Compound and resin

Abstract

To provide a compound and a resin which allow a resist pattern having good line edge roughness (LER) to be produced.SOLUTION: There are provided a compound represented by formula (I) and a resin. [R0 represents an alkyl group which may have a halogen atom, H or the like; X1 represents a bond selected from an ether bond, an ester bond and a carbonate ester bond, or a linking group in which a bond selected from a single bond, an ether bond, an ester bond and a carbonate ester bond is combined with an optionally substituted arylene group; L1 represents a single bond, a substituted / unsubstituted hydrocarbon group or the like; Ar represents a substituted / unsubstituted aromatic hydrocarbon group; X2 represents O or S; R1 represents F, Br, I or a haloalkyl group; R2 represents a halogen atom, a hydroxy group, a haloalkyl group or the like; m1 represents an integer of 1-6; and m2 represents an integer of 0-4.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound and a resin containing a structural unit derived from the compound. [Background technology]

[0002] Patent Document 1 describes a resist composition containing a resin containing a structural unit derived from the following compound: is stated. TIFF2025163074000001.tif2819

[0003] Patent Document 2 discloses a resist composition containing a resin containing a structural unit derived from the following compound: is stated. TIFF2025163074000002.tif2819 [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-095851 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-161823 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a resist composition containing a resin containing a structural unit derived from the above compound. The resist pattern has better line edge roughness (LER) than the resist pattern formed by A compound that forms a stop pattern is provided. [Means for solving the problem]

[0006] The present invention includes the following inventions. [1] A composition containing a resin having a structural unit derived from a compound represented by formula (I) and an acid generator. A resist composition. TIFF2025163074000003.tif4091 [In formula (I), R 0 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. represents a halogen atom. X 1 is selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond. or a bond type consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond. and optionally having at least one or two bond types and substituents selected from the group represents a linking group in which an arylene group is combined. L 1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, -CH2- contained in the hydrogen group is replaced by -O-, -S-, -SO2- or -CO-. It may be possible. Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. X 2 represents an oxygen atom or a sulfur atom. R 1 represents a halogen atom or a haloalkyl group having 1 to 12 carbon atoms. R 2 is a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, or a represents an alkyl group having a carbon number of 1 to 12, and -CH2- contained in the haloalkyl group and the alkyl group is , -O- or -CO-. m1 represents an integer of 1 to 6, and when m1 is 2 or more, the groups in the parentheses are mutually exclusive. They may be the same or different. m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R 2 are the same as each other They may be the same or different.] [2] X 1But the formula (X 1 -1)~Formula(X 1 -7) [1] The resist composition according to claim 1. TIFF2025163074000004.tif45141[expression(X 1 -1)~Formula(X 1 -7) Medium, *, ** represent binding sites, ** represents L 1 represents the binding site with [3] X 1 But the formula (X 1 -1), formula (X 1 -3) or formula (X 1 -4) is a group represented by The resist composition according to [2]. [4] L 1 is a single bond or *-L 2 -CO-O-(L 2 is a cyclic carbon with 3 to 18 carbon atoms. A compound consisting of a hydrogen group or a cyclic hydrocarbon group having 3 to 18 carbon atoms and an alkanediyl group having 1 to 4 carbon atoms. The cyclic hydrocarbon group may have a substituent, and the cyclic hydrocarbon group -CH2- contained in is replaced by -O-, -S-, -CO- or -SO2- The -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. * may be X 1 It is written in one of [1] to [3], which represents the binding site with The resist composition described above. [5] Ar is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. [1] The resist composition according to any one of items [1] to [4]. [6] X 2 The resist composition according to any one of [1] to [5], wherein is an oxygen atom. [7] R 1 is an iodine atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms The resist composition according to any one of [1] to [6]. [8] R 2 However, iodine atoms, fluorine atoms, hydroxyl groups, and perfluorocarbons with 1 to 3 carbon atoms The compound according to any one of [1] to [7], which is an alkyl group or an alkoxy group having 1 to 3 carbon atoms. gyst composition. [9] The resin has an acid labile group other than the structural unit derived from the compound represented by formula (I). The resist composition according to any one of [1] to [8], further comprising a structural unit represented by the formula:

[10] Any one of [1] to [9], wherein the acid generator contains a salt represented by formula (B1): A resist composition according to claim 1. TIFF2025163074000005.tif2855[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 SO2- or -CO-. Z + represents an organic cation.

[11] The composition further contains a salt that generates an acid weaker in acidity than the acid generated from the acid generator. The resist composition according to any one of [1] to

[10] .

[12] (1) A method of applying the resist composition according to any one of [1] to

[11] onto 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.

[13] A compound represented by formula (I): TIFF2025163074000006.tif4091 [In formula (I), R 0 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. represents a halogen atom. X 1 is selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond. or a bond type consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond. and optionally having at least one or two bond types and substituents selected from the group represents a linking group in which an arylene group is combined. L 1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, -CH2- contained in the hydrogen group is replaced by -O-, -S-, -SO2- or -CO-. It may be possible. Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. X 2 represents an oxygen atom or a sulfur atom. R 1 represents a halogen atom or a haloalkyl group having 1 to 12 carbon atoms. R 2 is a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, or a represents an alkyl group having a carbon number of 1 to 12, and -CH2- contained in the haloalkyl group and the alkyl group is , -O- or -CO-. m1 represents an integer of 1 to 6, and when m1 is 2 or more, the groups in the parentheses are mutually exclusive. They may be the same or different. m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R 2 are the same as each other They may be the same or different.]

[14] A resin containing a structural unit derived from the compound according to

[13] . [Effects of the Invention]

[0007] The resist composition contains a resin containing a structural unit derived from the compound of the present invention. This makes it possible to create resist patterns with good line edge roughness (LER). Cut. DETAILED DESCRIPTION OF THE INVENTION

[0008] In this specification, the term "(meth)acrylic monomer" refers to "acrylic monomer and "(Meth)acrylate" and "at least one methacrylic monomer" are used. The expressions "(meth)acrylic acid" and the like also have the same meaning. In the case where the hydrocarbon can have either a linear structure or a branched structure, either structure may be used. When -CH2- contained in the group is replaced with -O-, -S-, -CO- or -SO2- The same examples apply to each group. "Combined groups" refer to groups that are exemplified above. It means a group in which two or more types are bonded together, and the valence of these groups may be changed appropriately depending on the bonding form. "Derived from" or "derived from" means that the polymerizable C=C bond contained in the molecule is polymerized. When stereoisomers exist, all Includes stereoisomers.

[0009] [Compound represented by formula (I)] The compound of the present invention is a compound represented by formula (I) (hereinafter, sometimes referred to as "compound (I)"). (Regarding). TIFF2025163074000007.tif4091 [In formula (I), all symbols have the same meanings as defined above.]

[0010] In formula (I), R 0 The alkyl group of the formula (I) is a methyl group, an ethyl group, or an n-propyl group. , isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-butyl group and n-hexyl group, and preferably an alkyl group having 1 to 4 carbon atoms. More preferably, it is a methyl group or an ethyl group. R 0 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. can be done. R 0 Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoromethyl group, and perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoro Pentyl group, perfluorohexyl group, perchloromethyl group, perbromomethyl group and pentyl group Examples thereof include an iodomethyl group. R 0 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom, a methyl group, or An ethyl group is more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0011] In formula (I), X 1 However, single bonds, ether bonds, ester bonds and carbonate ester bonds and having at least one or two bond types and substituents selected from the group consisting of In the case of a linking group in which an optionally substituted arylene group is combined, the linking group is represented by the following formula (X10): Preferably, the linking group is a linking group that can be bonded to the hydroxyl group. TIFF2025163074000008.tif3449 formula (X10), Ax is L 1 represents the bond type that bonds with, and includes single bonds, ether bonds, ester bonds, and carbonate bonds. represents one type of bond selected from the group consisting of ester bonds. Ay is R 0 represents the bond type that bonds with the carbon atom to which the It represents one type of bond selected from the group consisting of ester bonds and carbonate ester bonds. When Ax is a single bond, Ay is an ether bond, an ester bond, or a carbonate ester bond. It is preferable that Ax is one type of bond selected from the group consisting of One bond selected from the group consisting of a tert-bond, an ester bond, and a carbonate ester bond. When the compound is a compound, Ay is selected from a single bond, an ether bond, an ester bond, and a carbonate ester bond. Preferably, the binding species is one selected from the group consisting of: Rx is a halogen atom, a hydroxy group, a fluoroalkyl group having 1 to 6 carbon atoms, a 18 alkyl group or alkoxy group having 1 to 6 carbon atoms. A methyl atom, a trifluoromethyl group, a methyl group or an ethyl group is preferred. mx represents an integer of 0 to 4, and preferably 0, 1 or 2. When mx is an integer of 2 or more, When Rx is a number, the multiple Rx may be the same or different. The bonding position of Ay in the arylene group is the m-position or p-position relative to the bonding position of Ax. It is preferable that the amino acid is in the p-position, and more preferable that the amino acid is in the p-position. X 1 For example, the following formula (X 1 -1), formula (X 1 -2')~expression(X 1 -7') and the formula (X 1 -8) * denotes a group represented by -R0 Bond with the carbon atom to which ** indicates L 1 represents the binding site with TIFF2025163074000009.tif51156 formula (X 1 -2')~expression(X 1 Specific examples of the group represented by -7') include the following groups: can be done. TIFF2025163074000010.tif78122Among them, X 1 is the formula (X 1 -1)~Formula(X 1 -7) and preferably, the formula (X 1 -1), a group represented by the formula (X 1 -3), a group represented by the formula (X 1 - 4) or a group represented by formula (X 1 It is more preferable that the group is a group represented by the formula (X -5), 1 -1), a group represented by the formula (X 1 -3) or a group represented by the formula (X 1 -4) is a group represented by It is more preferred that the formula (X 1 -1) or a group represented by the formula (X 1 -4) It is even more preferred that the formula (X 1 It is particularly preferred that the group is represented by stomach. L 1 The hydrocarbon group in the formula (I) is a divalent chain hydrocarbon group such as an alkanediyl group, a monocyclic or polycyclic (including spiro) divalent alicyclic hydrocarbon groups, divalent aromatic hydrocarbon groups and groups in which two or more of these groups are combined (for example, a group in which an alicyclic hydrocarbon group and an alkane group are combined). A divalent hydrocarbon group formed from a cyclohexyl group and a candiyl group may also be used. Examples of the alkanediyl group include a methylene group, an ethylene group, and a 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 group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,1 2-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, Pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane linear alkanediyl groups such as alkane-1,17-diyl groups and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and branched alkanediyl groups such as a 2-methylbutane-1,4-diyl group. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 18, and more preferably 1 to 12. More preferably, it is 1 to 9, even more preferably, it is 1 to 6, and even more preferably, it is Usually it is 1 to 4. Examples of the monocyclic or polycyclic divalent alicyclic hydrocarbon group include the following groups: The site can be at any location. TIFF2025163074000011.tif43166Specifically, the alicyclic hydrocarbon group includes a cyclobutane-1,3-diyl group, a cyclopent ... hexane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5 a monocyclic divalent alicyclic hydrocarbon group such as a cycloalkanediyl group, e.g., a -diyl group; Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic hydrocarbons such as 1,5-diyl group and adamantane-2,6-diyl group Examples of such groups include: The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 3 to 16 carbon atoms. and more preferably 3 to 12. The divalent aromatic hydrocarbon group includes a phenylene group, a naphthylene group, an anthrylene group, a biphenyl group, a phenylene group, a naphthylene group, a phenylene ... Examples include aromatic hydrocarbon groups such as arylene groups such as a phenylene group and a phenanthrylene group. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. and more preferably 6 to 10. The group consisting of two or more groups may be a group consisting of an alicyclic hydrocarbon group and an alkanediyl group. a group combining an aromatic hydrocarbon group and an alkanediyl group; a group combining an aromatic hydrocarbon group and an alkanediyl group; and an alicyclic hydrocarbon group. In the combination, an alicyclic hydrocarbon group may be used. The hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group may each be a combination of two or more types. In addition, which group is X 1 may be bound to Examples of the group combining an alicyclic hydrocarbon group and an alkanediyl group include a -divalent Alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group -alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group-, etc. . Examples of the group combining an aromatic hydrocarbon group and an alkanediyl group include a -divalent Aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group -alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-, etc. . Examples of the group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group include: -aromatic hydrocarbon Group-alicyclic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, -alicyclic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, and the like. L 1 -CH2- contained in the hydrocarbon group having 1 to 28 carbon atoms is -O-, -S-, -SO It may be replaced by 2- or -CO-. L 1 The -CH2- contained in the hydrocarbon group having 1 to 28 carbon atoms is -O-, -S-, -SO2 When the hydrocarbon group is substituted with - or -CO-, the number of carbon atoms before the substitution is the number of carbon atoms of the hydrocarbon group. Let's say. -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -SO2- or -CO-. The substituted group is a hydroxy group (-CH2- contained in a methyl group is replaced with -O-). substituted), carboxy group (-CH2-CH2- contained in the ethyl group is replaced by -O-CO- thiol group (-CH2- in the methyl group is replaced by -S-) an alkoxy group (a group in which -CH2- at any position in the alkyl group is replaced with -O- alkylthio groups (groups where -CH2- is substituted at any position in the alkyl group) is replaced by -S-), alkoxycarbonyl group (any group contained in an alkyl group -CH2-CH2- at position (a) is replaced by -O-CO-), alkylcarbonyl group (a group in which -CH2- at any position in an alkyl group is replaced with -CO-), alkylsulfonyl group (where -CH2- at any position in the alkyl group is replaced with -SO2-) substituted groups), alkylcarbonyloxy groups (alkyl groups at any position -CH2-CH2- is replaced by -CO-O-), alkanediyloxy group (alkanediyloxy group a group in which any -CH2- at any position in a candiyl group is replaced with -O-), alkanediyloxycarbonyl group (-CH2- at any position contained in the alkanediyl group) CH2- is replaced by -O-CO-), alkanediylcarbonyl group (alkane a diyl group in which any -CH2- at any position is replaced by -CO-), an alkane alkanediylcarbonyloxy group (-CH2-C at any position in the alkanediyl group) H2- is replaced by -CO-O-), alkanediylsulfonyl group (alkanedi a group in which any -CH2- in an alkyl group is replaced with -SO2-), Alkandiylthio group (-CH2- at any position in the alkanediyl group is replaced with -S-) substituted groups), cycloalkoxy groups, cycloalkylalkoxy groups, alkoxycarbonyl groups a hydroxyl group, an aromatic hydrocarbon group-carbonyloxy group, or a combination of two or more of these groups and the like. The alkoxy group includes an alkoxy group having 1 to 17 carbon atoms, for example, methoxy. group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, oxy octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, un The alkoxy group preferably has 1 to 11 carbon atoms, and More preferably, it is 1 to 6, even more preferably, it is 1 to 4, and even more preferably, it is 1 ~3. The alkylthio group includes alkylthio groups having 1 to 17 carbon atoms, such as methyl. Examples of the alkylthio group include an alkylthio group, an ethylthio group, a propylthio group, and a butylthio group. The number of carbon atoms in the group is preferably 1 to 11, more preferably 1 to 6, and even more preferably Preferably, it is 1 to 4, and even more preferably 1 to 3. 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. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms. Examples of such groups include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 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 17 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 11, and more preferably 2. The number of carbon atoms is preferably 1 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably 2 to 6. It is more preferably 2 to 4, and even more preferably 2 or 3. The carbonyloxy group preferably has 2 to 11 carbon atoms, more preferably 2 to 6 carbon atoms. , more preferably 2 to 4, and even more preferably 2 or 3. The alkylsulfonyl group includes alkylsulfonyl groups having 1 to 17 carbon atoms. Examples include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 11, and more preferably 1. It is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyloxy group include alkanediyloxy groups having 1 to 17 carbon atoms. Examples of such groups include methyleneoxy groups, ethyleneoxy groups, propanediyloxy groups, butanediyloxy groups, and the like. Examples of the carbon atom of the alkanediyloxy group include an alkanediyloxy group and a pentanediyloxy group. The number is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to 11. It is 4, and even more preferably 1 to 3. The alkanediyloxycarbonyl group is an alkanediyloxy group having 2 to 17 carbon atoms. carbonyl groups, such as methyleneoxycarbonyl and ethyleneoxycarbonyl groups. Examples of the hydroxyl group include a propanediyloxycarbonyl group, a butanediyloxycarbonyl group, and the like. The alkanediylcarbonyl group is an alkanediylcarbonyl group having 2 to 18 carbon atoms. Examples of the alkyl group include a methylenecarbonyl group, an ethylenecarbonyl group, and a propanediyl group. Examples of the arylcarbonyl group include a butanediylcarbonyl group and a pentanediylcarbonyl group. The alkanediylcarbonyloxy group is an alkanediylcarbonyloxy group having 2 to 17 carbon atoms. Examples of such groups include a methylenecarbonyloxy group and an ethylenecarbonyloxy group. hydroxyl group, propanediylcarbonyloxy group, butanediylcarbonyloxy group, etc. The number of carbon atoms in the alkanediyloxycarbonyl group is preferably 2 to 11. , more preferably 2 to 6, even more preferably 2 to 4, and even more preferably The number of carbon atoms in the alkanediylcarbonyl group is preferably 2 to 12. More preferably, it is 2 to 6, even more preferably, it is 2 to 4, and even more preferably, it is 2 or 3. The number of carbon atoms in the alkanediylcarbonyloxy group is preferably 2 to 11. More preferably, it is 2 to 6, even more preferably 2 to 4, and even more preferably is 2 or 3. The alkanediylsulfonyl group is an alkanediylsulfonyl group having 1 to 17 carbon atoms. Examples thereof include a methylene sulfonyl group, an ethylene sulfonyl group, and a propylene sulfonyl group. The number of carbon atoms in the alkanediylsulfonyl group is preferably 1 to 11. It is more preferably 1 to 6, even more preferably 1 to 4, and even more preferably Usually it is 1 to 3. Examples of the alkanediylthio group include alkanediylthio groups having 1 to 17 carbon atoms. Examples include a methylenethio group, an ethylenethio group, and a propylenethio group. The diylthio group preferably has 1 to 11 carbon atoms, more preferably 1 to 6 carbon atoms, More preferably, it is 1 to 4, and even more preferably, it is 1 to 3. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms, such as Examples of the cycloalkylalkoxy group include a cyclohexyloxy group and the like. and cycloalkylalkoxy groups having a prime number of 4 to 17, such as cyclohexylmethoxy. The alkoxycarbonyloxy group includes an alkoxy group having 2 to 16 carbon atoms. and oxycarbonyloxy groups, for example, butoxycarbonyloxy groups. The aromatic hydrocarbon group-carbonyloxy group is an aromatic hydrocarbon group having 7 to 17 carbon atoms. Examples of the group include a carbonyloxy group, such as a benzoyloxy group. In addition, -CH2- contained in the alicyclic hydrocarbon group may be -O-, -S-, -CO- or -S Examples of the group substituted with O2- include the following groups: -O- in the groups shown below Or -CO- may be replaced by -S- or -SO2-, respectively. The binding site is optional. The position can be: TIFF2025163074000012.tif46166

[0012] L 1 The substituents which may be contained in the alkyl group include a hydroxy group, a carboxy group, a halogen atom, a silyl group, a hydroxy group, a carboxyl group, a hydroxy group, a hydroxyl ... Aromatic groups, alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, and alkoxy groups having 2 to 13 carbon atoms. an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, Examples thereof include alkylcarbonyloxy groups and groups in combination thereof. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl Examples thereof include a methyl group and a nonyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a bromine group, and a methyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl hydroxyl group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group etc. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and and the alkylcarbonyloxy group having 2 to 13 carbon atoms is the alkyl or alkoxy group described above. represents a group in which a carbonyl group or a carbonyloxy group is bonded to a group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy group, and carbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 13 carbon atoms. Examples of the alkyl group include an acetyl group, a propionyl group, and a butyryl group, and the alkyl group has 2 to 1 carbon atoms. The alkylcarbonyloxy group of 3 includes an acetyloxy group, a propionyloxy group, butyryloxy group and the like. The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group, or a halogen atom. Preferably, it is an alkyl group having 1 to 4 carbon atoms or a halogen atom, and more preferably, it is methyl. It is more preferably a group or a fluorine atom.

[0013] L 1 is a single bond, an alkanediyl group having 1 to 8 carbon atoms (provided that the alkanediyl group does not include -CH2- may be replaced by -O- or -CO-), A compound comprising a combination of an alkanediyl group and an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have a substituent. (However, -CH2- contained in the alkanediyl group is not -O- or -CO-.) The —CH2— contained in the alicyclic hydrocarbon group may be replaced by —O—, —S -, -SO2- or -CO- may be substituted.) or an alkane having 1 to 6 carbon atoms A diyl group and an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have a substituent, in combination. (However, -CH2- contained in the alkanediyl group is replaced by -O- or -CO-.) It is preferable that the alkyl group is a single bond or an alkanediyl group having 1 to 6 carbon atoms. (However, -CH2- contained in the alkanediyl group is replaced with -O- or -CO-. The alkanediyl group having 1 to 4 carbon atoms and the alkanediyl group having 3 to 4 carbon atoms which may have a substituent may be used. A group formed by combining an alicyclic hydrocarbon group of 18 (provided that the alkanediyl group -CH2- may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group -CH2- contained in the alkyl group may be replaced by -O- or -CO-. and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. A group obtained by combining (provided that the -CH2- contained in the alkanediyl group is not -O- or -C It is more preferable that the aryl group is substituted with O-. Also, L 1 is a single bond, *-L 2 -CO-O- or *-L 2 -O-CO-O-(L 2 teeth a cyclic hydrocarbon group having 3 to 18 carbon atoms, or a cyclic hydrocarbon group having 3 to 18 carbon atoms and a cyclic hydrocarbon group having 1 to 4 carbon atoms and an alkanediyl group represented by the formula (I) above, and the cyclic hydrocarbon group has a substituent. The -CH2- contained in the cyclic hydrocarbon group may be -O-, -S-, -CO- or - The —CH2— contained in the alkanediyl group may be replaced by —O * may be replaced by - or -CO-. 1 It represents the binding site with Both are preferable. In addition, the combination of the alkanediyl group with the alicyclic hydrocarbon group or the aromatic hydrocarbon group The combination is *-alkanediyl group-alicyclic hydrocarbon group or aromatic hydrocarbon group-, *-alicyclic Hydrocarbon group or aromatic hydrocarbon group-alkanediyl group-, *-alkanediyl group-alicyclic Examples include hydrocarbon groups or aromatic hydrocarbon groups -alkanediyl groups. * denotes X 1 Bond with Represents the binding site. L 2 The cyclic hydrocarbon group and alkanediyl group in the formula (I) are the same as those exemplified above. Examples of the group include the following. L 2 represents a polycyclic divalent cyclic hydrocarbon group having 6 to 12 carbon atoms or a polycyclic and an alkanediyl group having 1 to 4 carbon atoms (the cyclic The hydrocarbon group may have a substituent, and the —CH— contained in the cyclic hydrocarbon group is may be replaced by -O-, -S-, -CO- or -SO2-, -CH2- contained in the group may be replaced by -O- or -CO-. and a polycyclic divalent alicyclic hydrocarbon group having 7 to 11 carbon atoms or a divalent alicyclic hydrocarbon group having 7 to 11 carbon atoms is preferred. A group that combines a polycyclic divalent alicyclic hydrocarbon group with an alkanediyl group having 1 to 3 carbon atoms (The -CH2- contained in the alicyclic hydrocarbon group is replaced with -O- or -CO-. The -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. It is more preferable that the compound is represented by the following formula (L 2 -1), a group represented by the formula (L 2 -2), a group represented by the formula (L 2 -3) and a group represented by the formula (L 2 -4) or a group selected from the group consisting of the following formula (L 2 -1), a group represented by the formula (L 2 -2) The group of formula (L 2 -3) and a group represented by the formula (L 2 -4) from the group consisting of groups represented by A group obtained by combining the selected group with an alkanediyl group having 1 to 3 carbon atoms (the alkanediyl group -CH2- contained in may be replaced by -O- or -CO-. More preferably, the formula (L 2 The group represented by -2) is more preferred. * represents a bonding site. . TIFF2025163074000013.tif3096

[0014] The aromatic hydrocarbon group in Ar is, in the case of a divalent group, a phenylene group, a naphthylene group, Aromatic carbons such as arylene groups such as anthrylene groups, biphenylene groups, and phenanthrylene groups In the case of trivalent alkyl groups, benzenetriyl groups, naphthalenetriyl groups, and anthraquinone groups are examples. Aromatic hydrocarbons such as lacentriyl, biphenyltriyl, and phenanthrenetriyl groups In the case of tetravalent groups, benzenetetrayl group, naphthalenetetrayl group, ammonium tetrayl group, Aromatic groups such as tetrathylenetetrayl group, biphenyltetrayl group, and phenanthrenetetrayl group In the case of pentavalent groups, benzene pentavalent groups and naphthalene pentavalent groups are examples. group, anthracene pentaylene group, biphenyl pentaylene group, phenanthrene pentaylene group In the case of hexavalent groups, aromatic hydrocarbon groups such as benzenehexyl group and naphthalene group are used. Hexyl group, anthracenehexyl group, biphenylhexyl group, phenanthrenehexyl group Examples of the aromatic hydrocarbon groups include a silyl group. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. It is more preferably 6 to 10, and even more preferably 6.

[0015] The substituents that Ar may have include a hydroxy group, a carboxy group, a halogen atom, a silyl group, and the like. Aromatic groups, alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, and alkoxy groups having 2 to 13 carbon atoms. an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, Examples thereof include alkylcarbonyloxy groups and groups in combination thereof. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl Examples thereof include a methyl group and a nonyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a bromine group, and a methyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl hydroxyl group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group etc. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and and the alkylcarbonyloxy group having 2 to 13 carbon atoms is the alkyl or alkoxy group described above. represents a group in which a carbonyl group or a carbonyloxy group is bonded to a group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy group, and carbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 13 carbon atoms. Examples of the alkyl group include an acetyl group, a propionyl group, and a butyryl group, and the alkyl group has 2 to 1 carbon atoms. The alkylcarbonyloxy group of 3 includes an acetyloxy group, a propionyloxy group, butyryloxy group and the like. The substituents are alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, hydroxyl groups, and the like. A group, a carboxy group or a halogen atom is preferred, an alkyl group having 1 to 6 carbon atoms, a More preferably, the alkyl group is an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, or a halogen atom. an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxy group, or a halogen atom It is even more preferable that: Ar is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent. It is more preferable that the aromatic hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. It is more preferable that the aromatic hydrocarbon group has 6 carbon atoms and may have a substituent. It is even more preferable that the phenylene group has a substituent. an alkyl group having 1 to 12 carbon atoms or a carboxyl group, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a carboxyl group having 1 to 1 Alkoxy groups of 2 are preferred, and hydroxy groups, halogen atoms, and alkyl groups having 1 to 6 carbon atoms are also preferred. Or an alkoxy group having 1 to 6 carbon atoms is more preferred, and a hydroxy group, a halogen atom, a An alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is more preferred.

[0016] R 1 and R 2 The halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples include children. R 1 and R 2 The haloalkyl group having 1 to 12 carbon atoms is a carbon atom having a halogen atom. Represents an alkyl group having 1 to 12 prime numbers, a fluorinated alkyl group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, alkyl chlorides, alkyl bromides having 1 to 12 carbon atoms, alkyl iodides having 1 to 12 carbon atoms Examples of haloalkyl groups include perfluoroalkyl groups having 1 to 12 carbon atoms. (Trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluoropropyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, propyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group Examples include a chlorobutyl group, a chloromethyl group, a bromomethyl group, and an iodomethyl group. 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, and even more preferably, it is 1 to 3. R 2Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an isopropyl group. Propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, Examples of the alkyl group include an octyl group and a nonyl group. The number of carbon atoms in the alkyl group is preferably It is 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably More preferably, it is 1 to 3. R 2 The —CH2— contained in the haloalkyl group or alkyl group represented by the following formula is —O— or — When the haloalkyl group is replaced with CO-, the number of carbon atoms before the replacement is The total number of carbon atoms in the methyl group is used as the substituted group. -CH2- is replaced by -O-), carboxyl group (-CH2 contained in ethyl group) -CH2- is replaced by -O-CO-), alkoxy group (a group contained in an alkyl group a group in which any -CH2- at any position is replaced with -O-), an alkoxycarbonyl group (an alkoxycarbonyl group A group in which any -CH2-CH2- in an alkyl group is replaced by -O-CO- ), alkylcarbonyl group (wherein any -CH2- in the alkyl group is -CO -substituted), alkylcarbonyloxy group (a group substituted with - at any position in the alkyl group) a haloalkoxy group (a group in which the -CH2-CH2- position is replaced by -CO-O-); a group in which any -CH2- in an alkyl group is replaced with -O-), A haloalkyl group (wherein any of -CH2-CH2- at any position in the haloalkyl group is - O-CO- replaced), haloalkylcarbonyl group (a group contained in a haloalkyl group) a group in which any one of -CH2- at any position is replaced by -CO-), haloalkylcarbonyl An oxy group (a haloalkyl group in which -CH2-CH2- at any position is replaced with -CO-O-) and groups in which two or more of these groups are combined. The alkoxy group includes an alkoxy group having 1 to 11 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 in the alkoxy group is preferably 1 to 6, and more preferably 1 to 6. More preferably, it is 1 to 4, and further preferably, it is 1 to 3. 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 11 carbon atoms. Examples of such groups include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 12 carbon atoms. Examples include an acetyl group, a propionyl group, and a butyryl group. Examples of the carbonyloxy group include alkylcarbonyloxy groups having 2 to 11 carbon atoms. Examples include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkoxycarbonyl group preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. The number of carbon atoms in the alkylcarbonyl group is preferably 2 or 3. It is 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The carbon number of the arylcarbonyloxy group is preferably 2 to 6, and more preferably 2 to 4. and more preferably 2 or 3. Haloalkoxy group, haloalkoxycarbonyl group, haloalkylcarbonyl group, haloa The alkylcarbonyloxy group is preferably a haloalkoxy group having 1 to 11 carbon atoms, a haloalkoxy group having 2 to 1 carbon atoms, haloalkoxycarbonyl groups having 1 to 12 carbon atoms, haloalkylcarbonyl groups having 2 to 12 carbon atoms, 2 to 11 haloalkylcarbonyloxy groups, for example, one of the groups exemplified above. Examples of the groups include those in which the hydrogen atoms are replaced with halogen atoms. X 2 is preferably an oxygen atom. When Ar is an aromatic hydrocarbon group having 6 carbon atoms which may have a substituent, X 2 To Ar The bonding position of L 1 The bonding position may be either the o-position, m-position or p-position. , if m1 is 1, then X 1 L 1 The bond is p- or m-position relative to the bonding position of Preferably, m1 is bonded to the p-position, and more preferably to the p-position. 1 L 1 of With respect to the bonding position, one is bonded to the o- or m-position, and the other is bonded to the o- or m-position. It is preferable that m1 is 3, and more preferable that two of them are bonded to the m-position. X 1 L 1 Two are bonded to the o- or m-position, and one is bonded to the p- or Preferably, two are bonded to the m position, and one is bonded to the p position. It is more preferable that m1 is 4. 1 L 1 For the bonding position of Preferably, two of them are bonded at the p- or m-position, and two of them are bonded at the p- or m-position. It is more preferred that one is bonded to the o-position and two are bonded to the m-position. m1 is preferably 1, 2, 3, 4 or 5, and is preferably 1, 2, 3 or 4. More preferably, it is 1, 2 or 4. m2 is preferably 0, 1, 2 or 4, more preferably 0, 2 or 4. It's nice. R 1 is preferably an iodine atom, a fluorine atom, or a haloalkyl group having 1 to 6 carbon atoms. Preferably, it is an iodine atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms. More preferably, it is an iodine atom, a fluorine atom, or a trifluoromethyl group. Preferably, it is an iodine atom or a fluorine atom, even more preferably. R 2 represents an iodine atom, a fluorine atom, a hydroxy group, a haloalkyl group having 1 to 6 carbon atoms, or An alkyl group having 1 to 6 carbon atoms (the haloalkyl group and —CH2— contained in the alkyl group) , -O- or -CO-) are preferred, and iodine atoms, fluorine atoms , a hydroxy group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a group having 1 to 4 carbon atoms An alkoxy group having 1 to 3 carbon atoms is more preferred, and an iodine atom, a fluorine atom, a hydroxy group, a A perfluoroalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is more preferred. A fluorine atom, a hydroxy group, a trifluoromethyl group or a methoxy group is more preferred. More preferable. R 1 The bonding position of to the benzene ring is X 1 The bond position is either o-position, m-position, or p-position. Among them, R 1 The bonding position of to the benzene ring is X 1 For the bonding position of m Preferably, it is in the p-position or the p-position. R 2 The bonding position of to the benzene ring is X 1 The bond position is either o-position, m-position, or p-position. Among them, when m2 is 1, R 2 The bonding position of to the benzene ring is X 1 The result It is preferably m-position or p-position relative to the X position. 1 Bonding position of It is preferred that one is at the o-position or m-position and the other is at the o-position or p-position. If 2 is 4, then X 1 With respect to the bonding position of The p-position is preferred.

[0017] Examples of Compound (I) include the following compounds: TIFF2025163074000014.tif159168

[0018] TIFF2025163074000015.tif252168

[0019] TIFF2025163074000016.tif221168

[0020] TIFF2025163074000017.tif112153

[0021] In the compounds represented by formulas (I-1) to (I-64), R 1 equivalent to A methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. Compounds of formula (I-1) to (I-2) are also specific examples of compound (I). Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-8), Formula (I-10) to Formula (I- 30), and compounds represented by formulae (I-42) to (I-50).

[0022] <Method for producing compound (I)> In compound (I), X 1 But the formula (X 1 -1), formula (X 1 -3) or formula (X 1 -4) The compound (hereinafter sometimes referred to as compound (I1)) is a group represented by the formula The compound represented by (I1-a) is reacted with carbonyldiimidazole in a solvent, and then Furthermore, it can be obtained by reacting with a compound represented by formula (Ib). TIFF2025163074000018.tif45161 (wherein all symbols have the same meanings as above. X 1A is a single bond, -Ar 1 - or -CO-O-Ar 1 -* represents Ar 1 represents a 1,4-phenylene group. * represents a carbonyl group. represents the bonding site with the carbon atom of the alkyl group.

[0023] Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile. do. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours. The compound represented by formula (I1-a) includes compounds represented by the following formula: It can be easily obtained from the market. TIFF2025163074000019.tif36163

[0024] The compound represented by formula (Ib) includes compounds represented by the following formula, and is commercially available. It can be more easily obtained. TIFF2025163074000020.tif113164

[0025] In compound (I), X 1 But the formula (X 1 -2) or formula (X1 -5) is a group represented by The compound represented by formula (I2) can be prepared by reacting a compound represented by formula (I2-a) with a compound represented by formula (I2-b). Ib) in the presence of a base in a solvent. can be done. TIFF2025163074000021.tif50152 (wherein all symbols have the same meanings as above. X 1B -Ar 1 -or-C OO-Ar 1 -*. * represents the bonding site with the oxygen atom.)

[0026] Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile. do. The base includes potassium hydroxide and the like. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours. The compound represented by formula (I2-a) includes compounds represented by the following formula: It can be easily obtained from the market. TIFF2025163074000022.tif36156

[0027] In compound (I), X 1 But the formula (X 1 -6) or formula (X 1 -7) is a group represented by The compound represented by formula (I3) can be obtained by the reaction of a compound represented by formula (I2-a) with a carbo and 2-(2-methyl-2-phenyl-2-imidazoline)-1,2-diimidazoline in a solvent, and then further reacting the compound represented by formula (Ib) It can be obtained by reacting with TIFF2025163074000023.tif52157 (wherein all symbols have the same meanings as above. X 1B -Ar 1 -or-C OO-Ar 1-*. * represents the bonding site with the oxygen atom.)

[0028] Examples of the solvent include tetrahydrofuran, chloroform, and acetonitrile. do. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0029] In compound (I), L 1 However, alkanediyl groups with 1 to 4 carbon atoms and alkanediyl groups with 3 to 18 carbon atoms A group formed by combining an alicyclic hydrocarbon group (provided that the —CH 2- may be replaced by -O- or -CO-, and is included in the alicyclic hydrocarbon group. -CH2- may be replaced by -O-, -S-, -SO2- or -CO-. The compound represented by formula (I1-a) can be used in the synthesis of the compounds represented by formula (I1) to formula (I3). ) or a compound represented by formula (I2-a) is replaced with a compound represented by the following formula: It can be produced by replacing TIFF2025163074000024.tif30150

[0030] 〔resin〕 The resin of the present invention contains a structural unit derived from compound (I) (hereinafter referred to as "structural unit (I)"). Resin (A) is a resin containing The structural unit (I) may be a homopolymer of the structural unit (I), or a copolymer consisting of only the structural unit (I). It may be a polymer, or a polymer containing one or more structural units other than the structural unit (I). The structural unit other than the structural unit (I) may be a structural unit having an acid labile group other than the structural unit (I). a structural unit (hereinafter sometimes referred to as "structural unit (a1)") having an acid labile group; A structural unit other than a unit having a halogen atom (hereinafter referred to as "structural unit (a4)") a structural unit having no acid labile group (hereinafter referred to as "structural unit (s)"); In some cases, a structural unit having a non-leaving hydrocarbon group (hereinafter referred to as "structural unit (a5)") Here, the acid labile group has a leaving group and is released by contact with an acid. The leaving group refers to a group that leaves to form a hydrophilic group (e.g., a hydroxy group or a carboxy group). Taste. The content of the structural unit (I) is usually 1 mol % or more based on the total structural units in the resin (A). The content is preferably 2 mol % or more, and more preferably 3 mol % or more. It is usually 90 mol % or less, preferably 80 mol % or less, more preferably 50 mol % or less. It is usually 1 to 90 mol %, preferably 1 to 80 mol %, and more preferably More preferably, it is 3 to 50 mol %.

[0031] <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. TIFF2025163074000025.tif1988[In formula (1), R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 8 carbon atoms. alkyl groups having 2 to 8 carbon atoms, alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and alkyl groups having 6 to 1 carbon atoms. 8 or a combination thereof, or R a1 and R a2 are bonded to each other and form a non-aromatic hydrocarbon ring of 3 to 20 carbon atoms together with the carbon atom to which they are attached. . ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * denotes a binding site.] TIFF2025163074000026.tif2171[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 ring is formed, and -CH2- contained in the hydrocarbon group and the heterocyclic ring is -O- or -S- may be replaced by . X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * denotes a binding site.]

[0032] 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 octenyl group include a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, and a nonenyl group. can be done. R a1 , R a2 and R a3 The 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 carbonization of The hydrogen group preferably has 3 to 16 carbon atoms. TIFF2025163074000027.tif10150R 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. R a1 and R a2-C(R a1 )(R a2 )(R a3 ) includes the following rings. The non-aromatic hydrocarbon ring is preferably a carbon The numbers are 3 to 12. * indicates the bonding site with -O-. TIFF2025163074000028.tif30138

[0033] 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 the like), 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 ring, -C(R a1’ )(R a2’ )-XR a3’ Examples of rings include the following: * indicates a binding site. TIFF2025163074000029.tif18130R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0034] 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 Forming 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. TIFF2025163074000030.tif154163

[0035] Specific examples of group (2) include the following groups: * represents a binding site. TIFF2025163074000031.tif55153

[0036] 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.

[0037] 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.

[0038] As a structural unit derived from a (meth)acrylic monomer having a group (1), 0) (hereinafter, may be referred to as structural unit (a1-0)), -1) (hereinafter, may be referred to as structural unit (a1-1)) or a structural unit represented by the formula ( a1-2) (hereinafter, sometimes referred to as structural unit (a1-2)) Preferably, the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a 1-2) is at least one structural unit selected from the group consisting of At least one structural unit selected from the group consisting of structural units (a1-1) and structural units (a1-2) These are structural units. They may be used alone or in combination of two or more. TIFF2025163074000032.tif44143 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or -O-(CH2) k1 - represents CO-O-, k1 represents an integer of 1 to 7, and * represents the bonding site with -CO-. represent. R a01 , R a4 and R a5 are each independently a hydrogen atom, a halogen atom or a halogen atom It represents an alkyl group having 1 to 6 carbon atoms which may have one or more atoms. 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. 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 formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0039] R a01 , R a4 and R a5 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. It is a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or —O—(CH2) k01 -C OO- (wherein k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 and R a04alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and and groups combining these groups, R in group (1) a1 , R a2 and R a3 Similar to the groups listed in Examples of such groups include: 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 The groups listed in Similar groups are mentioned. R a02 , R a03 , and R a04 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. A group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. do. R a6 and R a7 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. , more preferably 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 a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably It is 5 to 12, and more preferably 5 to 10. R a02 , R a03 , R a04 , R a6and R a7 The number of carbon atoms in the aromatic hydrocarbon group is preferably It is 6 to 12, and more 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 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. 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 0 or 1.

[0040] 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 A structure in which the alkyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group. Examples of structural units include formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13) , and a structural unit represented by formula (a1-0-14) are preferred. TIFF2025163074000033.tif89161

[0041] 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 The corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. A structural unit represented by any one of formulas (a1-1-1) to (a1-1-4) is preferred. The structural unit is more preferred. TIFF2025163074000034.tif38168

[0042] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to formula (a1-2-14). R in the structural unit (a1-2) and the structural unit (a1-2) a5 The methyl group corresponding to Examples of structural units include those substituted with hydrogen atoms, halogen atoms, haloalkyl groups, or other alkyl groups. Formula (a1-2-2), Formula (a1-2-5), Formula (a1-2-6) and Formula (a1- A structural unit represented by any one of formulas (a1-2-10) to (a1-2-14) is preferred. TIFF2025163074000035.tif67163

[0043] 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 mol % or more, preferably 10 mol % or more, based on the positions. 0 mol % or less, preferably 75 mol % or less, more preferably 70 mol % or less The content is usually 5 to 80 mol %, preferably 5 to 75 mol %, and more preferably The content is preferably 10 to 70 mol %. When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), The total content of these is usually 10 mol % or more based on the total structural units of the resin (A), and is preferably It is preferably 15 mol % or more, more preferably 20 mol % or more. % or less, preferably 85 mol % or less, and more preferably 80 mol % or less. It is more preferably 75 mol % or less, and even more preferably 70 mol % or less. The content is usually 10 to 90 mol %, preferably 15 to 85 mol %, and more preferably Preferably, it is 20 to 80 mol %, more preferably 20 to 75 mol %, and even more preferably The content is preferably 20 to 70 mol %.

[0044] 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)"). TIFF2025163074000036.tif4564[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1 group optionally having a halogen atom Represents an alkyl group of 1 to 6. R a33is 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.]

[0045] 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. 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 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 a33 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 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.

[0046] *-X a31 -(A a32 -X a32 ) nc - includes *-O-, *-CO-O-, *-OC O-, *-CO-OA a32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO-, Among them, *-CO-O- and *-CO-OA are a32 -CO-O- or *- Office Automation a32 -CO-O- is preferred.

[0047] 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.

[0048] 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.

[0049] 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. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. 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: TIFF2025163074000037.tif10151Aromatic 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:

[0050] 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.

[0051] 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. -4-24) and R in the structural unit (a1-4) a32 to A structure in which the corresponding hydrogen atom is replaced by a halogen atom, a haloalkyl group, or an alkyl group. More preferably, the units are those of the formula (a1-4-1) to the formula (a1-4-5), -4-10), (a1-4-13), and (a1-4-14) Rankings include: TIFF2025163074000038.tif129162

[0052] When the resin (A) contains the structural unit (a1-4), the content thereof is determined based on the total structure of the resin (A). It is preferably 3 to 80 mol %, more preferably 5 to 75 mol %, based on the total of the units. More preferably, the content is 7 to 70 mol %, and even more preferably, 7 to 65 mol %. It is even more preferable that the content is 10 to 60 mol %.

[0053] 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. TIFF2025163074000039.tif4558 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 a halogen 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.

[0054] 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, and an ethyl group. group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoro group Examples of such groups include a trifluoromethyl group and a 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—.

[0055] 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. TIFF2025163074000040.tif33133

[0056] When the resin (A) contains 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 unit. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0057] Further, examples of the structural unit (a1) include the following structural units. TIFF2025163074000041.tif31162

[0058] When the resin (A) contains structural units such as those of (a1-3-1) to (a1-3-7) The content thereof is preferably 10 to 95 mol % based on the total structural units of the resin (A), and more preferably 15 to 95 mol %. More preferably, the content is 20 to 90 mol %, even more preferably, 20 to 85 mol %, and 20 to 70 mol %. It is even more preferable, and 20 to 60 mol % is particularly preferable.

[0059] Further, examples of the structural unit (a1) include the following structural units. TIFF2025163074000042.tif5195When resin (A) contains structural units such as (a1-6-1) to (a1-6-3) 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.

[0060] <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 containing 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.

[0061] <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.

[0062] 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. TIFF2025163074000043.tif4753[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.]

[0063] 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.

[0064] *-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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] The structural unit (a2-A) is represented by formula (a2-2-1) to formula (a2-2-24). In the structural units represented by formulas (a2-2-1) to (a2-2-24), R in structural unit (a2-A) a50 The corresponding methyl group is a hydrogen atom, a halogen atom, or a halo. Examples of the structural unit (a2) include a structural unit in which the alkyl group is substituted with an alkyl group or another alkyl group. -A) is a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), Unit, structural unit represented by formula (a2-2-6), structural unit represented by formula (a2-2-8) and structural units represented by formulae (a2-2-12) to (a2-2-14) and structural units represented by formula (a2- 2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2- 6), a structural unit represented by formula (a2-2-8) and a structural unit represented by formula (a2-2-1 2) In the structural unit represented by formula (a2-2-14), RuR a50 is preferably a structural unit in which a methyl group corresponding to Structural units represented by formula (a2-2-3), structural units represented by formula (a2-2-8), and structural units represented by formula ( a2-2-12) to (a2-2-14) and structural units represented by formula (a2-2-3) a structural unit represented by formula (a2-2-8), a structural unit represented by formula (a2-2-12) to In the structural unit represented by formula (a2-2-14), R in the structural unit (a2-A) a 50More preferably, the structural unit is a structural unit in which a methyl group corresponding to In the structural unit represented by formula (a2-2-8) and the structural unit represented by formula (a2-2-8), In the structural unit (a2-A), R a50 The methyl group corresponding to It is more preferable that the structural unit is a structural unit having the structure: TIFF2025163074000044.tif79168

[0070] Content of structural unit (a2-A) when structural unit (a2-A) is contained in resin (A) is preferably 5 mol % or more, more preferably 10 mol % or more, based on all structural units. More preferably, it is 15 mol % or more, and even more preferably, it is 20 mol % or more. In addition, it is preferably 80 mol % or less, and more preferably 70 mol % or less. It is more preferably 65 mol % or less, and more preferably 5 to 80 mol %. More preferably, it is 10 to 70 mol %, even more preferably, it is 15 to 65 mol %, and even more preferably, it is 10 to 70 mol %. More preferably, it is 20 to 65 mol %. 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.

[0071] 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: TIFF2025163074000045.tif4461 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 site 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.

[0072] 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.

[0073] 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 examples. ) is preferred, and a structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) The structural unit represented by formula (a2-1-1) or formula (a2-1- The structural unit represented by 3) is more preferred. TIFF2025163074000046.tif50139

[0074] When the resin (A) contains the structural unit (a2-1), its content is determined based on the total structural units of the resin (A). It is usually 1 mol % or more, and usually 45 mol % or less, preferably 45 mol % or less, based on the positions. 0 mol % or less, more preferably 35 mol % or less, and even more preferably 20 mol % or less, and more preferably 10 mol % or less. is preferably 1 to 40 mol %, more preferably 1 to 35 mol %, and The content is preferably 1 to 20 mol %, and even more preferably 1 to 10 mol %.

[0075] <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, it 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:

[0076] 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. TIFF2025163074000047.tif48155 [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-, *-OLa8 -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 site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 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. 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.]

[0077] R a21 , R a22 , R a23 and Ra25 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.

[0078] 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.

[0079] 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. R a22 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.

[0080] 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)'. TIFF2025163074000048.tif3848(in the formula, R a24 , L a7 has the same meaning as above.)

[0081] 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.

[0082] TIFF2025163074000049.tif116165

[0083] 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 mol % or more, preferably 3 mol % or more, more preferably 1 mol % or more, based on the position. It is 5 mol % or more, and usually 70 mol % or less, preferably 65 mol % or less. It is usually 1 to 70 mol %, preferably 60 mol % or less. is 3 to 65 mol %, more preferably 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) relative to the total structural units of the resin (A) is preferably It is 1 mol % or more, more preferably 3 mol % or more, and even more preferably 5 mol % or more. In addition, it is preferably 60 mol % or less, and more preferably 50 mol % or less. In addition, 1 to 60 mol % is preferable, 3 to 50 mol % is more preferable, and 5 to 50 mol % is particularly preferable. is more preferable.

[0084] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025163074000050.tif2962[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.

[0085] 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. TIFF2025163074000051.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.

[0086] 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). TIFF2025163074000052.tif4551[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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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. TIFF2025163074000053.tif96166

[0091] TIFF2025163074000054.tif4866[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). TIFF2025163074000055.tif1487 [In formula (a-g1), s represents 0 or 1. A a42 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 ]

[0092] R a42 The saturated hydrocarbon group in the formula (I) is a chain saturated hydrocarbon group or a monocyclic or polycyclic alicyclic group. saturated hydrocarbon groups of the formula: do.

[0093] 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. TIFF2025163074000056.tif10160The 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.

[0094] 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 a fluorine atom, a salt atom, or a fluorine atom. Examples of the fluorine atom include a fluorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. TIFF2025163074000057.tif855[In formula (a-g3), X a43represents 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.

[0095] 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 silyl, hexadecyl, heptadecyl, and octadecyl groups; Monocyclic groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups alicyclic hydrocarbon groups; and decahydronaphthyl groups, adamantyl groups, norbornyl groups, and and polycyclic and alicyclic hydrocarbon groups such as the following groups (* represents a bonding site): TIFF2025163074000058.tif10160The 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.

[0096] 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.

[0097] 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). TIFF2025163074000059.tif871[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 a44represents **-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.]

[0098] 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 A a 47 is more preferably a cyclohexyl group or an adamantyl group.

[0099] 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). TIFF2025163074000060.tif14160

[0100] 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 of the alkoxy group include alkoxy groups 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.

[0101] 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.

[0102] 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 TIFF2025163074000061.tif47140

[0103] 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: TIFF2025163074000062.tif99145

[0104] TIFF2025163074000063.tif132150

[0105] 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). TIFF2025163074000064.tif4356[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and —C H2- 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.]

[0106] 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.

[0107] 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.

[0108] TIFF2025163074000065.tif5671[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.

[0109] L 5 The alkanediyl group in a41 The same as those exemplified for the alkanediyl group The following groups are mentioned:

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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 f7The 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.

[0114] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF2025163074000066.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.]

[0115] 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.

[0116] 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.

[0117] 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. TIFF2025163074000067.tif86160

[0118] 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.

[0119] <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 the formula (a5-1): . TIFF2025163074000068.tif3351[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—.

[0120] 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.

[0121] L 55 The 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.

[0122] 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. TIFF2025163074000069.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 x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 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 x9and W x1 The total number of carbon atoms is 15 or less.

[0123] 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.

[0124] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF2025163074000070.tif53136

[0125] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2025163074000071.tif23130

[0126] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2025163074000072.tif15148

[0127] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2025163074000073.tif26114

[0128] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0129] 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. TIFF2025163074000074.tif111150When 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.

[0130] <Structural unit (a6)> The structural unit (a6) is a structural unit having an -SO2- group, and has an -SO2- group in a side chain. It is preferable to do so. The structural unit having an -SO2- group may have a linear structure having an -SO2- group. Alternatively, it may have a branched structure having an -SO2- group, or a ring structure having an -SO2- group. It may have a ring structure (monocyclic or polycyclic structure). Preferably, it is a ring having an -SO2- group. It is a structural unit having a cyclic structure, and more preferably, a cyclic structure containing -SO2-O- (sulfur It is a structural unit that has a thion ring.

[0131] The sultone ring may be a ring having the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula ( T 1 The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. means a bridged ring containing -SO2-O- as an atomic group constituting the ring, and the formula (T 1 -1 ) and formula (T 1 The sultone ring is represented by the formula (T 1 -2) In addition to -SO2-O-, the ring also contains heteroatoms. The heteroatom may include an oxygen atom, a sulfur atom, or a nitrogen atom. , preferably an oxygen atom. TIFF2025163074000075.tif3087

[0132] The sultone ring may have a substituent, and the substituent may be a halogen atom or a hydroxy group. an alkyl group having 1 to 12 carbon atoms, which may have a halogen atom, a hydroxy group, a cyano group, groups, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, aryl groups having 7 to 12 carbon atoms Ralalkyl groups, glycidyloxy groups, alkoxycarbonyl groups having 2 to 12 carbon atoms, and Examples include alkylcarbonyl groups having 2 to 4 carbon atoms.

[0133] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. . Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl. Examples of the alkyl group include a silyl group, an octyl group, and a decyl group, and preferably an alkyl group having 1 to 6 carbon atoms. More preferably, it is a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, and a methyl group. perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, Perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl perfluorohexyl, trichloromethyl, tribromomethyl and triiodomethyl groups. A trifluoromethyl group is preferred. Examples of alkyl groups having a hydroxy group include a hydroxymethyl group and a 2-hydroxyethyl group. Examples of the hydroxyalkyl group include a hydroxyalkyl group having a methyl 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 aryl group includes a phenyl group, a naphthyl group, an anthryl group, and a p-methylphenyl group. , p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group group, cumyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group Examples include the phenyl group and the 2-methyl-6-ethylphenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and the like. Examples include ethyl and naphthylethyl groups. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Examples include a group in which an alkoxy group and a carbonyl group are bonded, and preferably an alkoxy group having 6 or less carbon atoms. An example thereof is an oxycarbonyl group, and more preferably a methoxycarbonyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be.

[0134] From the viewpoint of ease of production of the monomer from which the structural unit (a6) is derived, A sultone ring is preferred. The sultone ring is preferably a ring represented by the following formula (T1'). TIFF2025163074000076.tif3072[In formula (T1'), X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group. alkyl groups, halogen atoms, hydroxy groups, cyano groups, alkoxy groups with 1 to 12 carbon atoms, Aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, glycidyloxy groups, and groups having 2 carbon atoms. It represents an alkoxycarbonyl group having from 1 to 12 carbon atoms or an alkylcarbonyl group having from 2 to 4 carbon atoms. ma represents an integer of 0 to 9. When ma is 2 or more, multiple R 41 are identical It may be the same or different. The binding site is at any position.] X 11 is preferably an oxygen atom or a methylene group, more preferably a methylene group. do. R 41 Examples of the substituents include the same as those of the sultone ring, and include a halogen atom or a hydroxyl group. An alkyl group having 1 to 12 carbon atoms which may have an alkoxy group is preferred.

[0135] The sultone ring is more preferably a ring represented by formula (T1). TIFF2025163074000077.tif3049[In formula (T1), R 8 is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group. groups, halogen atoms, hydroxy groups, cyano groups, alkoxy groups having 1 to 12 carbon atoms, and alkoxy groups having 6 carbon atoms Aryl groups having 7 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, glycidyloxy groups, and groups having 2 to 12 carbon atoms. 12 alkoxycarbonyl group or alkylcarbonyl group having 2 to 4 carbon atoms. m represents an integer of 0 to 9. When m is 2 or more, a plurality of R 8 are identical and may also be different. The binding site is at any position.]

[0136] R 8 is R 41 The same can be mentioned. ma in formula (T1') and m in formula (T1) are preferably 0 or 1, More preferably, it is 0.

[0137] Examples of the ring represented by formula (T1') and the ring represented by formula (T1) include the following rings: The binding site is at an arbitrary position. TIFF2025163074000078.tif47144

[0138] The structural unit having a sultone ring preferably has the following group: * in the following group represents the binding site. TIFF2025163074000079.tif45144

[0139] The structural unit having a -SO2- group preferably further has a group derived from a polymerizable group. The polymerizable group may be a vinyl group, an acryloyl group, a methacryloyl group, an acryloyl group, or a methyl group. Oxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, Examples include an acryloylthio group and a methacryloylthio group. Among them, the monomer from which the structural unit (a6) is derived is preferably a monomer having an ethylenically unsaturated bond. It is preferably a monomer having a (meth)acrylic group, and more preferably a (meth)acrylic monomer.

[0140] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF2025163074000080.tif4956[In formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represents an atom or a halogen atom. A xx is an oxygen atom, -N(R c )- or a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- is -O-, -CO- or -N(R d )- may be replaced. X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group. alkyl groups, halogen atoms, hydroxy groups, cyano groups, alkoxy groups with 1 to 12 carbon atoms, Aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, glycidyloxy groups, and groups having 2 carbon atoms. It represents an alkoxycarbonyl group having from 1 to 12 carbon atoms or an alkylcarbonyl group having from 2 to 4 carbon atoms. ma represents an integer of 0 to 9. When ma is 2 or more, multiple R 41 are identical It may be the same or different. R c and Rd each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0141] R x Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. can be done. R x Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and the like. butyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n -hexyl group, etc., and is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably is a methyl group or an ethyl group. R x Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a phenyl group, and a phenyl group. perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Fluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group group and triiodomethyl group. R x is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. It is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

[0142] A x The divalent saturated hydrocarbon group includes a linear alkanediyl group, a branched alkanediyl group, and and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. It may be a combination of more than one species. 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 Decane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,1 4-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group , heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1- linear alkanediyl groups such as diyl and propane-2,2-diyl groups; Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane Pan-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group branched alkanediyl groups such as alkanediyl 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.

[0143] R 41 , X 11 and ma may be the same as those in formula (T1'). Examples of the sultone ring include those mentioned above, and among them, those mentioned above in which the bonding position is specified are It is preferable that:

[0144] Examples of the structural unit (a6) include the following structural units. TIFF2025163074000081.tif93150

[0145] Among them, formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula ( The structural units represented by the formula (a6-8) and formula (a6-12) are preferred, and the structural units represented by the formula (a6-1) and formula (a6-2) are preferred. a6-2), and structural units represented by formulae (a6-7) and (a6-8) are more preferred. When the resin (A) has the structural unit (a6), the content thereof is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 50 mol %, more preferably 2 to 40 mol %, and more preferably 3 to 30 mol % is more preferred.

[0146] <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, which have a sulfonyl group at 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.

[0147] 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'). TIFF2025163074000082.tif3089 [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. Ax1 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.

[0148] 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.

[0149] 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 ru radical; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa cycloalkanediyl groups such as cyclohexene-1,4-diyl and cyclooctane-1,5-diyl divalent monocyclic alicyclic saturated hydrocarbon groups such as; Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Divalent polycyclic alicyclic saturated hydrocarbons such as 1,5-diyl group and adamantane-2,6-diyl group Examples include an elemental group.

[0150] -CH2- in saturated hydrocarbon groups is replaced with -O-, -S- or -CO- Examples of the divalent groups include those represented by the 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 TIFF2025163074000083.tif145161

[0151] 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.

[0152] 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. The cation (hereinafter, depending on the formula number, it may be referred to as "cation (b2-1)" etc.) Examples include:

[0153] The structural unit represented by formula (II-2-A') is a structural unit represented by formula (II-2-A) It is preferable that: JPEG2025163074000084.jpg37109 [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.]

[0154] 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:

[0155] 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 . TIFF2025163074000085.tif5576 [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.

[0156] 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.

[0157] 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 TIFF2025163074000086.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.]

[0158] Examples of the structural unit represented by formula (II-2-A') include the following structural units, R III3 The group corresponding to the methyl group 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. TIFF2025163074000087.tif86163

[0159] 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. TIFF2025163074000088.tif3689 [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.

[0160] Examples of the cation-containing structural unit in formula (II-1-1) include structural units represented by the following formulas: R II4The 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. TIFF2025163074000089.tif85130

[0161] 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 the sulfonate anion is preferably a sulfonate anion as described below. Examples include the anion represented by formula (B1).

[0162] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2025163074000090.tif36136

[0163] Examples of sulfonylmethide anions include the following: TIFF2025163074000091.tif29123

[0164] Examples of carboxylate anions include the following: TIFF2025163074000092.tif45152

[0165] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2025163074000093.tif88149

[0166] 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 %.

[0167] The resin (A) may have structural units other than the above-mentioned structural units. The moieties include structural units known in the art.

[0168] The resin (A) is preferably a resin comprising the structural unit (I) and the structural unit (a1), A resin comprising a unit (I) and a structural unit (s), a resin comprising a structural unit (I), a structural unit (a1), and a structural unit (a2). A resin comprising a structural unit (I), a structural unit (a1), a structural unit (s), and a structural unit (s). Resins consisting of units (a4) and / or structural units (a5), resins consisting of only structural units (I), A resin consisting of only the structural unit (I) and the structural unit (a4) is more preferred. or a resin comprising the structural unit (I), the structural unit (a1) and the structural unit (s); A resin comprising the structural unit (I) and the structural unit (s), or a resin comprising the structural unit (I) and the structural unit (a4) and the structural unit (a5), and a resin consisting only of the structural unit (I) and the structural unit (a4). a resin consisting of only the structural unit (I), the structural unit (a4) and the structural unit (a1); be.

[0169] The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group) The structural unit (a1) is preferably at least one selected from the group consisting of -0), structural units (a1-1) and structural units (a1-2) (preferably cyclohexyl groups) or the structural unit having a cyclopentyl group) be. The structural unit (s) is preferably selected from the group consisting of the structural unit (a2) and the structural unit (a3): The structural unit (a2) is preferably at least one selected from the structural unit (a2-A). The structural unit (a3) ​​is preferably a structural unit (a2-1) represented by the formula (a3-1): a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-4) It is at least one selected from the group consisting of units.

[0170] 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.

[0171] [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)").

[0172] <Resins other than Resin (A)> The resist composition of the present invention may contain a resin other than the resin (A). The resin is a resin that does not contain the structural unit (I), and examples of such a resin include: A resin having a structural unit having an acid labile group and not containing the structural unit (I) (hereinafter referred to as "resin ( A2)), a resin consisting only of the structural unit (a4) and a resin consisting only of the structural unit (a4) and the structural unit (a5) (hereinafter referred to as a resin consisting of only the structural unit (a4), and The resin consisting of the structural unit (a4) and the structural unit (a5) may be collectively referred to as resin (X). Examples include: 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. 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 weight of the resin (A2) and the resin (X) is preferably 6, 000 or more (more preferably 7,000 or more), 80,000 or less (more preferably 60 The weight average molecular weight of the resin (A2) and the resin (X) is measured by The same as in the case of fat (A). When the resist composition of the present invention contains resin (A2), the content thereof is preferably 10% by weight of resin (A). 0 parts by mass, usually 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) is. 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.

[0173] 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.

[0174] <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. 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.

[0175] 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)"). TIFF2025163074000094.tif2958[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 SO2- or -CO-. Z + represents an organic cation.

[0176] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) includes a trifluoromethyl group, a pentafluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a fluoropentyl group and a perfluorohexyl group. Q b1 and Q b2 are each independently a fluorine atom or a trifluoromethyl group. and more preferably, both are fluorine atoms.

[0177] L b1 The divalent saturated hydrocarbon group in candiyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these groups It may also be a group formed by combining two or more of the following. 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.

[0178] L b1 -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, groups represented by formula (b1-1) to formula (b1-3) and their components are exemplified. In the exemplary groups represented by formulae (b1-4) to (b1-11), * and ** represent bonds. represents the site, and * represents the binding site with -Y.

[0179] TIFF2025163074000095.tif26118[In formula (b1-1), L b2represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b6and L b7 The total number of carbon atoms is 23 or less.

[0180] 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 mentioned above. can be.

[0181] 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 hydrogen 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 hydrocarbon group may be substituted with fluorine atoms. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. The —CH2— contained in the divalent saturated hydrocarbon group is replaced with —O— or —CO—. That's fine.

[0182] L b1 -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: TIFF2025163074000096.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. 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 contained -CH2- 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 hydrocarbon 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 hydrocarbon 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 b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon 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, The -CH2- contained in the formula may be replaced with -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, The hydrogen atoms contained in the hydrocarbon 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.

[0183] 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, more preferably More 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 b13is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably More 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, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0184] 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: TIFF2025163074000097.tif23140[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 b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —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 Lb26 The total number of carbon atoms is 21 or less.

[0185] 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.

[0186] Examples of the group represented by formula (b1-4) include the following. TIFF2025163074000098.tif16154

[0187] Examples of the group represented by formula (b1-5) include the following. TIFF2025163074000099.tif68152

[0188] Examples of the group represented by formula (b1-6) include the following. TIFF2025163074000100.tif29150

[0189] Examples of the group represented by formula (b1-7) include the following. TIFF2025163074000101.tif57146

[0190] Examples of the group represented by formula (b1-8) include the following. TIFF2025163074000102.tif23150

[0191] Examples of the group represented by formula (b1-2) include the following. TIFF2025163074000103.tif31161

[0192] Examples of the group represented by formula (b1-9) include the following. TIFF2025163074000104.tif44137

[0193] Examples of the group represented by formula (b1-10) include the following. TIFF2025163074000105.tif92165

[0194] Examples of the group represented by formula (b1-11) include the following. TIFF2025163074000106.tif84164

[0195] 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-, -SO2- or -CO When substituted with -, the number may be one or more. and groups represented by formulae (Y12) to (Y35) and (Y39) to (Y43). * is L b1 represents the binding site with

[0196] The alicyclic hydrocarbon group represented by TIFF2025163074000107.tif83167Y 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 formulas (Y28) to (Y35), (Y39), and (Y 40), formula (Y42), formula (Y43), etc., when it is a spiro ring having 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.

[0197] 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 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, a to 18 aromatic hydrocarbon groups or groups combining these, and -CH2- contained in the hydrocarbon group is replaced by -O-, -SO2- or -CO-. The hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be The atom may be substituted with a hydroxy group or a fluorine atom. It represents any integer. 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.)

[0198] 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 chain hydrocarbon group and a carboxyl group. Examples of the alkyl group include a methylcyclohexyl group and a dimethylcyclohexyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, and more preferably 3 to 10. be. 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. More preferably, it is 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-, -SO2-, or -CO-, etc. The group includes an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkyl carbonyl group, alkylcarbonyloxy group, or a combination thereof. do. 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 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a propyl The alkylsulfonyl group preferably has 1 to 12 carbon atoms. 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. -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2-, -CO-, etc. The groups represented by formula (Y12) to formula (Y35) and formula (Y39) to formula (Y43) are Examples of such groups include:

[0199] Examples of Y include the following: TIFF2025163074000108.tif129165

[0200] TIFF2025163074000109.tif36150

[0201] 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, More preferably, it is an adamantyl group which may have a substituent, and the alicyclic hydrocarbon The -CH2- constituting the group or adamantyl group is replaced with -CO-, -SO2- or -CO-. Y is preferably an adamantyl group, a hydroxyadamantine group, or a hydroxyadamantyl group. an oxoadamantyl group, an oxoadamantyl group, or a group represented by formula (Y42), formula (Y100) to formula (Y114), It is a group that can be

[0202] 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. TIFF2025163074000110.tif232165

[0203] TIFF2025163074000111.tif238165

[0204] TIFF2025163074000112.tif168160 Here R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 is, for example, 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.

[0205] 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. TIFF2025163074000113.tif238158

[0206] TIFF2025163074000114.tif129154

[0207] 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.

[0208] Z +The organic cations include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations and Among these, organic sulfonium cations are and organic iodonium cations are preferred, with arylsulfonium cations being more preferred. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter , and may be referred to as "cation (b2-1)" etc. depending on the formula number.

[0209] TIFF2025163074000115.tif47166In 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, Aliphatic hydrocarbon group, fluorinated alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms Represents. 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. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the chain hydrocarbon group are It may be substituted with an aromatic hydrocarbon group having 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, Aliphatic hydrocarbon group, fluorinated alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms Represents. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4; u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14 are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, r2 When is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 teeth Identical or different, when t2 is 2 or more, multiple R b18 are the same or different. The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. 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. TIFF2025163074000116.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. 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. fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl group, etc. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 9, and more preferably 1. It is preferably 1 to 6, and more preferably 1 to 4. 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 substituted or unsubstituted alkyl group, and may have an aromatic hydrocarbon group ( tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert -butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group etc.) and aromatic hydrocarbon groups having an alicyclic hydrocarbon group having 3 to 18 carbon atoms (p-cyclohexane, etc.) Examples of aromatic hydrocarbons include phenyl groups, p-adamantylphenyl groups, etc. When the alkyl group has a chain hydrocarbon group or an alicyclic hydrocarbon group, it is a chain hydrocarbon group having 1 to 18 carbon atoms. Hydrocarbon groups and alicyclic hydrocarbon groups 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. 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. 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 rings shown below, where * represents a binding site. TIFF2025163074000117.tif23144R 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.

[0210] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2025163074000118.tif117161

[0211] TIFF2025163074000119.tif70164 Examples of the cation (b2-2) include the following cations. TIFF2025163074000120.tif18150Examples of the cation (b2-3) include the following cations. TIFF2025163074000121.tif26140 Examples of the cation (b2-4) include the following cations. TIFF2025163074000122.tif127165

[0212] 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:

[0213] The acid generator (B) is preferably a compound represented by formula (B1-1) to formula (B1-57), 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 (B1-57) are particularly preferred. JPEG2025163074000123.jpg191166

[0214] TIFF2025163074000124.tif250153

[0215] TIFF2025163074000125.tif205166

[0216] In the resist composition of the present invention, the content of the acid generator is Preferably, the amount is 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less. parts by mass or less, and more preferably from 3 parts by mass to 35 parts by mass. The acid generator (B) may contain one kind of acid generator (B) alone or a plurality of kinds of acid generators (B) may be contained.

[0217] <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.

[0218] <Quencher (C)> The quencher (C) is an acid that is weaker in acidity than the acid generated by the acid generator (B). Examples include the salts generated and the basic nitrogen-containing organic compounds. The content of the quencher (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, still more preferably about 0.1 to 8% by mass, and even more preferably about 0.1 to 7% by mass, based on the solid content of the resist composition.

[0219] [[Salt that generates an acid with a lower acidity than the acid generated from the acid generator]] The acidity of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is usually a salt with an acid dissociation constant of the acid generated from the salt of -3 < pKa, preferably a salt of -1 < pKa < 7, and more preferably a salt of 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as " intramolecular salt of weak acid (D)"), and 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. As the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B), preferably, a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion ), more preferably, an intramolecular salt of weak acid (D), and still more preferably, among the intramolecular salts of weak acid (D), a diphenyliodonium salt containing a phenyl group substituted with a carboxylic acid anion . TIFF2025163074000126.tif116167

[0220] As the weak acid inner salt (D), there is an iodonium cation with two phenyl groups bonded to it, At least one of the two phenyl groups bonded to the iodonium cation and a diphenyliodonium salt having a substituted carboxylic acid anion. Examples of suitable salts include those represented by the following formulas:

[0221] TIFF2025163074000127.tif2362[In formula (D), R D1 and R D2 are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkyl group having 1 to 6 carbon atoms, oxy group, acyl group having 2 to 7 carbon atoms, acyloxy group having 2 to 7 carbon atoms, acyl group having 2 to 7 carbon atoms represents a alkoxycarbonyl group, a nitro group or a halogen atom. m' and n' each independently represent an integer of 0 to 4, and when m' is 2 or more, In this case, multiple R D1 may be the same or different, and when n' is 2 or more, a plurality of R D2 The same They may be the same or different.] R D1 and R D2 The hydrocarbon group may be a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or the like. Examples include hydrogen groups and groups formed by combining these groups. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. alkyl groups such as isobutyl, tert-butyl, pentyl, hexyl, and nonyl groups Examples of such groups include aryl groups. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and may be either saturated or unsaturated. Any of the following may be used: a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group group, a cycloalkyl group such as a cyclononyl group or a cyclododecyl group, a norbornyl group, an adamantan group Examples include a methyl group. Aromatic hydrocarbon groups include phenyl, 1-naphthyl, 2-naphthyl, and 2-methyl groups. phenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t -butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthracene p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl , biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group and aryl groups such as phenyl and the like. Examples of groups formed by combining these include alkyl-cycloalkyl groups. , cycloalkyl-alkyl groups, aralkyl groups (e.g., phenylmethyl groups, 1-phenyl ethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2 -propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl- phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group etc.) Examples of the alkoxy group include a methoxy group and an ethoxy group. The acyl group includes an acetyl group, a propanoyl group, a benzoyl group, a cyclohexane group, and Examples include a hydroxyl group. Examples of the acyloxy group include a group in which an oxy group (—O—) is bonded to the above-mentioned acyl group. can be. The alkoxycarbonyl group is an alkoxy group bonded to a carbonyl group (—CO—). Examples of such groups include a group obtained by combining two or more groups. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. R D1 and R D2 are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, alkyl groups, alkoxy groups having 1 to 6 carbon atoms, acyl groups having 2 to 4 carbon atoms, an acyloxy group, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or a halogen atom preferable. Preferably, m' and n' are each independently an integer of 0 to 2, and 0 When m' is 2 or more, a plurality of R D1 are the same but different If n' is 2 or more, multiple R D2 may be the same or different.

[0222] More specifically, the following salts are included: TIFF2025163074000128.tif72165

[0223] 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.

[0224] <Other ingredients> The resist composition of the present invention may contain components other than the above-mentioned components (hereinafter referred to as "other components") as needed. It may contain other ingredients (F). The resist composition may contain additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc. Agents, dyes, etc. can be used.

[0225] <Preparation of Resist Composition> The resist composition of the present invention comprises the resin (A) of the present invention, the acid generator (B), and optionally Resin (A2), resin (X), quencher (C), solvent (E) and other components accordingly. (F) can be mixed in any order, and there is no particular limitation. The temperature during mixing ranges from 10 to 40°C, depending on the type of resin and the solvent used. An appropriate temperature can be selected depending on the solubility of (E). Depending on the conditions, an appropriate time can be selected from 0.5 to 24 hours. There are no particular limitations, and stirring and mixing or the like 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

[0226] <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.

[0227] To apply the resist composition to the substrate, a commonly used device such as a spin coater is used. The substrate may be an inorganic substrate such as a silicon wafer, or a substrate having a resist on the surface. Before applying the resist composition, the substrate is washed. An anti-reflection film or the like may be formed on the substrate. 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 10 5 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 preferably about 70 to 150°C. The hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating A chemical treatment (silylation) to adjust the film properties may be carried out. The steps of applying a resist composition, drying, exposing, and heating may be repeated on the composition layer. 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.

[0228] <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 ArF excimer laser exposure, electron beam It is suitable as a resist composition for (EB) exposure or EUV exposure, It is useful for semiconductor microfabrication. [Example]

[0229] 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 was determined by gel permeation chromatography under the following conditions: value. Device: HLC-8120GPC model (Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guard column (Tosoh) 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 also determined by mass spectrometry (LC: Agilent 1100, MASS: A The molecular ion peak was measured using a Gilent LC / MSD. In the following examples, the value of this molecular ion peak is indicated as "MASS."

[0230] Example 1: Synthesis of compound represented by formula (I-1) TIFF2025163074000129.tif3297 2.24 parts of a compound represented by formula (I-1-a), 4 parts of a compound represented by formula (I-1-b) 0.40 parts of dimethylformamide and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the mixture, 1.76 parts of potassium carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was stirred at 90° C. for 3 hours. The mixture was cooled to 23° C., and then 50 parts of chloroform was added. 20 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, and then the organic layer was separated. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and washed with water five times. The concentrated mixture was then passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / 1) As a result, 2.14 parts of the compound represented by formula (I-1-c) was obtained. TIFF2025163074000130.tif47157 0.65 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 2.35 parts of the compound was added, and the mixture was stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes. After that, the organic layer was separated and separated. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The resulting organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1 ) to obtain 2.24 parts of the compound represented by formula (I-1). MASS:381.0[M+H] +

[0231] Example 2: Synthesis of compound represented by formula (I-2) TIFF2025163074000131.tif4397 2.24 parts of the compound represented by formula (I-1-a), 9 parts of the compound represented by formula (I-2-b) 0.44 parts of dimethylformamide and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the mixture, 1.76 parts of potassium carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was stirred at 90° C. for 3 hours. The mixture was cooled to 23° C., and then 50 parts of chloroform was added. 20 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, and then the organic layer was separated. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and washed with water five times. The concentrated mixture was then passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / 1) As a result, 3.37 parts of the compound represented by formula (I-2-c) was obtained. TIFF2025163074000132.tif47158 0.65 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 4.25 parts of the compound was added, and the mixture was stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes. After that, the organic layer was separated and separated. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The resulting organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1 ) to obtain 4.03 parts of the compound represented by formula (I-2). MASS:632.8[M+H] +

[0232] Example 3: Synthesis of compound represented by formula (I-5) TIFF2025163074000133.tif40100 2.24 parts of a compound represented by formula (I-1-a), 3 parts of a compound represented by formula (I-5-b) 0.64 parts of dimethylformamide and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the mixture, 1.76 parts of potassium carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was stirred at 90° C. for 3 hours. The mixture was cooled to 23° C., and then 50 parts of chloroform was added. 20 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes, and then the organic layer was separated. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and washed with water five times. The concentrated mixture was then passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / 1) As a result, 1.46 parts of the compound represented by formula (I-5-c) was obtained. TIFF2025163074000134.tif47161 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 0.94 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 1.45 parts of the compound was added, and the mixture was stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes. After that, the organic layer was separated and separated. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed five times. The resulting organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1 ) to obtain 1.22 parts of the compound represented by formula (I-5). MASS:343.1[M+H] +

[0233] Example 4: Synthesis of compound represented by formula (I-13) TIFF2025163074000135.tif4399 2.24 parts of a compound represented by formula (I-1-a), a compound represented by formula (I-13-b) 7.24 parts of methyl 2-hydroxybenzoate and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the resulting mixture, 1.76 parts of potassium carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was stirred at 90° C. for 3 hours. The resulting mixture was cooled to 23° C., and then 50 mL of chloroform was added. Add 20 parts of ethanol and 20 parts of ion-exchanged water, stir at 23°C for 30 minutes, then separate the solution and take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. The concentrated mixture was then passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical The mixture was separated using a developing solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Epson Corporation. As a result, 5.68 parts of the compound represented by formula (I-13-c) was obtained. TIFF2025163074000136.tif62144 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 0.94 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 2.40 parts of the compound (I) was added thereto, and the mixture was stirred at 50°C for 2 hours. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After that, the organic layer was separated and extracted. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral ) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 2.34 parts of the compound represented by formula (I-13). MASS:522.9[M+H] +

[0234] Example 5: Synthesis of compound represented by formula (I-14) TIFF2025163074000137.tif4190 2.24 parts of a compound represented by formula (I-1-a), a compound represented by formula (I-14-b) 5.32 parts of methylformamide and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the resulting mixture, 1.76 parts of potassium carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was stirred at 90° C. for 3 hours. The resulting mixture was cooled to 23° C., and then 50 mL of chloroform was added. Add 20 parts of ethanol and 20 parts of ion-exchanged water, stir at 23°C for 30 minutes, then separate the solution and take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. The concentrated mixture was then passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical The mixture was separated using a developing solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Epson Corporation. As a result, 4.91 parts of the compound represented by formula (I-14-c) was obtained. TIFF2025163074000138.tif62146 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 0.94 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 1.89 parts of the compound (I) was added, and the mixture was stirred at 50°C for 2 hours. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After that, the organic layer was separated and extracted. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral ) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 1.78 parts of the compound represented by formula (I-14). MASS: 427.0 [M+H] +

[0235] Example 6: Synthesis of compound represented by formula (I-15) TIFF2025163074000139.tif4188 2.24 parts of a compound represented by formula (I-1-a), a compound represented by formula (I-15-b) 4.72 parts of the hydroxybenzoate and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the resulting mixture, 1.76 parts of potassium carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was stirred at 90° C. for 3 hours. The resulting mixture was cooled to 23° C., and then 50 mL of chloroform was added. Add 20 parts of ethanol and 20 parts of ion-exchanged water, stir at 23°C for 30 minutes, then separate the solution and take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. The concentrated mixture was then passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical The mixture was separated using a developing solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Epson Corporation. As a result, 3.92 parts of the compound represented by formula (I-15-c) was obtained. TIFF2025163074000140.tif62144 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 0.94 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 1.73 parts of the compound (I) was added, and the mixture was stirred at 50°C for 2 hours. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After that, the organic layer was separated and extracted. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral ) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 1.34 parts of the compound represented by formula (I-15). MASS:397.0[M+H] +

[0236] Example 7: Synthesis of compound represented by formula (I-7) TIFF2025163074000141.tif72152 1.22 parts of the compound represented by formula (I-7-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 2.70 parts of the compound (I) was added thereto, and the mixture was stirred at 50°C for 2 hours. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After that, the organic layer was separated and extracted. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral ) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 2.75 parts of the compound represented by formula (I-7). MASS:503.0[M+H]+

[0237] Example 8: Synthesis of compound represented by formula (I-8) TIFF2025163074000142.tif76153 1.55 parts of the compound represented by formula (I-8-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 2.70 parts of the compound (I) was added thereto, and the mixture was stirred at 50°C for 2 hours. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After that, the organic layer was separated and extracted. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral ) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 2.86 parts of the compound represented by formula (I-8). MASS:547.0[M+H] +

[0238] Example 9: Synthesis of compound represented by formula (I-26) TIFF2025163074000143.tif65163 2.00 parts of the compound represented by formula (I-26-d) and 20 parts of acetonitrile were mixed, After stirring at 23°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 2.70 parts of the compound to be prepared was added, and the mixture was stirred at 50°C for 2 hours. After cooling at 40°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After stirring, the mixture was separated and the organic layer was taken out. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, medium 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 2.98 parts of the compound represented by formula (I-26). . MASS:607.0[M+H] +

[0239] Example 10: Synthesis of salt represented by formula (I-18) TIFF2025163074000144.tif5595 3.92 parts of a compound represented by formula (I-18-a), 1.02 parts of a compound represented by formula (I-18-b) 5.32 parts of the product and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the resulting mixture, 1.76 parts of potassium carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The resulting mixture was stirred at 90°C for 3 hours. After cooling to 23°C, 5 mL of chloroform was added. 0 parts of the solution and 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the organic layer was separated. To the resulting organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. This water washing procedure was repeated five times. The concentrated mixture was then loaded onto a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto The eluent was prepared using a 1 / 1 ratio of n-heptane / ethyl acetate (manufactured by Chemical Industry Co., Ltd.). As a result, 6.13 parts of the compound represented by formula (I-18) was obtained. MASS: 443.0 [M+H]+

[0240] Example 11: Synthesis of compound represented by formula (I-42) TIFF2025163074000145.tif4399 2.24 parts of a compound represented by formula (I-1-a), a compound represented by formula (I-42-b) 7.24 parts of methyl 2-hydroxybenzoate and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the resulting mixture, 1.76 parts of potassium carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was stirred at 90° C. for 3 hours. The resulting mixture was cooled to 23° C., and then 50 mL of chloroform was added. Add 20 parts of ethanol and 20 parts of ion-exchanged water, stir at 23°C for 30 minutes, then separate the solution and take out the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. The concentrated mixture was then passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical The mixture was separated using a developing solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Epson Corporation. As a result, 2.81 parts of the compound represented by the formula (I-42-c) was obtained. TIFF2025163074000146.tif61144 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile were mixed, and 2 After stirring at 3°C ​​for 30 minutes, 0.94 parts of the compound represented by formula (I-1-e) was added, and After heating to 0°C, the mixture was stirred at 50°C for 2 hours. 2.40 parts of the compound (I) was added thereto, and the mixture was stirred at 50°C for 2 hours. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After that, the organic layer was separated and extracted. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral ) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 1.89 parts of the compound represented by formula (I-42). MASS:522.9[M+H] +

[0241] Example 12: Synthesis of compound represented by formula (I-47) TIFF2025163074000147.tif59170 2.00 parts of the compound represented by formula (I-26-d) and 20 parts of acetonitrile were mixed, After stirring at 23°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 3.42 parts of the compound to be prepared was added, and the mixture was stirred at 50°C for 2 hours. After cooling at 40°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After stirring, the mixture was separated and the organic layer was taken out. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, medium 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 4.38 parts of the compound represented by formula (I-47). . MASS:702.9[M+H] +

[0242] Example 13: Synthesis of compound represented by formula (I-48) TIFF2025163074000148.tif59170 2.00 parts of the compound represented by formula (I-26-d) and 20 parts of acetonitrile were mixed, After stirring at 23°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 3.42 parts of the compound to be prepared was added, and the mixture was stirred at 50°C for 2 hours. After cooling at 40°C, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After stirring, the mixture was separated and the organic layer was taken out. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, medium 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate=1 / 1) to obtain 2.89 parts of the compound represented by formula (I-48). . MASS:702.9[M+H] +

[0243] Example 14: Synthesis of compound represented by formula (I-50) TIFF2025163074000149.tif55165 2.00 parts of the compound represented by formula (I-26-d) and 20 parts of acetonitrile were mixed, After stirring at 23°C for 30 minutes, 1.34 parts of the compound represented by formula (I-1-e) was added, After heating to 50°C, the mixture was stirred at 50°C for 2 hours. 2.35 parts of the compound (I) was added thereto, and the mixture was stirred at 50°C for 2 hours. After cooling, 50 parts of chloroform and 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After that, the organic layer was separated and extracted. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed with water five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spherical, neutral ) 100-210 μm; Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 3.67 parts of the compound represented by formula (I-50). MASS:561.0[M+H] +

[0244] Resin synthesis The compounds (monomers) used in the synthesis of the resin are shown below. TIFF2025163074000150.tif196163Hereinafter, these compounds will be referred to as "monomer (a1-2-6)" etc. according to their formula numbers.

[0245] Example 15 [Synthesis of Resin A1] As monomers, acetoxystyrene, monomer (I-1), monomer (a1-2-6 ), monomer (a2-1-3) and monomer (a3-4-2) were used in a molar ratio of [acetate]. Monomer (a1-2-6): Monomer (a2-1): Monomer (a2-1) -3):monomer (a3-4-2) in a ratio of 32:10:43:3:12 and then adding 1.5 mass % of methyl methyl acrylate to the monomer mixture based on the total mass of all the monomers. The resulting mixture was mixed with 2 times the amount of methyl isobutyl ketone. butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total monomer amount These were heated at 73°C for about 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the layers were separated. The recovered organic layer was poured into a large amount of n-heptane to remove the resin. By precipitating, filtering and recovering, the weight-average molecular weight was approximately 5.5 × 10 3 Resin A Resin A1 was obtained in a yield of 78%. This resin A1 has the following structural units. TIFF2025163074000151.tif37161

[0246] Example 16 [Synthesis of Resin A2] As monomers, acetoxystyrene, monomer (I-2), monomer (a1-2-6 ), monomer (a2-1-3) and monomer (a3-4-2) were used in a molar ratio of [acetate]. Monomer (a1-2-6): Monomer (a2-1): Monomer (a2-1) -3):monomer (a3-4-2) in a ratio of 32:10:43:3:12 and then adding 1.5 mass % of methyl methyl acrylate to the monomer mixture based on the total mass of all the monomers. The resulting mixture was mixed with 2 times the amount of methyl isobutyl ketone. butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total monomer amount These were heated at 73°C for about 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the layers were separated. The recovered organic layer was poured into a large amount of n-heptane to remove the resin. By precipitating, filtering and recovering, the weight-average molecular weight was approximately 5.6 × 10 3 Resin A Resin A2 was obtained in a yield of 73%. This resin A2 has the following structural units. TIFF2025163074000152.tif37164

[0247] Example 17 [Synthesis of Resin A3] As monomers, acetoxystyrene, monomer (I-5), monomer (a1-2-6 ), monomer (a2-1-3) and monomer (a3-4-2) were used in a molar ratio of [acetate]. Monomer (a1-2-6): Monomer (a2-1): Monomer (a2-1) -3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 and then adding 1.5 mass % of methyl methyl acrylate to the monomer mixture based on the total mass of all the monomers. The resulting mixture was mixed with 2 times the amount of methyl isobutyl ketone. butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total monomer amount These were heated at 73°C for about 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the layers were separated. The recovered organic layer was poured into a large amount of n-heptane to remove the resin. By precipitating, filtering and recovering, the weight-average molecular weight was approximately 5.3 × 10 3 Resin A Resin A3 was obtained in a yield of 73%. This resin A3 has the following structural units. TIFF2025163074000153.tif38158

[0248] Example 18 [Synthesis of Resin A4] As monomers, acetoxystyrene, monomer (I-7), monomer (a1-2-6 ), monomer (a2-1-3) and monomer (a3-4-2) were used in a molar ratio of [acetate]. Monomer (a1-2-6): Monomer (a2-1): Monomer (a2-1) -3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 and then adding 1.5 mass % of methyl methyl acrylate to the monomer mixture based on the total mass of all the monomers. The resulting mixture was mixed with 2 times the amount of methyl isobutyl ketone. butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total monomer amount These were heated at 73°C for about 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the layers were separated. The recovered organic layer was poured into a large amount of n-heptane to remove the resin. By precipitating, filtering and recovering, the weight-average molecular weight was approximately 5.2 × 10 3 Resin A Resin A4 was obtained in a yield of 78%. This resin A4 has the following structural units. TIFF2025163074000154.tif57156

[0249] Example 19 [Synthesis of Resin A5] As monomers, acetoxystyrene, monomer (I-8), monomer (a1-2-6 ), monomer (a2-1-3) and monomer (a3-4-2) were used in a molar ratio of [acetate]. Monomer (a1-2-6): Monomer (a2-1): Monomer (a2-1) -3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 and then adding 1.5 mass % of methyl methyl acrylate to the monomer mixture based on the total mass of all the monomers. The resulting mixture was mixed with 2 times the amount of methyl isobutyl ketone. butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total monomer amount These were heated at 73°C for about 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the layers were separated. The recovered organic layer was poured into a large amount of n-heptane to remove the resin. By precipitating, filtering and recovering, the weight-average molecular weight was approximately 5.5 × 10 3 Resin A Resin A5 was obtained in a yield of 80%. This resin A5 has the following structural units. TIFF2025163074000155.tif65158

[0250] Example 20 [Synthesis of Resin A6] As monomers, acetoxystyrene, monomer (I-13), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-13): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.3 × 10 3 A tree Resin A6 was obtained in a yield of 68%. This resin A6 has the following structural units. TIFF2025163074000156.tif44160

[0251] Example 21 [Synthesis of Resin A7] As monomers, acetoxystyrene, monomer (I-14), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-14): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.4 × 10 3 A tree Resin A7 was obtained in a yield of 83%. This resin A7 has the following structural units. TIFF2025163074000157.tif44160

[0252] Example 22 [Synthesis of Resin A8] As monomers, acetoxystyrene, monomer (I-15), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-15): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.3 × 10 3 A tree Resin A8 was obtained in a yield of 76%. This resin A8 has the following structural units. TIFF2025163074000158.tif43159

[0253] Example 23 [Synthesis of Resin A9] As monomers, acetoxystyrene, monomer (I-18), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-18): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.4 × 103 A tree Resin A9 was obtained in a yield of 79%. This resin A9 has the following structural units. TIFF2025163074000159.tif45159

[0254] Example 24 [Synthesis of Resin A10] As monomers, acetoxystyrene, monomer (I-26), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-26): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.7 × 10 3 A tree Resin A10 was obtained in a yield of 85%. This resin A10 has the following structural units. TIFF2025163074000160.tif50164

[0255] Example 25 [Synthesis of Resin A11] As monomers, acetoxystyrene, monomer (I-42), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-42): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.1 × 10 3 A tree Resin A11 was obtained in a yield of 63%. This resin A11 has the following structural units. TIFF2025163074000161.tif45162

[0256] Example 26 [Synthesis of Resin A12] As monomers, acetoxystyrene, monomer (I-47), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-47): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.5 × 10 3 A tree Resin A12 was obtained in a yield of 78%. This resin A12 has the following structural units. TIFF2025163074000162.tif50163

[0257] Example 27 [Synthesis of Resin A13] As monomers, acetoxystyrene, monomer (I-48), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-48): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.2 × 103 A tree Resin A13 was obtained in a yield of 66%. This resin A13 has the following structural units. TIFF2025163074000163.tif50163

[0258] Example 28 [Synthesis of Resin A14] As monomers, acetoxystyrene, monomer (I-50), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (I-50): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.6 × 10 3 A tree Resin A14 was obtained in a yield of 88%. This resin A14 has the following structural units. TIFF2025163074000164.tif50163

[0259] Synthesis Example 1 [Synthesis of Resin AX1] As the monomer, acetoxystyrene, monomer (IX-1), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (IX-1): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 27:10:48:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.5 × 10 3 A tree Resin AX1 was obtained in a yield of 77%. This resin AX1 has the following structural units. TIFF2025163074000165.tif38163

[0260] Synthesis Example 2 [Synthesis of Resin AX2] As the monomer, acetoxystyrene, monomer (IX-2), monomer (a1-2- 6), monomer (a2-1-3) and monomer (a3-4-2) were used in the molar ratio [A Sethoxystyrene: Monomer (IX-2): Monomer (a1-2-6): Monomer (a2 -1-3):monomer (a3-4-2) in a ratio of 32:10:43:3:12 Further, 1.5% by weight of the monomers was added to the monomer mixture. The mixture was mixed with methyl isobutyl ketone in an amount twice the mass of the initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) in total monomer amount 1.2 mol% and 3.6 mol% of these were added to the mixture, and the mixture was heated at 73°C for about 5 hours. After that, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. The organic layer was poured into a large amount of n-heptane and the mixture was stirred for 12 hours. The weight-average molecular weight of the oil is approximately 5.8 × 10 3 A tree Resin AX2 was obtained in a yield of 71%. This resin AX2 has the following structural units: TIFF2025163074000166.tif38163

[0261] <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]

[0262] <Resin> A1 to A14, AX1, AX2: Resin A1 to Resin A14, Resin AX1, Resin AX2 <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) TIFF2025163074000168.tif4383<Quencher (C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF2025163074000169.tif4347D1: (Tokyo Chemical Industry Co., Ltd.) TIFF2025163074000170.tif1932<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-butyrolactone 5 parts

[0263] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer is heated on a direct hot plate with hexamethyldisilazane. The silicon wafer was treated at 90°C for 60 seconds 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 electron beam lithography using an electron beam lithography machine (ELS-F1 manufactured by Elionix Co., Ltd.). The exposure dose was gradually changed using a 25 125 keV system, and after development, line and square patterns were obtained. Direct writing was performed to create a base pattern (pitch 60 nm / line width 30 nm). 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. Assuming that the line width and space width of a line and space pattern with a pitch of 60 nm are 1: The exposure amount at which the sensitivity reached 1 was defined as the effective sensitivity.

[0264] 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] Compared with Comparative Compositions 1 and 2, Compositions 1 to 15 show a decrease in the unevenness of the sidewall surface of the resist pattern. The fluctuation range was small, and the line edge roughness evaluation was good. [Industrial Applicability]

[0265] A resist composition comprising the compound of the present invention and a resin containing a structural unit derived from said compound has good line edge roughness (LER) and is useful for semiconductor microfabrication.

Claims

1. A compound represented by formula (I): [In formula (I), R ０ represents an alkyl group having 1 to 6 carbon atoms which may have one or more halogen atoms, a hydrogen atom, or a halogen atom. X １ represents a linking group comprising a bond type selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond, or a combination of at least one or two bond types selected from the group consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond and an arylene group which may have a substituent. L １ represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and —CH 2 - is -O-, -S-, -SO ２ It may be replaced by - or -CO-. Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. X ２ represents an oxygen atom or a sulfur atom. R １ represents a fluorine atom, a bromine atom, an iodine atom, or a haloalkyl group having 1 to 12 carbon atoms. R ２ represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and —CH 2 - may be replaced by -O- or -CO-. m1 represents an integer of 1 to 6, and when m1 is 2 or more, the groups in the parentheses may be the same or different. m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R ２ may be the same or different.]

2. X １ is the formula (X １ -1) ~Formula (X １ The compound according to claim 1, wherein the compound is a group represented by any one of the following formulas: [Formula (X)] １ -1) ~ Equation (X) １ -7) Middle * and ** represent binding sites, and ** represents L 1 represents the binding site with

3. X １ is the formula (X １ -1), formula (X １ -3) or formula (X １ The compound according to claim 2, wherein the group is a group represented by the formula (I-4).

4. L １ is a single bond or *-L ２ -CO-O-(L ２ represents a cyclic hydrocarbon group having 3 to 18 carbon atoms or a group in which a cyclic hydrocarbon group having 3 to 18 carbon atoms is combined with an alkanediyl group having 1 to 4 carbon atoms, and the cyclic hydrocarbon group may have a substituent, and —CH 2 - is -O-, -S-, -CO- or -SO ２ may be replaced by -, and -CH contained in the alkanediyl group 2 - may be replaced by -O- or -CO-. * represents X １ The compound according to any one of claims 1 to 3, wherein

5. 5. The compound according to claim 1, wherein Ar is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.

6. X ２ The compound according to any one of claims 1 to 5, wherein is an oxygen atom.

7. R １ The compound according to any one of claims 1 to 6, wherein is an iodine atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms.

8. R ２ The compound according to any one of claims 1 to 7, wherein is an iodine atom, a fluorine atom, a hydroxy group, a perfluoroalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.

9. A resin comprising a structural unit derived from the compound according to any one of claims 1 to 8.

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