioned. R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, groups, butyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups. Preferred are alkyl groups having 1 to 4 carbon atoms, and more preferred are methyl groups or is an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Fluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group group, triiodomethyl group, and the like.

[0159] L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane group, -1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, penta hexane-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 2-methylbutane-1,4-diyl group.

[0160] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably is -O- or *-O-(CH 2 ) k3 In -CO-O-, k3 is any one of 1 to 4 Groups which are integers, more preferably -O- and *-O-CH 2 -CO-O-, more preferably Most of the atoms are oxygen atoms. 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. It is. p1, q1 and r1 each independently represent an integer of preferably 0 to 2; More preferably, it is 0 or 1.

[0161] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A group, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom. It is 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 *-OL a8 -CO-O-, more preferably -O -, -O-CH 2 -CO-O- or -OC 2 H 4 -CO-O-. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF2025041750000134.tif4051(in the formula, R a24 , L a7 has the same meaning as above.)

[0162] As the structural unit (a3), a monomer described in JP-A-2010-204646 can be used. , Monomers described in JP 2000-122294 A, and JP 2012-41274 A Examples of the structural unit (a3) ​​include structural units derived from the monomers described in the above publication. , 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 structural unit, the structural unit represented by any one of the formulas (a3-1) to (a3-2) R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to Substituted structural units are preferred. TIFF2025041750000135.tif116165When resin (A) contains structural unit (a3), the total content is the total content of all structural units of resin (A). The amount is usually 1 to 70 mol %, preferably 1 to 65 mol %, more preferably The content is usually 1 to 60 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit The content of the units (a3-4) is 1 to 60 moieties relative to the total structural units of the resin (A). % by mole is preferable, 1 to 50 mol % is more preferable, and 1 to 50 mol % is even more preferable.

[0163] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025041750000136.tif3165[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, -CH 2 - may be replaced by -O- or -CO-. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain hydrocarbon group and a monocyclic or polycyclic alicyclic hydrocarbon group. groups, as well as groups formed by combining these groups.

[0164] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexa Examples include decyl, heptadecyl and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, Cycloalkyl groups such as cycloheptyl and cyclooctyl; decahydronaphthyl, adipyl, Polycyclic alicyclic carbons such as manthyl group, norbornyl group, and the following groups (* indicates the bond position): Examples of the aryl group include aryl groups. TIFF2025041750000137.tif10160 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0165] The structural unit (a4) may be any of the following: a4-3) and at least one structure selected from the group consisting of formula (a4-4) Units include: TIFF2025041750000138.tif4155[In formula (a4-0), R 5a represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. Represents an orocycloalkanediyl group. R 6a represents a hydrogen atom or a fluorine atom.

[0166] L 4a The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane-1,3 -diyl group, butane-1,4-diyl group, and other linear alkanediyl groups; ethane-1,1- Diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane Branched alkanediyl groups such as 2-methylpropane-1,3-diyl and 2-methylpropane-1,2-diyl groups Examples of the aryl group include the aryl group.

[0167] L 3a The perfluoroalkanediyl group in the formula (I) is a difluoromethylene group, Perfluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane- 1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane- 2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2, 2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5 -diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3 -diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2 -diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4 -diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8 -diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3 -diyl group, perfluorooctane-4,4-diyl group, and the like. L 3a The perfluorocycloalkanediyl group in the Sandiyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group Examples of the alkyl group include a perfluoroadamantanediyl group and a perfluoroadamantanediyl group.

[0168] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond. In the latter case, it is a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably Most commonly, it is a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0169] The structural unit (a4-0) may be any of the structural units shown below and the structural units ( a4-0) in R5a The structural unit in which the methyl group corresponding to the can be. TIFF2025041750000139.tif95165

[0170] TIFF2025041750000140.tif5170[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -CH contained in the hydrocarbon group 2 - may be replaced by -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, or a group represented by the formula (ag 1), where A a41 and R a42 At least one of the following is a substituent: It has a halogen atom (preferably a fluorine atom). TIFF2025041750000141.tif1383 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represents a divalent alkyl group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 is a divalent aliphatic hydrocarbon having 1 to 5 carbon atoms which may have a single bond or a substituent. Represents a group. X a41 and X a42 each independently represents -O-, -CO-, -CO-O-, or -O-CO - represents. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates the bond position, and the * on the right is -O-CO-R a42 ]

[0171] R a42 The saturated hydrocarbon group in the formula (I) is preferably a chain saturated hydrocarbon group or a monocyclic or polycyclic alicyclic and groups formed by combining these. do.

[0172] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, heptyl group, Examples include xadecyl, heptadecyl and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic alicyclic rings such as adamantyl group, norbornyl group, and the following groups (* indicates the bond position): Saturated hydrocarbon groups of the formula: TIFF2025041750000142.tif10160 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more saturated alicyclic hydrocarbon groups. Examples of the alkyl groups include -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkyl Examples of the alkyl group include an alkyl group, -alkanediyl group-saturated alicyclic hydrocarbon group-alkyl group, and the like.

[0173] R a42 The substituent of is selected from a halogen atom and a group represented by formula (a-g3): Examples of the halogen atom include a fluorine atom, a chlorine atom, Examples of the atom include a bromine atom and an iodine atom, and a fluorine atom is preferred. TIFF2025041750000143.tif752[In 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. . * stands for R a42 represents the bond position with However, R a42 -X a43 -A a45 In R a42 When A does not have a halogen atom, a4 5 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom .

[0174] A a45 The aliphatic hydrocarbon group in the formula (I) is a methyl group, an ethyl group, a propyl group, a butyl group, group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, penta Alkyl groups such as decyl, hexadecyl, heptadecyl and octadecyl groups; cyclo Monocyclic alicyclic groups such as pentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups Hydrocarbon groups of the formula: and polycyclic alicyclic hydrocarbon groups such as the following group (where * represents a bonding position). TIFF2025041750000144.tif10160 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0175] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and / or a saturated hydrocarbon group having a group represented by formula (a-g3) is preferably This is more preferable. R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom. More preferably, it is a saturated hydrocarbon group having a fluoroalkyl group or a perfluorosilyl group. Preferably, the alkyl group is a chloroalkyl group, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a perfluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro perfluorooctyl and perfluoroheptyl groups. Examples of the aryl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3), including the number of carbon atoms contained in the group represented by R a42 The total number of carbon atoms is preferably 15 or less. When the alkyl group has a group represented by formula (a-g3) as a substituent, The number is preferably one.

[0176] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 Yes, More preferably, it is a group represented by formula (a-g2). TIFF2025041750000145.tif874[In formula (a-g2), A a46represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. represent. X a44 represents *-O-CO- or *-CO-O- (* represents A a46 It represents the bond position with . A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 of At least one of them has at least one halogen atom. * indicates the bond position with the carbonyl group.

[0177] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. A a47 The aliphatic hydrocarbon group 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.

[0178] A preferred structure of the group represented by formula (a-g2) is the following structure (* represents a carbonyl group). (This is the bonding site with ). TIFF2025041750000146.tif13161

[0179] A a41 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 linear alkanediyl groups such as propane-1,2-diyl, butane-1,6-diyl; ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- and branched alkanediyl groups such as 2-methylbutane-1,4-diyl and the like. do. A a41 The substituents in the alkanediyl group represented by the formula (I) are a hydroxy group and an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkoxy group include alkoxy groups represented by the formula (6). A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably It is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

[0180] A in the group represented by formula (a-g1) a42 , A a43 and A a44 The divalent saturated hydrocarbon The substituents include linear or branched alkanediyl groups and monocyclic or polycyclic divalent alicyclic hydrocarbons. A divalent alicyclic hydrocarbon group is formed by combining an alkyl group and an alkanediyl group. Specifically, methylene group, ethylene group, propane-1,3-diamine group, etc. propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane -1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1 , 2-diyl group, etc. A a42 , A a43 and A a44 The substituent of the divalent saturated hydrocarbon group represented by is a hydroxy group. and alkoxy groups having 1 to 6 carbon atoms. It is preferred that s is 0.

[0181] In the group represented by formula (a-g1), X a42 is -O-, -CO-, -CO-O- or Examples of the -O-CO- group include the following groups. In the following examples, * and ** indicates the bond position, and ** is -O-CO-R. a42 This is the bonding position with. TIFF2025041750000147.tif48153

[0182] The structural unit represented by formula (a4-1) includes the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to Examples of structural units that have been replaced include: TIFF2025041750000148.tif100142

[0183] TIFF2025041750000149.tif123140

[0184] As the structural unit represented by formula (a4-1), a structural unit represented by formula (a4-2) is preferred. I wish. TIFF2025041750000150.tif3251[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, H 2 - may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The total number of carbon atoms in the molecule is limited to 21.

[0185] L 44 The alkanediyl group of A a41 Examples of the groups include the same groups as those exemplified in the above. R f6 The saturated hydrocarbon group of R a42 Examples of the groups include the same groups as those exemplified in the above. L 44The alkanediyl group in is preferably an alkanediyl group having 2 to 4 carbon atoms. Of these, an ethylene group is more preferred.

[0186] Examples of the structural unit represented by formula (a4-2) include the structural units represented by formulae (a4-1-1) to (a4 -1-11) are structural units represented by the following formulas. R f5 The structural unit in which the corresponding methyl group is replaced with a hydrogen atom is also represented by formula (a4-2). It can be mentioned as a structural unit.

[0187] TIFF2025041750000151.tif5164[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. vinegar. X f12 is *-O-CO- or *-CO-O-(* is A f13 represents the bond position with . A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may contain a fluorine atom. However, A f13 and A f14 At least one of L has a fluorine atom. 5 , A f13 and A f14 The total number of carbon atoms in the molecule is limited to 20.

[0188] L 5 The alkanediyl group in a41 The same as those exemplified for the alkanediyl group The following groups are mentioned: A f13The divalent saturated hydrocarbon group which may have a fluorine atom in or a divalent chain saturated hydrocarbon group which may have a fluorine atom and a It is preferably a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkane dialkyl group. It is a aryl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include a methylene group, an ethylene alkanediyl groups such as propanediyl, butanediyl and pentanediyl groups; Fluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoro perfluoroalkanediyl groups such as perfluorobutanediyl and perfluoropentanediyl groups Examples thereof include the aryl group. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either a monocyclic or a polycyclic group. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexa Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and the like. diyl group, perfluoroadamantanediyl group, and the like.

[0189] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are represented by R a42 in The same groups as those exemplified above can be mentioned. Among them, trifluoromethyl group, difluoromethyl group, ethyl 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 perfluorohexyl group. Fluorinated alkyl groups such as fluorooctyl group, cyclopropylmethyl group, cyclopropyl group , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl group A methyl group and the like are preferred.

[0190] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group is a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent chain hydrocarbon group having 3 A group containing a divalent alicyclic hydrocarbon group having from 1 to 12 carbon atoms is preferred, and a divalent chain hydrocarbon group having from 2 to 3 carbon atoms is preferred. A base is more preferred. A f14 The saturated hydrocarbon group is a chain hydrocarbon group having 3 to 12 carbon atoms and an aliphatic hydrocarbon group having 3 to 12 carbon atoms. Groups containing cyclic hydrocarbon groups are preferred, and chain hydrocarbon groups having 3 to 10 carbon atoms and groups containing 3 to 1 More preferred is a group containing an alicyclic hydrocarbon group of A f14 is preferably carbon It is a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably, cyclopropylmethyl. groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups.

[0191] Examples of the structural unit represented by formula (a4-3) include the structural units represented by formulae (a4-1'-1) to (a 4-1'-11) are examples of structural units represented by the structural unit (a4-3). R f7The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-3). It can be mentioned as a structural unit.

[0192] The structural unit (a4) also includes a structural unit represented by the formula (a4-4). TIFF2025041750000152.tif4163[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH 2 ) j1 -, -(CH 2 ) j2 -O-(CH 2 ) j3 -or-(CH 2 ) j4 - CO-O-(CH 2 ) j5 - represents. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0193] R f22 The saturated hydrocarbon group of R a42 The saturated hydrocarbon group may be the same as that represented by the following formula: R f22 represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or a carbon An alicyclic hydrocarbon group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms and a fluorine atom is preferred. A fluorine atom-containing alkyl group having 1 to 6 carbon atoms is more preferred. In formula (a4-4), A f21 As an example, -(CH 2 ) j1 - is preferred, and ethylene group Or, a methylene group is more preferable, and a methylene group is even more preferable.

[0194] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by the formula (a4-4), R f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced by aryl groups. TIFF2025041750000153.tif87160When resin (A) has structural unit (a4), its content is the total of all structural units of resin (A). The ratio is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and more preferably 3 to 10 mol %. % is more preferred.

[0195] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) is a straight-chain, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The group is preferred. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1): . TIFF2025041750000154.tif3972[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in the alicyclic hydrocarbon group The atom 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, Included in -CH 2 - may be replaced by -O- or -CO-.

[0196] R 52 The alicyclic hydrocarbon group in may be either a monocyclic or polycyclic group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentene group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include, for example, , adamantyl group and norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl Examples of the alkyl group include an octyl group and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. do. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably Examples thereof include an adamantyl group, a norbornyl group, and a cyclohexyl group.

[0197] 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.

[0198] L 55 -CH contained in the divalent saturated hydrocarbon group represented by 2 - 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 ** represent bond positions, and * represents the bond position with an oxygen atom. TIFF2025041750000155.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 represents the bond position 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. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, 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 carbon atom having 1 to 14 carbon atoms; Represents a hydrogen group. However, 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 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0199] L x1 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 x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is 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 is preferred. 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 Preferably, it is 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 Preferably, it is 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.

[0200] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF2025041750000156.tif54134

[0201] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2025041750000157.tif24131

[0202] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2025041750000158.tif15145

[0203] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2025041750000159.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0204] The structural unit (a5-1) may be any of the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to the can be. TIFF2025041750000160.tif110150When resin (A) has structural unit (a5), its content is the total of all structural units of resin (A). The ratio is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and more preferably 3 to 15 mol %. % is more preferred.

[0205] <Structural unit (II)> The resin (A) further includes a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit The structural unit (II) may specifically include is a structural unit described in JP 2016-79235 A, and has a sulfonate group in the side chain. or a structural unit having a carboxylate group and an organic cation, or a sulfonio group on the side chain and an organic anion.

[0206] The structural unit having a sulfonate group or a carboxylate group in the side chain is represented by the formula (II-2 -A') is preferably a structural unit represented by the formula: TIFF2025041750000161.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, Ru-CH 2 - may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon may be The hydrogen atom contained in the alkyl group is replaced by a halogen atom or a alkyl group having 1 to 10 carbon atoms which may have a halogen atom. 6 may be substituted with an alkyl or hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. . RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: Z.A. + represents an organic cation.

[0207] R III3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms and the like can be mentioned. R III3The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the following formula: , R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by the following formula: Examples include: A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, Propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group yl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. . A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include trifluoroalkyl groups. perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group Examples of the alkyl group include a perfluoropentyl group and a perfluorohexyl group. X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched alkyl group. and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A combination of the above is also acceptable. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Linear alkanediyl groups such as decane-1,12-diyl group; butane-1,3-diyl group; 2-Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentamethylpropane Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohetane-1,3-diyl group, Cycloalkanediyl groups such as cyclohexanone-1,4-diyl group and cyclooctane-1,5-diyl group norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane Divalent polycyclic alicyclic saturated carbons such as cyclohexyl-1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like. -CH contained in saturated hydrocarbon groups 2 - is replaced by -O-, -S- or -CO- Examples of the divalent group include those represented by the formulae (X1) to (X53). and -CH contained in saturated hydrocarbon groups 2 - is replaced by -O-, -S- or -CO- The number of carbon atoms in front of each is 17 or less. In the following formula, * and ** represent binding sites. * is A x1 Represents a bond with . TIFF2025041750000162.tif145161

[0208] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X7 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.

[0209] ZA in formula (II-2-A') + represents the cation Z1 in the acid generator (B1). + Similar to Some examples include:

[0210] The structural unit represented by the formula (II-2-A') is a structural unit represented by the formula (II-2-A) It is preferable that: TIFF2025041750000163.tif38109 [In formula (II-2-A), R III3 , X III3 and Z.A. + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom, or a phenyl group having 1 to 6 carbon atoms; When z is 2 or more, multiple R III2 and R III4 are identical to each other may be the same or may be different. Q a and Q b each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents a aryl group. R III2 , R III4 , Q a and Q b As a perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula: The above Q b1 The perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula: do.

[0211] The structural unit represented by formula (II-2-A) is a structural unit represented by formula (II-2-A-1). It is preferable that the position is 1. TIFF2025041750000164.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and Z.A. + has the same meaning as above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents an integer of 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, -CH 2 - may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon The hydrogen atoms contained in the group may be substituted with halogen atoms or hydroxy groups. R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, and a propyl group. propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl aryl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups; Examples of the alkyl group include linear or branched alkyl groups such as a decyl group. X I2 As the divalent saturated hydrocarbon group represented by the formula: III3 Divalent saturated hydrocarbon represented by The same as those in the group can be mentioned.

[0212] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). More preferred are structural units in which TIFF2025041750000165.tif5287 [In formula (II-2-A-2), R III3 , RIII5 and Z.A. + has the same meaning as above. m and n each independently represent 1 or 2.

[0213] Examples of the structural unit represented by formula (II-2-A') include the following structural units, R III3 The group corresponding to the methyl group is a hydrogen atom, a halogen atom (e.g., a fluorine atom) or a halogen An alkyl group having 1 to 6 carbon atoms which may have one or more atoms (for example, a trifluoromethyl group, etc.) and structural units described in International Publication No. 2012 / 050015. It can be done. + represents an organic cation. TIFF2025041750000166.tif86163

[0214] The structural unit having a sulfonio group and an organic anion in the side chain is represented by the formula (II-1-1): It is preferable that the structural unit is a structural unit that is TIFF2025041750000167.tif3791 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 Reach BiR II3 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. R II4 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group. A - represents an organic anion. R II1Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I) include a phenylene group and and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, an alicyclic hydrocarbon group, an aromatic aromatic hydrocarbon groups and groups formed by combining these groups. Examples of the alkyl group and the alicyclic hydrocarbon group include the same as those mentioned above. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. , aralkyl groups such as benzyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl nyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group phenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic carbon Aromatic hydrocarbon groups having a hydride group (p-cyclohexylphenyl group, p-adamantyl phenyl group, phenylcyclohexyl group, and other aryl-cycloalkyl groups. can be. R II4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms and the like can be mentioned. R II4 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the following formula: , R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by the following formula: Examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated hydrocarbon having 1 to 18 carbon atoms. The divalent saturated hydrocarbon group includes a -CH2 - is -O-, -S- or Specifically, X may be replaced with -CO-. III3 2 with 1 to 18 carbon atoms The examples of the alkyl group include the same ones as those of the 4-valent saturated hydrocarbon group.

[0215] The structural unit containing a cation in formula (II-1-1) includes the structural units represented by the following formula: BiR II4 The group corresponding to the methyl group in the formula (1) is a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. Examples include replaced structural units. TIFF2025041750000168.tif85130

[0216] A - As the organic anion represented by the formula (I), a sulfonate anion, a sulfonylimide anion, Examples of the anion include sulfonylmethide anion and carboxylate anion. - Represented by The organic anion is preferably a sulfonate anion. More preferably, it is an anion contained in the salt represented by formula (B1).

[0217] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2025041750000169.tif36136

[0218] Examples of sulfonylmethide anions include the following: TIFF2025041750000170.tif29123

[0219] Examples of carboxylate anions include the following: TIFF2025041750000171.tif44153

[0220] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2025041750000172.tif99155When the resin (A) contains the structural unit (II), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 4 mol %, based on the total structural units of the oil (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0221] The resin (A) may have structural units other than the above-mentioned structural units. The positions include structural units known in the art.

[0222] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s). . The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably a cyclohexyl group or a structural unit having a cyclopentyl group) At least one selected from the group consisting of structural units, more preferably at least two It is. The structural unit (s) is preferably selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably represented by the formula (a2-A): The structural unit (a3) ​​is preferably a structural unit represented by the formula (a2-1). or a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-3) a3-4) is at least one selected from the group consisting of structural units represented by the following formula:

[0223] Each structural unit constituting the resin (A) may be used alone or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (e.g., radical polymerization methods). The content of each structural unit in the resin (A) can be determined by the following procedure. This can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more). 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 In the present specification, the weight average molecular weight is preferably 1,000 or less, and more preferably 15,000 or less. The molecular weight is a value determined by gel permeation chromatography under the conditions described in the Examples. It is.

[0224] <Resins other than resin (A)> The resist composition of the present invention may contain a resin other than the resin (A) in combination. Examples of the resin other than the resin (A) include a resin containing the structural unit (a4) or the structural unit (a5). (hereinafter, may be referred to as resin (X)). As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In resin (X), the content of the structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, and more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. Examples of the structural unit that the resin (X) may further have include the structural unit (a2), the structural unit (a3) and structural units derived from other known monomers. X) is preferably a resin consisting of only the structural unit (a4) and / or the structural unit (a5). It is preferable that the resin is composed only of the structural unit (a4). Each structural unit constituting the resin (X) may be used alone or in combination of two or more kinds. Using monomers that derive these structural units, a known polymerization method (e.g., radical polymerization method) is performed. The content of each structural unit in the resin (X) can be determined by the following procedure. This can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more). 0 or more) and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight average molecular weight is the same as in the case of resin (A). Furthermore, when the resist composition contains resin (X), the content of resin (X) is parts, preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, More preferably, the content is 1 to 40 parts by mass, and particularly preferably, the content is 1 to 30 parts by mass. The amount is preferably 1 to 8 parts by mass.

[0225] The content of the resin (A) in the resist composition is 8 to 100% based on the solid content of the resist composition. It is preferably 0% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. In addition, when a resin other than the resin (A) is contained, the resin (A) and the resin other than the resin (A) are preferably mixed. The total content of the resin is 80% by mass or more and 99% by mass or less based on the solid content of the resist composition. The content of the resist is preferably 90% by mass or less and more preferably 99% by mass or less. The solid content of the product and the resin content relative to the solid content are measured by liquid chromatography or gas chromatography. It can be measured by known analytical means such as fluorography.

[0226] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less. It is preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of the solvent (E) is 99% by mass or less. The content of the solvent (E) is measured, for example, by liquid chromatography or gas chromatography. This can be measured by known analytical means such as chromatography. The solvent (E) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0227] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound or an acid generated from the acid generator (B). A salt that generates an acid having a weaker acidity than the above (excluding the carboxylate salt represented by formula (I)). In the case where the resist composition contains a quencher (C), The content of the compound is about 0.01 to 15 mass % based on the solid content of the resist composition. It is preferably about 0.01 to 10 mass %, more preferably about 0.01 to 5 mass %. %, and more preferably about 0.01 to 3 mass %. I wish. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary Amines include secondary amines and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylamine, aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine , octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine amine, triethylamine, trimethylamine, tripropylamine, tributylamine, Tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine , methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine, Ethyldibutyrate diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylamine xylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropylamine Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine amine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -Dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridinium 4-Methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3 - Di(4 - pyridyl)propane, 1,2 - di(4 - pyridyloxy)ethane, di( (2 - pyridyl)ketone, 4,4’ - dipyridyl sulfide, 4,4’ - dipyridyl disulfide, 2,2’ - dipyridylamine, 2,2’ - dipicolylamine, bipyridine, etc. are listed, preferably aromatic amines such as diisopropyl aniline, more preferably 2,6 - diisopropyl aniline. As the ammonium salt, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3 - (trifluoromethyl)phenyltrimethylammonium hydroxide, tetra - n - butylammonium salicylate, and choline, etc. are listed.

[0228] 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 salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually - 3 < pKa, preferably - 1 < pKa < 7, and more preferably 0 < pKa < 5. As the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B), the salts represented by the following formula, the salts represented by formula (D) described in JP - A - 2015 - 147926 (hereinafter, may be referred to as “weak acid intramolecular salt (D)”), and JP - A - 2012 - 229206, JP - A - 2012 - 6908, JP - A - 2012 - 72109, JP - A - 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. TIFF2025041750000173.tif89165

[0229] Examples of the weak acid inner salt (D) include the following salts. TIFF2025041750000174.tif72165

[0230] <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.

[0231] Preparation of Resist Composition The resist composition of the present invention comprises a carboxylate (I), a resin (A), an acid generator (B), and In addition, if necessary, resins other than resin (A), solvent (E), quencher (C) and the like The composition can be prepared by mixing the other component (F) in any order. The temperature during mixing is not limited. It can be from 10 to 40°C depending on the type of resin, etc. An appropriate temperature can be selected depending on the solubility of the compound in the solvent (E) such as the above. The mixing time is Depending on the mixing temperature, the appropriate time can be selected from 0.5 to 24 hours. The mixing means is not particularly limited, and stirring and mixing, etc. can be used. After mixing the components, filter the mixture using a filter with a pore size of about 0.003 to 0.2 μm. It is preferable that

[0232] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) 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) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating. To apply the resist composition onto a substrate, a commonly used device such as a spin coater is used. The substrate can be an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be cleaned, and an anti-reflection film or the like may be formed on the substrate. It may be possible. The composition after coating is dried to remove the solvent and form a composition layer. For example, the solvent can be evaporated using a heating device such as a hot plate (prebaking). The heating temperature is 50 to 200°C. It is preferable that the heating time is 10 to 180 seconds. The pressure during the process is 1 to 1.0×10 5 It is preferable that the pressure is about Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure light source may be a KrF excimer laser (wavelength 248 nm), an ArF excimer Laser (wavelength 193 nm), F 2 Ultraviolet lasers such as excimer lasers (wavelength 157 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert the wavelength and emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range, electron beams, Various types of light sources can be used, such as those that irradiate ultraviolet light (EUV). In this case, the irradiation of these radiations is sometimes collectively called "exposure". Exposure is usually carried out through a mask corresponding to the desired pattern. In the case of lines, exposure may be performed by direct writing without using a mask. The composition layer after exposure is subjected to a heat treatment (so-called heat treatment) in order to promote the deprotection reaction of the acid labile group. The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150 degrees Celsius. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of the method include the dip method, the paddle method, the spray method, and the dynamic dispense method. The development temperature is preferably, for example, 5 to 60° C., and the development time is, for example, 5 The time is preferably 300 seconds or less. By selecting the type of developer as follows: Either a positive resist pattern or a negative resist pattern can be produced. When a positive resist pattern is produced from the resist composition of the present invention, a developer An alkaline developer is used. The alkaline developer is any of the various alkaline solutions used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples of the aqueous solution ... ethyl)trimethylammonium hydroxide (commonly known as choline) include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers are ketones such as 2-hexanone and 2-heptanone. Solvents; glycol ether ethers such as propylene glycol monomethyl ether acetate Steryl solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and the like aromatic hydrocarbon solvents. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, The content is preferably from 95% by mass to 100% by mass, and more preferably substantially only an organic solvent. More preferred. Among them, organic developers include those containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 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. 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 (Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation) The structure of the compound was determined by mass spectrometry (LC: Agilent 1100, MASS: Agilent The molecular ion peak was measured using a LC / MSD (manufactured by Entec). In the examples, the value of this molecular ion peak is indicated as "MASS."

[0235] Example 1: Synthesis of a salt represented by formula (I-326) TIFF2025041750000175.tif33167 10 parts of potassium iodate, 28.62 parts of the compound represented by formula (I-326-a), acetic acid 30 parts of acetic acid and 15 parts of acetic anhydride were mixed and stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, 10 parts of sulfuric acid was added over 10 minutes, and the mixture was stirred at 5°C for 3 hours. The mixture was stirred at 23° C. for 5 hours. To the resulting mixture, 30 parts of tert-butyl methyl ether and The mixture was stirred at 23°C for 2 hours, filtered, and the filtrate was separated. The organic layer was separated by distillation, and 5 parts of sodium bromide and 1 part of ion-exchanged water were added to the obtained organic layer. The mixture was stirred at 23° C. for 2 hours, and then filtered to obtain a compound of the formula (I-3 3.35 parts of the salt represented by 26-b) were obtained. TIFF2025041750000176.tif55160 0.69 parts of a salt represented by formula (I-326-c), 1 part of a salt represented by formula (I-326-b) 0.43 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Add 5 parts of 5% oxalic acid aqueous solution to the mixture, stir at 23°C for 30 minutes, and then separate the mixture to obtain an organic layer. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.52 parts of a salt represented by the formula (I-326-d) was obtained. TIFF2025041750000177.tif24168 1.00 part of the salt represented by the formula (I-326-d), 30 parts of chloroform and 25% tetrahydrofuran Mix 10 parts of methylammonium hydroxide aqueous solution, stir at 23°C for 2 hours, and then mix. The organic layer was extracted by distillation, and 15 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the organic layer was separated and washed with water 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to give the compound of formula (I-326 0.49 parts of a salt represented by the formula (I) was obtained. MASS(ESI(+)Spectrum):M + 341.0 MASS(ESI(-)Spectrum):M - 193.1

[0236] Example 2: Synthesis of a salt represented by formula (I-328) TIFF2025041750000178.tif53154 1.03 parts of a salt represented by formula (I-328-c), 1. 0.43 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Add 5 parts of 5% oxalic acid aqueous solution to the mixture, stir at 23°C for 30 minutes, and then separate the mixture to obtain an organic layer. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.87 parts of a salt represented by the formula (I-328-d) was obtained. TIFF2025041750000179.tif33168 1.00 part of the salt represented by the formula (I-328-d), 30 parts of chloroform and 25% tetrahydrofuran Mix 10 parts of methylammonium hydroxide aqueous solution, stir at 23°C for 2 hours, and then mix. The organic layer was extracted by distillation, and 15 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the organic layer was separated and washed with water 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound of formula (I-328). 0.51 parts of a salt represented by the formula (I) was obtained. MASS(ESI(+)Spectrum):M + 341.0 MASS(ESI(-)Spectrum):M - 337.1

[0237] Example 3: Synthesis of salt represented by formula (I-380) TIFF2025041750000180.tif44161 0.39 parts of the salt represented by formula (I-326) and 10 parts of dimethylformamide were mixed, After stirring at 23°C for 30 minutes, 0.10 parts of potassium carbonate and 0.01 parts of potassium iodide were added. The mixture was cooled to 23° C. and then stirred at 50° C. for 1 hour. 0.17 parts of the compound represented by 80-a) was added and stirred at 23°C for 2 hours. To the mixture, 50 parts of chloroform and 10 parts of 1% aqueous oxalic acid solution were added and stirred at 23°C for 2 hours. After stirring, the mixture was separated to separate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with 20 mL of tert-butyl methyl ether. After stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the product with the formula: 0.28 parts of the salt represented by (I-380) was obtained. MASS(ESI(+)Spectrum):M + 457.1 MASS(ESI(-)Spectrum):M - 193.1

[0238] Example 4: Synthesis of a salt represented by formula (I-382) TIFF2025041750000181.tif56164 0.49 parts of the salt represented by formula (I-328) and 10 parts of dimethylformamide were mixed, After stirring at 23°C for 30 minutes, 0.10 parts of potassium carbonate and 0.01 parts of potassium iodide were added. The mixture was cooled to 23° C. and then stirred at 50° C. for 1 hour. 0.17 parts of the compound represented by 80-a) was added and stirred at 23°C for 2 hours. To the mixture, 50 parts of chloroform and 10 parts of 1% aqueous oxalic acid solution were added and stirred at 23°C for 2 hours. After stirring, the mixture was separated to separate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with 20 mL of tert-butyl methyl ether. After stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the product with the formula: 0.38 parts of the salt represented by (I-382) was obtained. MASS(ESI(+)Spectrum):M + 457.1 MASS(ESI(-)Spectrum):M - 337.1

[0239] Example 5: Synthesis of a salt represented by formula (I-166) TIFF2025041750000182.tif43159 5.32 parts of the compound represented by formula (I-166-a) and 6.40 parts of Oxone (registered trademark) The mixture was stirred at 23°C for 30 minutes and then cooled to 5°C. After adding 0.56 parts, the mixture was stirred at 5° C. for 30 minutes. A mixed solution of 3.68 parts of the compound represented by b) and 18.40 parts of chloroform was added, and the mixture was stirred for 5 After stirring at 23° C. for 30 minutes, the mixture was further stirred at 23° C. for 2 hours. The mixture was added to 120 parts of ethyl acetate, stirred at 23°C for 30 minutes, and then filtered. The filtrate was concentrated. To the concentrated residue, 125 parts of chloroform and 25 parts of acetonitrile were added, and the mixture was stirred at 23° C. for 30 After stirring for 30 minutes, 60 parts of 5% hydrochloric acid was added and stirred at 23°C for 30 minutes. The mixture was then separated to obtain an organic layer. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was separated and washed with water three times. The organic layer was concentrated. To the concentrated mixture, 45 parts of tert-butyl methyl ether was added, and the mixture was stirred at 23° C. for 30 minutes. Then, filtration was carried out to obtain 4.12 parts of the salt represented by the formula (I-166-c). TIFF2025041750000183.tif54158 1.03 parts of a salt represented by formula (I-328-c), 1 part of a salt represented by formula (I-166-c) 16 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Add 5 parts of 5% oxalic acid aqueous solution to the mixture, stir at 23°C for 30 minutes, and then separate the mixture to obtain an organic layer. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.29 parts of a salt represented by the formula (I-166-d) was obtained. TIFF2025041750000184.tif31168 1.00 part of the salt represented by formula (I-166-d), 30 parts of chloroform and 25% tetrahydrofuran Mix 10 parts of methylammonium hydroxide aqueous solution, stir at 23°C for 2 hours, and then mix. The organic layer was extracted by distillation, and 15 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the organic layer was separated and washed with water 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound of formula (I-166 0.59 parts of a salt represented by the formula (I) was obtained. MASS(ESI(+)Spectrum):M+ 367.1 MASS(ESI(-)Spectrum):M - 337.1

[0240] Example 6: Synthesis of salt represented by formula (I-220) TIFF2025041750000185.tif57166 0.51 parts of the salt represented by formula (I-166) and 10 parts of dimethylformamide were mixed, After stirring at 23°C for 30 minutes, 0.05 parts of potassium carbonate and 0.01 parts of potassium iodide were added. The mixture was cooled to 23° C. and then stirred at 50° C. for 1 hour. 0.09 parts of the compound represented by 80-a) was added and stirred at 23°C for 2 hours. To the mixture, 30 parts of chloroform and 10 parts of 1% oxalic acid aqueous solution were added and stirred at 23°C for 2 hours. After stirring, the mixture was separated to separate the organic layer. 10 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with 20 mL of tert-butyl methyl ether. After stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the product with the formula: 0.31 parts of the salt represented by (I-220) was obtained. MASS(ESI(+)Spectrum):M + 425.1 MASS(ESI(-)Spectrum):M - 337.1

[0241] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-3)" etc. depending on their formula numbers. TIFF2025041750000186.tif4179

[0242] Synthesis Example 1 [Synthesis of Resin A1] As the monomer, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) was used, and the molar ratio [monomer (a1-4-2):monomer (a1-1 -3):monomer (a1-2-6) in a ratio of 38:24:38. Further, this monomer mixture was mixed with 1.5 times by mass of methyl ether based on the total mass of all monomers. Isobutyl ketone was mixed in the mixture. Azobisisobutyronite was added as an initiator to the mixture. Add 7 mol% of propylene to the total number of moles of all monomers, and heat the mixture at 85°C. The polymerization was carried out by heating at 40° C. for about 5 hours. After that, the polymerization reaction solution was diluted with p-toluenesulfone The acid solution was added, and the mixture was stirred for 6 hours, and then separated. The obtained organic layer was diluted with a large amount of n-heptane. The resin was precipitated by pouring it into a flask, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.3 × 10 3 Resin A1 (copolymer) was obtained in a yield of 78%. This resin A1 has the following structural units: This is what we do. TIFF2025041750000187.tif29126

[0243] Synthesis Example 2 [Synthesis of Resin A2] As the monomers, monomer (a1-4-2) and monomer (a1-2-6) were used. The molar ratio of monomer (a1-4-2):monomer (a1-2-6) was 38:62. The monomer mixture is mixed so that the total weight of all the monomers is equal to the total weight of the monomers. 1.5 times by mass of methyl isobutyl ketone was mixed into the obtained mixture. Azobisisobutyronitrile was added at 7 mol% based on the total moles of all monomers. The mixture was then heated at 85°C for about 5 hours to carry out polymerization. An aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 6 hours, and then separated. The resin was precipitated by pouring it into a large amount of n-heptane, and then filtered and collected to obtain the weight average The amount of molecules is about 5.4 x 10 3 Resin A2 (copolymer) was obtained in a yield of 89%. has the following structural unit: TIFF2025041750000188.tif2887

[0244] <Preparation of resist composition> As shown in Table 2, the following components were mixed, and the resulting mixture was passed through a fluorine-containing filter with a pore size of 0.2 μm. The mixture was filtered through a resin filter to prepare a resist composition. [Table 2]

[0245] <Resin> A1, A2: Resin A1, Resin A2 <Acid Generator (B)> B1-25: A salt represented by the formula (B1-25); described in JP 2011-126869 A Synthesized by the method TIFF2025041750000190.tif2667<Carboxylate(I)> I-166: A salt represented by the formula (I-166) I-220: A salt represented by the formula (I-220) I-326: A salt represented by the formula (I-326) I-328: A salt represented by the formula (I-328) I-380: A salt represented by the formula (I-380) I-382: A salt represented by the formula (I-382) <Quencher (C)> IX-1 IX-2 IX-3 IX-4 IX-5 IX-6 IX-7 TIFF2025041750000191.tif83155<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0246] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer is heated on a direct hot plate with hexamethyldisilazane. The silicon wafer was treated at 90° C. for 60 seconds. The layer was spin-coated to a thickness of 0.04 μm. The substrate was prebaked for 60 seconds at the temperature shown in the "PB" column of Table 2 to form a composition layer. The composition layer formed on the wafer was then subjected to an electron beam lithography machine (HL-800D manufactured by Hitachi, Ltd.). A line and space pattern was created by changing the exposure dose stepwise using a laser with an energy of 50 keV. Directly painted. After exposure, post-exposure was performed for 60 seconds on a hot plate at the temperature shown in the "PEB" column of Table 2. The jar was baked and then immersed in 2.38% tetramethylammonium hydroxide aqueous solution. A resist pattern was obtained by puddle development in a solution for 60 seconds. The resulting resist pattern (line and space pattern) was observed with a scanning electron microscope. In other words, the line width and space width of the 60 nm line and space pattern are 1:1. The exposure amount at which the light was emitted was taken as the effective sensitivity.

[0247] Line Edge Roughness Evaluation (LER): Sidewall of resist pattern produced at effective sensitivity The amplitude of the unevenness of the surface was measured using a scanning electron microscope to obtain the line edge roughness. The results are shown in Table 3. [Table 3] Compared with the comparative compositions 1 to 7, the compositions 1 to 8 have good line edge roughness (LER). It was good. [Industrial Applicability]

[0248] The carboxylate of the present invention and the resist composition containing the carboxylate are It has good elasticity and is useful for microfabrication of semiconductors.

Claims

1. A carboxylic acid generator containing a carboxylate represented by formula (I), and A resist composition comprising a resin that includes a structural unit having an acid labile group and a structural unit represented by formula (a2-A): [In formula (I), R １ａ represents a hydrogen atom or an acid labile group. R ２ represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and the —CH 2 - may be replaced by -O- or -CO-. R ３ is a halogen atom, a fluoroalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or -L 11' -O-R １ｂ and the fluorinated alkyl group and the —CH 2 - may be replaced by -O- or -CO-. L 11 and L 11' each independently represents an alkanediyl group having 1 to 6 carbon atoms, and —CH ２ - may be replaced by -O- or -CO-. R １ｂ represents a hydrogen atom or an acid labile group. m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R ２ may be the same or different from each other. m3 represents an integer of 0 to 5, and when m3 is 2 or more, a plurality of R ３ may be the same or different from each other. X ０ represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and the —CH 2 - is -O-, -S-, -CO- or -SO ２ - may be replaced. [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 alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 - (A a52 -X a52 ) nｂ -, * is -R a50 represents the bonding site with the carbon atom to which it is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, a plurality of R a51 may be the same or different.

2. R １ａ and R １ｂ 2. The resist composition according to claim 1, wherein each of the acid labile groups is independently a group represented by formula (R1-1) or formula (R1-2): [In formula (R1-1), R ４ , R ５ and R ６ each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof; R ４ and R ５ are bonded to each other to form, together with the carbon atoms to which they are attached, a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. m represents 0 or 1. * indicates a binding site.] [In formula (R1-2), R ７ and R ８ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; R ９ represents a hydrocarbon group having 1 to 20 carbon atoms, or R ８ and R ９ are bonded to each other and to the carbon atom to which they are bonded and to X X and form a heterocycle having 3 to 20 carbon atoms together with the hydrocarbon group, and the —CH ２ - may be replaced by -O- or -S-. X X represents an oxygen atom or a sulfur atom. n represents 0 or 1. * indicates a binding site.]

3. X ０ is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that the —CH 2 - is -O-, -S-, -CO- or -SO ２ 3. The resist composition according to claim 1, wherein:

4. X ０ is an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxyl group (-CH contained in the alicyclic hydrocarbon group) 2 - may be replaced by -O- or -CO-) or a group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are combined (the -CH 2 The resist composition according to any one of claims 1 to 3, wherein - may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxyl group.

5. 5. The resist composition according to claim 1, further comprising an acid generator other than a carboxylic acid generator.

6. 6. The resist composition according to claim 1, wherein the structural unit having an acid labile group is a resin containing 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 are each independently -O- or *-O-(CH ２ ) k１ It represents --CO--O--, k1 represents an integer of 1 to 7, and * represents a bond to --CO--. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

7. (1) A step of applying the resist composition according to any one of claims 1 to 6 onto a substrate; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) developing the composition layer after heating; A method for producing a resist pattern comprising the steps of:

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