Resist composition for organic solvent development

Abstract

To provide a resist composition for organic solvent development capable of producing a resist pattern having good CD uniformity (CDU).SOLUTION: The resist composition for organic solvent development contains a resin containing a structural unit having an ethylenically unsaturated double bond in a side chain, a structural unit represented by formula (a3-4) and a structural unit having an acid labile group, and an acid generator. Wherein La7 represents -O -, * -O - La8 -O -, * -O - La8 - CO -O -, * -O - La8 - CO -O - La9 - CO -O -, or * -O - La8 -O - CO - La9 -O -; La8 and La9 each independently represent an alkanediyl group. Ra24 is hydrogen, halogen, or alkyl optionally substituted with halogen. Ra25 represents a carboxyl group, a cyano group or an aliphatic hydrocarbyl group. ] SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist composition for organic solvent development. [Background technology]

[0002] Patent Document 1 describes a method for coating a resist composition containing a resin of the following structural formula and an acid generator, The method for producing a resist pattern is described, which involves exposure and development with a developer containing an organic solvent. do. TIFF2026004581000001.tif44133 Patent Document 2 describes a resin having the following structural formula. TIFF2026004581000002.tif40143 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-107186 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-095087 Summary of the Invention [Problem to be solved by the invention]

[0004] The method for producing a resist pattern formed from the resist composition has a higher CD uniformity ( To provide a resist pattern manufacturing method in which a good resist pattern is formed by CDU The following are the challenges. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A method for producing a resist pattern, comprising the following steps (1) to (5): (1) A step of applying a resist composition onto a substrate, the resist composition being ethylene Resin containing a structural unit having a side chain with a non-saturated double bond and a structural unit having an acid labile group a resist composition containing an acid generator; (2) a step of drying the applied resist composition to form a composition layer; (3) exposing the composition layer to light; (4) a step of heating the composition layer after exposure; (5) A step of developing the heated composition layer with a developer containing an organic solvent. [2] The step (5) is a step of developing by a dynamic dispensing method [1 The method for producing a resist pattern according to the present invention. [3] The resist pattern according to [1] or [2], wherein the developer containing an organic solvent is butyl acetate. How to make a turn. [4] The structural unit having an ethylenically unsaturated double bond in a side chain has a structure having a glycidyl group. A polymer containing a structural unit and a copolymer having at least one selected from a carboxy group and an acid anhydride group. The reaction product of the vinyl monomer with the carboxyl group-containing structural unit and the glycerol-containing polymer Reaction product with a vinyl monomer having at least one group selected from a vinyl group and a hydroxy group The method for producing a resist pattern according to any one of [1] to [3], wherein [5] The structural unit having an ethylenically unsaturated double bond in a side chain is a structure represented by formula (I): The method for producing a resist pattern according to any one of [1] to [4], wherein the unit is a polyimide. TIFF2026004581000003.tif4155 [In formula (I), R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom; represents an alkyl group, a hydrogen atom or a halogen atom. X 1 and X 2 each independently represents an ether bond, an ester bond, and a carbonate ester bond. A bond type selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond. and at least one or two bond types selected from the group consisting of aryl bonds. represents a linking group formed by combining a group and a group. L 1 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and The -CH2- contained in the hydroxyl group may be replaced by -O-, -S-, -SO2- or -CO-. stomach.] [6] The structural unit having an acid labile group is a structural unit represented by formula (a1-0), a structural unit represented by formula (a1 -1) and a structural unit represented by formula (a1-2), The method for producing a resist pattern according to any one of [1] to [5], wherein the method is at least one of . TIFF2026004581000004.tif39127 [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 a7are 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. [7] The compound according to any one of [1] to [6], wherein the acid generator contains a salt represented by formula (B1): A method for producing a resist pattern. TIFF2026004581000005.tif2859[In formula (B1), Q b1 and Q b2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents an alkyl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the divalent saturated hydrocarbon group The contained —CH2— may be replaced by —O— or —CO—, and the divalent saturated carbon The hydrogen atoms contained in the hydrogen hydride group may be substituted with fluorine atoms or hydroxy groups. Y is a methyl group which may have a substituent or a methyl group having 3 to 2 carbon atoms which may have a substituent. 4, and -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by SO2- or -CO-. Z + represents an organic cation. [8] The composition further contains a salt that generates an acid weaker in acidity than the acid generated from the acid generator. The method for producing a resist pattern according to any one of [1] to [7]. [9] A structural unit having an ethylenically unsaturated double bond in a side chain and a structural unit having an acid labile group a resin containing a substituent; A resist composition for organic solvent development containing an acid generator.

[10] The structural unit having an ethylenically unsaturated double bond in a side chain has a glycidyl group. A polymer containing a structural unit and at least one selected from a carboxy group and an acid anhydride group or a polymer containing a structural unit having a carboxy group and a reaction product with a vinyl monomer having the same or a polymer containing a structural unit having a carboxy group. Reaction with a vinyl monomer having at least one group selected from a lysidyl group and a hydroxy group The resist composition for organic solvent development according to [9], which is a product.

[11] The structural unit having an ethylenically unsaturated double bond in a side chain is a structure represented by formula (I): The resist composition for organic solvent development according to [9] or

[10] , wherein the compound is a structural unit. TIFF2026004581000006.tif4155[In formula (I), R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom; represents an alkyl group, a hydrogen atom or a halogen atom. X 1 and X 2 are each independently *-O-**, *-CO-O-**, *-O-CO -O-** or *-Ay-Ph-Ax-**. Ph represents a phenylene group. Ax is selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond. represents one kind of group represented by Ay is a group consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond. represents one bond type selected from * indicates R 1 or R 2 represents the bonding site with the carbon atom to which it is bonded, and ** represents L 1 Binding site with Represents. L 1 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and The -CH2- contained in the hydroxyl group may be replaced by -O-, -S-, -SO2- or -CO-. stomach.] [Effects of the Invention]

[0006] According to the manufacturing method of the present invention, a resist pattern can be manufactured with good CD uniformity (CDU). It is possible. DETAILED DESCRIPTION OF THE INVENTION

[0007] In this specification, the term "(meth)acrylic monomer" refers to a monomer having a structure such as "CH2=CH-CO-" Monomers having the structure "CH2=C(CH3)-CO-" and monomers having the structure "CH2=C(CH3)-CO-" Similarly, "(meth)acrylate" and "(Meth)acrylic acid" refers to "a group consisting of acrylate and methacrylate" "At least one selected from the group consisting of acrylic acid and methacrylic acid" and "at least one selected from the group consisting of acrylic acid and methacrylic acid "at least one of" "CH2=C(CH3)-CO-" or "CH2=CH-C When a structural unit having "O-" is exemplified, structural units having both groups are also exemplified. "Derived from" or "derived from" means that the molecule is This refers to the formation of a single bond (-CC- group) by polymerization of a polymerizable C=C bond. In the groups described herein, those which can have both a straight-chain structure and a branched structure are Any of the -CH2- contained in the hydrocarbon group etc. may be used. When replaced by SO2-, the same examples apply to each group. The term "group formed by bonding two or more of the exemplified groups" means a group formed by bonding two or more of the exemplified groups, and the valence of the groups depends on the bonding form. Therefore, the term may be changed as appropriate. When stereoisomers exist, all stereoisomers are included. In this specification, the term "solid content of the resist composition" refers to the amount of the solid content of the resist composition that is the remaining amount of the resist composition. This refers to the total of all components excluding the solvent (E) described below.

[0008] The method for producing a resist pattern of the present invention comprises the steps of: (1) A step of applying a resist composition onto a substrate (hereinafter sometimes referred to as "step (1)"). cormorant.); (2) A step of drying the applied resist composition to form a composition layer (hereinafter, sometimes referred to as This is referred to as "Step (2)"); (3) a step of exposing the composition layer to light (hereinafter sometimes referred to as “step (3)”); (4) A step of heating the composition layer after exposure (hereinafter sometimes referred to as “step (4)”) ; (5) A step of developing the heated composition layer with a developer containing an organic solvent (hereinafter, in some cases, This is referred to as "step (5)". The resist composition used in step (1) (hereinafter simply referred to as the "resist composition") is It contains a structural unit having an ethylenically unsaturated double bond in the side chain and a structural unit having an acid labile group. A resin (hereinafter sometimes referred to as "resin (A)") and an acid generator (hereinafter sometimes referred to as "acid generator (B)") are )). The "acid labile group" here has a leaving group and reacts with an acid. Upon contact with the compound, the leaving group is eliminated, leaving a hydrophilic group (e.g., a hydroxy group or a carboxy group). The term "group" refers to a group that converts into a structural unit having the formula (I). 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)").

[0009] <Resin (A)> Resin (A) contains a structural unit having an ethylenically unsaturated double bond in the side chain (hereinafter referred to as "structural unit"). (I')) and a structural unit having an acid labile group (hereinafter referred to as "structural unit ( a1)" is sometimes referred to as ".) Resin (A) is characterized in that it decomposes under the action of acid and its solubility in a developer containing an organic solvent decreases. It is preferable that the polymer has the following properties. The resin (A) further contains a structural unit other than the structural unit (I') and the structural unit (a1). The structural units other than the structural unit (I') and the structural unit (a1) are preferably unsaturated. A structural unit that does not have a saturated double bond in the side chain and does not have an acid labile group (hereinafter referred to as "structural unit (s )), structural units other than the structural unit (I), the structural unit (a1) and the structural unit (s) A structural unit (for example, a structural unit having a halogen atom, which will be described later (hereinafter referred to as "structural unit (a4)") a structural unit having a non-leaving hydrocarbon group (hereinafter referred to as "structural unit (a 5)) and other structural units derived from monomers known in the art. Examples include:

[0010] <Structural unit represented by formula (I')> In the structural unit (I'), specific examples of the group containing an ethylenically unsaturated double bond include: , and a group represented by formula (Ia): TIFF2026004581000007.tif2845[In formula (Ia), R 1 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 *-O-**, *-CO-O-**, *-O-CO-O-** or *-Ay- Represents Ph-Ax-**. Ph represents a phenylene group. Ax represents an ether bond, an ester bond, and a carbonate ester bond. represents one group selected from the group consisting of Ay is a group consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond. represents one bond type selected from * indicates R 1 represents the bonding site with the carbon atom to which it is attached.]

[0011] Examples of the structural unit (I') containing a group represented by formula (Ia) include the structure represented by the following formula: Examples include structural unit (I). TIFF2026004581000008.tif4155[In formula (I), R 1 and R 2 each independently represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom; represents an alkyl group, a hydrogen atom or a halogen atom. X 1 and X 2 are each independently *-O-**, *-CO-O-**, *-O-CO -O-** or *-Ay-Ph-Ax-**. Ph, Ax, and Ay are the same as in formula (I). * indicates R 1 and R 2 In conclusion The ** indicates the bond site with the carbon atom bonded to the L 1 represents the binding site with L 1 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and The -CH2- contained in the hydroxyl group may be replaced by -O-, -S-, -SO2- or -CO-. stomach.]

[0012] R 1 and R 2 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine atoms. Examples include uran atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. groups and hexyl groups. The alkyl group having a halogen atom is an alkyl group in which a hydrogen atom contained in the alkyl group is a halogen atom. Preferably, a hydrogen atom in the alkyl group is substituted with a fluorine atom. Such groups include, for example, trifluoromethyl groups, perfluoromethyl groups, and the like. perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutanol group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a perfluoropentyl group and a perfluorohexyl group. R 1 and R 2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. group, and more preferably a hydrogen atom, a methyl group, or an ethyl group.

[0013] 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 2-methylbutane-1,4-diyl groups. The number of carbon atoms in the lucanediyl 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.

[0014] Examples of the divalent alicyclic saturated hydrocarbon group include the following groups. The binding site can be any position. Specifically, a cyclobutane-1,3-diyl group, a cyclopentane -1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group monocyclic divalent saturated alicyclic hydrocarbon groups such as cycloalkanediyl groups, and 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 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, and more preferably It is preferably 3 to 16, and more preferably 3 to 12. TIFF2026004581000009.tif44168 Examples of divalent aromatic hydrocarbon groups include phenylene groups, naphthylene groups, anthrylene groups, and biphenyl groups. 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.

[0015] The group combining two or more types includes a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group. a group combining an aromatic hydrocarbon group and a chain hydrocarbon group; a group combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group; In the combination, an alicyclic hydrocarbon group may be used. The alkyl group, aromatic hydrocarbon group, and chain hydrocarbon group may each be a combination of two or more types. Also, which group is X 2 may be bound to Examples of the group combining an alicyclic hydrocarbon group and a chain hydrocarbon group include a -2-valent alicyclic hydrocarbon group. Cyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group- Examples thereof include an alkanediyl group-, an alkanediyl group-divalent alicyclic hydrocarbon group-, and the like. Examples of the group combining an aromatic hydrocarbon group and a chain hydrocarbon group include a -2-valent aromatic Aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group- Examples thereof include an alkanediyl group-, an alkanediyl group-divalent aromatic hydrocarbon group-, and the like. 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.

[0016] 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 -CH2- contained in the hydrocarbon group having 1 to 28 carbon atoms is -O-, -S-, -SO2 When the hydrocarbon group is replaced with - or -CO-, the number of carbon atoms before the replacement 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 (the -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 group (a group in which -CH2- at any position in the alkyl , -S- substituted), alkoxycarbonyl group (any group contained in an alkyl group -CH2-CH2- is replaced with -O-CO-), alkylcarbonyl group ( A group in which any -CH2- in an alkyl group is replaced with -CO-), A hydroxysulfonyl group (where -CH2- at any position in the alkyl group is replaced with -SO2-) alkylcarbonyloxy group (a group in which the alkyl group is substituted) -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-), cycloalkoxy group, cycloalkylalkoxy group oxy group, alkoxycarbonyloxy group, aromatic hydrocarbon group-carbonyloxy group, Examples include groups in which two or more of these groups are combined. 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 Examples thereof include a decyloxy group. 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 The numbers are 1 to 4. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group are A carbonyl group or a carbonyloxy group is bonded to the alkyl group or the alkoxy group. Represents a group. 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. do. 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, and more preferably 1 to 4. 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 aryloxy group include a pentanediyloxy group and a pentanediyloxy group. 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. Examples include: 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.

[0017] In addition, -CH2- contained in the alicyclic hydrocarbon group may be -O-, -S-, -CO- or -S Examples of groups substituted with O2- include the following groups. The binding site can be at any position. It is possible. TIFF2026004581000010.tif47156

[0018] 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 hydroxy group.

[0019] L 1 represents an alkanediyl group having 1 to 6 carbon atoms (provided that the —C H2- may be replaced by -O- or -CO-, and the alkanediyl group is group), an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that the alicyclic hydrocarbon The —CH2— contained in the group may be replaced by —O— or —CO—, and the alicyclic The hydrocarbon group may have a substituent.) An alkanediyl group having 1 to 6 carbon atoms and a carbon a group formed by combining an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that the group formed by combining The contained —CH2— may be replaced with —O— or —CO—, and the combination thereof The group may have a substituent.) or an alkanediyl group having 1 to 6 carbon atoms and a group having 1 to 6 carbon atoms A group formed by combining 6 to 18 aromatic hydrocarbon groups (provided that the alkanediyl group does not contain The -CH2- may be replaced by -O- or -CO-, and the combination thereof The group may have a substituent.) is preferably an alkanedi group having 1 to 4 carbon atoms. alkanediyl group (provided that -CH2- contained in the alkanediyl group is replaced with -O- or -CO-) The alkanediyl group may have a substituent. an alicyclic hydrocarbon group of up to 18 (provided that -CH2- contained in the alicyclic hydrocarbon group is not -O- or -CO-, and the alicyclic hydrocarbon group may have a substituent. It is preferable to use a cycloaliphatic alkyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. a group obtained by combining (provided that the -CH2- included in the group obtained by combining is -O- or - CO- may be substituted, and the combined group may have a substituent. ) or a combination of an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms. (However, -CH2- contained in the alkanediyl group is not -O- or -CO-. -, and the combined group may have a substituent. It is more preferable that the alkanediyl group has 1 to 4 carbon atoms (provided that the alkanediyl The —CH2— contained in the group may be replaced by —O— or —CO—, and the alkane The diyl group may have a substituent. The combination of the alkanediyl group with an alicyclic hydrocarbon group or an aromatic hydrocarbon group is *-a Lactanediyl group-alicyclic hydrocarbon group or aromatic hydrocarbon group-, *-alicyclic hydrocarbon group or Aromatic hydrocarbon group-alkanediyl group-, *-alkanediyl group-alicyclic hydrocarbon group, or Examples include aromatic hydrocarbon groups, alkanediyl groups, etc. * denotes X 2 Represents a bond with .

[0020] X 1 or X 2 In this case, *-Ay-Ph-Ax-** is expressed by the following formula (X10). Examples of the linking groups include those represented by the following formula: TIFF2026004581000011.tif3449 formula (X10), Ax is a bond containing ** in formula (Ia) or L 1 Bonding with It represents a compound consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond. represents one binding species selected from the group. Ay is R in formula (Ia) or formula (I). 1 The bonded species bonded to the carbon atom to which Or in formula (I), R 2 represents the bond type that bonds with the carbon atom to which Ax is bonded. Ay is selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond. In addition, Ax is composed of an ether bond, an ester bond, and a carbonate ester. In the case where Ay is one bond selected from the group consisting of a single bond, an ether bond, an ester bond, an ester The bond represents one type of bond selected from the group consisting of a carboxylic acid ester bond and a carbonate ester bond. Rx is a halogen atom, a hydroxy group, a fluorinated alkyl group having 1 to 6 carbon atoms, or a It represents an alkyl group having 1 to 18 carbon atoms, and an 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, In the case of a number, the multiple Rx's may be the same or different from each other. The bonding position of Ay in the aryl group is preferably the m-position or p-position relative to Ax. It is more preferable that the amino acid is in the p-position.

[0021] X 1 and X 2 For example, the following formula (X 1 -1), formula (X 1 -2')~expression(X 1 -7') and formula (X 1 -8) * denotes a group represented by -R 1 The carbon atom to which and -R 2 represents the bond position with the carbon atom to which L is bonded. 1 represents the bond position to . TIFF2026004581000012.tif51155 formula (X 1 -2')~expression(X 1 Specific examples of the group represented by -7') include the following groups: can be done. TIFF2026004581000013.tif79123Among them, X 10 , that is, X 1 and X 2 are the formulas (X 1 -1)~Formula(X 1 - 7) is preferred, and the group represented by the formula (X 1 -1), a group represented by the formula (X 1 -3) group, formula (X 1 -4) or a group represented by the formula (X 1 It is more preferred that the group is represented by the formula (5). Shikkuri, R 1 and R 2 are bonded to the carbon atoms bonded to each other via -CO-O- Expression(X 1 -1), a group represented by the formula (X 1 -4) or a group represented by the formula (X 1 -5) It is even more preferred that the group is a group represented by the formula (X 1 -1) or a group represented by the formula (X 1 -4) It is even more preferable that the group is a group represented by the following formula:

[0022] Specific examples of the structural unit (I) are shown below. TIFF2026004581000014.tif208152

[0023] TIFF2026004581000015.tif205150

[0024] In these specific examples, R 1 and R 2 The methyl group corresponding to an alkyl group having 1 to 6 carbon atoms (excluding methyl groups) or a halogen atom; Specific examples of the structural unit (I) include those in which a hydroxyl group is substituted with a hydroxyl atom.

[0025] <Method for producing structural unit (I)> The structural unit (I) is a compound represented by the formula (Ia) and the formula (Ib). or a structural unit represented by formula (Ic) and a compound represented by formula (Id) are catalyzed The compound can be obtained by reacting the compound in a solvent in the presence of a solvent. TIFF2026004581000016.tif91137 (wherein all symbols have the same meanings as defined above.)

[0026] In the structural unit (I), L 1 *-CH2-CHOH-L 2 - (* is X 2 The structural unit (hereinafter referred to as "structural unit (IA)") is The method for producing the compound represented by formula (IA-e) is to react a structural unit represented by formula (Ic) with a compound represented by formula (IA-e) under a catalyst. The compound can be obtained by reacting the compound in a solvent in the presence of In addition, in the structural unit (I), L 1 But *-L 2 A group represented by -CHOH-CH2- (* is X 2 The structural unit (hereinafter referred to as "structural unit (IB)") is a In some cases, the structural unit represented by formula (IA-f) and the compound represented by formula (Ib) are The compound can be obtained by reacting the compound in a solvent in the presence of a catalyst. TIFF2026004581000017.tif102133 (wherein all symbols have the same meanings as above. L 2 may have a substituent. represents a hydrocarbon group having 1 to 25 carbon atoms, and -CH2- contained in the hydrocarbon group is -O-, may be replaced by -S-, -SO2- or -CO-.

[0027] Catalysts for this reaction include tetrabutylammonium bromide and potassium iodide. , potassium carbonate, pyridine, triethylamine, carbonyldiimidazole, etc. do. The solvent used in this reaction is propylene glycol monomethyl ether acetate. chloroform, acetonitrile, dimethylformamide, etc. The reaction temperature is usually 5°C to 100°C, and the reaction time is usually 0.5 to 24 hours.

[0028] Examples of the structural unit represented by formula (Ia) include structural units represented by the following formula: It can be easily produced by a known production method. TIFF2026004581000018.tif49157 Examples of the compound represented by formula (Ib) include compounds represented by the following formula, which are commercially available: It can be more easily obtained. TIFF2026004581000019.tif38134 Examples of the structural unit represented by formula (Ic) include structural units represented by the following formula: It can be easily produced by a known production method. TIFF2026004581000020.tif38155 Examples of the compound represented by formula (Id) include compounds represented by the following formula, and are commercially available. It is more readily available and can be easily produced by known production methods. Cut. TIFF2026004581000021.tif49138 Examples of the compound represented by formula (IA-e) include compounds represented by the following formula: It is readily available from the market and can be easily produced by known production methods. can. TIFF2026004581000022.tif53140 Examples of the structural unit represented by formula (IA-f) include structural units represented by the following formula: The compound can be easily produced by a known production method. TIFF2026004581000023.tif54159

[0029] The structural unit (I') and the structural unit (I) are polymers containing a structural unit having a glycidyl group. a copolymer and a vinyl monomer having at least one selected from a carboxy group and an acid anhydride group; and a polymer containing a structural unit having a carboxy group and a glycidyl group and It is a reaction product with a vinyl monomer having at least one hydroxy group selected from the group consisting of Preferably, a polymer containing a structural unit having a carboxy group and a glycidyl group and a hydroxyl group is used. It is more preferred that the compound is a reaction product with a vinyl monomer having at least one selected from the group consisting of methyl, ... Specifically, a polymer containing a structural unit having a carboxyl group and a vinyl unit having a glycidyl group It is more preferably a reaction product with a monomer.

[0030] The content of the structural unit (I') or the structural unit (I) relative to the total structural units of the resin (A) is: It is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and even more preferably 3 to 15 mol %. I wish.

[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. TIFF2026004581000024.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.] TIFF2026004581000025.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 octynyl group include hexenyl, heptenyl, octynyl, isooctynyl, and nonenyl groups. 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. TIFF2026004581000026.tif10150R a1 , R a2and 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., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, alkyl groups Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups with alicyclic hydrocarbon groups (p-cyclohexane adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. An aryl-cycloalkyl group is exemplified. 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-. TIFF2026004581000027.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., alkylcycloalkyl group or cycloalkylalkyl group), alkyl groups such as benzyl group, Aromatic hydrocarbon groups containing ralkyl groups and alkyl groups (p-methylphenyl group, p-tert-butylphenyl group, etc.) t-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diene aromatic hydrocarbons having an alicyclic hydrocarbon group, such as 2-methyl-6-ethylphenyl group, 2-methyl-6-ethylphenyl group, etc. Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), Examples include aryl-cycloalkyl groups such as an arylcyclohexyl 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. TIFF2026004581000028.tif19130R 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 Forms a methyl group, R a3 is an alkyl group, ma=0, and na=1. In formula (1), R a1 and R a2 are each independently an alkyl group, and R a3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following: * represents a binding site. TIFF2026004581000029.tif154163

[0035] Specific examples of group (2) include the following groups: * represents a binding site. TIFF2026004581000030.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 (a1-1) is selected from the group consisting of the structural unit (a1-2). These may be used alone or in combination of two or more. They may be used in combination. TIFF2026004581000031.tif46150 [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 , Ra4 and R a5 is preferably a hydrogen atom or a methyl group, and more preferably It is a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or —O—(CH2) k01 -C OO- (wherein k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 Alkyl groups, alkenyl groups, alicyclic groups The hydrocarbon group, aromatic hydrocarbon group, and a group formed by combining these groups include R a1 , R a2 and R a3 Examples of the groups include the same groups as those listed in the above. R a02 , R a03 , and R a04 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. A 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 , Ra04 , 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 a6 and 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. TIFF2026004581000032.tif96161

[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. TIFF2026004581000033.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. TIFF2026004581000034.tif60160

[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 to 80 mol %, preferably 5 to 75 mol %, more preferably The content is usually 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 to 90 mol % based on the total structural units of the resin (A), and preferably It is preferably 15 to 85 mol %, more preferably 20 to 80 mol %, and even more preferably Preferably, it is 20 to 75 mol %, and even more preferably, it is 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)"). TIFF2026004581000035.tif5374[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 a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxy group having 2 to 12 carbon atoms Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms It represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a30 is a single bond or * -X a31 -(A a32 -X a32 ) nc - represents -R a32 is combined represents the bonding site with the carbon atom. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O- or -O-CO-. nc represents 0 or 1. Ia represents an integer of 0 to 4. When Ia is an integer of 2 or more, R in Numbers a33 may be the same or different from each other. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH2- contained in the alkyl group and the divalent hydrocarbon group is replaced by -O- or -S-. That's fine.]

[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 ... 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 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] Examples of the alkanediyl group include a methylene group, an ethylene group, and a propane-1,3-diyl group. Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and and 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[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. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a methyl group. Examples include a sil group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the cyclopentyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, butyl group, adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include: TIFF2026004581000036.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., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, alkyl groups Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups with alicyclic hydrocarbon groups (p-cyclohexane adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36 As for carbon number 1 to 18, alkyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Examples of groups include groups formed by combining these.

[0050] R a34 is preferably a hydrogen atom. R a35is 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 aliphatic hydrocarbon group having 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. a36 in The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 Fragrance in The aromatic hydrocarbon 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. -4-18) 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: TIFF2026004581000037.tif99157

[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. TIFF2026004581000038.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 -, and 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. TIFF2026004581000039.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. TIFF2026004581000040.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. TIFF2026004581000041.tif5295When 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 having the structural unit (a3) ​​is used in the resist composition of the present invention, This can improve the resolution of the resist pattern and the adhesion to the substrate.

[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. TIFF2026004581000042.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 a50is a single bond or *-X a51 -(A a52 -X a52 ) nb - represents -R a50 is combined represents the bond position with the carbon atom. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, multiple R in Numbers a51 may be the same or different.]

[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 and R a51 and an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, Examples include trifluoromethyl, difluoromethyl, methyl, and perfluoroethyl groups. , 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, perfluorobutyl 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-nonyl group Fluoropentyl, pentyl, hexyl and perfluorohexyl groups are included. . 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 a51The 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] Examples of the alkanediyl group include a methylene group, an ethylene group, and a propane-1,3-diyl group. Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and and 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group.

[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 (a2-2-16). In the structural units represented by formulas (a2-2-1) to (a2-2-16), R in the structural unit (a2-A) a50 The methyl group corresponding to Examples of the structural unit include a structural unit substituted with a haloalkyl group or other alkyl group. 2-A) is a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), Structural units, structural units represented by formula (a2-2-6), structural units represented by formula (a2-2-8) Positions, structural units represented by formulas (a2-2-12) to (a2-2-14) and In the structural unit, R in the structural unit (a2-A) a50 The methyl group corresponding to The structural unit represented by formula (a2-2-3) is preferably a structural unit represented by formula (a2-2-3) , structural units represented by formula (a2-2-8), formulas (a2-2-12) to (a2-2-14) ) and a structural unit represented by formula (a2-2-3) or a structural unit represented by formula (a2-2-8) ), structural units represented by formulas (a2-2-12) to (a2-2-14) At the position, R in the structural unit (a2-A) a50 A methyl group corresponding to The structural unit represented by formula (a2-2-8) is more preferably a structural unit represented by formula (a2-2-8) and in the structural unit represented by formula (a2-2-8), R in the structural unit (a2-A) a50 It is more preferable that the structural unit is a structural unit in which a methyl group corresponding to stomach. TIFF2026004581000043.tif57169

[0070] Content of structural unit (a2-A) when structural unit (a2-A) is contained in resin (A) is preferably 5 to 80 mol %, more preferably 10 to 75 mol %, based on all structural units. % by mole, more preferably 15 to 70 mol %, and even more preferably 20 to 30 mol %. It is 70 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: TIFF2026004581000044.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 position with —CO—. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer between 0 and 10.

[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. TIFF2026004581000045.tif50139

[0074] When the resin (A) contains the structural unit (a2-1), its content is determined based on the total amount of all structural units in the resin (A). It is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably It is preferably 1 to 35 mol %, more preferably 1 to 30 mol %, and even more preferably The content is usually 1 to 25 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, the ring is a γ-butyrolactone ring, an adamantane lactone ring, or a γ -Bridged ring containing a butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) Examples include:

[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. TIFF2026004581000046.tif51164 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or -O-(CH2) k3 -C It represents a group represented by OO-(k3 represents an integer of 1 to 7). L a7 -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- vinegar. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding position with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or represents a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 are each independently a carboxy group, a cyano group or a carbon atom. It represents an aliphatic hydrocarbon group having 1 to 4 prime numbers. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 may be the same or different.]

[0077] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in butyl, sec-butyl and tert-butyl groups. Examples include alkyl groups such as t-butyl groups. R a24 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine. Examples include atoms. R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Preferably, the alkyl group has 1 to 4 carbon atoms, and more preferably, the methyl group. or an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group Examples include a methyl group and a triiodomethyl group.

[0078] L a8 and L a9The 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)'. TIFF2026004581000047.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] TIFF2026004581000048.tif117168

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

[0084] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2026004581000049.tif2862[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. TIFF2026004581000050.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). TIFF2026004581000051.tif4652[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 54The structural unit in which the methyl group corresponding to can be. TIFF2026004581000052.tif95166

[0091] TIFF2026004581000053.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). TIFF2026004581000054.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) includes a chain hydrocarbon group and a monocyclic or polycyclic saturated alicyclic group. and groups formed by combining these.

[0093] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include a decyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic saturated alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups; Polycyclic aliphatic groups such as adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include cyclic hydrocarbon groups. TIFF2026004581000055.tif10159The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more saturated alicyclic hydrocarbon groups. -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkanediyl group Examples include an alkyl group, -alkanediyl group-saturated alicyclic hydrocarbon group-alkyl group, and the like.

[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 at least one selected from the group consisting of fluorine, Examples of the fluorine atom include a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. TIFF2026004581000056.tif855[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * denotes R a42 represents the binding site with However, R a42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a4 5 represents a saturated hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom.

[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): TIFF2026004581000057.tif10159The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0096] R a42is 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). TIFF2026004581000058.tif872[In formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. represent. X a44 represents **-O-CO- or **-CO-O- (** represents A a46 The binding site represent.). A a47 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 of At least one of them has at least one halogen atom. * indicates the bonding site with the carbonyl group.]

[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). TIFF2026004581000059.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 each binding site, and ** indicates -O-CO-Ra42 This is the binding site for TIFF2026004581000060.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: TIFF2026004581000061.tif99145

[0104] TIFF2026004581000062.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). TIFF2026004581000063.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 44The 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] TIFF2026004581000064.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 f13The 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 f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-3). It is one of the structural units that can be mentioned.

[0114] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF2026004581000065.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. TIFF2026004581000066.tif87160

[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): . TIFF2026004581000067.tif3555[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. TIFF2026004581000068.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 x1represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[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. TIFF2026004581000069.tif53136

[0125] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2026004581000070.tif23130

[0126] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2026004581000071.tif16146

[0127] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2026004581000072.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. TIFF2026004581000073.tif110150When 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. <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 (sulfur) containing -SO2-O-. It is a structural unit that has a thion ring.

[0130] 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. TIFF2026004581000074.tif3087

[0131] 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.

[0132] Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. . The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a methyl group. Examples 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.

[0133] 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'). TIFF2026004581000075.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 41Examples 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.

[0134] The sultone ring is more preferably a ring represented by formula (T1). TIFF2026004581000076.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.]

[0135] 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.

[0136] 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. TIFF2026004581000077.tif47144

[0137] The structural unit having a sultone ring preferably has the following group: * in the following group represents the binding site. TIFF2026004581000078.tif45144

[0138] 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.

[0139] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF2026004581000079.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 R d each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0140] 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.

[0141] 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.

[0142] 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:

[0143] Examples of the structural unit (a6) include the following structural units. TIFF2026004581000080.tif93150

[0144] 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), its content 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.

[0145] <Structural unit (II)> The resin (A) further contains a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit”). The structural unit (II) may include, for example, Examples of the structural units include those described in JP-A-2016-79235, and those having a sulfonyl group in the side chain. A structural unit having a carboxylate group or a carboxylate group and an organic cation, or a sulfonate group in a side chain A structural unit having an aryl group and an organic anion is preferred.

[0146] 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'). TIFF2026004581000081.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. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the water contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. stomach. RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a group having 1 carbon atom which may have a halogen atom Represents an alkyl group of 1 to 6. ZA + represents an organic cation.

[0147] 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 uran 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 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include trifluoroalkyl groups. Fluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroiso Propyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group Examples of the alkyl group include a perfluoropentyl group, a perfluorohexyl group, and the like.

[0148] 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, cyclohexane -1,4-diyl group, cycloalkanediyl group such as cyclooctane-1,5-diyl group, etc. a divalent monocyclic alicyclic saturated hydrocarbon radical; Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1 Divalent polycyclic alicyclic saturated hydrocarbons such as 2,5-diyl group, adamantane-2,6-diyl group, etc. groups, etc.

[0149] -CH2- in saturated hydrocarbon groups is replaced with -O-, -S- or -CO- Examples of such groups include divalent groups represented by formulae (X1) to (X53). The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-. The number of carbon atoms in each of the preceding groups is 17 or less. In the following formula, * and ** represent binding sites. * is A x1 represents the binding site with TIFF2026004581000082.tif145161

[0150] 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.

[0151] 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 the above formulas (b2-1) to (b2-4) is Cation (hereinafter, depending on the formula number, it may be referred to as "cation (b2-1)" etc.) Examples include:

[0152] The structural unit represented by formula (II-2-A') is a structural unit represented by formula (II-2-A) It is preferable that: JPEG2026004581000083.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.]

[0153] 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:

[0154] 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 . TIFF2026004581000084.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.

[0155] 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.

[0156] 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 TIFF2026004581000085.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.]

[0157] 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. TIFF2026004581000086.tif86163

[0158] 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. TIFF2026004581000087.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 RII3 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.

[0159] Examples of the cation-containing structural unit in formula (II-1-1) include structural units represented by the following formulas: R II4 The group corresponding to the methyl group in the formula (I) is a hydrogen atom, a halogen atom (e.g., a fluorine atom), or An alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, trifluoromethyl Examples of such structural units include those in which the aryl group is replaced by a methyl group, etc. TIFF2026004581000088.tif85130

[0160] 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. Examples of the anion include the anion represented by formula (B1).

[0161] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2026004581000089.tif36135 Examples of sulfonylmethide anions include the following: TIFF2026004581000090.tif29123Carboxylate anions include the following: TIFF2026004581000091.tif51152

[0162] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2026004581000092.tif88149

[0163] 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 %.

[0164] The resin (A) may have structural units other than the above-mentioned structural units. The moieties include structural units known in the art.

[0165] The resin (A) preferably comprises the structural unit (I), the structural unit (a1) and the structural unit (s). It is a resin consisting of the following. The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2), a structural unit (a1-3), a structural unit (a1-4), a structural unit (a1-5), a structural unit (a1-6), a structural unit (a1-7), a structural unit (a1-8), a structural unit (a1-9), a structural unit (a1-1 ... Unit (a1-2) (preferably the structure having a cyclohexyl group and a cyclopentyl group) unit) and structural unit (a1-4), and more preferably Preferably, the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2) (preferably or a cyclohexyl group, and a cyclopentyl group) At least one of the above-mentioned compounds is preferably used, more preferably at least two of the above-mentioned compounds are preferably used, and even more preferably or at least one selected from the group consisting of structural units (a1-1) and structural units (a1-2). There are two types of both. The structural unit (s) is preferably selected from the group consisting of the structural unit (a2) and the structural unit (a3): The structural unit (a2) is preferably represented by the formula (a2-1): The structural unit (a3) ​​is preferably a structural unit represented by the formula (a2-A). or a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-3). a3-4) is at least one selected from the group consisting of structural units represented by the formula:

[0166] The structural units constituting the resin (A) may be used singly or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (for example, radical polymerization methods). The content of each structural unit contained in the resin (A) 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 (A) is preferably 2,000 or more (more preferably 2,500 or more). 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 In this specification, the weight average molecular weight is 1,000 or less, and more preferably 15,000 or less. The molecular weight is determined by gel permeation chromatography under the conditions described in the examples. is.

[0167] <Resins other than Resin (A)> The resist composition of the present invention may contain a resin other than the resin (A). Examples of resins other than the resin (A) include those containing the structural unit (a4) or the structural unit (a5). Examples of the resin include a resin having the above structure (hereinafter, sometimes referred to as resin (X)).

[0168] As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In resin (X), the content of structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. Examples of structural units that the resin (X) may further have include the structural unit (a2), the structural unit (a3) and structural units derived from other known monomers. X) is preferably a resin consisting of only the structural unit (a4) and / or the structural unit (a5). It is more preferable that the resin is composed only of the structural unit (a4). 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 (X) is preferably 6,000 or more (more preferably 7,000 or more). 0 or more) and 80,000 or less (more preferably 60,000 or less). The weight average molecular weight can be measured by the same method as in the case of resin (A). When the resist composition contains resin (X), the content thereof is The content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further Preferably, it is 1 to 40 parts by mass, and even more preferably, it is 1 to 30 parts by mass, and further preferably, The amount of the layer is preferably 1 to 8 parts by mass.

[0169] 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.

[0170] <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 62-69263, JP 63-146038, JP 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.

[0171] 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)"). TIFF2026004581000093.tif3058[In formula (B1), Q b1 and Qb2 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.

[0172] 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.

[0173] 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.

[0174] 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 a bond to -Y.

[0175] TIFF2026004581000094.tif26118[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated 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 b6 and L b7 The total number of carbon atoms is 23 or less.

[0176] 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.

[0177] 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.

[0178] 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: TIFF2026004581000095.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.

[0179] 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 b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably 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.

[0180] 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: TIFF2026004581000096.tif23139 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 b26represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atom may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0181] 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.

[0182] Examples of the group represented by formula (b1-4) include the following. TIFF2026004581000097.tif16154Examples of the group represented by formula (b1-5) include the following. TIFF2026004581000098.tif68152Examples of the group represented by formula (b1-6) include the following. TIFF2026004581000099.tif29150Examples of the group represented by formula (b1-7) include the following. TIFF2026004581000100.tif57146Examples of the group represented by formula (b1-8) include the following. TIFF2026004581000101.tif23150

[0183] Examples of the group represented by formula (b1-2) include the following. TIFF2026004581000102.tif31161Examples of the group represented by formula (b1-9) include the following. TIFF2026004581000103.tif44137Examples of the group represented by formula (b1-10) include the following. TIFF2026004581000104.tif92165Examples of the group represented by formula (b1-11) include the following. TIFF2026004581000105.tif84164

[0184] 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). .

[0185] The alicyclic hydrocarbon group represented by TIFF2026004581000106.tif85167Y is preferably a group represented by formula (Y1) to formula (Y20), Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43) and more preferably a group represented by formula (Y11), formula (Y15), or formula (Y16 ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39), a group represented by 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 following 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.

[0186] 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.)

[0187] 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 11 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:

[0188] Examples of Y include the following: TIFF2026004581000107.tif149158

[0189] 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

[0190] 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.

[0191] TIFF2026004581000108.tif231164

[0192] TIFF2026004581000109.tif238165

[0193] TIFF2026004581000110.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.

[0194] 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. TIFF2026004581000111.tif238158

[0195] TIFF2026004581000112.tif129154

[0196] Among them, the compounds represented by formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a- 16), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a- 38) is preferred.

[0197] 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.

[0198] TIFF2026004581000113.tif41147In 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 b8are 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. TIFF2026004581000114.tif11158 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. Examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a perfluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 9, and more preferably 1 to 9. It is preferably 6, and more preferably 1 to 4.

[0199] 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. TIFF2026004581000115.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.

[0200] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2026004581000116.tif80161

[0201] TIFF2026004581000117.tif109165Examples of the cation (b2-2) include the following cations. TIFF2026004581000118.tif18150Examples of the cation (b2-3) include the following cations. TIFF2026004581000119.tif26139Examples of the cation (b2-4) include the following cations. TIFF2026004581000120.tif127165

[0202] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, The acid generator (B) is preferably a compound represented by the formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), an aniline represented by any one of formulas (B1a-22) to (B1a-38) A combination of an onion and a cation (b2-1), a cation (b2-3), or a cation (b2-4) Examples include combinations.

[0203] 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. JPEG2026004581000121.jpg214167

[0204] TIFF2026004581000122.tif235160

[0205] TIFF2026004581000123.tif205166

[0206] 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.

[0207] <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.

[0208] <Quencher (C)> The quencher (C) is an acid that is weaker in acidity than the acid generated by the acid generator (B). These include the salts generated and basic nitrogen-containing organic compounds. The content of the photoresist is preferably about 0.01 to 15 mass % based on the solid content of the resist composition. It is more preferably about 0.01 to 10% by mass, and more preferably about 0.1 to 8% by mass, and even more preferably about 0.1 to 7% by mass.

[0209] The acidity in the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 < pKa, preferably 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 the salt represented by the following formula, the salt represented by formula (D) described in JP-A-2015-147926 (hereinafter, sometimes referred to as "weak acid intramolecular salt (D)"), and the salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. 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 ), and more preferably, a weak acid intramolecular salt (D). JPEG2026004581000124.jpg113161

[0210] Examples of the weak acid intramolecular salt (D) include an iodonium cation to which two phenyl groups are bonded and , at least one of the two phenyl groups bonded to the iodonium cation and a diphenyliodonium salt having a carboxy anion substituted with a group. Preferred and specific examples of the salts include the following: TIFF2026004581000125.tif72165

[0211] 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.

[0212] <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.

[0213] <Preparation of Resist Composition> The resist composition of the present invention comprises the resin (A) of the present invention, the acid generator (B), and a photosensitive compound (P) generated from the acid generator. a salt that generates an acid weaker in acidity than the acid generated, and, if necessary, a resin (A2), By mixing the fat (X), the quencher (C), the solvent (E) and other components (F), The order of mixing is not particularly limited and may be any order. The temperature during the reaction varies from 10 to 40°C depending on the type of resin, the solubility of the resin in the solvent (E), etc. The appropriate temperature can be selected depending on the mixing time. The mixing time is 0.5 to 24 hours depending on the mixing temperature. The mixing time can be selected from the appropriate time. etc. can be used. After mixing the components, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable that

[0214] <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 heated composition layer with a developer containing an organic solvent is included.

[0215] 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 (i.e., a heat treatment) to promote the deprotection reaction of the acid labile groups. 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 developing time is preferably 300 seconds or less. By selecting the type of developer, a positive resist pattern or Negative resist patterns can be produced. In the present invention, the developer contains an organic solvent (hereinafter, sometimes referred to as an "organic developer"). By using a developer containing an organic solvent, it is possible to mainly develop negative resist patterns. It is possible to manufacture 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.

[0216] <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]

[0217] 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."

[0218] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-1)" etc. according to their formula numbers. TIFF2026004581000126.tif89165

[0219] Synthesis Example 1 [Synthesis of Resin AX1] As the monomers, monomer (a1-1-3), monomer (a1-2-5), monomer ( a2-1-1), methacrylic acid and monomer (a3-4-2) were used in the molar ratio [mono Monomer (a1-1-3): Monomer (a1-2-5): Monomer (a2-1-1): Methacrylamide The ratio of acrylic acid to monomer (a3-4-2) was 25:24.5:5.5:10:35. Further, to this monomer mixture, 1 0.5 times by mass of propylene glycol monomethyl ether acetate was mixed. The mixture contained azobisisobutyronitrile and azobis(2,4-dimethylbutyronitrile) as initiators. The total amount of monomers was 1 mol% and 3 mol% of methyl methyl nitrile. The mixture was heated at 75°C for about 5 hours. The resulting reaction mixture was added to a large amount of a methanol / water mixed solvent. The resin was then precipitated by pouring and filtered. The solution obtained by dissolving in methyl ether acetate was dissolved in a methanol / water mixed solvent. The resin was precipitated by pouring the resin into a glass tube and then filtered. This reprecipitation procedure was repeated twice to obtain the weight average Molecular weight 8.8×10 3 Resin AX1 (copolymer) was obtained in a yield of 77%. It has the following structural units: TIFF2026004581000127.tif37157

[0220] Synthesis Example 2 [Synthesis of Resin A1] Resin AX1 and monomer (ax) were used, and the molar ratio [resin AX1:monomer (ax)] ] are mixed in a ratio of 100:10, and then the total mass of the mixture is The amount of propylene glycol monomethyl ether acetate was mixed with 3 times the amount of propylene glycol monomethyl ether acetate. The resulting mixture was mixed with tetrabutylammonium bromide as a catalyst to obtain a resin AX1. 10 mol% and 1.6 mol% of 4-methoxyphenol were added to resin AX1. The mixture was heated at 90° C. for about 2 hours. The resulting reaction mixture was added to a large amount of a methanol / water mixture. The resin was poured into the combined solvent to precipitate, and the resin was filtered. The solution obtained by dissolving in glycol monomethyl ether acetate was mixed with methanol / water. The resin was poured into a mixed solvent to precipitate, and the resin was then filtered. This reprecipitation procedure was repeated twice. Weight average molecular weight 1.0×10 4 Resin A1 (copolymer) was obtained in a yield of 62%. has the following structural unit: TIFF2026004581000128.tif42153

[0221] Synthesis Example 3 [Synthesis of Resin AX2] As the monomers, monomer (a1-1-3), monomer (a1-2-5), monomer ( a2-1-1 and monomer (a3-4-2) were used, and the molar ratio [monomer (a1-1 -3): Monomer (a1-2-5): Monomer (a2-1-1): Monomer (a3-4- 2)) are mixed in a ratio of 45:14:2.5:38.5, and then The monomer mixture was mixed with 1.5 times the mass of propylene glycol monomer relative to the total mass of all monomers. The resulting mixture was mixed with azobisisopropyl acetate as an initiator. butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total monomer amount These were heated at 75°C for about 5 hours. The reaction mixture was poured into a large amount of a methanol / water mixed solvent to precipitate the resin, which was then filtered. The resulting resin was dissolved again in propylene glycol monomethyl ether acetate. The resulting solution is poured into a methanol / water mixed solvent to precipitate the resin. The reprecipitation procedure was repeated twice, and the weight-average molecular weight was 7.9 × 10 3 Resin AX2 (common The resin AX2 was obtained in a yield of 70%. This resin AX2 has the following structural units. TIFF2026004581000129.tif37157

[0222] Synthesis Example 4 [Synthesis of Resin AX3] As the monomers, monomer (a1-1-3), monomer (a1-2-5), monomer ( a2-1-1), methacrylic acid and monomer (a3-4-2) were used in the molar ratio [mono Monomer (a1-1-3): Monomer (a1-2-5): Monomer (a2-1-1): Methacrylamide The ratio of acrylic acid:monomer (a3-4-2) was 35:14:2.5:10:38.5. Further, to this monomer mixture, 1 0.5 times by mass of propylene glycol monomethyl ether acetate was mixed. The mixture contained azobisisobutyronitrile and azobis(2,4-dimethylbutyronitrile) as initiators. The total amount of monomers was 1 mol% and 3 mol% of methyl methyl nitrile. The mixture was heated at 75°C for about 5 hours. The resulting reaction mixture was added to a large amount of a methanol / water mixed solvent. The resin was then precipitated by pouring and filtered. The solution obtained by dissolving in methyl ether acetate was dissolved in a methanol / water mixed solvent. The resin was precipitated by pouring the resin into a glass tube and then filtered. This reprecipitation procedure was repeated twice to obtain the weight average Molecular mass 8.5×10 3 Resin AX3 (copolymer) was obtained in a yield of 75%. It has the following structural units: TIFF2026004581000130.tif37157

[0223] Synthesis Example 5 [Synthesis of Resin A2] Resin AX3 and monomer (ax) were used, and the molar ratio [Resin AX3:Monomer (ax)] ] are mixed in a ratio of 100:10, and then the total mass of the mixture is The amount of propylene glycol monomethyl ether acetate was mixed with 3 times the amount of propylene glycol monomethyl ether acetate. The resulting mixture was mixed with tetrabutylammonium bromide as a catalyst to obtain a resin AX3. 10 mol% and 1.6 mol% of 4-methoxyphenol were added to resin AX3. The mixture was heated at 90° C. for about 2 hours. The resulting reaction mixture was added to a large amount of a methanol / water mixture. The resin was poured into the combined solvent to precipitate, and the resin was filtered. The solution obtained by dissolving in glycol monomethyl ether acetate was mixed with methanol / water. The resin was poured into a mixed solvent to precipitate, and the resin was then filtered. This reprecipitation procedure was repeated twice. Weight average molecular weight 1.0×10 4 Resin A2 (copolymer) was obtained in a yield of 60%. has the following structural unit: TIFF2026004581000131.tif42153

[0224] Synthesis Example 6 [Synthesis of Resin AX4] As the monomers, monomer (a1-1-1), monomer (a2-1-1), monomer ( a3-1-1) and monomer (ax) were used, and the molar ratio [monomer (a1-1-1): Monomer (a2-1-1): Monomer (a3-1-1): Monomer (ax)] is 24: The monomer mixture was mixed in a ratio of 23:48:5, and then the total monomers were added to the monomer mixture. 1.5 times the total mass of propylene glycol monomethyl ether acetate The resulting mixture was mixed with azobisisobutyronitrile and azobisisobutyronitrile as initiators. 2,4-dimethylvaleronitrile was added at 1 mol% and 3 mol% of the total monomer amount, respectively. mol % of methylcellulose was added, and the mixture was heated at 75°C for about 5 hours. The resin was precipitated by pouring it into a mixed solvent of ethanol and water, and the resin was filtered. and a solution obtained by dissolving it in propylene glycol monomethyl ether acetate. A reprecipitation process in which the resin is precipitated by pouring it into a methanol / water mixed solvent and then filtering the resin. The weight-average molecular weight was 9.0 × 10 3 Resin AX4 (copolymer) was obtained with a yield of 89%. This resin AX4 has the following structural units: TIFF2026004581000132.tif26131

[0225] Synthesis Example 7 [Synthesis of Resin A3] Resin AX4 and methacrylic acid were used, and the molar ratio [resin AX4:methacrylic acid] was 1 The mixture was mixed in a ratio of 0.00:5, and then the total mass of the mixture was Then, 3 times the mass of propylene glycol monomethyl ether acetate was mixed. The mixture was added with 5 mol of tetrabutylammonium bromide as a catalyst relative to the resin AX4. % and 4-methoxyphenol were added to resin AX4 at 1.6 mol %. The mixture was heated at 0°C for about 2 hours, and the resulting reaction mixture was poured into a large amount of a mixed solvent of methanol and water. The resin was precipitated with propylene glycol monohydrate and filtered. The solution obtained by dissolving it in methyl ether acetate is poured into a methanol / water mixed solvent. The resin was precipitated in water and then filtered, and the reprecipitation procedure was repeated twice to obtain a weight-average molecular weight of 1.5g. 1.0×10 4 Resin A3 (copolymer) was obtained in a yield of 74%. This resin A3 has the following structure: It has a structural unit. TIFF2026004581000133.tif42130

[0226] Synthesis Example 8 [Synthesis of Resin AX5] As the monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( a2-1-3), monomer (a3-4-2), methacrylic acid and monomer (a1-4-1 3), and the molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer Monomer (a2-1-3): Monomer (a3-4-2): Methacrylic acid: Monomer (a1-4 -13) were mixed in a ratio of 20:30:3:15:5:27, and then The monomer mixture is mixed with 1.5 times the mass of methyl isobutyl ether based on the total mass of all monomers. The resulting mixture was mixed with azobisisobutyronitrile and benzophenone as initiators. 1.2 mol of bis(2,4-dimethylvaleronitrile) based on the total amount of monomers % and 3.6 mol % were added, and the mixture was heated at 73°C for about 5 hours. Then, 2.0 times the mass of the total mass of all monomers was added to the p-toluenesulfonic acid aqueous solution (2 The organic layer was separated after stirring for 12 hours. The resin was poured into heptane to precipitate, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.3. x10 3 Resin AX5, which has the following structural units, was obtained in a yield of 63%. This is what we do. TIFF2026004581000134.tif36159

[0227] Synthesis Example 9 [Synthesis of Resin A4] Resin AX5 and monomer (ax) were used, and the molar ratio [Resin AX5:Monomer (ax)] ] are mixed in a ratio of 100:5, and then the total mass of the mixture is Propylene glycol monomethyl ether acetate was mixed in an amount three times by mass of the propylene glycol monomethyl ether acetate. The resulting mixture was mixed with tetrabutylammonium bromide as a catalyst in an amount of 1:1000 to 1:1000 relative to the resin AX5. 5 mol% and 4-methoxyphenol were added to resin AX5 at 1.6 mol%, The mixture was heated at 90°C for about 2 hours. The resulting reaction mixture was added to a large amount of a mixed solvent of methanol and water. The resin was then poured into a solvent to precipitate the resin, which was then filtered. The solution obtained by dissolving in cholesteryl methyl ether acetate was mixed with methanol / water. The resin was poured into a solvent to precipitate, and the resin was then filtered. This reprecipitation procedure was repeated twice, and the weight average was Average molecular weight 7.1×10 3 Resin A4 (copolymer) was obtained in a yield of 63%. It has the following structural units: TIFF2026004581000135.tif43167

[0228] Synthesis Example 10 [Synthesis of Resin AX6] As the monomers, monomer (a1-1-3), monomer (a1-2-5), monomer ( ax2) and monomer (a3-4-2) were used, and the molar ratio [monomer (a1-1-3) : Monomer (a1-2-5): Monomer (ax2): Monomer (a3-4-2)] is 4 The monomer mixture was mixed in a ratio of 5:15:5:35, and then the total monomers were added to the mixture. 1.5 times the mass of propylene glycol monomethyl ether acetate relative to the total mass of mers To the resulting mixture, azobisisobutyronitrile and acetone were added as initiators. and 1 mol% of benzobis(2,4-dimethylvaleronitrile) based on the total amount of monomers. The resulting mixture was heated at 75°C for about 5 hours. The resin was precipitated by pouring into a methanol / water mixed solvent, and the resin was filtered. The resulting solution was dissolved again in propylene glycol monomethyl ether acetate. The liquid is poured into a methanol / water mixed solvent to precipitate the resin, which is then filtered. The procedure was repeated twice to obtain a weight-average molecular weight of 8.2 × 10 3 Resin AX6 (copolymer) was produced with a yield of 77% This resin AX6 has the following structural units: TIFF2026004581000136.tif37157

[0229] Synthesis Example 11 [Synthesis of Resin A5] Resin AX6 and a 1:1 reaction product of methacrylic acid and carbonyldiimidazole were used. The molar ratio of [Resin AX6: 1:1 reaction product of methacrylic acid and carbonyldiimidazole] , and mixed in a ratio of 100:5, and then, to this mixture, Then, 3 times the mass of propylene glycol monomethyl ether acetate was mixed. The mixture was heated at 50°C for about 2 hours. The resulting reaction mixture was added to a large amount of a methanol / water mixed solvent. The resin was then precipitated by pouring and filtered. The solution obtained by dissolving in methyl ether acetate was dissolved in a methanol / water mixed solvent. The resin was precipitated by pouring the resin into a glass tube and then filtered. This reprecipitation procedure was repeated twice to obtain the weight average Molecular mass 8.9×10 3 Resin A5 (copolymer) was obtained in a yield of 79%. It has the structural unit: TIFF2026004581000137.tif38153

[0230] Synthesis Example 12 [Synthesis of Resin AX7] As the monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( a2-1-3), monomer (a3-4-2), methacrylic acid and monomer (a1-4-2 ) and the molar ratio [monomer (a1-1-3):monomer (a1-2-6):monomer -(a2-1-3): Monomer (a3-4-2): Methacrylic acid: Monomer (a1-4- 2) were mixed in a ratio of 20:30:3:15:5:27, and then The monomer mixture was mixed with 1.5 times the mass of methyl isobutyl ketone relative to the total mass of all monomers. The resulting mixture was mixed with azobisisobutyronitrile and azobisisobutyronitrile as initiators. 1.2 mol% and 2,4-dimethylvaleronitrile based on the total amount of monomers, respectively. and 3.6 mol % of methylcellulose were added, and the mixture was heated at 73°C for about 5 hours. A p-toluenesulfonic acid aqueous solution (2.5 times by mass) was added to the total mass of all monomers. % by weight was added, and the mixture was stirred for 12 hours, followed by separation. The resin was poured into a tank to precipitate, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.5 x 1 0 3 Resin AX7, which has the following structural units, was obtained in a yield of 65%. It is something. TIFF2026004581000138.tif36159

[0231] Synthesis Example 13 [Synthesis of Resin A6] Resin AX7 and monomer (ax) were used, and the molar ratio [Resin AX7:Monomer (ax)] ] are mixed in a ratio of 100:5, and then the total mass of the mixture is Propylene glycol monomethyl ether acetate was mixed in an amount three times by mass of the propylene glycol monomethyl ether acetate. The resulting mixture was treated with tetrabutylammonium bromide as a catalyst in an amount of 1:1 relative to Resin AX7. 5 mol% and 1.6 mol% of 4-methoxyphenol was added to resin AX7. The mixture was heated at 90°C for about 2 hours. The resulting reaction mixture was added to a large amount of a mixed solvent of methanol and water. The resin was then poured into a solvent to precipitate, and the resulting resin was filtered. The solution obtained by dissolving in cholesteryl methyl ether acetate was mixed with methanol / water. The resin was poured into a solvent to precipitate, and the resin was then filtered. This reprecipitation procedure was repeated twice, and the weight average was Average molecular weight 7.5×10 3 Resin A6 (copolymer) was obtained in a yield of 65%. It has the following structural units: TIFF2026004581000139.tif43167

[0232] Synthesis Example 14 [Synthesis of Resin AX8] As the monomers, monomer (a1-2-6), monomer (a2-1-3), monomer ( a3-4-2), methacrylic acid and monomer (a1-4-13) were used, and the molar ratio [monomer Monomer (a1-2-6): Monomer (a2-1-3): Monomer (a3-4-2): Meta Acrylic acid:monomer (a1-4-13) in a ratio of 50:3:15:5:27 Further, 1.5 mass % of the total mass of all the monomers was added to this monomer mixture. The resulting mixture was mixed with methyl isobutyl ketone in an amount of 1:1. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total monomer amount These were heated at 73°C for about 5 hours. Thereafter, 2.0 times by mass of p-toluene was added to the polymerization reaction solution relative to the total mass of all monomers. An aqueous solution of benzoxazole sulfonic acid (2.5% by weight) was added, and the mixture was stirred for 12 hours, followed by separation of the liquid. The organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered to obtain the heavy The weight-average molecular weight is approximately 5.1 x 103 Resin AX8 was obtained in a yield of 80%. has the following structural unit: TIFF2026004581000140.tif36135

[0233] Synthesis Example 15 [Synthesis of Resin A7] Resin AX8 and monomer (ax) were used, and the molar ratio [Resin AX8:Monomer (ax)] ] are mixed in a ratio of 100:5, and then the total mass of the mixture is Propylene glycol monomethyl ether acetate was mixed in an amount three times by mass of the propylene glycol monomethyl ether acetate. The resulting mixture was mixed with tetrabutylammonium bromide as a catalyst in an amount of 1000 ppm relative to the resin AX8. 5 mol% and 1.6 mol% of 4-methoxyphenol was added to the resin AX8. The mixture was heated at 90°C for about 2 hours. The resulting reaction mixture was added to a large amount of a mixed solvent of methanol and water. The resin was then poured into a solvent to precipitate the resin, which was then filtered. The solution obtained by dissolving in cholesteryl methyl ether acetate was mixed with methanol / water. The resin was poured into a solvent to precipitate, and the resin was then filtered. This reprecipitation procedure was repeated twice, and the weight average was Average molecular weight 6.7×10 3 Resin A7 (copolymer) was obtained in a yield of 76%. It has the following structural units: TIFF2026004581000141.tif43142

[0234] Synthesis Example 16 [Synthesis of Resin X1] Monomer (a5-1-1) and monomer (a4-0-12) were used as monomers, The molar ratio [monomer (a5-1-1):monomer (a4-0-12)] was 50:50. Mix well until the mixture becomes uniform, and then add methyl isobutyl ketone in an amount 1.2 times the mass of the total monomer amount to form a solution. To this solution, azobis(2,4-dimethylvaleronitrile) was added as an initiator. The resulting reaction mixture was heated at 70°C for about 5 hours. The resin was then poured into a large amount of methanol / water mixed solvent to precipitate, and the resin was filtered and the weight average Molecular weight 1.0×10 4 Resin X1 (copolymer) was obtained in a yield of 91%. It has the following structural unit: TIFF2026004581000142.tif3583

[0235] <Preparation of Resist Composition> As shown in Table 1, the following components were mixed, and the resulting mixture was passed through a fluorine-containing filter with a pore size of 0.2 μm. The mixture was filtered through a resin filter to prepare a resist composition. [Table 1]

[0236] <Resin> A1~A3, A5, X1, AX1~AX4, AX6: Resin A1~Resin A3, Resin A5, Resin X1, Resin AX1 to Resin AX4, Resin AX6 <Acid generator (B)> B1-21: A salt represented by the formula (B1-21) (see JP 2012-224611 A) (Synthesize according to the example) B1-22: A salt represented by formula (B1-22) (see JP 2012-224611 A) (Synthesize according to the example) TIFF2026004581000144.tif36100<Quencher (C)> D1: (Tokyo Chemical Industry Co., Ltd.) TIFF2026004581000145.tif1932<solvent> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts

[0237] <Resist pattern production and evaluation> A silicon wafer was coated with an organic anti-reflective coating composition (ARC-29; Nissan Chemical Co., Ltd.). The wafer was then baked at 205°C for 60 seconds to form a 78 nm thick film. An organic anti-reflective film was formed. Then, the resist composition was applied onto the organic anti-reflective film. The solution was applied (spin coated) so that the film thickness after drying would be 85 nm. Place the wafer on a direct hot plate and heat it for 60 seconds at the temperature listed in the "PB" column of Table 1. The silicon wafer on which the composition layer was formed was subjected to immersion exposure. ArF excimer stepper (XT:1900Gi; ASML, NA=1.35, 3 / 4Annular XY polarization, contact hole pattern (hole pitch 90n The exposure dose was gradually changed using a mask to form a 55 nm hole diameter. Ultrapure water was used as the immersion medium. After exposure, post-process the film on a hot plate for 60 seconds at the temperature specified in the "PEB" column of Table 1. Then, the composition layer on the silicon wafer was exposed to a developer. Dynamic decontamination was performed using butyl acetate (Tokyo Chemical Industry Co., Ltd.) at 23°C for 20 seconds. Development was carried out by a dispense method to produce a negative resist pattern.

[0238] In the resist pattern obtained after development, the diameter of the hole formed using the mask is The exposure amount resulting in 50 nm was defined as the effective sensitivity.

[0239] <CD Uniformity (CDU) Evaluation> In terms of effective sensitivity, the hole diameter of the pattern formed with a mask having a hole diameter of 55 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. For 400 locations of the average hole diameter of the pattern formed with a mask having a hole diameter of 55 nm within the same wafer, the standard deviation was obtained with the measured values as the population. The results are shown in Tables 2 and 3. The numerical values in the tables indicate the standard deviation (nm). The results are shown in Tables 2 and 3. The numerical values in the tables indicate the standard deviation (nm).

Table 2

[0240] [[ID=[]] [[ID=[]]<000392]]

[0240] <Preparation of Resist Composition> As shown in Table 4, the following components were mixed, and the resulting mixture was filtered through a fluororesin filter with a pore diameter of 0.2 μm to prepare a resist composition. [[ID=[]] [[ID=[]]

Table 4

[0241] [[ID=[]] [[ID=[]] <Resin> ​​​​​​A4, A6, A7, AX5, AX7, AX8: Resin A4, Resin A6, Resin A7, Resin A X5, resin AX7, resin AX8 <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) TIFF2026004581000149.tif4381<Quencher (C)> D1: (Tokyo Chemical Industry Co., Ltd.) TIFF2026004581000150.tif1932<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-butyrolactone 5 parts

[0242] (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 on the sheet for 60 seconds at the temperature shown in the "PB" column of Table 4 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 laser with an energy of 25 125 keV to form a contact hole pattern. (Hole pitch 40 nm / hole diameter 17 nm) was directly written. After exposure, the film was post-exposed on a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 4. 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 development according to a method.

[0243] In the resist pattern obtained after development, the exposure amount at which the formed hole diameter becomes 17 nm was defined as the effective sensitivity. was used as the effective sensitivity.

[0244] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times for each hole, and the average value was defined as the average hole diameter of one hole. The average hole diameters of the patterns formed with a hole diameter of 17 nm within the same wafer were measured at 400 locations and used as the population to calculate the standard deviation. and the average value was taken as the average hole diameter of one hole. The average hole diameters of the patterns formed with a hole diameter of 17 nm within the same wafer were measured at 400 locations and used as the population to calculate the standard deviation. and the standard deviation was calculated using them as the population. The results are shown in Tables 5 and 6. The numerical values in the tables indicate the standard deviation (nm). The results are shown in Tables 5 and 6. The numerical values in the tables indicate the standard deviation (nm).

Table 5

Table 6

Industrial Applicability

[0245] The method for manufacturing a resist pattern using the resist composition for organic solvent development of the present invention can obtain a resist pattern having good CD uniformity (CDU), and thus is suitable for fine processing of semiconductors and is extremely useful industrially. and is suitable for fine processing of semiconductors and is extremely useful industrially. and is extremely useful industrially.

Claims

1. A resin including a structural unit having an ethylenically unsaturated double bond in a side chain, a structural unit represented by formula (a3-4), and a structural unit having an acid labile group; and A resist composition for organic solvent development containing an acid generator. [In formula (a3-4), L ａ７ represents -O-, *-O-L ａ８ -O-, *-O-L ａ８ -CO-O-, *-O-L ａ８ -CO-O-L ａ９ -CO-O- or *-O-L ａ８ -O-CO-L ａ９ represents -O-. L ａ８ and L ａ９ each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R ａ２４ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ａ２５ represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. w1 represents an integer of 0 to 8. When w1 is 2 or more, a plurality of R ａ２５ may be the same as or different from each other.

2. 2. The resist composition for organic solvent development according to claim 1, wherein the structural unit having an ethylenically unsaturated double bond in a side chain is a reaction product of a polymer containing a structural unit having a glycidyl group and a vinyl monomer having at least one group selected from a carboxy group and an acid anhydride group, or a reaction product of a polymer containing a structural unit having a carboxy group and a vinyl monomer having at least one group selected from a glycidyl group and a hydroxy group.

3. 3. The resist composition for organic solvent development according to claim 1, wherein the structural unit having an ethylenically unsaturated double bond in a side chain is a structural unit represented by formula (I): [In formula (I), R １ and R ２ each independently represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom. X １ and X ２ each independently represents *-O-**, *-CO-O-**, *-O-CO-O-** or *-Ay-Ph-Ax-**. Ph represents a phenylene group. Ax represents one group selected from the group consisting of an ether bond, an ester bond, and a carbonate ester bond; Ay represents one bond selected from the group consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond; * indicates R １ or R ２ represents the bonding site with the carbon atom to which it is bonded, and ** represents L １ represents the binding site with L 1 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and —CH 2 - is -O-, -S-, -SO ２ - or -CO- may be substituted.]

4. The resist composition for organic solvent development according to any one of claims 1 to 3, wherein the structural unit having an acid labile group is at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2): [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L ａ１ and L ａ２ are each independently —O— or *—O—(CH ２ ) ｋ１ represents —CO—O—, k1 represents an integer of 1 to 7, and * represents the bonding site with —CO—. R a01 , R ａ４ and R ａ５ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R ａ６ and R ａ７ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1′ represents an integer of 0 to 3.]

5. 5. The resist composition for organic solvent development according to claim 1, wherein the acid generator comprises a salt represented by formula (B1): [In formula (B1), Q ｂ１ and Q ｂ２ each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L ｂ１ represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ２ The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms, and —CH ２ - is -O-, -SO ２ It may be replaced by - or -CO-. Z ＋ represents an organic cation.

6. 6. The resist composition for organic solvent development according to claim 1, further comprising a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator.

7. 7. The resist composition for organic solvent development according to claim 1, which is for development with butyl acetate.

8. 8. The resist composition for organic solvent development according to claim 1, wherein the resin further contains a structural unit represented by formula (a2-A): [In formula (a2-A), R ａ５０ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R ａ５１ represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A ａ５０ is a single bond or *-X ａ５１ - (A ａ５２ -X ａ５２ ) ｎｂ -, * represents -R ａ５０ represents the bond position with the carbon atom to which it is bonded. A ａ５２ represents an alkanediyl group having 1 to 6 carbon atoms. X ａ５１ and X ａ５２ each independently represents —O—, —CO—O—, or —O—CO—. nb represents 0 or 1. mb represents an integer of 0 to 4; When mb is an integer of 2 or more, a plurality of R ａ５１ may be the same or different.

9. mb represents an integer of 1 to 4, R greater than or equal to 1 ａ５１ 9. The resist composition for organic solvent development according to claim 8, wherein at least one of the following is a hydroxy group.

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