Compound and resin

Abstract

To provide a compound and a resin for constituting a resist composition from which a resist pattern can be produced with good line edge roughness (LER).SOLUTION: The compound is represented by formula (IA). [Ar1 represents an aromatic hydrocarbon group; and R5 represents a halogen atom, a fluorinated alkyl group or an alkyl group.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compounds and resins. [Background technology]

[0002] Patent Document 1 describes a resin containing the following structural unit: TIFF2025169323000001.tif4898 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 10-186642 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a resist pattern formed from a resist composition containing the above resin. Furthermore, we provide resins that form resist patterns with good line edge roughness (LER). The goal is to [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A structural unit represented by formula (I), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a 1-2) and at least one structural unit selected from the group consisting of structural units represented by resin. TIFF2025169323000002.tif5272 [In formula (I), R 1 represents a hydrogen atom or a methyl group. X 1 is a single bond or -CO-O-* (* is Ar 1 represents the bonding position with . X2 -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH2) mm - O-* or -O-(CH2) nn -CO-O-* (* is Ar 2 represents the bond position with represent. mm and nn represent 0 or 1. Ar 1 and Ar 2 each independently represents an aromatic group having 6 to 36 carbon atoms which may have a substituent. represents an aromatic hydrocarbon group. R 2 each independently represents a hydrogen atom or an acid labile group, or R 2 If there are two or more Two R 2 may be combined together to form a group having an acetal ring structure. n represents an integer of 1 to 3. When n is an integer of 2 or more, multiple R 2 may be the same or different from each other.] TIFF2025169323000003.tif46102 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or -O-(CH2) k1 -CO-O represents -, k1 represents an integer of 1 to 7, and * represents the bonding site with -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 are each independently an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 8 carbon atoms, alkenyl group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms or represents a group 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. [2]X 1 is a single bond. [3]X 2 -CO-O-* or -O-* (* is Ar 2 represents the bond position with The resin according to [1] or [2]. [4] The resin according to any one of [1] to [3], wherein n is 1 or 2. [5]R 2 wherein the acid labile group is a group represented by formula (1a) or a group represented by formula (2a) The resin according to any one of [1] to [4], wherein the group is a group. TIFF2025169323000004.tif2166 [In formula (1a), R aa1 , R aa2 and R aa3 may each independently have a substituent. an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms which may have a substituent; an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may be optionally substituted, or R aa1 and R aa2 are mutually They combine with the carbon atoms to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms. do. naa represents 0 or 1. * represents a bond.] TIFF2025169323000005.tif2155[In formula (2a), R aa1’ and R aa2’ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms, represents a hydrocarbon group of 2, and R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other and they combine -CX a- and carbon number 3 to 20 A heterocyclic group is formed, and -CH2- contained in the hydrocarbon group and the heterocyclic group is -O- or - May be replaced with S-. X a represents an oxygen atom or a sulfur atom. * represents a bond.] [6]R 2 is a hydrogen atom, or n is 2 or more and two R 2 together The resin according to any one of [1] to [5], which forms a group having an acetal ring structure. [7] Any one of [1] to [6] further containing a structural unit represented by formula (a2-A) Resin used. TIFF2025169323000006.tif4653[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 hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxy group having 2 to 12 carbon atoms Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms It represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or * -X a51 -(A a52 -X a52 ) nb - represents -R a50 is combined represents the bonding site 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, multiple R in Numbers a51 may be the same or different from each other.] [8] A resist composition comprising the resin according to any one of [1] to [7] and an acid generator. thing. [9] The resist composition according to [8], wherein the acid generator comprises a salt represented by formula (B1): TIFF2025169323000007.tif2859[In formula (B1), Q b1 and Q b2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents an alkyl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the divalent saturated hydrocarbon group The contained —CH2— may be replaced by —O— or —CO—, and the divalent saturated carbon The hydrogen atoms contained in the hydrogen hydride group may be substituted with fluorine atoms or hydroxy groups. 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 -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z + represents an organic cation.

[10] The composition further contains a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator. The resist composition according to [8] or [9].

[11] (1) A method for coating a resist composition according to any one of [8] to

[10] on a substrate. a process of (2) 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.

[12] A compound represented by formula (IA). TIFF2025169323000008.tif6660[In formula (IA), R 1 represents a hydrogen atom or a methyl group. X 1 is a single bond or -CO-O-* (* is Ar 1 represents the bonding position with . X 2 -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH2) mm - O-* or -O-(CH2) nn -CO-O-* (* indicates the bonding position to the benzene ring. ) mm and nn represent 0 or 1. Ar 1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. R 3 and R 4 each independently represents a hydrogen atom or an acid labile group, or R 3 and R 4 One They may be combined to form a group having an acetal ring structure. R 5 is a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. The —CH2— contained in the alkyl group and the fluoroalkyl group represents —O— or — It may be replaced by CO-. n' represents an integer of 0 to 3, and when n' is 2 or more, a plurality of R 5 are the same as each other They may be the same or different.]

[13] X 1 is a single bond.

[12] The compound according to claim 12.

[14] X 2 However, -CO-O-* or -O-* (* represents the bonding position to the benzene ring. The compound according to

[12] or

[13] , wherein

[15] The compound according to any one of

[12] to

[14] , wherein n′ is 0.

[16] R 3 and R 4 is a hydrogen atom, or R 3 and R 4 Together they form the Aceta The compound according to any one of

[12] to

[15] , wherein a group having a phenyl ring structure is formed.

[17] A resin containing a structural unit derived from the compound according to any one of

[12] to

[16] . . [Effects of the Invention]

[0006] By using a resist composition that uses a resin containing the structural unit of the present invention, it is possible to obtain a good resist pattern. Resist patterns can be produced with in-edge roughness (LER). DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, the term "(meth)acrylic monomer" refers to a monomer having a structure such as "CH2=CH-CO-" Monomers having the structure "CH2=C(CH3)-CO-" and monomers having the structure "CH2=C(CH3)-CO-" Similarly, "(meth)acrylate" and "(Meth)acrylic acid" refers to "a 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 "at least one of" "CH2=C(CH3)-CO-" or "CH2=CH-C When a structural unit having "O-" is exemplified, structural units having both groups are also exemplified. In addition, in the groups described in this specification, a linear structure and a branched structure are For those which can have both structures, either one is acceptable. It means a group in which two or more of the indicated groups are bonded, and the valence of these groups changes appropriately depending on the bonding form. "Derived from" or "derived from" refers to a polymerizable C=C This means that the bond becomes a -CC- group by polymerization. When stereoisomers exist, all Includes stereoisomers. In this specification, the term "solid content of the resist composition" refers to the amount of the solid content of the resist composition that is the remaining amount of the resist composition. This refers to the total of all components excluding the solvent (E) described below.

[0008] 〔resin〕 The resin of the present invention contains a structural unit represented by formula (I) (hereinafter, sometimes referred to as structural unit (I)). ) and a structural unit represented by formula (a1-1) (hereinafter referred to as structural unit (a1-1) ) and a structural unit represented by formula (a1-2) (hereinafter referred to as structural unit (a1-2) and a resin (hereinafter referred to as "a resin") containing at least one structural unit selected from the group consisting of Resin (A) is sometimes referred to as "Resin (A)".

[0009] <Structural Unit (I)> The structural unit (I) is represented by the following formula: TIFF2025169323000009.tif5172 [In formula (I), R 1 represents a hydrogen atom or a methyl group. X 1 is a single bond or -CO-O-* (* is Ar 1 represents the bonding position with . X 2 -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH2) mm - O-* or -O-(CH2) nn -CO-O-* (* is Ar 2 represents the bond position with represent. mm and nn represent 0 or 1. Ar1 and Ar 2 each independently represents an aromatic group having 6 to 36 carbon atoms which may have a substituent. represents an aromatic hydrocarbon group. R 2 each independently represents a hydrogen atom or an acid labile group, or R 2 If there are two or more Two R 2 may be combined together to form a group having an acetal ring structure. n represents an integer of 1 to 3. When n is an integer of 2 or more, multiple R 2 may be the same or different from each other.]

[0010] Ar 1 and Ar 2 Examples of the divalent aromatic hydrocarbon group include benzenediyl group, naphthalene Examples thereof include a diyl group and an anthracenediyl group. Ar 2 Examples of the trivalent or tetravalent aromatic hydrocarbon group include a benzenetriyl group, a benzenetetrayl group, and a benzenetetrayl group. tolyl group, naphthalenetriyl group, naphthalenetetrayl group, anthracentriyl group , anthracenetetrayl group, and the like. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms. More preferably, it is 6 to 14, and even more preferably, it is 6 to 10. The number of layers is preferably 6. The substituent of the aromatic hydrocarbon group may be a hydroxy group, a halogen atom, a cyano group, or a group having a carbon number an alkyl group of 1 to 16 (wherein -CH2- in the alkyl group is replaced by -O- or -CO-) may be replaced by a fluorinated alkyl group having 1 to 12 carbon atoms (the fluorinated alkyl group may be replaced by a fluorinated alkyl group having 1 to 12 carbon atoms). The —CH2— contained therein may be replaced by —O— or —CO—. 12 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 10 carbon atoms, or combinations thereof Examples include the group. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. . Examples of the alkyl group having 1 to 16 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably Preferably, it is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. is. When -CH2- in the alkyl group is replaced with -O- or -CO-, the substitution The number of carbon atoms before the substitution is the total number of carbon atoms in the alkyl group. However, the group substituted with -O- or -CO- is a hydroxy group (containing a methyl group). a carboxyl group (a group in which -CH2- in an ethyl group is replaced with -O-), H2-CH2- is replaced by -O-CO-), alkoxy group (a group contained in an alkyl group) a group in which -CH2- at any position is replaced with -O-), an alkoxycarbonyl group ( Any -CH2-CH2- in the alkyl group is replaced with -O-CO- group), alkylcarbonyl group (wherein any -CH2- in the alkyl group is -C O-substituted), alkylcarbonyloxy group (any group contained in the alkyl group) -CH2-CH2- at position 1 is replaced with -CO-O-. The alkoxy group includes an alkoxy group having 1 to 15 carbon atoms, such as methoxy. group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, oxy octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, un The number of carbon atoms of the alkoxy group is preferably is 1 to 12, more preferably 1 to 11, even more preferably 1 to 6, More preferably, it is 1 to 4. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group are A carbonyl group or a carbonyloxy group is bonded to the alkyl group or the alkoxy group. Represents a group. The alkoxycarbonyl group includes an alkoxycarbonyl group having 2 to 15 carbon atoms. Examples of such groups include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 16 carbon atoms. Examples include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 15 carbon atoms. Examples thereof include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 13, and more preferably 2. The number of carbon atoms is preferably 1 to 11, more preferably 2 to 6, and even more preferably 2 to 4. The alkylcarbonyl group preferably has 2 to 13 carbon atoms, more preferably 2 to 12 carbon atoms. The alkyl group is preferably 2 to 6, more preferably 2 to 4. The carbonyloxy group preferably has 2 to 13 carbon atoms, more preferably 2 to 11 carbon atoms. It is more preferably 2 to 6, and even more preferably 2 to 4. Examples of the fluorinated alkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a difluoromethyl group, and a methyl group. perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, Trifluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoro Propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluoro Butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Fluorinated alkyl groups such as dipentyl and perfluorohexyl groups are also included. The alkyl group preferably has 1 to 9 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably Preferably, it is 1 to 4. -CH2- in the fluorinated alkyl group may be replaced by -O- or -CO-. In this case, the number of carbon atoms before substitution is the total number of carbon atoms in the fluorinated alkyl group. The groups in which -CH2- is replaced by -O- or -CO- include fluorinated alkoxy groups. A fluorinated alkyl group in which any -CH2- at any position is replaced with -O- group), fluorinated alkoxycarbonyl group (-C at any position contained in the fluorinated alkyl group H2-CH2- is replaced by -O-CO-), fluorinated alkylcarbonyl group (fluorine a group in which any -CH2- in a substituted alkyl group is replaced with -CO-), Fluorinated alkylcarbonyloxy group (-CH2 at any position contained in the fluorinated alkyl group) -CH2- is replaced with -CO-O-. Fluorinated alkoxy groups, fluorinated alkoxycarbonyl groups, fluorinated alkylcarbonyl groups, and and the fluorinated alkylcarbonyloxy group is a fluorinated alkoxy group having 1 to 11 carbon atoms; Fluorinated alkoxycarbonyl groups with 2 to 11 carbon atoms, fluorinated alkylcarbonyl groups with 2 to 12 carbon atoms and fluorinated alkylcarbonyloxy groups having 2 to 11 carbon atoms. One or more hydrogen atoms of the indicated group may be replaced with fluorine atoms. The alicyclic hydrocarbon group having 3 to 12 carbon atoms may be either monocyclic or polycyclic, and examples thereof include For example, the groups shown below can be mentioned, where ** indicates a bond to the aromatic hydrocarbon group. TIFF2025169323000010.tif16157 Examples of aromatic hydrocarbon groups having 6 to 10 carbon atoms include phenyl and naphthyl groups. . The combined groups in the substituents of the aromatic hydrocarbon group include a hydroxy group and a group having 1 carbon atom. a group combining an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms; a group combining an alkyl group having 1 to 12 carbon atoms with an alkoxy group having 6 to 10 carbon atoms; and groups in which an aromatic hydrocarbon group is combined. Examples of the group combining a hydroxy group with an alkyl group having 1 to 12 carbon atoms include hydroxy Examples include hydroxyalkyl groups having 1 to 12 carbon atoms, such as a methyl group and a hydroxyethyl group. do. a group formed by combining an alkoxy group having 1 to 12 carbon atoms with an alkoxy group having 1 to 12 carbon atoms; Examples thereof include alkoxyalkoxy groups having 2 to 24 carbon atoms, such as an ethoxyethoxy group. 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 a benzyl group.

[0011] The substituents are halogen atoms, fluoroalkyl groups having 1 to 6 carbon atoms, alkyl groups having 1 to 12 carbon atoms, and the like. alkyl groups, hydroxyl groups, alkoxy groups with 1 to 11 carbon atoms, alkoxy groups with 2 to 11 carbon atoms a carboxyl group, an alkylcarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 11 carbon atoms A bonyloxy group is preferred, and a halogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms is also preferred. , a hydroxy group, an alkoxy group having 1 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms an alkylcarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 11 carbon atoms A halogen atom, a hydroxy group, a fluoro group having 1 to 6 carbon atoms is more preferred. A fluorinated alkyl group or an alkoxy group having 1 to 11 carbon atoms is more preferred.

[0012] R 2 The acid labile group in R 2 Represented by The term "hydroxyl group" refers to a group that is eliminated to form a hydroxy group. R of the structural unit (I) used in the production of resin (A) 2 is an acid labile group, ) is converted to R by contact with acid. 2 Desorption (R 2 may be converted into a hydrogen atom), and the elimination The ratio is preferably 40% to 100%, more preferably 60% to 100%, and even more preferably 100%. preferable. Examples of the acid labile group include a group represented by formula (1a) (hereinafter sometimes referred to as "acid labile"). Group (1a)"), a group represented by formula (2a) (hereinafter sometimes referred to as "acid labile group (2 a)". ) are some examples. TIFF2025169323000011.tif2364 [In formula (1a), R aa1 , R aa2 and R aa3 may each independently have a substituent. an alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms which may have a substituent; an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may be optionally substituted, or R aa1 and R aa2 are mutually They combine with the carbon atoms to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms. do. naa represents 0 or 1. * represents a bond.] TIFF2025169323000012.tif2155[In formula (2a), R aa1’ and R aa2’ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms, represents a hydrocarbon group of 2, and R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other and they combine -CX a - and carbon number 3 to 20 A heterocyclic group is formed, and -CH2- contained in the hydrocarbon group and the heterocyclic group is -O- or - May be replaced with S-. X a represents an oxygen atom or a sulfur atom. * represents a bond.]

[0013] R aa1 , R aa2 and R aa3 The alkyl group includes methyl, ethyl, propyl, n n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. R aa1 , R aa2 and R aa3 The alkyl group preferably has 1 to 6 carbon atoms, More preferably, it is 1 to 3. R aa1 , R aa2 and R aa3 Examples of the alkenyl group include an ethenyl group, a propenyl group, an isoprenyl group, and an aryl group. pentenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl Examples of the alkyl groups include octynyl, heptenyl, octynyl, isooctynyl, and nonenyl groups. R aa1 , R aa2 and R aa3 The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclohexyl group. cycloalkyl groups such as cyclobutyl and cyclooctyl groups. Examples of the group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups: (* represents a bond.) aa1 , R aa2 and R aa3 Alicyclic hydrocarbons The group preferably has 3 to 16 carbon atoms, and more preferably 3 to 12 carbon atoms. TIFF2025169323000013.tif9159R aa1 , R aa2 and R aa3 Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an aryl group, and an aryl group. Examples of aryl groups include tolyl, biphenyl, and phenanthryl groups. aa1 , R aa2 and R aa3 The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, and more preferably It is 6 to 10.

[0014] The substituent of the alkyl group having 1 to 8 carbon atoms which may have a substituent is preferably a group having 2 to 8 carbon atoms. alkenyl groups, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms Examples of the substituent of the optionally substituted alkenyl group having 2 to 8 carbon atoms include: is an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a Aromatic hydrocarbon groups are examples of the aromatic hydrocarbon groups. Alicyclic hydrocarbon groups having 3 to 20 carbon atoms which may have a substituent are also examples. The substituent of the hydrogen group may be an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a carbon atom, or a carboxylic acid. Examples of the aromatic hydrocarbon groups include those having 6 to 18 carbon atoms and optionally having a substituent. The substituent of the aromatic hydrocarbon group of 8 is an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 8 carbon atoms, cyclohexane group, and alicyclic hydrocarbon groups having 3 to 20 carbon atoms. a group combining an alkyl group and an alicyclic hydrocarbon group (for example, a methylcyclohexyl group) , dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantyl group alkylcycloalkyl groups such as butylmethyl group, adamantyldimethyl group, and norbornylethyl group; alkyl groups or cycloalkylalkyl groups), aralkyl groups such as benzyl groups, alkyl groups Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, aryl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl aromatic hydrocarbon groups having alicyclic hydrocarbon groups (e.g., p-cyclohexyl-6-ethylphenyl group, etc.); p-Adamantylphenyl group, cyclohexylphenyl group, etc.), phenylcyclohexyl group, etc. and the like. naa is preferably 1.

[0015] R aa1 and R aa2 -C(R aa1 )( R aa2 )(R aa3 The number of carbon atoms in the alicyclic hydrocarbon group is preferably The number of atoms is preferably 3 to 16, and more preferably 3 to 12. * represents a bond to —O—. TIFF2025169323000014.tif34155

[0016] The group represented by formula (1a) includes a 1,1-dialkylalkoxycarbonyl group (formula ( In 1a) R aa1 , R aa2 and R aa3 is an alkyl group, preferably a tert- butoxycarbonyl group), 2-alkyladamantan-2-yloxycarbonyl group (formula (1a) Medium, R aa1 , R aa2 and the carbon atoms to which they are bonded form an adamantyl group, and R aa3 is an alkyl group) and 1-(adamantan-1-yl)-1-alkylalkoxy an oxycarbonyl group (in formula (1a), R aa1 and R aa2 is an alkyl group, and R aa3 Adama Examples include a butyl group.

[0017] R aa1' , R aa2' and R aa3' Examples of the hydrocarbon group include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups and groups formed by combining these groups. The alkyl group and the alicyclic hydrocarbon group are represented by R aa1 , R aa2 and R aa3 The same groups as those listed in Examples include: Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples include aryl groups such as 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., methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) , cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl alkylcycloalkyl groups or cycloalkylalkyl groups such as phenylethyl groups), benzyl Aralkyl groups such as alkyl groups, 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.), alicyclic hydrocarbon groups Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) and the like), and aryl-cycloalkyl groups such as phenylcyclohexyl group. R aa2' and R aa3' are bonded to each other and the carbon atoms to which they are bonded and X a together with heterocycles When forming a group, -C(R aa1' )(R aa2' )-X a -(R aa3' ) are the following groups: * represents a bond. TIFF2025169323000015.tif21149R aa1' and R aa2' At least one of these is preferably a hydrogen atom.

[0018] Specific examples of the acid labile group (1a) include the following groups: * represents a bond. TIFF2025169323000016.tif68167

[0019] Specific examples of the acid labile group (2a) include the following groups: * represents a bond. TIFF2025169323000017.tif85160 In the structural unit (I), multiple R 2 may be the same or different.

[0020] The Two R's 2 When these are taken together to form a group having an acetal ring structure, *-(R 2 ) 2 is a group represented by formula (3a) (hereinafter sometimes referred to as "group (3a)"). etc. TIFF2025169323000018.tif19149 [In formula (3a), R ab1 and R ab2 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, represents an alkyl group or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ab1 and R ab2 Mutually They are bonded to the carbon atoms to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms. The —CH2— contained in the alkyl group and the alicyclic hydrocarbon group is replaced with —O— or —CO—. May be replaced with -. * indicates a bond to the oxygen atom. The alkyl group and the alicyclic hydrocarbon group include R aa1 , R aa2 and R aa3 Similar to the groups listed in Examples of the group include the following. Examples of the group (3a) include the groups shown below. * represents a bond to an oxygen atom. vinegar. TIFF2025169323000019.tif17110 Also, two R 2 When these are taken together to form a group having an acetal ring structure, * -Ar 2 -(OR 2 ) 2 is a group represented by the following formula (wherein the benzene ring has no substituents): ) and the like. * represents X 2 Represents a bond with . TIFF2025169323000020.tif37153

[0021] R 2 The acid labile group in is preferably an acid labile group (2a). R 2 is a hydrogen atom or a group represented by formula (2a), or two R2 Together, It is preferable that the group has a cetal ring structure, and the group is a hydrogen atom or two R 2 More preferably, these are taken together to form a group having an acetal ring structure. Ar 1 is an aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent. Preferably, it is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. It is more preferable that the aromatic hydrocarbon group has 6 to 18 carbon atoms, and it is even more preferable that the aromatic hydrocarbon group has 6 to 18 carbon atoms. It is more preferable that the aromatic hydrocarbon group is an aromatic hydrocarbon group having 10 to 10 carbon atoms, and it ... is even more preferred. Ar 2 is an aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent. Preferably, it is an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. It is more preferable that the aromatic hydrocarbon group has 6 to 18 carbon atoms, and it is even more preferable that the aromatic hydrocarbon group has 6 to 18 carbon atoms. An aromatic hydrocarbon group having 10 to 10 carbon atoms is more preferred, and a benzenediyl group, a benzene It is even more preferably a benzenetriyl group or a benzenetetrayl group, and benzenediyl It is even more preferred that the aryl group is a benzenetriyl group or a benzenetriyl group. n is preferably 1 or 2, and more preferably 2. -OR 2 Ar 2 The bond position in X 2 The bond positions are о, m, and p. Either is fine. X 2 is preferably -CO-O-*, -O-* or -O-CO-*, and -CO It is more preferably -O-* or -O-*. Resin (A) is R 2When the structural unit (I) is a hydrogen atom, R 2 is a hydrogen atom The amount of the structural unit (I) is preferably 40 to 100 mol based on the total amount of the structural unit (I). %, more preferably 60 to 100 mol %, and even more preferably 100 mol %. be.

[0022] Examples of the structural unit (I) include the following structural units: The structural units (I-1) to (I-14), the structural units (I-17) to (I -20), Structural Unit (I-25) ~ Structural Unit (I-28), Structural Unit (I-33) ~ Structural The structural units (I-58), (I-67) to (I-92) are preferred, and the structural units (I-1)~Structural unit (I-8), structural unit (I-13), structural unit (I-14), structural Unit (I-17) ~ Structural Unit (I-20), Structural Unit (I-25) ~ Structural Unit (I-28) ), structural unit (I-33) ~ structural unit (I-58), structural unit (I-67), structural unit ( I-68), structural unit (I-71), structural unit (I-72), structural unit (I-81), structural The structural unit (I-82) is more preferred. TIFF2025169323000021.tif204155

[0023] TIFF2025169323000022.tif252156

[0024] TIFF2025169323000023.tif176158

[0025] TIFF2025169323000024.tif5975

[0026] TIFF2025169323000025.tif237165

[0027] TIFF2025169323000026.tif97152

[0028] TIFF2025169323000027.tif105157

[0029] TIFF2025169323000028.tif108163

[0030] TIFF2025169323000029.tif114165

[0031] Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I- 11), formula (I-13), formula (I-15), formula (I-17), formula (I-19), formula (I- 21), formula (I-23), formula (I-25), formula (I-27), formula (I-29), formula (I- 31), formula (I-33), formula (I-35), formula (I-37), formula (I-39), formula (I- 41), formula (I-43), formula (I-45), formula (I-47), formula (I-49), formula (I- 51), formula (I-53), formula (I-55) to formula (I-70), formula (I-71), formula (I- 73), formula (I-75), formula (I-77), formula (I-79), formula (I-81), formula (I- 83), Equation (I-85), Equation (I-87), Equation (I-89), and Equation (I-91), respectively. In the structural unit represented by R 1 A structural unit in which the hydrogen atom corresponding to , and formula (I-2), formula (I-4), formula (I-6), formula (I-8), formula (I-10) , Formula (I-12), Formula (I-14), Formula (I-16), Formula (I-18), Formula (I-20) , Formula (I-22), Formula (I-24), Formula (I-26), Formula (I-28), Formula (I-30) , Formula (I-32), Formula (I-34), Formula (I-36), Formula (I-38), Formula (I-40) , Formula (I-42), Formula (I-44), Formula (I-46), Formula (I-48), Formula (I-50) , Formula (I-52), Formula (I-54), Formula (I-72), Formula (I-74), Formula (I-76) , Equation (I-78), Equation (I-80), Equation (I-82), Equation (I-84), Equation (I-86) In the structural units represented by formula (I-88), formula (I-90), and formula (I-92), Te, R 1 The structural unit in which the methyl group corresponding to the structural unit (I) is replaced by a hydrogen atom is also called structural unit (I). These include:

[0032] The content of the structural unit (I) in the resin (A) is preferably 3 to 80% based on the total structural units. mol %, more preferably 5 to 60 mol %, and even more preferably 5 to 55 mol % More preferably, it is 5 to 50 mol %. The resin (A) may contain only one type of structural unit (I), or two types of structural units (I). It may include the above.

[0033] <Structural unit (a1-1) and structural unit (a1-2)> The structural unit (a1-1) and the structural unit (a1-2) are represented by the following formulas. TIFF2025169323000030.tif4499 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or -O-(CH2) k1 -CO-O represents -, k1 represents an integer of 1 to 7, and * represents the bonding site with -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 are each independently an alkyl group having 1 to 8 carbon atoms, an alkyl group having 2 to 8 carbon atoms, alkenyl group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms or represents a group 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.

[0034] R a4 and R a5 is preferably a methyl group. L a1 and L a2 is preferably an oxygen atom or —O—(CH2) k01 -CO-O- (wherein k01 is preferably an integer of 1 to 4, more preferably 1) ), more preferably an oxygen atom. R a6 and R a7 Alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups The hydrogen group and the group formed by combining these groups include R a1 , R a2 and R a3 Listed in Examples of the groups include the same groups as those that can be used to form the alkyl groups. 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 a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, Preferred is an ethyl group, an isopropyl group, or a t-butyl group. R a6 and R a7 The alkenyl group in the formula (I) is preferably an alkenyl group having 2 to 6 carbon atoms. and more preferably an ethenyl group, a propenyl group, an isopropenyl group, or a butenyl group. do. R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 5 to 12, and more preferably Preferably 5 to 10. R a6 and R a7 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 12, and more preferably Preferably 6 to 10. The group in which an alkyl group and an alicyclic hydrocarbon group are combined is The total number of carbon atoms in combination with the group is preferably 18 or less. The group in which an alkyl group and an aromatic hydrocarbon group are combined is The total number of carbon atoms in combination with the group is preferably 18 or less. R a6 and R a7 are each independently preferably an alkyl group having 1 to 6 carbon atoms, It is preferably an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group. butyl group, ethyl group, isopropyl group, t-butyl group, ethenyl group, phenyl group or naphthyl group and more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, or is a phenyl group. 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 an integer of 0 to 2, more preferably 0 or 1. .

[0035] 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 -1-7) and R in the structural unit (a1-1) a4 In accordance with Structural units in which the corresponding methyl group is replaced with a hydrogen atom are preferred, and those represented by the formulae (a1-1-1) to (a1-1-2) are A structural unit represented by any one of (a1-1-4) is more preferred. TIFF2025169323000031.tif41169

[0036] The content of the structural unit (a1-1) in the resin (A) is preferably 1:1 based on the total structural units. The content is preferably from 1 to 60 mol %, more preferably from 1 to 55 mol %, and even more preferably from 2 to 55 % by mole, and even more preferably 2 to 50 mol %.

[0037] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to formula (a1-2-12): R in the structural unit (a1-2) and the structural unit (a1-2) a5 The methyl group corresponding to The structural units in which elementary atoms are replaced include formula (a1-2-2), formula (a1-2-5), Represented by any one of formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-12) The structural unit is preferably JPEG2025169323000032.jpg65157

[0038] The content of the structural unit (a1-2) in the resin (A) is preferably 5% by weight based on the total amount of the structural units. The content is preferably 10 to 70 mol %, more preferably 10 to 65 mol %, and even more preferably 15 to 65 mol %. It is preferably 65 mol %, and even more preferably 15 to 60 mol %. The total content of the structural unit (a1-1) and the structural unit (a1-2) is the total content of the structural unit (a1-1) and the structural unit (a1-2) in the entire structure of the resin (A). It is usually 10 to 95 mol %, preferably 15 to 80 mol %, based on the unit. Preferably, it is 15 to 75 mol %, more preferably 20 to 70 mol %, and further preferably More preferably, it is 25 to 65 mol %.

[0039] The resin (A) of the present invention comprises the structural unit (I), the structural unit (a1-1) and the structural unit (a1- The polymer may contain one or more structural units other than the structural unit (I), the structural unit (2). The structural units other than the structural unit (a1-1) and the structural unit (a1-2) include the structural unit (I), the structural unit (II), the structural unit (III), the structural unit (IV ... A structural unit having an acid labile group other than the structural unit (a1-1) and the structural unit (a1-2) (hereinafter referred to as "structural unit") structural unit (a1)) other than a structural unit having an acid labile group a structural unit having a halogen atom (hereinafter sometimes referred to as "structural unit (a4)"); A structural unit other than structural unit (I) that does not have an acid labile group (hereinafter referred to as "structural unit (s)") a structural unit having a non-leaving hydrocarbon group (hereinafter sometimes referred to as "structural unit (a5)"); Here, the acid labile group has a leaving group and is released upon contact with an acid. A group that forms a hydrophilic group (e.g., a hydroxy group or a carboxy group) upon elimination. do.

[0040] <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. TIFF2025169323000033.tif2298[In formula (1), R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 8 carbon atoms. , an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an alicyclic hydrocarbon group having 6 to 18 carbon atoms represents an aromatic hydrocarbon group or a group consisting of these groups, or R a1 and R a2are combined with each other Together with the carbon atom to which they are bonded, they form an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * denotes a binding site.] TIFF2025169323000034.tif2378[In formula (2), R a1’ and R a2’ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms, represents a hydrocarbon group of 2, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ Reach BiR a3’ are bonded to each other and together with the carbon atoms to which they are bonded and X, form a group having 3 to 20 carbon atoms. A heterocyclic group is formed, and -CH2- contained in the hydrocarbon group and the heterocyclic group is -O- or - May be replaced with S-. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * denotes a binding site.]

[0041] R a1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, or a propyl group. Examples of the alkyl group include an alkyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alkenyl group in the formula (I) is an ethenyl group or a propenyl group. , isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl Examples of the octynyl group include hexenyl, heptenyl, octynyl, isooctynyl, and nonenyl groups. can be done. R a1 , R a2 and R a3The alicyclic hydrocarbon group in Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, ... Examples of cycloalkyl groups include cycloheptyl and cyclooctyl groups. Examples of the hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups: (* indicates a bonding site.) a1 , R a2 and R a3 Alicyclic hydrocarbons The group preferably has 3 to 16 carbon atoms. TIFF2025169323000035.tif10159R a1 , R a2 and R a3 The aromatic hydrocarbon group in aryl groups such as an anthryl group, a biphenyl group, and 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., methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) , cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl alkylcycloalkyl groups or cycloalkylalkyl groups such as phenylethyl groups), benzyl Aralkyl groups such as alkyl groups, 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.), alicyclic hydrocarbon groups Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) and the like), and aryl-cycloalkyl groups such as phenylcyclohexyl group. Preferably, ma is 0 and na is 1. Ra1 and R a2 -C(R a1 )(R a2 )(R a3 The alicyclic hydrocarbon group preferably has 3 carbon atoms. ~12. * indicates the bonding site with -O-. TIFF2025169323000036.tif30138

[0042] R a1’ , R a2’ and R a3’ The hydrocarbon group in the Examples of the alkyl group include a hydroxyl group, an aromatic hydrocarbon group, and a group formed by combining these groups. can be done. The alkyl group and the alicyclic hydrocarbon group are represented by R a1 , R a2 and R a3 The same groups as those listed in Examples include: Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples include aryl groups such as 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., methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) , cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl alkylcycloalkyl groups or cycloalkylalkyl groups such as phenylethyl groups), benzyl Aralkyl groups such as alkyl groups, 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.), alicyclic hydrocarbon groups Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) and aryl-cycloalkyl groups such as phenylcyclohexyl group. R a2’ and R a3’ are bonded to each other and together with the carbon atoms to which they are bonded and X, When forming a cyclic group, -C(R a1’ )(R a2’ )-XR a3’ Examples of the groups include the following: * indicates a binding site. TIFF2025169323000037.tif18124R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0043] 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 n A group where a=1. As the group, a tert-butoxycarbonyl group is preferred. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamannes Forms a methyl 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, and R a3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following: * represents a binding site. TIFF2025169323000038.tif171163

[0044] Specific examples of group (2) include the following groups: * represents a binding site. TIFF2025169323000039.tif68162

[0045] 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.

[0046] Among the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of the compound having a bulky structure such as an alicyclic hydrocarbon group include: 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.

[0047] As the structural unit derived from a (meth)acrylic monomer having the group (1), preferably , a structural unit represented by formula (a1-0) (hereinafter, may be referred to as structural unit (a1-0) These may be used alone or in combination of two or more. TIFF2025169323000040.tif4638[In formula (a1-0), L a01 is -O- or * -O-(CH2) k1 represents -CO-O-, and k1 is an integer from 1 to 7. * indicates the bonding site with -CO-. R a01 represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 are each independently an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof represents a group.]

[0048] R a01 is preferably a methyl group. L a01 is preferably an oxygen atom or —O—(CH2) k01 -CO-O- (but k01 is preferably an integer of 1 to 4, more preferably 1. An oxygen atom is preferred. R a02 , R a03 and R a04 The alkyl group includes methyl, ethyl, propyl, n n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. It can be obtained. R a02 , R a03 and R a04 The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclohexyl group. cycloalkyl groups such as cyclobutyl and cyclooctyl groups. The groups include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents the binding site.) etc. a02 , R a03 and R a04 The carbon of the alicyclic hydrocarbon group The prime number is preferably 3 to 16. TIFF2025169323000041.tif11165R a02 , R a03 and R a04 Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an aryl group, and an aryl group. Examples of the aryl groups include tolyl, biphenyl, and phenanthryl groups. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) , cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl alkylcycloalkyl groups or cycloalkylalkyl groups such as phenylethyl groups), benzyl Aralkyl groups such as alkyl groups, 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.), alicyclic hydrocarbon groups Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) and the like), and aryl-cycloalkyl groups such as phenylcyclohexyl 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. R a02 , R a03 and R a04 The aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, More preferably, it is 6 to 10. The group in which an alkyl group and an alicyclic hydrocarbon group are combined is The total number of carbon atoms in combination with the group is preferably 18 or less. The group in which an alkyl group and an aromatic hydrocarbon group are combined is The total number of carbon atoms in combination with the group is preferably 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms. It is a hydrocarbon group, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group. do. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. be.

[0049] Examples of the structural unit (a1-0) include those represented by the formulae (a1-0-1) to (a1-0-18): and R in the structural unit (a1-0) a01 The equivalent The structural units in which a methyl group is replaced with a hydrogen atom include those represented by the formula (a1-0-1) to the formula (a1- 0-10), formula (a1-0-13), or formula (a1-0-14) Position is preferred. TIFF2025169323000042.tif98165

[0050] When the resin (A) contains the structural unit (a1-0), its content is determined based on the total structural units of the resin (A). It is usually 5 to 60 mol %, preferably 5 to 50 mol %, more preferably The content is usually 10 to 40 mol %.

[0051] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of such structural units include those (hereinafter, may be referred to as "structural unit (a1-4)"). TIFF2025169323000043.tif4868[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1-6 alkyl group optionally having a halogen atom represents an alkyl group represented by the formula: R a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxy group having 2 to 12 carbon atoms Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms It represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a30 is a single bond or * -X a31 -(A a32 -X a32 ) nc - represents -R a32 is combined represents the bonding site with the carbon atom. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O- or -O-CO-. nc represents 0 or 1. Ia represents an integer of 0 to 4. When Ia is an integer of 2 or more, R in Numbers a33 may be the same or different from each other. 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 -CH2- contained in the alkyl group and the divalent hydrocarbon group is replaced by -O- or -S-. That's fine.]

[0052] 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: R a32 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-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, phenyl group fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, ethyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples include pentyl, pentyl, hexyl and perfluorohexyl groups. R a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is more preferably an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, or the like. Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. can be done. R a33 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an isopropyl ... Propoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group The alkoxy group includes an alkoxy group having 1 to 4 carbon atoms. A methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. R a33 The alkoxyalkyl group in the formula (I) is a methoxymethyl group or an ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples of the alkoxyalkyl group include a methyl group and a tert-butoxymethyl group. An alkoxyalkyl group having 2 to 8 carbon atoms is preferred, and a methoxymethyl group or an ethoxyethyl group is more preferred. A methoxymethyl group is more preferred. R a33The alkoxyalkoxy group in the formula (I) is a methoxymethoxy group, a methoxyethoxy group, oxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxy group butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy The alkoxyalkoxy group is an alkoxyalkoxy group having 2 to 8 carbon atoms. A koxy group is preferred, and a methoxyethoxy group or an ethoxyethoxy group is more preferred. R a33 The alkylcarbonyl group in the formula (I) includes an acetyl group, a propionyl group, and a butyl group. The alkylcarbonyl group is an alkylcarbonyl group having 2 to 3 carbon atoms. is preferred, and an acetyl group is more preferred. R a33 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, or The alkylcarbonyloxy group includes a hydroxyl group and a butyryloxy group. An alkylcarbonyloxy group having 2 to 3 carbon atoms is preferred, and an acetyloxy group is more preferred. R a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, a An alkoxy group or an alkoxyalkoxy group having 2 to 8 carbon atoms is preferred, and a fluorine atom, an iodide atom, a hydrogen atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxy group A methoxy group is more preferred, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, More preferred are methoxy and ethoxyethoxy groups.

[0053] *-X a31 -(A a32 -X a32 ) nc - includes *-O-, *-CO-O-, *-OC O-, *-CO-OA a32 -CO-O-, *-O-CO-Aa32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO-, Among them, *-CO-O- and *-CO-OA are a32 -CO-O- or *- Office Automation a32 -CO-O- is preferred.

[0054] A a32 The alkanediyl group in the formula (I) includes a methylene group, an ethylene group, 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-methyl Propane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, 4-diyl group and 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[0055] A a30 is a single bond, *-CO-O- or *-CO-OA a32 -CO-O- Preferably, it is a single bond, *-CO-O-, or *-CO-O-CH2-CO-O-. A single bond or *-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred.

[0056] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 , R a35 and R a36 The hydrocarbon group in the formula (I) may be an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups combining these groups. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a methyl group. Examples include a sil group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the cyclopentyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, butyl group, adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include: TIFF2025169323000044.tif11150Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples include aryl groups such as 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., methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) , cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl alkylcycloalkyl groups or cycloalkylalkyl groups such as phenylethyl groups), benzyl Aralkyl groups such as alkyl groups, 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.), alicyclic hydrocarbon groups Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) and the like), and aryl-cycloalkyl groups such as phenylcyclohexyl groups. , R a36 Examples of the alkyl group include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, Aromatic hydrocarbon groups having 6 to 18 carbon atoms or groups formed by combining these Examples include:

[0057] R a34 is preferably a hydrogen atom. R a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a It is an alicyclic hydrocarbon group, more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, a Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is a group formed by an alkyl group having 1 to 18 carbon atoms, a group formed by an alkyl group having 3 to 1 carbon atoms, R is an alicyclic hydrocarbon group having 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. a36 Archi in 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. -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid), it is eliminated to form a hydroxy group. -OC(R a34 )(R a35 )-OR a36 is attached to the o- or p-position of the benzene ring It is preferable that the bond is at the p-position, and it is more preferable that the bond is at the p-position.

[0058] Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a1-4-1) to formula (a1-4-2) are preferred. -4-18) and R in the structural unit (a1-4) a32 to The structural unit in which the corresponding hydrogen atom is replaced by a methyl group is preferred, and more preferred is a structural unit represented by the formula ( a1-4-1) ~ Formula (a1-4-5), Formula (a1-4-10), Formula (a1-4-13), Examples of structural units are those represented by formula (a1-4-14). TIFF2025169323000045.tif103167

[0059] When the resin (A) has the structural unit (a1-4), the content thereof is determined based on the total structure of the resin (A). It is preferably 1 to 60 mol %, more preferably 2 to 50 mol %, based on the total of the structural units. It is more preferable that the content is 3 to 40 mol %.

[0060] The structural unit derived from a (meth)acrylic monomer having the group (2) includes a structural unit represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can be. TIFF2025169323000046.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 atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 represents the binding site 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.

[0061] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms 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 include the methyl 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 Among these, it is preferred that one is —O— and the other is —S—. s1 is preferably 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or —CH2—CO—O—.

[0062] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers of formula (a1-5-1) to formula (a1-5- 4), and the structural units represented by formula (a1-5-1) or formula (a1-5-2) are preferred. ) is more preferred. TIFF2025169323000047.tif31130

[0063] When the resin (A) has the structural unit (a1-5), the content thereof is determined based on the total structure of the resin (A). The content is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %, based on the structural units. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0064] Further, examples of the structural unit (a1) include the following structural units. TIFF2025169323000048.tif28163

[0065] When the resin (A) contains the above structural unit, the content thereof is The content is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %. More preferable.

[0066] Further, examples of the structural unit (a1) include the following structural units. TIFF2025169323000049.tif5296 When resin (A) contains structural units such as (a1-6-1) to (a1-6-3) above The content thereof is preferably 10 to 60 mol % based on the total structural units of the resin (A), and more preferably 15 to 60 mol %. More preferably, the content is 20 to 55 mol %, even more preferably, 20 to 50 mol %, and 20 to 45 mol %. It is even more preferable, and 20 to 40 mol % is particularly preferable.

[0067] <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 without 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 not having an 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, This can improve the resolution of the resist pattern and the adhesion to the substrate.

[0068] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may also be a hydroxyl group. When a resist pattern is produced from the resist composition of the present invention, KrF is used as the exposure light source. High energy rays such as excimer laser (248 nm), electron beam, or EUV (extreme ultraviolet) are used. In this case, the structural unit (a2) may be 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 an ArF excimer laser (193 nm) or the like is used, 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.

[0069] The structural unit (a2) having a phenolic hydroxy group is a structural unit of the formula (a 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") can be done. TIFF2025169323000050.tif4652[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 hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxy group having 2 to 12 carbon atoms Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms It represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - represents -R a50 is 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, multiple R in Numbers a51 may be the same or different.]

[0070] R a50 and R a51 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: R a50 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-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, phenyl group fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, ethyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples include pentyl, pentyl, hexyl and perfluorohexyl groups. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is more preferably an ethyl group, and even more 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, or the like. Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group or an ethyl group. A methyl group is more preferred. R a51 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an isopropyl ... Examples include a propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and is preferably a methoxy group or an ethoxy group. More preferred is a methoxy group. R a51 The alkoxyalkyl group in the formula (I) is a methoxymethyl group or an ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples of the alkoxyalkyl group include a methyl group and a tert-butoxymethyl group. An alkoxyalkyl group having 2 to 8 carbon atoms is preferred, and a methoxymethyl group or an ethoxyethyl group is more preferred. A methoxymethyl group is more preferred. R a51 The alkoxyalkoxy group in the formula (I) is a methoxymethoxy group, a methoxyethoxy group, oxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxy group butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy The alkoxyalkoxy group is an alkoxyalkoxy group having 2 to 8 carbon atoms. A koxy group is preferred, and a methoxyethoxy group or an ethoxyethoxy group is more preferred. R a51 The alkylcarbonyl group in the formula (I) includes an acetyl group, a propionyl group, and a butyl group. The alkylcarbonyl group is an alkylcarbonyl group having 2 to 3 carbon atoms. is preferred, and an acetyl group is more preferred. R a51 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, or The alkylcarbonyloxy group includes a hydroxyl group and a butyryloxy group. An alkylcarbonyloxy group having 2 to 3 carbon atoms is preferred, and an acetyloxy group is more preferred. R a51 is a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, a An alkoxy group or an alkoxyalkoxy group having 2 to 8 carbon atoms is preferred, and a fluorine atom, an iodide atom, a hydrogen atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxy group A methoxy group is more preferred, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, More preferred are methoxy and ethoxyethoxy groups.

[0071] *-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 a52 -CO-O- or *- Office Automation a52 -CO-O- is preferred.

[0072] A a52 The alkanediyl group in the formula (I) includes a methylene group, an ethylene group, 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-methyl Propane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, 4-diyl group and 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group.

[0073] A a50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- Preferably, it is a single bond, *-CO-O-, or *-CO-O-CH2-CO-O-. A single bond or *-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred.

[0074] mb is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. The hydroxy group is preferably bonded to the o- or p-position of the benzene ring, and more preferably to the p-position. It is more preferable to combine them.

[0075] 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 Japanese Patent Publication No. 12577.

[0076] The structural unit (a2-A) is represented by formula (a2-2-1) to formula (a2-2-16). In the structural units represented by formulas (a2-2-1) to (a2-2-16), R in structural unit (a2-A) a50 The structure 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), a structural unit represented by formula ( a2-2-8) and structural units represented by formulas (a2-2-12) to (a2-2-14) In the structural units represented by the formula (a2-A) and the structural units represented by the formula (a2-A), R a50 It is preferable that the structural unit is a structural unit in which a methyl group corresponding to the following formula is substituted with a hydrogen atom: TIFF2025169323000051.tif57169

[0077] Content of structural unit (a2-A) when structural unit (a2-A) is contained in resin (A) is preferably 1 to 80 mol %, more preferably 3 to 70 mol %, based on all structural units. %, more preferably 5 to 60 mol %, and even more preferably 10 to 50 It is in mole percent. The structural unit (a2-A) can be prepared by, for example, polymerizing the structural unit (a1-4) and then reacting the polymer with p-toluenesulfonyl ether. It can be incorporated into the resin (A) by treating it with an acid such as enesulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0078] The structural unit (a2) having an alcoholic hydroxy group includes a structural unit represented by the formula ( a2-1) (hereinafter referred to as "structural unit (a2-1)") Examples include: TIFF2025169323000052.tif4359 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 represents -CO-O-, k2 represents an integer 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 between 0 and 10.

[0079] In equation (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0080] 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 exemplified. ), and structural units represented by any one of formulas (a2-1-1) to (a2-1-4) are preferred. The structural unit represented by formula (a2-1-1) or formula (a2-1- The structural unit represented by 3) is more preferred. TIFF2025169323000053.tif49136

[0081] When the resin (A) contains the structural unit (a2-1), its content is determined based on the total amount of all structural units in the resin (A). It 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 %.

[0082] <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 condensed ring of a monocyclic lactone ring with another ring. Preferably, the ring is 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:

[0083] The structural unit (a3) ​​is preferably a structural unit 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. TIFF2025169323000054.tif52157 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or -O-(CH2) k3 -C It represents a group represented by OO-(k3 represents an integer of 1 to 7). L a7 -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- vinegar. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding position with the carbonyl group. R a18 , Ra19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is 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 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 are each independently a carboxy group, a cyano group or a carbon atom. It represents an aliphatic hydrocarbon group having 1 to 4 prime numbers. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 may be the same or different.]

[0084] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in butyl, sec-butyl and tert-butyl groups. Examples include alkyl groups such as t-butyl groups. R a24 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine. Examples include atoms. R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Preferably, the alkyl group has 1 to 4 carbon atoms, and more preferably, the methyl group. or an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group Examples include a methyl group and a triiodomethyl group.

[0085] L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane group, or a methyl group. Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pe 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, pentaerythritol Examples include 2-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

[0086] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferred or -O- or *-O-(CH2) k3 In -CO-O-, k3 is any one of 1 to 4 A group in which each of the integers is 0 or 1, more preferably -O- and *-O-CH2-CO-O-, even more preferably Preferably it is an oxygen atom. R a18 ~R a21 is preferably a methyl group. Ra22 and R a23 are each independently preferably a carboxy group, a cyano group or a methyl group. It is a methyl group. p1, q1, and r1 each independently represent an integer of preferably 0 to 2, More preferably, it is 0 or 1.

[0087] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a 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-CH2-CO-O- or -O-C2H4-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)'. TIFF2025169323000055.tif4052(in the formula, R a24 , L a7 has the same meaning as above.)

[0088] The structural unit (a3) ​​may be a monomer described in JP-A-2010-204646. , the monomers described in JP-A-2000-122294, and JP-A-2012-41274 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 formula (a3-1) to formula (a3-2) R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to Structural units that replace elementary atoms are preferred.

[0089] TIFF2025169323000056.tif117168

[0090] When the resin (A) contains the structural unit (a3), the total content of the structural unit (a3) ​​is the total content of all structural units of the resin (A). It is usually 1 to 70 mol %, preferably 3 to 65 mol %, more preferably The content is usually 5 to 60 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) The content of the units (a3-4) is 1 to 60 moles relative to the total structural units of the resin (A). % by mole, more preferably 3 to 50 mol %, and even more preferably 5 to 50 mol %.

[0091] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025169323000057.tif3064[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 halogen atom, The —CH2— contained in the radical may be replaced by —O— or —CO—. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group. Examples of the hydrocarbon group include hydrocarbon groups and groups formed by combining these groups.

[0092] 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 a decyl group, a heptadecyl group, and an octadecyl group. 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 aliphatic groups such as adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include cyclic saturated hydrocarbon groups. TIFF2025169323000058.tif10146 The group formed by the combination may include one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic saturated hydrocarbon groups. -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkanediyl group Examples include an -alkanediyl group, -alicyclic saturated hydrocarbon group, and -alkyl group.

[0093] The structural unit (a4) may be a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), and a structural unit represented by formula (a4-4). TIFF2025169323000059.tif4350[In formula (a4-0), R 54 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 a fluorocycloalkanediyl group. R 64 represents a hydrogen atom or a fluorine atom.

[0094] L 4a The alkanediyl group in the formula (I) includes a methylene group, an ethylene group, a propane-1, linear alkanediyl groups such as butane-1,3-diyl and butane-1,4-diyl; -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane Branched alkanes such as pan-1,3-diyl and 2-methylpropane-1,2-diyl groups An example is a diyl group.

[0095] L 3a The perfluoroalkanediyl group in Fluoroethylene group, perfluoroethylfluoromethylene 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 perfluorocyclopentanediyl group, perfluorocycloheptanediyl group yl group, perfluoroadamantanediyl group, and the like.

[0096] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond, bond, a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably or a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0097] The structural unit (a4-0) may be the following structural unit or a structural unit ( a4-0) in R 54 The structural unit in which the methyl group corresponding to can be. TIFF2025169323000060.tif97168

[0098] TIFF2025169323000061.tif4867[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, The -CH2- contained in the hydrocarbon group may be replaced with -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 The group has a halogen atom (preferably a fluorine atom). TIFF2025169323000062.tif1489 [In formula (a-g1), s represents 0 or 1. Aa42 and A a44 are each independently a divalent group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 represents a single bond or a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. Represents. X a41 and X a42 are each independently -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 binding site, and the * on the right is -O-CO-R a42 ]

[0099] R a42 The saturated hydrocarbon group in the formula (I) includes a chain hydrocarbon group and a monocyclic or polycyclic saturated alicyclic group. and groups formed by combining these.

[0100] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include a decyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic saturated alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups; Polycyclic aliphatic groups such as adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include cyclic hydrocarbon groups. TIFF2025169323000063.tif10159The 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. -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkanediyl group Examples include an alkyl group, -alkanediyl group-saturated alicyclic hydrocarbon group-alkyl group, and the like.

[0101] R a42 The substituents of the compound (a-g1) are a halogen atom and a group represented by formula (a-g3): The halogen atom may be at least one selected from the group consisting of fluorine, Examples of the fluorine atom include a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. TIFF2025169323000064.tif855[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * denotes R a42 represents the binding site with However, R a42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a4 5 represents a saturated hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom.

[0102] A a45 The saturated hydrocarbon group in the formula (I) is a methyl group, an ethyl group, a propyl group, or a butyl group. , pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadeca alkyl groups such as cyclohexyl, hexadecyl, heptadecyl and octadecyl groups; monocyclic alicyclic groups such as butyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; Hydrocarbon groups; and decahydronaphthyl groups, adamantyl groups, norbornyl groups, and the following groups: and polycyclic and alicyclic hydrocarbon groups such as the group (* represents a bonding site). TIFF2025169323000065.tif10159The 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. -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0103] 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) 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. It is preferably a saturated hydrocarbon group having a fluorocarbon group, more preferably a perfluoroalkyl 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 fluoro groups include perfluoromethyl, perfluoroethyl, and perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples of perfluorocycloalkyl groups include perfluoroheptyl and perfluorooctyl groups. Examples of the cyclohexyl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3) and 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.

[0104] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 Yes, More preferred is a group represented by formula (a-g2). TIFF2025169323000066.tif872[In formula (a-g2), A a46 represents 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 The binding site represent.). A a47 represents a saturated 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 bonding site with the carbonyl group.]

[0105] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. A a47 The saturated hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and Aa 47 is more preferably a cyclohexyl group or an adamantyl group.

[0106] A preferred structure of the group represented by formula (a-g2) is the following structure (* indicates a carbonyl group): (This is the binding site for ATP). TIFF2025169323000067.tif14160

[0107] A a41 The alkanediyl group in the formula (I) includes 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 2-methylbutane-1,4-diyl. do. A a41 The substituents in the alkanediyl group represented by the formula (I) include a hydroxy group and an alkanediyl group having 1 to 10 carbon atoms. Examples thereof include the alkoxy group of 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.

[0108] A in the group represented by formula (a-g1) a42 , A a43 and A a44 represents the divalent saturated hydrocarbon The element groups include linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated hydrocarbon groups. and a divalent alicyclic saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon groups include methylene groups, ethylene groups, polypropylene groups, and the like. propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2- Examples include a methylpropane-1,2-diyl group. 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. Preferably, s is 0.

[0109] 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: ** indicates the binding site, and ** indicates -O-CO-R a42 This is the binding site for TIFF2025169323000068.tif46140

[0110] The structural unit represented by formula (a4-1) includes the following structural units and 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: TIFF2025169323000069.tif95140

[0111] TIFF2025169323000070.tif132150

[0112] The structural unit represented by formula (a4-1) includes a structural unit represented by formula (a4-2) and Examples of the structural unit include those represented by formula (a4-3). TIFF2025169323000071.tif4459[In formula (a4-2), Rf5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and —C H2- 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 maximum total carbon number is 21.]

[0113] L 44 The alkanediyl group having 1 to 6 carbon atoms is A a41 The same groups as those exemplified in can be. R f6 The saturated hydrocarbon group of R 42 Examples of the groups include the same groups as those exemplified in L 44 The alkanediyl group in the formula (I) is preferably an alkanediyl group having 2 to 4 carbon atoms. An ethylene group is more preferred.

[0114] Examples of the structural unit represented by formula (a4-2) include those represented by formula (a4-1-1) to formula (a4 -1-11) are structural units represented by the structural unit (a4-2). R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It is one of the structural units.

[0115] TIFF2025169323000072.tif5974[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 represents *-O-CO- or *-CO-O- (* represents A f13 represents the binding site 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 a molecule is limited to 20.

[0116] L 5 The alkanediyl group in a41 The same as those exemplified for the alkanediyl group The following groups are mentioned:

[0117] A f13 The divalent saturated hydrocarbon group optionally having a fluorine atom in or a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent chain saturated hydrocarbon group which may have a fluorine atom It is a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanediyl group. It is a aryl group. The divalent chain saturated hydrocarbon group which may have a fluorine atom includes a methylene group, an ethylene group, alkanediyl groups such as ethylene, propanediyl, butanediyl, and pentanediyl groups; ;Difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoroalkanes such as perfluorobutanediyl and perfluoropentanediyl groups Examples thereof include a diyl group. The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. The monocyclic group may be a cyclohexanediyl group or a perfluorocyclohexane group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and the like. Examples thereof include a nandiyl group and a perfluoroadamantanediyl group.

[0118] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are 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 groups, cyclopropylmethyl groups, cyclopropyl groups , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantine A methyl group is preferred.

[0119] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group is a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and a carbon A group containing a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms is preferred, and a divalent chain having 2 to 3 carbon atoms is preferred. Saturated hydrocarbon groups of the formula are more preferred. A f14 The saturated hydrocarbon group is a chain saturated hydrocarbon group having 3 to 12 carbon atoms and a A group containing an alicyclic saturated hydrocarbon group such as the above is preferred, and a chain saturated hydrocarbon group having 3 to 10 carbon atoms and A group containing an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms is more preferred. f14 teeth , preferably a group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, more preferably Cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and a It is a damantyl group.

[0120] Examples of the structural unit represented by formula (a4-3) include those represented by formula (a4-1'-1) to formula (a 4-1'-11) are structural units represented by the following formulas. KerR f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-3). It is one of the structural units that can be mentioned.

[0121] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF2025169323000073.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -or-(CH2) j4 - CO-O-(CH2) 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.]

[0122] R f22 The saturated hydrocarbon group of R a42 Examples include the saturated hydrocarbon groups represented by the following formula: .R f22 is an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, or a carbon atom having a fluorine atom An alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms and a fluorine atom is preferred. An alkyl group is more preferred, and an alkyl group having 1 to 6 carbon atoms and a fluorine atom is even more preferred. It's nice.

[0123] In formula (a4-4), A f21 As -(CH2) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0124] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by R in the structural unit (a4-4) f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced. TIFF2025169323000074.tif87162

[0125] When the resin (A) has the structural unit (a4), its content is determined based on the total structural units of the 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.

[0126] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) may be a straight-chain, branched or cyclic hydrocarbon group. Among these, 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 formula (a5-1): . TIFF2025169323000075.tif3553[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, The —CH2— contained in the formula may be replaced with —O— or —CO—.

[0127] 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 cyclopentyl group, and a cyclopentyl group. Examples of the polycyclic alicyclic hydrocarbon group include: , an adamantyl group, and a norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an isopropyl group. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group Examples of alkyl groups 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.

[0128] L 55The divalent saturated hydrocarbon group in the above is a divalent chain saturated hydrocarbon group and a divalent fatty acid group. Examples 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 propanediol group. alkanediyl groups such as butanediyl, pentanediyl, and the like. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adatom group. Examples include a mantanediyl group and a norbornanediyl group.

[0129] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. TIFF2025169323000076.tif18164 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 ) . L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, 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 x4represents 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 are each independently 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.

[0130] 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 Preferably, it is a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably 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.

[0131] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF2025169323000077.tif53136

[0132] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2025169323000078.tif23131

[0133] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2025169323000079.tif16145

[0134] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2025169323000080.tif26114

[0135] L 55is preferably a single bond or a group represented by formula (L1-1).

[0136] The structural unit (a5-1) includes the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to can be. TIFF2025169323000081.tif77158

[0137] TIFF2025169323000082.tif39159When the resin (A) has the structural unit (a5), its content is determined based on the total structural units of the 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.

[0138] <Structural unit (II)> The resin (A) further contains a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit”). The structural unit (II) may include, for example, Examples of the structural units include those described in JP-A-2016-79235, and those having a sulfonyl group in the side chain. A structural unit having a carboxylate group or a carboxylate group and an organic cation, or a sulfonate group in a side chain A structural unit having an aryl group and an organic anion is preferred.

[0139] A structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF2025169323000083.tif3189 [In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- contained in the saturated carbon may be replaced by -O-, -S- or -CO-. The hydrogen atom contained in the hydrogen hydride group is a halogen atom, a carbon number which may have a halogen atom It may be substituted with 1 to 6 alkyl groups or hydroxy groups. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the water contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. stomach. RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a group having 1 carbon atom which may have a halogen atom Represents an alkyl group of 1 to 6. ZA + represents an organic cation.

[0140] R III3 The halogen atom represented by the formula (I) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples include uron atoms. R III3 The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom is represented by the formula: R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by Examples include the same things. 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, and the like. , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples thereof include a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. do. A x1 In the above, the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted is , trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotetrafluoroethylene group Examples include a rt-butyl group, a perfluoropentyl group, and a perfluorohexyl group.

[0141] X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched hydrocarbon group. and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. It may be a combination of the above. 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; butane-1,3-diyl; 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentaerythritol Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohetane-1,3-diyl group, Cycloalkanediyl groups such as cyclohexan-1,4-diyl group and cyclooctane-1,5-diyl group divalent monocyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, ... Adamantane-2,5-diyl group, Adamantane-1,5-diyl group, Adamantane-2,6- Examples include divalent polycyclic alicyclic saturated hydrocarbon groups such as a diyl group.

[0142] -CH2- in saturated hydrocarbon groups is replaced with -O-, -S- or -CO- Examples of such groups include divalent groups represented by formulae (X1) to (X53). The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-. The number of carbon atoms in each of the preceding groups is 17 or less. In the following formula, * and ** represent binding sites. * is A x1 represents the binding site with TIFF2025169323000084.tif145161

[0143] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0144] ZA + Examples of the organic cation represented by the formula include organic onium cations, organic sulfonium cations, and the like. Thione, organic iodonium cation, organic ammonium cation, benzothiazolium cation Among these, organic sulfonium cations are preferred. Preferred are iodonium cations and organic iodonium cations, and arylsulfonium cations. More preferably, the compound represented by any one of formulas (b2-1) to (b2-4) described below is used. Examples of cations that can be used include:

[0145] The structural unit represented by formula (II-2-A') is a structural unit represented by formula (II-2-A) It is preferable that: JPEG2025169323000085.jpg37108 [In formula (II-2-A), R III3 , X III3 and ZA + has the same meaning as above. z represents an integer of 0 to 6; R III2 and R III4 are each independently a hydrogen atom, a fluorine atom, or a group having 1 carbon atom represents a perfluoroalkyl group having a number of 1 to 6, and when z is 2 or more, a plurality of R III2 and R II I4 may be the same or different from each other. Q a and Q b are each independently a fluorine atom or a perfluoroalkane having 1 to 6 carbon atoms. represents a alkyl group.]

[0146] R III2 , R III4 , Q a and Q b Perfluoroalkyl groups having 1 to 6 carbon atoms, represented by As the aryl group, the Q group described below b1 The same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by Examples include:

[0147] 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 . TIFF2025169323000086.tif5575 [In formula (II-2-A-1), R III2, R III3 , R III4 , Q a , Q b , z and ZA + has the same meaning as above represent. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and the saturated hydrocarbon group -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon The hydrogen atoms contained in the alkyl group may be substituted with halogen atoms or hydroxy groups.

[0148] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula include a methyl group, an ethyl group, and , propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and and dodecyl groups. X I2 As the divalent saturated hydrocarbon group represented by X III3 Divalent saturated carbon represented by The same as the hydrogen chloride group can be mentioned.

[0149] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). The structural unit is preferably TIFF2025169323000087.tif5287 [In formula (II-2-A-2), R III3 , R III5 and ZA + has the same meaning as above. m and nA each independently represent 1 or 2.]

[0150] Examples of the structural unit represented by formula (II-2-A') include the following structural units, RIII3 The group corresponding to the methyl group in the formula (I) is a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a halogen atom. an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom (for example, a trifluoromethyl group, etc.); ) and the structural units described in WO 2012 / 050015 ZA + represents an organic cation. TIFF2025169323000088.tif86163

[0151] The structural unit having a sulfonio group and an organic anion in the side chain is represented by formula (II-1-1): It is preferable that the structural unit is a structural unit that can be formed by the above-mentioned method. TIFF2025169323000089.tif3380[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 and R II3 are bonded to each other to form a ring with the sulfur atom to which they are attached. That's fine. R II4 is a hydrogen atom, a halogen atom, or a group having 1 to 10 carbon atoms which may have a halogen atom 6 represents an alkyl group. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I) include a phenylene group. and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group and an alicyclic hydrocarbon group. , 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 described above. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples include aryl groups such as 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 containing hydrogen hydride groups (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 iodide atom. Examples include elementary atoms. R II4 As an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by is R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by Some examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated carbon atom having 1 to 18 carbon atoms. The -CH2- contained in the divalent saturated hydrocarbon group may be -O-, -S- or may be replaced by -CO-. Specifically, X III3 The number of carbon atoms is 1 to 1 Examples thereof include the same divalent saturated hydrocarbon groups as those of 8.

[0152] Examples of the cation-containing structural unit in formula (II-1-1) include structural units represented by the following formulas: R II4 The group corresponding to the methyl group in the formula (I) is a hydrogen atom, a halogen atom (e.g., a fluorine atom), or An alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, trifluoromethyl Examples of such structural units include those in which the aryl group is replaced by a methyl group, etc. TIFF2025169323000090.tif88136

[0153] A - Examples of the organic anion represented by the formula include a sulfonate anion, a sulfonylimide anion, and Examples include sulfonylmethide anions, carboxylic acid anions, and the like. - is expressed as The organic anion is preferably a sulfonate anion, and examples of the sulfonate anion include those described below. Examples of the anion include the anion represented by formula (B1).

[0154] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2025169323000091.tif36136

[0155] Examples of sulfonylmethide anions include the following: TIFF2025169323000092.tif29123

[0156] Examples of carboxylate anions include the following: TIFF2025169323000093.tif51152

[0157] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2025169323000094.tif88149

[0158] When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 30 mol %, based on the total structural units of the fat (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0159] The resin (A) may have structural units other than the above-mentioned structural units. The moieties include structural units known in the art.

[0160] The resin (A) preferably comprises the structural unit (I), the structural unit (a1-1), and the structural unit (a1 -2), a resin comprising the structural unit (I) and the structural unit (a1-1), Resins comprising structural units (I) and structural units (a1-2), ), a resin comprising a structural unit (a1-2) and a structural unit (s), a resin comprising a structural unit (I) and a structural unit (s), A tree consisting of (a1-1), structural unit (a1-2), structural unit (a1) and structural unit (s) Resin, a resin comprising structural units (I), structural units (a1-1), and structural units (s), structural units a resin comprising the structural unit (I), the structural unit (a1-2), and the structural unit (s); Unit (a1-1), structural unit (a1-2), structural unit (s), structural unit (a4) and / or is a resin composed of the structural unit (a5), or the structural unit (I) and the structural unit (a1-1) and a resin consisting only of the structural unit (a1-2) and the structural unit (a4), and more preferably A resin comprising the structural unit (I), the structural unit (a1-1), and the structural unit (a1-2), A tree consisting of a position (I), a structural unit (a1-1), a structural unit (a1-2), and a structural unit (s) Fat, structural unit (I), structural unit (a1-1), structural unit (a1-2), and structural unit (a1) and a structural unit (s), a resin comprising a structural unit (I), a structural unit (a1-1) and a structural unit ( a resin consisting of structural units (I), (a1-2) and (s); It is a resin.

[0161] The structural unit (a1) is preferably the structural unit (a1-4). Preferably, at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3) The structural unit (a2) is preferably a structural unit (a2-1) and a structural unit (a2-A The structural unit (a3) ​​is preferably at least one selected from the group consisting of the formula ( a3-1), a structural unit represented by formula (a3-2), and a structural unit represented by formula (a3-4) The structural unit is at least one selected from the group consisting of structural units represented by the following formula:

[0162] The structural units constituting the resin (A) may be used alone or in combination of two or more. These structural units are derived from monomers by known polymerization methods (for example, radical polymerization). The content of each structural unit in the resin (A) can be determined by the ratio of the monomers used in the polymerization. This can be adjusted by the amount of mer used. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more). 0 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30, 000 or less, more preferably 15,000 or less). In this specification, the weight average molecular weight is determined by gel permeation chromatography. The gel permeation chromatography was carried out by the same method as in the examples. It can be measured by adjusting the analytical conditions.

[0163] <Compound (IA)> The compound of the present invention is a compound represented by formula (IA) (hereinafter referred to as "compound (IA)"). (There is a possibility that TIFF2025169323000095.tif6659[In formula (IA), R 1 represents a hydrogen atom or a methyl group. X 1 is a single bond or -CO-O-* (* is Ar 1 represents the bonding position with . X 2 -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH2) mm - O-* or -O-(CH2) nn -CO-O-* (* indicates the bonding position to the benzene ring. ) mm and nn represent 0 or 1. Ar 1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. R 3 and R 4 each independently represents a hydrogen atom or an acid labile group, or R 3 and R 4 One They may be combined to form a group having an acetal ring structure. R 5 is a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. The —CH2— contained in the alkyl group and the fluoroalkyl group represents —O— or — It may be replaced by CO-. n' represents an integer of 0 to 3, and when n' is 2 or more, a plurality of R 5 are the same as each other They may be the same or different.] The compound represented by formula (IA) includes a compound represented by formula (IA1) (hereinafter referred to as "compound Compound (IA1)) or a compound represented by formula (IA2) (hereinafter referred to as "compound (IA3)"). (IA2)). TIFF2025169323000096.tif68134 [In formula (IA1) and formula (IA2), R 1 , X 1 , X 2 , mm, nn, Ar 1 , R 3 , R 4 , R 5 and n' have the same meaning as above. Denotes taste.]

[0164] Compound (IA) is a compound represented by the formula (I), 2 is a trivalent or higher benzene ring, and n=2 and each -OR 2 Such a compound (IA) is For example, the above-mentioned formulas (I-13) to (I-16) and formulas (I-19) to (I-24) , structural units represented by formulae (I-27) to (I-66), and formulae (I-71) to (I-92) It is a monomer that leads to the position. Compound (IA1) is a compound represented by the formula (I), 2 is a trivalent or higher benzene ring , n=2, and each -OR 2 is X 2 Compounds bonded at meta and para positions relative to the bond position of Such a compound (IA1) can be, for example, a compound represented by the above-mentioned formula (I-13) to formula (I- 16), Formula (I-19) to Formula (I-24), Formula (I-27) to Formula (I-66) It is a monomer that leads to structural units. Compound (IA2) is a compound represented by the formula (I), 2 is a trivalent or higher benzene ring, and n= 2, and each -OR 2 is X 2 Compounds bonded at the ortho and meta positions relative to the bonding position of Such a compound (IA2) can be, for example, a compound represented by the above-mentioned formula (I-71) to formula (I-92) ) is a monomer that leads to a structural unit represented by

[0165] Ar 1 The aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent is represented by the formula ( I) Ar 1 The aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent is Examples of the groups include the same groups as those mentioned above.

[0166] R 3 and R 4 The acid labile group in formula (I) is R 2 The acid labile groups of Examples thereof include the same groups as the acid labile group (1a) or the acid labile group (2a), etc.

[0167] R 3 and R 4 are taken together to form a group having an acetal ring structure, Such groups include the two R 2 together form an acetal ring structure Examples of the group include the same groups as those exemplified as the group when forming a group (such as group (3a)). Also, R 3 and R 4 are taken together to form a group having an acetal ring structure, Examples of such groups, including benzene rings, include the groups shown below. * represents X 2 Represents a bond with . TIFF2025169323000097.tif50156

[0168] R 5 a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms The —CH2— contained in the alkyl group and the fluorinated alkyl group is —O— or —CO—. The Ar in formula (I) may be substituted. 2 The groups listed as substituents of The same groups as those shown below can be mentioned. n' is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. I wish.

[0169] Examples of compound (IA) include the following: TIFF2025169323000098.tif58154

[0170] TIFF2025169323000099.tif225165

[0171] TIFF2025169323000100.tif190150

[0172] TIFF2025169323000101.tif243168

[0173] TIFF2025169323000102.tif123151

[0174] TIFF2025169323000103.tif176152

[0175] TIFF2025169323000104.tif60157

[0176] TIFF2025169323000105.tif119169

[0177] Formula (IA-13), Formula (IA-15), Formula (IA-19), Formula (IA-21), Formula (I A-23), formula (IA-27), formula (IA-29), formula (IA-31), formula (IA-33) ), formula (IA-35), formula (IA-37), formula (IA-39), formula (IA-41), formula ( IA-43), Formula (IA-45), Formula (IA-47), Formula (IA-49), Formula (IA-5 1), Formula (IA-53), Formula (IA-55) ~ Formula (IA-66), Formula (IA-71), Formula (IA-73), formula (IA-75), formula (IA-77), formula (IA-79), formula (IA- 81), formula (IA-83), formula (IA-85), formula (IA-87), formula (IA-89), In the compounds represented by formula (IA-91), R 1 The hydrogen atom corresponding to The compounds of formula (IA-14), formula (IA-16), formula (IA-2 0), formula (IA-22), formula (IA-24), formula (IA-28), formula (IA-30), formula (IA-32), Formula (IA-34), Formula (IA-36), Formula (IA-38), Formula (IA- 40), formula (IA-42), formula (IA-44), formula (IA-46), formula (IA-48), Formula (IA-50), Formula (IA-52), Formula (IA-54), Formula (IA-72), Formula (IA -74), formula (IA-76), formula (IA-78), formula (IA-80), formula (IA-82) , formula (IA-84), formula (IA-86), formula (IA-88), formula (IA-90), formula (I A-92), in which R 1 A methyl group corresponding to The substituted compound is also included as compound (IA).

[0178] <Method for producing compound (IA)> Compound (IA) is a compound represented by formula (Ia) and a compound represented by formula (Ib) and in a solvent in the presence of a catalyst. TIFF2025169323000106.tif62152 [wherein all symbols have the same meanings as above] The solvents include methyl isobutyl ketone, chloroform, tetrahydrofuran, and toluene. En, etc. Examples of the catalyst include pyridine, dimethylaminopyridine, N-methylpiperidine, N-methylpyrrolidine, potassium hydroxide, or other base catalysts, or carbonyldiimidazo Examples include: The compound represented by formula (Ia) includes salts represented by the following formula, which are commercially available: It is easily available. TIFF2025169323000107.tif4497 Examples of the compound represented by formula (Ib) include salts represented by the following formula, which are commercially available: It is readily available and can be easily produced by known methods. TIFF2025169323000108.tif48125

[0179] [Resist Composition] The resist composition of the present invention comprises a resin (A) and an acid generator (hereinafter referred to as an acid generator) known in the resist field. It is preferable that the catalyst contains a generating agent (B). The resist composition of the present invention may further contain a resin other than the resin (A). The resist composition of the present invention generates an acid that is weaker in acidity than the acid generated from the acid generator. It may contain a quencher such as salt (hereinafter referred to as "quencher (C)"). It is preferable that the ink contains a solvent (hereinafter, sometimes referred to as "solvent (E)").

[0180] <Resins other than Resin (A)> Resins other than resin (A) include those containing the structural unit (I) or the structural unit (a1-1) and the structural unit (a2-2). It is sufficient that the resin does not contain at least one selected from the group consisting of units (a1-2). Such a resin may be, for example, a resin obtained by removing the structural unit (I) from the resin (A) (hereinafter referred to as "resin"). Resin (A) is sometimes referred to as "A-1" and the structural unit (a1-1) and the structural unit ( a1-2) (hereinafter referred to as "Resin (AZ)") excluding at least one selected from the group consisting of (hereinafter, referred to as "a resin"), and a resin consisting only of the structural unit (a4) and the structural unit (a5) (hereinafter, referred to as "a resin"). Resin (X)).

[0181] As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In resin (X), the content of structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. Examples of structural units that the resin (X) may further have include the structural unit (a2), the structural unit (a3) and structural units derived from other known monomers. X) is preferably a resin consisting of only the structural unit (a4) and / or the structural unit (a5). I wish. The structural units constituting the resin (X) may be used alone or in combination of two or more. Using monomers that derive these structural units, a known polymerization method (e.g., radical polymerization method) can be used. The content of each structural unit in the resin (X) can be determined by the following procedure. It can be adjusted by the amount of monomer used. The weight average molecular weights of the resin (AY), the resin (AZ), and the resin (X) are each independently Preferably 6,000 or more (more preferably 7,000 or more), 80,000 or less (more preferably The weight average molecular weight of the resin (AY) and the resin (X) is preferably 60,000 or less. The measurement method is the same as in the case of resin (A). When the resist composition of the present invention contains resin (AY), the total content of resin (AY) is Usually, 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) per 100 parts by mass (Part). Furthermore, when the resist composition contains resin (X), the content of resin (X) is 100 mass % of resin (A). parts, preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, More preferably, it is 1 to 40 parts by mass, and even more preferably, it is 1 to 30 parts by mass. Even more preferably, it is 1 to 8 parts by mass.

[0182] In the resist composition of the present invention, the resin (A) may be used in combination with a resin other than the resin (A). When resins other than resin (A) are used in combination, resins containing structural units having acid labile groups and It is preferable to use a resin containing a structural unit having a fluorine atom in combination with the resin (AY). It is more preferable to use resin (AZ) and / or resin (X) in combination. The content of resin (A) in the resist composition is 8% by weight 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 of the solid content of the resist composition. The content is preferably 90% by mass or more and more preferably 99% by mass or less. The solid content of the product and the resin content relative to it are measured by liquid chromatography or gas chromatography. It can be measured by known analytical means such as graphy.

[0183] <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., disulfones, ketones Examples of ionic acid generators include ionic acid generators such as ionic acid generators (sulfones, sulfonyldiazomethanes, etc.). Onium salts containing ammonium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples of onium salts include sulfonate anions. anion, sulfonylimide anion, sulfonylmethide anion, etc.

[0184] Examples of the acid generator (B) include those disclosed in JP-A-63-26653 and JP-A-55-164824; JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP 62-153853 A, JP 63-146029 A, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate acids when exposed to radiation, such as those described in US Pat. No. 126,712, can be used. In addition, compounds produced by known methods may be used. The acid generator (B) may be a mixture of two or more compounds. They may also be used in combination.

[0185] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a compound represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)"). TIFF2025169323000109.tif2961[In formula (B1), Q b1 and Q b2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents a methyl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the divalent saturated hydrocarbon group The -CH2- contained in the carboxylic acid may be replaced by -O- or -CO-, and the divalent saturated carbon atom The hydrogen atom contained in the hydrogen group may be substituted with 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 -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + represents an organic cation.

[0186] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) includes 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 perfluoropentyl 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.

[0187] L b1 The divalent saturated hydrocarbon group in 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 groups; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa cycloalkanediyl groups such as cyclohexene-1,4-diyl and cyclooctane-1,5-diyl 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 Examples include a hydrogen group.

[0188] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group may be, for example, a group represented by any one of formulas (b1-1) to (b1-3). In addition, the groups represented by formulae (b1-1) to (b1-3) and their specific examples are In the examples of groups represented by formulae (b1-4) to (b1-11), * and ** represent bonds. and * represents a bond to -Y.

[0189] TIFF2025169323000110.tif26118[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 may be substituted with fluorine atoms or hydroxy groups. The -CH2- contained in the hydrogen hydride group 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 may be substituted with fluorine atoms or hydroxy groups. The -CH2- contained in the hydrogen hydride group 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 may be substituted with fluorine atoms or hydroxy groups. The -CH2- contained in the hydrogen hydride group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less. * and ** represent bonds, and * represents a bond to Y.]

[0190] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group When -CH2- 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 do. L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the divalent saturated hydrocarbon The hydrogen atoms contained in the group may be substituted with fluorine atoms. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, The hydrogen atoms contained in the hydrogen 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 -CH2- contained in the divalent saturated hydrocarbon group is replaced with -O- or -CO-. Good too.

[0191] L b1The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group is preferably a group represented by formula (b1-1) or formula (b1-3). The group represented by formula (b1-1) includes those represented by formulas (b1-4) to (b1-8), respectively. Examples of such groups include: TIFF2025169323000111.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, and the divalent saturated hydrocarbon group The -CH2- contained therein 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 atoms contained in the hydrogen hydride group may be substituted with fluorine atoms or hydroxy groups. 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 atoms contained in the hydrogen hydride group may be substituted with fluorine atoms or hydroxy groups. 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 b14represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the hydrogen hydride group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrogen hydride group may be substituted with fluorine atoms or hydroxy groups. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the divalent saturated hydrocarbon group The contained -CH2- 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 atoms contained in the hydrogen hydride group may be substituted with fluorine atoms or hydroxy groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. * and ** represent bonds, and * represents a bond to Y.] 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 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0192] The group represented by formula (b1-3) is represented by formulas (b1-9) to (b1-11), respectively. Examples include groups represented by the following formula: TIFF2025169323000112.tif22140[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 —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atom may be substituted with a hydroxy group. However, L b19 and L b20The 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 —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group 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 —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group 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. * and ** represent bonds, and * represents a bond to Y.]

[0193] In addition, in the groups represented by formula (b1-9) to formula (b1-11), saturated When a hydrogen atom contained in a mono- or di-hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is the number of carbon atoms of the saturated hydrocarbon group. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a bromide group, and a bromine group. Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0194] Examples of the group represented by formula (b1-4) include the following. TIFF2025169323000113.tif17150 (* and ** represent bonds, * represents a bond to Y.)

[0195] Examples of the group represented by formula (b1-5) include the following. TIFF2025169323000114.tif72149 (* and ** represent bonds, * represents a bond to Y.)

[0196] Examples of the group represented by formula (b1-6) include the following. TIFF2025169323000115.tif29150 (* and ** represent bonds, * represents a bond to Y.)

[0197] Examples of the group represented by formula (b1-7) include the following. TIFF2025169323000116.tif64151 (* and ** represent bonds, * represents a bond to Y.)

[0198] Examples of the group represented by formula (b1-8) include the following. TIFF2025169323000117.tif23150 (* and ** represent bonds, * represents a bond to Y.)

[0199] Examples of the group represented by formula (b1-2) include the following. TIFF2025169323000118.tif31161 (* and ** represent bonds, * represents a bond to Y.)

[0200] Examples of the group represented by formula (b1-9) include the following. TIFF2025169323000119.tif44137 (* and ** represent bonds, * represents a bond to Y.)

[0201] Examples of the group represented by formula (b1-10) include the following. TIFF2025169323000120.tif89157 (* and ** represent bonds, * represents a bond to Y.)

[0202] Examples of the group represented by formula (b1-11) include the following. TIFF2025169323000121.tif82158 (* and ** represent bonds, * represents a bond to Y.)

[0203] The alicyclic hydrocarbon group represented by Y includes those represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y37) Examples include a group represented by formula (Y38). The —CH2— contained in the alicyclic hydrocarbon group represented by Y is —O—, —S(O)2— or — When the group is replaced with CO-, the number of CO- may be one or more. Examples thereof include groups represented by formulae (Y12) to (Y35) and (Y39) to (Y43). * is L b1 Represents a bond with . The alicyclic hydrocarbon group represented by TIFF2025169323000122.tif82166Y is preferably a group represented by formula (Y1) to formula (Y20), formula ( 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 formula (Y40), formula (Y42) or 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 formula: The alicyclic hydrocarbon group represented by Y is selected from the group consisting of the formulae (Y28) to (Y35), the formulae (Y39) to (Y 40), formula (Y42) or formula (Y43), etc., when it is a spiro ring containing an oxygen atom, 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 unsubstituted with a fluorine atom.

[0204] 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, or 6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -( CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 teeth, Alkyl groups having 1 to 16 carbon atoms, alicyclic hydrocarbon groups having 3 to 16 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms and the alkyl group and the alicyclic hydrocarbon group are each a cyclic group or a group in which the alkyl group and the alicyclic hydrocarbon group are combined. The —CH2— contained in the group may be replaced by —O—, —SO2— or —CO—. The hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group are each independently selected from the group consisting of aryl, ... may be substituted with a hydroxy group or a fluorine atom; ja is an integer of 0 to 4; ) and others. The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxy group, a hydroxyl group ... an alkyl group having 1 to 16 carbon atoms which may be substituted with an alkyl group; -CH2- may be replaced by -O- or -CO-), cyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, aralkyl groups having 7 to 21 carbon atoms, Glycidyloxy group, -(CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO -R b1 group (in the formula, R b1 represents alkyl groups having 1 to 16 carbon atoms, alicyclic hydrocarbons having 3 to 16 carbon atoms, an alkyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these; The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group is -O-, -SO2- or -CO- and the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with The hydrogen atoms contained in may be replaced by hydroxy groups or fluorine atoms. , and represents an integer of 0 to 4.)

[0205] 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 methylcyclohexyl group, and a cyclohexyl group. cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, Examples of the alicyclic hydrocarbon group include a carboxyl group, 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, more preferably 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 aromatic hydrocarbon groups include aryl groups such as an alkyl group and a phenanthryl group. It may have a hydrocarbon group or an alicyclic hydrocarbon group, and may have a chain hydrocarbon group having 1 to 18 carbon atoms. Aromatic hydrocarbon groups (tolyl, xylyl, cumenyl, mesityl, p-methyl Phenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethyl phenyl group, 2-methyl-6-ethylphenyl group, etc.), and alicyclic carbons having 3 to 18 carbon atoms Aromatic hydrocarbon groups containing hydrogen hydride groups (p-adamantylphenyl group, p-cyclohexyl The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. It is more preferably 6 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromine 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 alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 It is preferably 1 to 6, and more preferably 1 to 4. Examples of alkyl groups substituted with hydroxy groups include hydroxymethyl groups, hydroxy Examples include hydroxyalkyl groups such as an ethyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and the like. Examples include an ethyl group and a naphthylethyl group. -CH2- in the alkyl group is replaced with -O-, -S(O)2- or -CO-, etc. The groups include an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkoxy group, an alkyl ... Examples of the alkyl group include a hydroxyl group, ... The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hydroxyl group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy groups. The number of carbon atoms in 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 Preferably, it is 2 to 6, and more preferably, it is 2 to 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, a group combining an alkoxy group and an alkylcarbonyl group, and a group combining an alkoxy group and an alkylcarbonyloxy group. Examples include: Examples of the group combining an alkoxy group and an alkyl group include a methoxymethyl group, Alkoxyalkyl groups such as methoxyethyl, ethoxyethyl, and ethoxymethyl groups are The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, and more preferably It is preferably 2 to 6, and more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkoxy group include a methoxymethoxy group, a methoxy group, a methyl ... alkoxyalkoxy groups such as ethoxyethoxy, ethoxymethoxy, and ethoxyethoxy groups The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, and more preferably Preferably, it is 2 to 6, and more preferably, it is 2 to 4. Examples of a group combining 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 even more preferably 3 to 5. be. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include methoxy groups. Cetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, ethoxy Examples include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the oxyalkylcarbonyloxy group is preferably 3 to 13, more preferably It is preferably 3 to 7, and more preferably 3 to 5. The -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S(O)2-, -CO-, etc. The groups replaced include those represented by formula (Y12) to formula (Y35) and formula (Y39) to formula (Y43). and the like.

[0206] Examples of Y include the following: TIFF2025169323000123.tif160165

[0207] 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, Even more preferably, it is an adamantyl group which may have a substituent, and the alicyclic hydrocarbon The -CH2- constituting the alkyl group or adamantyl group is -CO-, -S(O)2- or -CO- Y is preferably an adamantyl group, a hydroxyadamantyl group, or a hydroxyadamantyl group. a mantyl group, an oxoadamantyl group, or a group represented by the formula (Y42), the formula (Y100) to the formula (Y114) It is a group represented by the formula:

[0208] The anion in the salt represented by formula (B1) includes the anions represented by formula (B1-A-1) to formula (B1- A-59) (hereinafter, "anion (B1-A-1)" and so on 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 preferred.

[0209] TIFF2025169323000124.tif143153

[0210] TIFF2025169323000125.tif66157

[0211] TIFF2025169323000126.tif100158

[0212] TIFF2025169323000127.tif121153

[0213] TIFF2025169323000128.tif50138

[0214] TIFF2025169323000129.tif185167

[0215] where 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, a chain hydrocarbon group having 1 to 12 carbon atoms. Preferably, the alkyl group has 1 to 4 carbon atoms, the alicyclic hydrocarbon group has 5 to 12 carbon atoms, or more preferably a methyl group, an ethyl group, a cyclohexyl group, L is a methyl group or an adamantyl group. A41 is a single bond or an alkanediyl having 1 to 4 carbon atoms. It is a base. 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 anions include those described in JP-A-4646.

[0216] The anion in the salt represented by formula (B1) is preferably a compound represented by formula (B1a-1) to formula (B1a-2). B1a-38) are examples of anions. TIFF2025169323000130.tif125153

[0217] TIFF2025169323000131.tif91138

[0218] TIFF2025169323000132.tif168155

[0219] Among them, the formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-1 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a-3) 8) is preferred.

[0220] 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 Below, depending on the formula number, it may be called "cation (b2-1)" etc.). TIFF2025169323000133.tif48169In equations (b2-1) to (b2-4), R b4 ~R b6 are each independently a chain hydrocarbon group having 1 to 30 carbon atoms, a chain hydrocarbon group having 3 to 36 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 with 1 to 12 carbon atoms, and alkyl groups with 3 to 12 carbon atoms. It 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 atoms contained in the aromatic hydrocarbon group are substituted with halogen atoms, hydroxy groups, and groups having 1 to 10 carbon atoms. aliphatic hydrocarbon groups of 18, fluorinated alkyl groups of 1 to 12 carbon atoms or alkyl groups of 1 to 12 carbon atoms It may be substituted with a koxy group. R b4 and R b5 are bonded to each other and form a ring with the sulfur atom to which they are attached. -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. good. R b7 and R b8 are each independently a halogen atom, a hydroxyl group, a fatty acid having 1 to 12 carbon atoms, It represents an aliphatic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5; When m2 is 2 or more, 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 are each independently 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 to each other and form a ring with the sulfur atom to which they are attached -CH2- contained in the ring may be 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. Rb12 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 6 to 18 prime numbers, 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 are bonded to each other to form a ring including the -CH-CO- to which they are attached. -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. It is also possible. R b13 ~R b18 are each independently a halogen atom, a hydroxyl group, a fatty acid having 1 to 12 carbon atoms, It represents an aliphatic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4; u2 represents 0 or 1. When o2 is 2 or more, 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.

[0221] 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. group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and An example of an alkyl group is a 2-ethylhexyl group. 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, and a monocyclic alicyclic hydrocarbon group may be 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. TIFF2025169323000134.tif10158 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.

[0222] Examples of alicyclic hydrocarbon groups in which hydrogen atoms are substituted with aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 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 1. Preferably it is 20 or less. The fluorinated alkyl group refers to an alkyl group having 1 to 12 carbon atoms and a fluorine atom. Examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a perfluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 9, and more preferably 1 to 9. It is preferably 6, and more preferably 1 to 4.

[0223] Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group. It may have a hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group (tolyl group, xylyl group, etc.) phenyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and alicyclic carbons Aromatic hydrocarbon groups containing hydrogen hydride groups (p-cyclohexylphenyl group, p-adamantyl phenyl group, etc. In addition, when the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, A chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples thereof include a methyl group. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include a benzyl group, a phenyl group, and a phenyl group. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples include aralkyl groups.

[0224] The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hydroxyl group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group 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. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group and an ethylcarbonyloxy group. Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group silyl group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include an oxy group and a 2-ethylhexylcarbonyloxy group.

[0225] R b4 and R b5 and bond together with the sulfur atom to which they are attached to form a ring The ring may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. The ring may have 3 to 18 carbon atoms, and preferably has 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 include the following rings: * represents a bond. TIFF2025169323000135.tif23143

[0226] R b9 and R b10 The ring formed by combining and can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. 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 thiolan-1-ium ring (tetrahydrothio) thiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring, etc. It can be obtained. R b11 and R b12 The ring formed by combining and can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. 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.

[0227] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2025169323000136.tif80158

[0228] TIFF2025169323000137.tif74165

[0229] TIFF2025169323000138.tif3496

[0230] Examples of the cation (b2-2) include the following cations. TIFF2025169323000139.tif18150

[0231] Examples of the cation (b2-3) include the following cations. TIFF2025169323000140.tif26140

[0232] Examples of the cation (b2-4) include the following cations. TIFF2025169323000141.tif83167

[0233] TIFF2025169323000142.tif3041

[0234] 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) ~ Formula (B1a-16), Formula (B1a-18), Formula ( B1a-19), an anion represented by any one of formulas (B1a-22) to (B1a-38) a combination of an anion with a cation (b2-1), a cation (b2-3), or a cation (b2-4); Examples include:

[0235] 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 (1-31) to (B1-56) are particularly preferred. TIFF2025169323000143.tif119149

[0236] TIFF2025169323000144.tif77147

[0237] TIFF2025169323000145.tif147147

[0238] TIFF2025169323000146.tif65165

[0239] TIFF2025169323000147.tif113150

[0240] TIFF2025169323000148.tif92158

[0241] In the resist composition of the present invention, the content of the acid generator is 100% by mass of the aforementioned resin (A). With respect to the amount of the hydroxybenzoate, the amount is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 45 parts by mass or less. 0 parts by mass or less, more preferably 3 parts by mass or more and 40 parts by mass or less, and even more preferably 1 The content is 0 parts by mass or more and 40 parts by mass or less.

[0242] <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 by, for example, liquid chromatography or gas chromatography. It 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 esters; ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; γ-butyrolactone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0243] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound or an acid generated from the acid generator (B). The resist composition may include a salt that generates an acid having a weaker acidity than the quencher (C). In the case where the resist composition contains the quencher (C), the content of the quencher (C) is determined based on the solid content of the resist composition. It is preferably about 0.01 to 15% by mass, and more preferably about 0.01 to 10% by mass. is more preferable, and about 0.1 to 5 mass% is even more preferable, and 0.1 to 3 mass% It is even more preferable that the amount is about 1000 .mu.m. 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, Amines include secondary amines and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, and 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, Ethyldibutylamine diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexane 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, pyridine 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-Pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide amine, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Among them, preferred are aromatic amines such as diisopropylaniline, and more preferred are aromatic amines such as diisopropylaniline. Examples include 2,6-diisopropylaniline. Ammonium salts include tetramethylammonium hydroxide, tetraisopropyl ammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl Ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide methylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium ammonium hydroxide, tetra-n-butylammonium salicylate, and choline. can be done.

[0244] The acidity of a salt that generates an acid weaker than the acid generated from the acid generator (B) is: It is expressed as the acid dissociation constant (pKa). It is an acid that is weaker in acidity than the acid generated from the acid generator (B). The salt that generates [it] is a salt with an acid dissociation constant of the acid generated from the salt usually being -3 < pKa, preferably a salt with -1 < pKa < 7, more preferably a salt with 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include 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 " intramolecular salt of weak acid (D)"), and the salts described in JP-A-2012-229206 , JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. Preferably is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), more preferably an intramolecular salt of weak acid (D). TIFF2025169323000149.tif89165

[0245] Examples of the intramolecular salt of weak acid (D) include the following salts. TIFF2025169323000150.tif72165

[0246] 〈Other components〉 The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter may be referred to as "other components (F)"). There is no particular limitation on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used.

[0247] 〈Preparation of resist composition〉 The resist composition of the present invention is prepared by mixing the resin (A), the acid generator (B), and, if necessary, a resin other than the resin (A), the solvent (E), the quencher (C), and the other components (F). ​​​​​ The order of mixing is not particularly limited. The temperature during mixing ranges from 10 to 40°C depending on the type of resin and the solvent (E) used. An appropriate temperature can be selected depending on the solubility, etc. The mixing time can be adjusted to 0. The appropriate time can be selected from 5 to 24 hours. There are no particular limitations on the mixing method. , stirring and mixing, etc. can be used. After mixing the components, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable that

[0248] <Method for producing a 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) 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 is included. To apply the resist composition to the 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. The heating time is preferably 10 to 180 seconds. The pressure during this process is 1 to 1.0 x 105 It is preferable that the pressure is about Pa. The resulting 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), F2 excimer laser (wavelength 157 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert 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". The 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 (or The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150°C. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of methods include the dip method, paddle method, spray method, and 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 a type of alkaline water used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include an aqueous solution 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 removed. It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, a developer A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers include ketones such as 2-hexanone and 2-heptanone. Glycol ether solvents such as propylene glycol monomethyl ether acetate Ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and aromatic hydrocarbon solvents such as the above. 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 more preferably 95% by mass or more and 100% by mass or less, and more preferably substantially only an organic solvent. More preferable. Among them, organic developers include developers 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 more preferable that the mixture is qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 100%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. After development, the resist pattern is preferably washed with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and solvents containing general organic solvents are also usable. A solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0249] <Application> The resist composition of the present invention is a resist composition for exposure to KrF excimer laser, ArF excimer laser, Resist composition for exposure to ultraviolet laser, resist composition for exposure to electron beam (EB) or EU resist compositions for V exposure, particularly resist compositions for electron beam (EB) exposure or EUV exposure The composition is suitable as a resist composition for semiconductors and is useful for microfabrication of semiconductors. [Example]

[0250] The present invention will be explained 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 ent). In the examples, the value of this molecular ion peak is indicated by "MASS."

[0251] Synthesis Example 1: Synthesis of compound represented by formula (I-17) TIFF2025169323000151.tif38134 20 parts of the compound represented by formula (I-17-a), 2 parts of the compound represented by formula (I-17-c) 0.28 parts of ethyl acetate, 100 parts of ethyl acetate, and 15 parts of tetrahydrofuran were mixed and heated at 23°C for 30 minutes. To the resulting mixed solution, 6.55 parts of the compound represented by formula (I-17-b) was added. The mixture was added and stirred at 23° C. for 18 hours. To the resulting reaction mass, 20 parts of n-heptane and ion 70 parts of exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated and collected. To the organic layer, 60 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, and then the layers were separated. The resulting organic layer was concentrated and the concentrated mass was collected. Column (Silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., development) Solvent: n-heptane / ethyl acetate = 1 / 1) to obtain the compound represented by formula (I-17-d). 7.48 parts of the compound represented by the formula were obtained. TIFF2025169323000152.tif40146 5.90 parts of a compound represented by formula (I-17-e), 1.00 parts of a compound represented by formula (I-17-f) 7.10 parts of the product and 30 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes, and then heated to 60°C. The mixture was stirred at room temperature for 1 hour. To the resulting mixture was added 7.26 parts of the compound represented by formula (I-17-d) The resulting reaction mass was cooled to 23°C, and then acetic acid ethyl ester was added. Add 100 parts of ethyl alcohol and 50 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the liquids. The organic layer was taken out. This water washing procedure was repeated four times. The obtained organic layer was concentrated to give a concentrated mass. The column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., By separating the compound (solvent: n-heptane / ethyl acetate = 5 / 1), the compound represented by formula (I-17) was obtained. 9.44 parts of the compound of interest were obtained. MASS (mass spectrometry):313.1[M+H] +

[0252] Synthesis Example 2: Synthesis of compound represented by formula (I-25) TIFF2025169323000153.tif45124 5.00 parts of a compound represented by formula (I-25-a), 5.00 parts of a compound represented by formula (I-17-d) 10.39 parts of the product, 50 parts of dimethylformamide, and 11.14 parts of potassium carbonate were mixed, After stirring at 23°C for 30 minutes, the mixture was stirred at 120°C for 18 hours. After cooling at 40°C, 150 parts of ion-exchanged water and 150 parts of ethyl acetate were added and the mixture was stirred at 23°C for 30 minutes. After stirring, the mixture was separated to separate the organic layer, and 150 parts of ion-exchanged water was added to the obtained organic layer. After adding the mixture and stirring at 23°C for 30 minutes, the organic layer was separated and extracted. This water washing procedure was repeated three times. The obtained organic layer was concentrated, and the concentrated mass was passed through a column (silica gel 60N (spherical, medium 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate=5 / 1) was separated and collected to obtain 10.61 parts of the compound represented by formula (I-25-b). TIFF2025169323000154.tif5083 17.16 parts of the compound represented by formula (I-25-c), 17.16 parts of the compound represented by formula (I-25-d) 5.39 parts of the mixture and 120 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes. The mixture was cooled to 5° C. The compound represented by formula (I-25-b) 10.58 parts of ethanol was added over 30 minutes, and the mixture was heated to 23°C. After stirring at 23°C for 12 hours, the mixture was filtered. To the obtained filtrate, 100 parts of ion-exchanged water and 200 parts of ethyl acetate were added, and the mixture was heated to 23°C. After stirring for 30 minutes, the organic layer was separated and extracted. 100 parts of the mixture was added and stirred at 23°C for 30 minutes, after which the organic layer was separated and taken out. The operation was repeated three times. The obtained organic layer was concentrated, and the concentrated mass was passed through a column (silica gel 60N (Spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / acetic acid ethyl acetate=5 / 1) to obtain 6.82 parts of the compound represented by formula (I-25). Ta. MASS (mass spectrometry):285.1[M+H] +

[0253] Example 1: Synthesis of compound represented by formula (I-43) TIFF2025169323000155.tif43125 5.00 parts of a compound represented by formula (I-43-a), 1.00 parts of a compound represented by formula (I-17-c) 0.008 parts of the product and 50 parts of toluene were mixed, stirred at 23°C for 30 minutes, and then heated to 100°C. The resulting mixed solution was heated to 100° C. Compound 6 represented by formula (I-43-b) was added to the resulting mixed solution at 100° C. 0.19 parts of ethanol was added dropwise, and the mixture was stirred at 110°C for 2 hours and then cooled to 23°C. 25 parts of ethyl acetate and 30 parts of ion-exchanged water were added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was collected by adding 30 parts of ion-exchanged water and the mixture was stirred at 23°C. After stirring for 30 minutes, the organic layer was separated and washed with water three times. The organic layer was concentrated to give 5.85 parts of the compound represented by formula (I-43-d). Got it. TIFF2025169323000156.tif52138 4.20 parts of a compound represented by formula (I-17-e), 1.20 parts of a compound represented by formula (I-17-f) 5.06 parts of the product and 30 parts of acetonitrile were mixed, stirred at 23°C for 30 minutes, and then heated to 60°C. The mixture was stirred at room temperature for 1 hour. To the resulting mixture was added 5.79 parts of the compound represented by formula (I-43-d) The resulting reaction mass was cooled to 23°C, and then acetic acid ethyl ester was added. Add 100 parts of ethyl alcohol and 50 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the liquids. The organic layer was removed, and 50 parts of ion-exchanged water was added to the recovered organic layer, followed by stirring at 23°C for 30 minutes. After stirring, the mixture was separated and the organic layer was taken out. This water washing procedure was repeated three times. The concentrate was concentrated and the concentrated mass was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm (manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) As a result, 3.10 parts of the compound represented by formula (I-43) was obtained. MASS (mass spectrometry):297.1[M+H] +

[0254] Example 2: Synthesis of compound represented by formula (I-33) TIFF2025169323000157.tif4589 2.95 parts of the compound represented by formula (I-43), 1.89 parts of p-toluenesulfonic acid, and 30 parts of acetonitrile was mixed, and the mixture was stirred at 23°C for 30 minutes, and then stirred at 60°C for 10 hours. The resulting mixture was cooled to 23°C, and then 50 parts of ethyl acetate and 20 parts of ion-exchanged water were added. The mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. This water washing procedure was repeated three times. The obtained organic layer was concentrated to obtain a compound of formula (I-3 1.95 parts of the compound represented by 3) was obtained. MASS (mass spectrometry):257.1[M+H] +

[0255] Synthesis Example 3: Synthesis of compound represented by formula (I-67) TIFF2025169323000158.tif40135 20 parts of the compound represented by formula (I-67-a), 2 parts of the compound represented by formula (I-17-c) 0.28 parts of ethyl acetate, 100 parts of ethyl acetate, and 14 parts of tetrahydrofuran were mixed and heated at 23°C for 30 minutes. After stirring for 1 hour, the mixture was cooled to 10° C. To the resulting mixed solution, a compound of the formula (I-17-b 6.55 parts of the compound represented by the formula (I) was added dropwise, and the temperature was raised to 23°C, followed by stirring at 23°C for 2 hours. To the resulting mixture, 70 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, and then the liquid was separated to obtain a useful The organic layer was taken out. This water washing procedure was repeated five times. The obtained organic layer was concentrated to give a concentrated mass. The column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., The compound of formula (I-67-d 8.75 parts of a compound represented by the formula (II) were obtained. TIFF2025169323000159.tif49143 6.40 parts of a compound represented by formula (I-17-e), 6.40 parts of a compound represented by formula (I-17-f) 7.70 parts of the product and 32 parts of acetonitrile were mixed and stirred at 23°C for 30 minutes, and then heated to 60°C. The mixture was stirred at room temperature for 1 hour. To the resulting mixture was added 8.65 parts of a compound represented by formula (I-67-d). The resulting reaction mass was cooled to 23°C, and then acetic acid ethyl ester was added. Add 100 parts of ethyl alcohol and 50 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the liquids. The organic layer was taken out. This water washing procedure was repeated four times. The obtained organic layer was concentrated to give a concentrated mass. The column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., By separating the compound (solvent: n-heptane / ethyl acetate = 5 / 1), the compound represented by formula (I-67) was obtained. 9.84 parts of the compound of interest were obtained. MASS (mass spectrometry):313.1[M+H] +

[0256] Synthesis Example 4: Synthesis of compound represented by formula (I-68) TIFF2025169323000160.tif4599 5.00 parts of the compound represented by formula (I-67), 20 parts of 1N hydrochloric acid, and 30 parts of acetonitrile The mixture was mixed and stirred at 23° C. for 10 hours. 50 parts of ethyl acetate was added to the resulting mixture. After stirring at 23°C for 30 minutes, the organic layer was separated and extracted. 20 parts of exchanged water was added and the mixture was stirred at 23°C for 30 minutes, after which the organic layer was separated and taken out. The water washing operation was repeated three times. The obtained organic layer was concentrated, and then 100 parts of n-heptane was added. The mixture was stirred at 23°C for 30 minutes, and then filtered to obtain the compound represented by formula (I-68). 3.75 parts of product were obtained. MASS (mass spectrometry):241.1[M+H] +

[0257] Example 3: Synthesis of compound represented by formula (I-49) TIFF2025169323000161.tif45119 2.50 parts of a compound represented by formula (I-25-a), 2.50 parts of a compound represented by formula (I-43-d) 4.74 parts of the product, 25 parts of dimethylformamide, and 5.57 parts of potassium carbonate were mixed, and 23 The mixture was stirred at 120°C for 30 minutes, and then stirred at 120°C for 18 hours. The resulting mixture was cooled to 23°C. After cooling, 80 parts of ion-exchanged water and 80 parts of ethyl acetate were added and stirred at 23°C for 30 minutes. Then, the organic layer was separated and extracted. 80 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred for 23 minutes. After stirring at ℃ for 30 minutes, the organic layer was separated and separated. This water washing procedure was repeated three times. The obtained organic layer was concentrated, and the concentrated mass was passed through a column (silica gel 60N (spherical, neutral) 100 -210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 5 / 1) This gave 5.01 parts of a compound represented by formula (I-49-b). TIFF2025169323000162.tif4693 8.58 parts of the compound represented by formula (I-25-c), 8.58 parts of the compound represented by formula (I-25-d) 2.70 parts of the product and 60 parts of tetrahydrofuran were mixed and stirred at 23°C for 30 minutes. The mixture was cooled to 5°C. Compound 5. 00 parts was added over 30 minutes, and the temperature was raised to 23°C. After stirring at 23°C for 12 hours, the mixture was filtered. To the obtained filtrate, 100 parts of ion-exchanged water and 200 parts of ethyl acetate were added and the mixture was stirred at 23°C for 30 minutes. After stirring for 1 minute, the organic layer was separated and extracted. After adding the water-washing solution and stirring at 23°C for 30 minutes, the organic layer was separated and extracted. The obtained organic layer was concentrated, and the concentrated mass was passed through a column (silica gel 60N (spherical) , neutral) 100-210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate =5 / 1) to obtain 3.22 parts of the compound represented by formula (I-49). MASS (mass spectrometry):269.1[M+H] +

[0258] Example 4: Synthesis of compound represented by formula (I-37) TIFF2025169323000163.tif4484 2.67 parts of the compound represented by formula (I-49), 1.89 parts of p-toluenesulfonic acid, and 30 parts of acetonitrile was mixed, and the mixture was stirred at 23°C for 30 minutes, and then stirred at 60°C for 10 hours. The resulting mixture was cooled to 23°C, and then 50 parts of ethyl acetate and 20 parts of ion-exchanged water were added. The mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. This water washing procedure was repeated three times. The obtained organic layer was concentrated to obtain a compound of formula (I-3 1.69 parts of the compound represented by formula 7) was obtained. MASS (mass spectrometry):229.1[M+H] +

[0259] Example 5: Synthesis of compound represented by formula (I-81) TIFF2025169323000164.tif43125 5.00 parts of a compound represented by formula (I-81-a), 5.00 parts of a compound represented by formula (I-17-c) 0.008 parts of the product and 50 parts of toluene were mixed, stirred at 23°C for 30 minutes, and then heated to 100°C. The resulting mixed solution was heated to 100° C. Compound 7 represented by formula (I-81-b) was added to the resulting mixed solution at 100° C. 0.05 parts was added, and the mixture was stirred at 110°C for 2 hours, and then cooled to 23°C. 25 parts of ethyl acetate and 30 parts of ion-exchanged water were added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was collected by adding 30 parts of ion-exchanged water and the mixture was stirred at 23°C. After stirring for 30 minutes, the organic layer was separated and washed with water three times. The organic layer was concentrated, and the concentrated mass was then passed through a column (silica gel 60N (spherical, neutral) 100-2 10 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) As a result, 2.19 parts of the compound represented by the formula (I-81-d) was obtained. TIFF2025169323000165.tif46139 1.40 parts of a compound represented by formula (I-17-e), 1.40 parts of a compound represented by formula (I-17-f) 1.69 parts of the product and 20 parts of acetonitrile were mixed, stirred at 23°C for 30 minutes, and then heated to 60°C. The mixture was stirred at room temperature for 1 hour. To the resulting mixture was added 2.12 parts of the compound represented by formula (I-81-d). The resulting reaction mass was cooled to 23°C, and then acetic acid ethyl ester was added. Add 50 parts of ethyl acetate and 25 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the organic layer. To the recovered organic layer, 25 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes. After stirring, the organic layer was separated and washed with water three times. The layer was concentrated and the concentrated mass was loaded onto a column (silica gel 60N (spherical, neutral) 100-210 μm; (manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) As a result, 1.03 parts of the compound represented by formula (I-81) was obtained. MASS (mass spectrometry):313.1[M+H] +

[0260] Example 6: Synthesis of compound represented by formula (I-71) TIFF2025169323000166.tif40112 1.03 parts of the compound represented by formula (I-81), 0.63 parts of p-toluenesulfonic acid, and 10 parts of acetonitrile was mixed, and the mixture was stirred at 23°C for 30 minutes, and then stirred at 60°C for 10 hours. The resulting mixture was cooled to 23°C, and then 30 parts of ethyl acetate and 15 parts of ion-exchanged water were added. The mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. 15 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. This water washing procedure was repeated three times. The obtained organic layer was concentrated to obtain a compound of formula (I-7) 0.38 parts of the compound represented by 1) was obtained. MASS (mass spectrometry):257.1[M+H] +

[0261] Resin synthesis The compounds (monomers) used in the synthesis of the resin are shown below. TIFF2025169323000167.tif143161Hereinafter, these monomers will be referred to as "monomer (a1-1-3)" etc. according to their formula numbers.

[0262] Example 7 [Synthesis of Resin A1] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( Monomer (a1-4-2) and Monomer (I-17) were used in a molar ratio of ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (I-17) , and mixed in a ratio of 19:25:38:18, and further added to this monomer mixture, Methyl isobutyl ketone was mixed in an amount 1.5 times by mass relative to the total mass of all the monomers. The resulting mixture was treated with azobisisobutyronitrile and azobis(2,4-dimethylamino)nitrile as initiators. valeronitrile) were added at 1.2 mol% and 3.6 mol% of the total monomer amount, respectively. The mixture was heated at 73°C for about 5 hours. After stirring for 12 hours, the organic layer was separated. The resin was poured into heptane to precipitate, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.6. x10 3 Resin A1 was obtained in a yield of 62%. This resin A1 contained the following structural units (monomers): The ethoxy groups in all ethoxyethyl groups of (a1-4-2) and monomer (I-17) The elimination rate of the ethyl group is 100%. JPEG2025169323000168.jpg47145

[0263] Example 8 [Synthesis of Resin A2] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( Monomer (a1-4-2) and Monomer (I-17) were used in a molar ratio of ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (I-17) , and mixed in a ratio of 19:25:38:18, and further added to this monomer mixture, Methyl isobutyl ketone was mixed in an amount 1.5 times by mass relative to the total mass of all the monomers. The resulting mixture was treated with azobisisobutyronitrile and azobis(2,4-dimethylamino)nitrile as initiators. valeronitrile) were added at 1.2 mol% and 3.6 mol% of the total monomer amount, respectively. The mixture was heated at 73°C for about 5 hours. After that, the polymerization reaction mixture was cooled to 15°C. After adding an aqueous solution of p-toluenesulfonic acid and stirring for 6 hours, the liquids were separated. The layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected to obtain a weight average Molecular weight is approximately 5.9 × 10 3 Resin A2 was obtained in a yield of 58%. The total ethoxyethyl groups in the structural units (monomer (a1-4-2) and monomer (I-17) The elimination rate of the ethoxyethyl group in this case is 72%. JPEG2025169323000169.jpg46160

[0264] Example 9 [Synthesis of Resin A3] As the monomers, the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-17) was used, and the molar ratio [monomer (a1-1-3):monomer (a1-2-6 ): Monomer (I-17)) were mixed in a ratio of 25:38:37, and further This monomer mixture was mixed with 1.5 times by mass of methyl isobutylene based on the total mass of all monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator and ketone. Azobis(2,4-dimethylvaleronitrile) was used at 1.2 mo 1% and 3.6 mol% were added, and these were heated at 73°C for about 5 hours. A p-toluenesulfonic acid aqueous solution was added to the liquid, and after stirring for 12 hours, the liquids were separated. The organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered to obtain the heavy The weight-average molecular weight is approximately 5.5 x 10 3 Resin A3 was obtained in a yield of 65%. The ethoxyethyl group in the total ethoxyethyl groups of the following structural unit (monomer (I-17) The desorption rate is 100%. TIFF2025169323000170.tif47115

[0265] Example 10 [Synthesis of Resin A4] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer ( I-17), and the molar ratio [monomer (a1-4-2):monomer (a1-1-3)] Monomer (a1-2-6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (I-17) were mixed in a ratio of 12:20:35:3:15:15. Furthermore, this monomer mixture is added with 1.5 times the mass of the total mass of all the monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator. Nitrile and azobis(2,4-dimethylvaleronitrile) based on the total amount of monomers , 1.2 mol % and 3.6 mol % were added, and these were heated at 73°C for about 5 hours. After that, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, and after stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered. As a result, the weight average molecular weight is approximately 5.8 × 10 3 Resin A4 was obtained in a yield of 63%. Resin A4 is a resin having the following structural units (monomer (a1-4-2) and monomer (I-17) in total). The elimination rate of the ethoxyethyl group in the ethoxyethyl group is 100%. JPEG2025169323000171.jpg44163

[0266] Example 11 [Synthesis of Resin A5] As the monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( a2-1-3), monomer (a3-4-2) and monomer (I-17) were used, and the mol Ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3) : Monomer (a3-4-2): Monomer (I-17) ] 20:35:3:15:27 The monomer mixture is mixed in a ratio of 1:1 based on the total mass of all monomers. Then, 1.5 times by mass of methyl isobutyl ketone was mixed in. The obtained mixture was added with an initiator and Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were used in total. The monomers were added in an amount of 1.2 mol% and 3.6 mol%, respectively, and the mixture was heated at 73°C. After heating for about 5 hours, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction mixture, and the resulting mixture was After stirring for 1 hour, the layers were separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin. By filtering and collecting the product, the weight-average molecular weight was found to be approximately 5.4 × 10 3 Resin A5 is The yield was 66%. This resin A5 was obtained by adding the following structural unit (monomer (I-17) to all ethoxylated monomers). The elimination rate of the ethoxyethyl group in the diethyl group is 100%. TIFF2025169323000172.tif44139

[0267] Example 12 [Synthesis of Resin A6] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( Monomer (a1-4-2) and Monomer (I-25) were used in a molar ratio of ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (I-25) , and mixed in a ratio of 19:25:38:18, and further added to this monomer mixture, Methyl isobutyl ketone was mixed in an amount 1.5 times by mass relative to the total mass of all the monomers. The resulting mixture was treated with azobisisobutyronitrile and azobis(2,4-dimethylamino)nitrile as initiators. valeronitrile) were added at 1.2 mol% and 3.6 mol% of the total monomer amount, respectively. The mixture was heated at 73°C for about 5 hours. After stirring for 12 hours, the organic layer was separated. The resin was poured into heptane to precipitate, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.2. x10 3 Resin A6 was obtained in a yield of 59%. This resin A6 contains the following structural units (monomers): The ethoxy groups in all ethoxyethyl groups of (a1-4-2) and monomer (I-25) The elimination rate of the ethyl group is 100%. TIFF2025169323000173.tif46146

[0268] Example 13 [Synthesis of Resin A7] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer ( I-25) was used, and the molar ratio [monomer (a1-4-2):monomer (a1-1-3)] Monomer (a1-2-6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (I-25) were mixed in a ratio of 12:20:35:3:15:15. Furthermore, this monomer mixture is added with 1.5 times the mass of the total mass of all the monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator. Nitrile and azobis(2,4-dimethylvaleronitrile) based on the total amount of monomers , 1.2 mol % and 3.6 mol % were added, and these were heated at 73°C for about 5 hours. After that, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, and after stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered. As a result, the weight average molecular weight is approximately 5.4 × 10 3 Resin A7 was obtained in a yield of 61%. Resin A7 is a resin having the following structural units (monomer (a1-4-2) and monomer (I-25) in total). The elimination rate of the ethoxyethyl group in the ethoxyethyl group is 100%. TIFF2025169323000174.tif43163

[0269] Example 14 [Synthesis of Resin A8] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( Monomer (a1-4-2) and Monomer (I-33) were used in a molar ratio of ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (I-33) , and mixed in a ratio of 19:25:38:18, and further added to this monomer mixture, Methyl isobutyl ketone was mixed in an amount 1.5 times by mass relative to the total mass of all the monomers. The resulting mixture was treated with azobisisobutyronitrile and azobis(2,4-dimethylamino)nitrile as initiators. valeronitrile) were added at 1.2 mol% and 3.6 mol% of the total monomer amount, respectively. The mixture was heated at 73°C for about 5 hours. After stirring for 12 hours, the organic layer was separated. The resin was poured into heptane to precipitate, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.2. x10 3 Resin A8 having the following structural units was obtained in a yield of 60%. It is something. TIFF2025169323000175.tif47146

[0270] Example 15 [Synthesis of Resin A9] As the monomers, the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-33) was used, and the molar ratio [monomer (a1-1-3):monomer (a1-2-6 ): Monomer (I-33)] were mixed in a ratio of 25:38:37, and further This monomer mixture was mixed with 1.5 times by mass of methyl isobutylene based on the total mass of all monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator and ketone. Azobis(2,4-dimethylvaleronitrile) was used at 1.2 mo 1% and 3.6 mol% were added, and these were heated at 73°C for about 5 hours. The liquid was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered to obtain a weight average Molecular weight is approximately 5.0 × 10 3 Resin A9 was obtained in a yield of 65%. It has structural units. TIFF2025169323000176.tif47115

[0271] Example 16 [Synthesis of Resin A10] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1- 2-6) and monomer (I-43), and the molar ratio [acetoxystyrene:monomer (a1-1-3):monomer (a1-2-6):monomer (I-43)] was 37:20 The monomer mixture was mixed in a ratio of 32:11. Methyl isobutyl ketone was added in an amount 1.5 times by mass relative to the total mass of the mixture. Azobisisobutyronitrile was used as an initiator in an amount of 7m moles relative to the total moles of all monomers. vol%, and the mixture was heated at 85°C for about 5 hours to carry out polymerization. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and the mixture was stirred for 12 hours. After stirring for 1 hour, the mixture was separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin. After filtration and recovery, the weight-average molecular weight was found to be approximately 5.3 x 10 3 Resin A10 (co- A polymer was obtained in a yield of 62%. This resin A10 has the following structural units. TIFF2025169323000177.tif45131

[0272] Example 17 [Synthesis of Resin A11] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer ( I-33), and the molar ratio [monomer (a1-4-2):monomer (a1-1-3)] Monomer (a1-2-6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (I-33)] were mixed in a ratio of 12:20:35:3:15:15. Furthermore, this monomer mixture is added with 1.5 times the mass of the total mass of all the monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator. Nitrile and azobis(2,4-dimethylvaleronitrile) based on the total amount of monomers , 1.2 mol % and 3.6 mol % were added, and these were heated at 73°C for about 5 hours. After that, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, and after stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered. As a result, the weight average molecular weight is approximately 5.1 × 10 3 Resin A11 was obtained in a yield of 62%. Resin A11 has the following structural units: TIFF2025169323000178.tif44166

[0273] Example 18 [Synthesis of Resin A12] As the monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( a2-1-3), monomer (a3-4-2) and monomer (I-33) were used, and the mol Ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3) : Monomer (a3-4-2): Monomer (I-33) ] 20:35:3:15:27 The monomer mixture is mixed in a ratio of 1:1 based on the total mass of all monomers. Then, 1.5 times by mass of methyl isobutyl ketone was mixed in. The obtained mixture was added with an initiator and Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were used in total. The monomers were added in an amount of 1.2 mol% and 3.6 mol%, respectively, and the mixture was heated at 73°C. After heating for about 5 hours, the polymerization reaction mixture was poured into a large amount of n-heptane to precipitate the resin. By filtering and collecting the product, the weight-average molecular weight was reduced to approximately 5.2 × 10 3 The yield of resin A12 is The resin A12 was obtained at a yield of 64%. The resin A12 has the following structural units: TIFF2025169323000179.tif44143

[0274] Example 19 [Synthesis of Resin A13] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( Monomer (a1-4-2) and Monomer (I-68) were used in a molar ratio of ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (I-68) , and mixed in a ratio of 19:25:38:18, and further added to this monomer mixture, Methyl isobutyl ketone was mixed in an amount 1.5 times by mass relative to the total mass of all the monomers. The resulting mixture was treated with azobisisobutyronitrile and azobis(2,4-dimethylamino)nitrile as initiators. valeronitrile) were added at 1.2 mol% and 3.6 mol% of the total monomer amount, respectively. The mixture was heated at 73°C for about 5 hours. The resin was poured into a filter to precipitate, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.3 × 10 3 Resin A13, which has the following structural units, was obtained in a yield of 60%. That is why. TIFF2025169323000180.tif37131

[0275] Example 20 [Synthesis of Resin A14] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1- 2-6) and monomer (I-67), and the molar ratio [acetoxystyrene:monomer (a1-1-3):monomer (a1-2-6):monomer (I-67)] was 37:20 The monomer mixture was mixed in a ratio of 32:11. Methyl isobutyl ketone was added in an amount 1.5 times by mass relative to the total mass of the mixture. Azobisisobutyronitrile was used as an initiator in an amount of 7m moles relative to the total moles of all monomers. vol%, and the mixture was heated at 85°C for about 5 hours to carry out polymerization. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and the mixture was stirred for 12 hours. After stirring for 1 hour, the mixture was separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin. After filtration and recovery, the weight-average molecular weight was found to be approximately 5.2 x 10 3 Resin A14 (co- A polymer was obtained in a yield of 63%. This resin A14 has the following structural units. TIFF2025169323000181.tif37131

[0276] Example 21 [Synthesis of Resin A15] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( Monomer (a1-4-2) and Monomer (I-37) were used in a molar ratio of ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (I-37) , and mixed in a ratio of 19:25:38:18, and further added to this monomer mixture, Methyl isobutyl ketone was mixed in an amount 1.5 times by mass relative to the total mass of all the monomers. The resulting mixture was treated with azobisisobutyronitrile and azobis(2,4-dimethylamino)nitrile as initiators. valeronitrile) were added at 1.2 mol% and 3.6 mol% of the total monomer amount, respectively. The mixture was heated at 73°C for about 5 hours. After stirring for 12 hours, the organic layer was separated. The resin was poured into heptane to precipitate, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.3. x10 3 Resin A15, which has the following structural units, was obtained in a yield of 63%. This is what we do. TIFF2025169323000182.tif45149

[0277] Example 22 [Synthesis of Resin A16] As the monomers, the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-37) was used, and the molar ratio [monomer (a1-1-3):monomer (a1-2-6 ): Monomer (I-37)] were mixed in a ratio of 25:38:37, and further This monomer mixture was mixed with 1.5 times by mass of methyl isobutylene based on the total mass of all monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator and ketone. Azobis(2,4-dimethylvaleronitrile) was used at 1.2 mo 1% and 3.6 mol% were added, and these were heated at 73°C for about 5 hours. The liquid was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered to obtain a weight average Molecular weight is approximately 5.2 × 10 3Resin A16 was obtained in a yield of 61%. It has the following structural unit: TIFF2025169323000183.tif45118

[0278] Example 23 [Synthesis of Resin A17] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1- 2-6) and monomer (I-49), and the molar ratio [acetoxystyrene:monomer (a1-1-3):monomer (a1-2-6):monomer (I-49)] was 37:20 The monomer mixture was mixed in a ratio of 32:11. Methyl isobutyl ketone was added in an amount 1.5 times by mass relative to the total mass of the mixture. Azobisisobutyronitrile was used as an initiator in an amount of 7m moles relative to the total moles of all monomers. vol%, and the mixture was heated at 85°C for about 5 hours to carry out polymerization. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and the mixture was stirred for 12 hours. After stirring for 1 hour, the mixture was separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin. After filtration and recovery, the weight-average molecular weight was found to be approximately 5.5 x 10 3 Resin A17 (co- Resin A17 was obtained in a yield of 60%. This resin A17 has the following structural units. TIFF2025169323000184.tif44131

[0279] Example 24 [Synthesis of Resin A18] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer ( I-37), and the molar ratio [monomer (a1-4-2):monomer (a1-1-3)] Monomer (a1-2-6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (I-37)] were mixed in a ratio of 12:20:35:3:15:15. Furthermore, this monomer mixture is added with 1.5 times the mass of the total mass of all the monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator. Nitrile and azobis(2,4-dimethylvaleronitrile) based on the total amount of monomers , 1.2 mol % and 3.6 mol % were added, and these were heated at 73°C for about 5 hours. After that, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, and after stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered. As a result, the weight average molecular weight is approximately 5.2 × 10 3 Resin A18 was obtained in a yield of 60%. Resin A18 has the following structural units: TIFF2025169323000185.tif43166

[0280] Example 25 [Synthesis of Resin A19] As the monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( a2-1-3), monomer (a3-4-2) and monomer (I-37) were used, and the mol Ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3) : Monomer (a3-4-2): Monomer (I-37) ] 20:35:3:15:27 The monomer mixture is mixed in a ratio of 1:1 based on the total mass of all monomers. Then, 1.5 times by mass of methyl isobutyl ketone was mixed in. The obtained mixture was added with an initiator and Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were used in total. The monomers were added in an amount of 1.2 mol% and 3.6 mol%, respectively, and the mixture was heated at 73°C. After heating for about 5 hours, the polymerization reaction mixture was poured into a large amount of n-heptane to precipitate the resin. By filtering and collecting the product, the weight-average molecular weight was reduced to approximately 5.3 × 10 3 The yield of resin A19 was Resin A19 was obtained at a yield of 63%. This resin A19 has the following structural units: TIFF2025169323000186.tif43143

[0281] Example 26 [Synthesis of Resin A20] As the monomers, the monomer (a1-1-3), the monomer (a1-2-6) and the monomer (I-71) was used, and the molar ratio [monomer (a1-1-3):monomer (a1-2-6 ): Monomer (I-71)) were mixed in a ratio of 25:38:37, and further This monomer mixture was mixed with 1.5 times by mass of methyl isobutylene based on the total mass of all monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator and ketone. Azobis(2,4-dimethylvaleronitrile) was used at 1.2 mo 1% and 3.6 mol% were added, and these were heated at 73°C for about 5 hours. The liquid was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered to obtain a weight average Molecular weight is approximately 5.5 × 10 3 Resin A20 was obtained in a yield of 58%. It has the following structural unit: TIFF2025169323000187.tif42118

[0282] Example 27 [Synthesis of Resin A21] As monomers, acetoxystyrene, monomer (a1-1-3), monomer (a1- 2-6) and monomer (I-81), and the molar ratio [acetoxystyrene:monomer (a1-1-3):monomer (a1-2-6):monomer (I-81) The monomer mixture was mixed in a ratio of 32:11. Methyl isobutyl ketone was added in an amount 1.5 times by mass relative to the total mass of the mixture. Azobisisobutyronitrile was used as an initiator in an amount of 7m moles relative to the total moles of all monomers. vol%, and the mixture was heated at 85°C for about 5 hours to carry out polymerization. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and the mixture was stirred for 12 hours. After stirring for 1 hour, the mixture was separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate the resin. After filtration and recovery, the weight-average molecular weight was found to be approximately 5.7 x 10 3 Resin A21 (co- A polymer was obtained in a yield of 55%. This resin A21 has the following structural units. TIFF2025169323000188.tif39131

[0283] Example 28 [Synthesis of Resin A22] As the monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( a2-1-3), monomer (a3-4-2) and monomer (I-71) were used, and the mol Ratio [monomer (a1-1-3):monomer (a1-2-6):monomer (a2-1-3) : Monomer (a3-4-2): Monomer (I-71) ] 20:35:3:15:27 The monomer mixture is mixed in a ratio of 1:1 based on the total mass of all monomers. Then, 1.5 times by mass of methyl isobutyl ketone was mixed in. The obtained mixture was added with an initiator and Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were used in total. The monomers were added in an amount of 1.2 mol% and 3.6 mol%, respectively, and the mixture was heated at 73°C. After heating for about 5 hours, the polymerization reaction mixture was poured into a large amount of n-heptane to precipitate the resin. By filtering and collecting the product, the weight-average molecular weight was reduced to approximately 5.4 × 10 3 The yield of resin A22 is The resin A22 was obtained at a yield of 59%. The resin A22 has the following structural units: TIFF2025169323000189.tif40143

[0284] Synthesis Example 5 [Synthesis of Resin AX1] As the monomers, monomer (ax-1), monomer (ax-2) and monomer (I-1 7), and the molar ratio [monomer (ax-1):monomer (ax-2):monomer (I -17)) were mixed in a ratio of 30:30:40, and then this monomer mixture was The material was mixed with 1.5 times the mass of methyl isobutyl ketone relative to the total mass of all monomers. The resulting mixture was added with azobisisobutyronitrile and azobis(2,4 -dimethylvaleronitrile) based on the total amount of monomers, respectively, at 1.2 mol% and 3.6 mol% vol% of toluene was added, and the mixture was heated at 73°C for about 5 hours. An aqueous solution of benzophenone sulfonic acid was added, and the mixture was stirred for 12 hours, followed by separation of the layers. The resin was precipitated by pouring it into n-heptane and then filtered and collected to obtain a resin with a weight average molecular weight of approximately 5.4×10 3 Resin AX1, which has the following structural unit, was obtained in a yield of 66%. The elimination rate of the ethoxyethyl group in the total ethoxyethyl groups of the monomer (I-17) is 1. 00%). JPEG2025169323000190.jpg45122

[0285] <Preparation of Resist Composition> The components shown in Table 1 were mixed and dissolved to obtain a mixture, which was then filtered through a filter with a pore size of 0.2 μm. The mixture was filtered through a fluororesin filter to prepare a resist composition. [Table 1]

[0286] <Resin> A1 to A22, AX1: Resin A1 to Resin A22, Resin AX1 <Acid generator (B)> B1-43: A salt represented by the formula (B1-43) (the embodiment of JP 2016-47815 A) (Synthesize according to the example) JPEG2025169323000192.jpg54101<Quencher (C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF2025169323000193.tif4347<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 150 parts γ-butyrolactone 5 parts

[0287] (Electron beam exposure evaluation of resist composition: alkaline development) 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 using a resist composition. 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 1 to form a composition layer. The composition layer formed on the wafer was subjected to an electron beam lithography machine (HL-800D manufactured by Hitachi, Ltd.). 50 keV] and gradually change the exposure dose to create a line and space pattern. Directly painted. After exposure, post-exposure was performed on a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 1. The mixture was then baked in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. A resist pattern was obtained by puddle development with a solution for 60 seconds. The resulting resist pattern (line and space pattern) was observed with a scanning electron microscope. Therefore, the line width and space width of the 60 nm line and space pattern are 1:1. The exposure amount was taken as the effective sensitivity.

[0288] Line Edge Roughness Evaluation (LER): Sidewall of resist pattern manufactured with effective sensitivity The amplitude of the unevenness of the surface was measured using a scanning electron microscope to determine the line edge roughness. The results are shown in Table 2. [Table 2]

[0289] (Electron beam exposure evaluation of resist composition: butyl acetate development) 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 using a resist composition. 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 1 to form a composition layer. The composition layer formed on the wafer was subjected to an electron beam lithography machine (HL-800D manufactured by Hitachi, Ltd.). 50 keV] and gradually change the exposure dose to create a line and space pattern. Directly painted. After exposure, post-exposure was performed on a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 1. The composition layer on the silicon wafer was then developed using acetic acid as a developer. Dynamic dispensing using butyl (Tokyo Chemical Industry Co., Ltd.) at 23°C for 20 seconds A resist pattern was obtained by developing the resist film by the method. The resulting resist pattern (line and space pattern) was observed with a scanning electron microscope. Therefore, the line width and space width of the 60 nm line and space pattern are 1:1. The exposure amount was taken as the effective sensitivity.

[0290] Line Edge Roughness Evaluation (LER): Sidewall of resist pattern manufactured with effective sensitivity The amplitude of the unevenness of the surface was measured using a scanning electron microscope to determine the line edge roughness. The results are shown in Table 3. [Table 3] [Industrial Applicability]

[0291] The resist composition containing the resin of the present invention has a line edge Because of its excellent roughness (LER), it is suitable for semiconductor microfabrication and is extremely useful in industry. be.

Claims

1. A compound represented by formula (IA): [In formula (IA), R １ represents a hydrogen atom or a methyl group. X １ is a single bond or -CO-O-* (* is Ar １ represents the bonding position with . X ２ are -CO-O-*, -O-*, -O-CO-*, -O-CO-(CH ２ ) ｍｍ -O-* or -O-(CH ２ ) ｎｎ -CO-O-* (* represents the bonding position to the benzene ring). mm and nn represent 0 or 1. Ar １ represents an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. R ３ and R ４ each independently represents a hydrogen atom or an acid labile group, or R ３ and R ４ may be combined together to form a group having an acetal ring structure. R ５ 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 —CH 2 - may be replaced by -O- or -CO-. n' represents an integer of 0 to 3, and when n' is 2 or more, a plurality of R ５ may be the same or different.]

2. X １ The compound according to claim 1, wherein is a single bond.

3. X ２ is —CO—O—* or —O—* (* represents the bonding position to the benzene ring).

4. The compound according to any one of claims 1 to 3, wherein n' is 0.

5. R ３ and R ４ is a hydrogen atom, or R ３ and R ４ The compound according to any one of claims 1 to 4, wherein

6. A resin comprising a structural unit derived from the compound according to any one of claims 1 to 5.

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