Resist Composition and Method for Producing Resist Pattern

Abstract

To provide a resist composition from which a resist pattern having good CD uniformity can be produced.SOLUTION: The resist composition contains: a compound represented by formula (I); a resin having an acid-labile group, which contains at least one of structural units represented by formula (a1-0), formula (a1-1) and formula (a1-2) and contains a structural unit represented by formula (a3-4); and an acid generator. [In the formula, L1 represents an optionally substituted (m2+1)-valent aliphatic hydrocarbon group; R1 represents a hydrogen atom or an acid-labile group; and R2 represents H, *-OH or *-O-R1.]SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Patent Document 1 describes a resist composition containing a compound of the following structural formula, a resin of the following structural formula, and an acid generator. TIFF0007712130000001.tif37147 Patent Document 2 describes a resist composition containing a compound of the following structural formula, a resin of the following structural formula, and an acid generator. TIFF0007712130000002.tif32145

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a resist composition that forms a resist pattern having better CD uniformity (CDU) than a resist pattern formed from the above resist composition.

Means for Solving the Problems

[0005] The present invention includes the following inventions. A resist composition containing a compound represented by formula (I), a resin having an acid-labile group, and an acid generator, wherein the resin having an acid-labile group comprises 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), and a structural unit represented by formula (a3-4). TIFF0007712130000003.tif877[In formula (I), L 1 represents a (m2 + 1)-valent aliphatic hydrocarbon group having 1 to 24 carbon atoms which may have a substituent. R 1 represents a hydrogen atom or an acid-labile group. R 2 represents a hydrogen atom, *-OH or *-O-R 1 where * represents the bonding site with L 1 R 1 and R 2 or two Rs 2 may together form a group having an acetal ring structure. m2 represents any integer from 1 to 7, and when m2 is 2 or more, a plurality of Rs 2 may be the same as or different from each other.] TIFF0007712130000004.tif42136[In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -CO-O-, k1 represents any integer from 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 a04Each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups. 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 groups. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3. TIFF0007712130000005.tif5346[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 -O-. L a8 and L a9 Each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents the bonding position with the carbonyl group. R a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or 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 any integer from 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] The resist composition according to [1], wherein L 1 is a (m2 + 1)-valent chain hydrocarbon group having 1 to 8 carbon atoms, (m2 + 1) alicyclic hydrocarbon groups having 3 to 10 carbon atoms, or a (m2 + 1)-valent group formed by combining these. [3] L1 The resist composition according to [2], wherein it is a (m2 + 1)-valent chain hydrocarbon group having 1 to 8 carbon atoms and m2 is 1 to 3. [4] L 1 The resist composition according to [2], wherein it is a (m2 + 1)-valent alicyclic hydrocarbon group having 3 to 10 carbon atoms or a (m2 + 1)-valent group combining a chain hydrocarbon group having 1 to 8 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and m2 is 1 to 3. [5] R 2 is -OR 1 represents, and R 1 represents an acid-labile group, and the resist composition according to any one of [1] to [4]. [6] R 1 The resist composition according to any one of [1] to [5], wherein it is a group represented by the formula (1a) or a group represented by the formula (2a). TIFF0007712130000006.tif2160 [In the formula (1a), R aa1 , R aa2 and R aa3 each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or R aa1 and R aa2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. naa represents 0 or 1. * represents a bond.] TIFF0007712130000007.tif2051 [In the formula (2a), R aa1’ and R aa2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other to their bonded -C-X a- together with a heterocyclic group having 3 to 20 carbon atoms, and -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X a represents an oxygen atom or a sulfur atom. * represents a bond. 〔7〕The resist composition according to any one of 〔1〕~〔6〕, wherein the acid generator is a salt represented by the formula (B1). TIFF0007712130000008.tif2959[In the formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-. Z + represents an organic cation. 〔8〕The resist composition according to any one of 〔1〕~〔7〕, further containing a salt that generates an acid having a lower acidity than the acid generated from the acid generator. 〔9〕(1) A step of applying the resist composition according to any one of 〔1〕~〔8〕 onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern including.

Advantages of the Invention

[0006] By using the resist composition of the present invention, a resist pattern can be manufactured with good CD uniformity (CDU).

Embodiments for Carrying Out the Invention

[0007] In this specification, the term “(meth)acrylic monomer” means “at least one of acrylic monomers and methacrylic monomers”. Expressions such as “(meth)acrylate” and “(meth)acrylic acid” also represent the same meaning. Among the groups described in this specification, those that can take both a linear structure and a branched structure may be either of them. When -CH2- contained in a hydrocarbon group or the like is replaced by -O-, -S-, -CO- or -SO2-, the same examples are applied to each group. The term “combined group” means a group formed by bonding two or more of the exemplified groups, and the valences of these groups may be appropriately changed depending on the bonding form. The terms “derived from” or “derived” refer to the fact that the polymerizable C=C bond contained in the molecule becomes a single bond (-C-C- group) by polymerization. When stereoisomers exist, all stereoisomers are included. In this specification, the “solid content of the resist composition” means the total of the components excluding the solvent (E) described later from the total amount of the resist composition.

[0008] 〔Resist Composition〕 The resist composition of the present invention contains a compound represented by formula (I) (hereinafter sometimes referred to as “compound (I)”), 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), and a resin having an acid-labile group containing a structural unit represented by formula (a3-4) (hereinafter sometimes referred to as “resin (A)”), and an acid generator (hereinafter sometimes referred to as “acid generator (B)”). Here, the “acid-labile group” has a leaving group and means a group that, upon contact with an acid, causes the leaving group to leave and converts to a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). The resist composition of the present invention may further contain a resin other than resin (A). The resist composition of the present invention preferably contains a quencher (hereinafter sometimes referred to as "quencher (C)") such as a salt that generates an acid having a lower acidity than the acid generated from the acid generator, and preferably contains a solvent (hereinafter sometimes referred to as "solvent (E)").

[0009] 〈Compound (I)〉 The resist composition of the present invention contains Compound (I). TIFF0007712130000009.tif877[In formula (I), all symbols have the same meanings as described above.]

[0010] L 1 Examples of the (m2 + 1)-valent aliphatic hydrocarbon group in L include a chain hydrocarbon group, an alicyclic hydrocarbon group, and a group combining these. Examples of the chain hydrocarbon group include an alkane-(m2 + 1)-yl group, an alkene-(m2 + 1)-yl group, and an alkyne-(m2 + 1)-yl group, which represent a group in which (m2) hydrogen atoms are replaced at the bonding sites from an alkyl group, an alkenyl group, or an alkynyl group. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 9, and even more preferably 1 to 8. Examples of the alkyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and nonyl group. The number of carbon atoms in the alkane-(m2 + 1)-yl group is preferably 2 to 10, more preferably 3 to 9, and still more preferably 4 to 8. Examples of the alkenyl group include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, and nonenyl group. Examples of the alkynyl group include ethynyl group, propynyl group, isopropynyl group, butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, and nonynyl group. The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include the following groups, etc. The bonding site can be at any position. Specifically, monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, etc., and polycyclic cycloalkyl groups such as norbornyl group, adamantyl group, etc. A group in which (m2) hydrogen atoms are replaced at the bonding site. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, still more preferably 3 to 12, and even more preferably 3 to 10. TIFF0007712130000010.tif44168

[0011] The combined group refers to A group in which (m2) hydrogen atoms are replaced at the bonding site from a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group such as an alkyl group, an alkenyl group and / or an alkynyl group. In the combined group, the alicyclic hydrocarbon group, and chain hydrocarbon groups such as an alkyl group, an alkenyl group, and an alkynyl group may be combined with two or more of each other. L 1 Substituents that the aliphatic hydrocarbon group of L may have include a halogen atom, a hydroxy group, a cyano group, a carboxy group, an alkyl group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a group formed by combining two or more of these groups. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, etc. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkyl fluoride group having 1 to 6 carbon atoms include alkyl fluoride groups such as trifluoromethyl group, difluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, perfluorohexyl group and the like. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 4, more preferably 1 to 3. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 4, more preferably 1 to 3. Examples of the group combined with two or more kinds include alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms and the like. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyloxy group having 2 to 13 carbon atoms and the like represent groups in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include acetyl group, propionyl group, butyryl group and the like. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include acetyloxy group, propionyloxy group, butyryloxy group and the like.

[0012] L 1 includes the groups represented below. Among them, L 1 is preferably a divalent, trivalent or tetravalent aliphatic hydrocarbon group. TIFF0007712130000011.tif111166

[0013] TIFF0007712130000012.tif59164

[0014] R 1 The acid-labile group means a group that, when contacted with an acid (e.g., p-toluenesulfonic acid), the group represented by R 1 is eliminated to form a hydroxy group. Examples of the acid-labile group include a group represented by the formula (1a) (hereinafter, sometimes referred to as "acid-labile group (1a)"), a group represented by the formula (2a) (hereinafter, sometimes referred to as "acid-labile group (2a)"), and the like. TIFF0007712130000013.tif2160[In the formula (1a), R aa1 , R aa2 and R aa3 each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or R aa1 and R aa2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. naa represents 0 or 1. * represents a bond.] TIFF0007712130000014.tif2051[In the formula (2a), R aa1’ and R aa2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the -C-X a - to which they are bonded, and the -CH2- contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X arepresents an oxygen atom or a sulfur atom. * represents a bond.]

[0015] R aa1 、R aa2 and R aa3 Examples of the alkyl groups of R aa1 、R aa2 and R aa3 are a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, etc. The number of carbon atoms in the alkyl groups of R R aa1 、R aa2 and R aa3 Examples of the alkenyl groups of R R aa1 、R aa2 and R aa3 The alicyclic hydrocarbon groups of R aa1 、R aa2 and R aa3 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. Examples of the polycyclic alicyclic hydrocarbon groups include, for example, a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond.). The number of carbon atoms in the alicyclic hydrocarbon groups of R TIFF0007712130000015.tif9159R aa1 、R aa2 and R aa3 Examples of the aromatic hydrocarbon groups of R aa1 、R aa2 and R aa3 are aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, etc. The number of carbon atoms in the aromatic hydrocarbon groups of R

[0016] Examples of the substituent of the alkyl group having 1 to 8 carbon atoms which may have a substituent include an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the alkenyl group having 2 to 8 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of the substituent of the aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alicyclic hydrocarbon group having 3 to 20 carbon atoms. More specifically, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, an alkylcycloalkyl group or cycloalkylalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), an aralkyl group such as benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), phenylcyclohexyl group, etc. are included. naa is preferably 1.

[0017] R aa1 and R aa2 When they are bonded to each other to form an alicyclic hydrocarbon group together with a carbon atom, -C(R aa1 )(R aa2 )(R aa3 ) includes the following groups. The alicyclic hydrocarbon group is preferably 3 to 16, more preferably 3 to 12 carbon atoms. * represents a bond to -O-. JPEG0007712130000016.jpg30140

[0018] Examples of the group represented by the formula (1a) include a 1,1,1-trialkyl group, a 1,1,1-trialkylalkoxycarbonyl group (wherein in the formula (1a), R aa1 , R aa2 and R aa3 are alkyl groups and naa is 0, preferably a tert-butyl group or a tert-butoxycarbonyl group), a 1,1-dialkylalkoxycarbonyl group (wherein in the formula (1a), R aa1 , R aa2 and R aa3 are alkyl groups and naa is 1, preferably a tert-butoxycarbonyl group), a 2-alkyladamantan-2-yloxycarbonyl group (wherein in the formula (1a), R aa1 , R aa2 and the carbon atom to which they are attached form an adamantyl group, and R aa3 is an alkyl group and naa is 1), a 1-(adamantan-1-yl)-1,1-dialkyl group (wherein in the formula (1a), R aa1 and R aa2 are alkyl groups, R aa3 is an adamantyl group and naa is 0), and a 1-(adamantan-1-yl)-1,1-dialkyl group, a 1-(adamantan-1-yl)-1,1-dialkylalkoxycarbonyl group (wherein in the formula (1a), R aa1 and R aa2 are alkyl groups, R aa3 is an adamantyl group and naa is 1), etc.

[0019] Examples of the hydrocarbon groups of R aa1' , R aa2' and R aa3' include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those exemplified for R aa1 , R aa2 and R aa3 . Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. Examples of the combined group include a group formed by combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, cycloalkylalkyl group or alkylcycloalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl group such as benzyl group, aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. R aa2' and R aa3' are bonded to each other and together with the carbon atom to which they are bonded and X a form a heterocyclic group, -C(R aa1' )(R aa2' )-X a -(R aa3' ) includes the following groups. * represents a bond. TIFF0007712130000017.tif20143R aa1' and R aa2' Preferably, at least one of them is a hydrogen atom.

[0020] Specific examples of the acid-labile group (1a) include the following groups. * represents a bond. TIFF0007712130000018.tif125162

[0021] Specific examples of the acid-labile group (2a) include the following groups. * represents a bond. TIFF0007712130000019.tif59164

[0022] R2 is preferably *-OH or *-O-R 1 and more preferably *-O-R 1 is even more preferable. m2 is preferably any integer from 1 to 5, more preferably any integer from 1 to 4, and even more preferably any integer from 1 to 3.

[0023] Compound (I) includes compounds represented by the following formula. TIFF0007712130000020.tif146157

[0024] TIFF0007712130000021.tif249158

[0025] TIFF0007712130000022.tif245154

[0026] TIFF0007712130000023.tif219155

[0027] The content of compound (I) is usually 0.001 to 20% by mass, preferably 0.003 to 15% by mass, based on the solid content of the resist composition.

[0028] <Method for producing compound (I)> Compound (I) can be prepared by using a known method or a product that is easily available on the market. In particular, among compound (I), R 1 is a hydrogen atom, and compound (IA) in which R 2 is a hydrogen atom or *-OH can be produced according to the production method described in JP-A-2004-246276. Among compound (I), compound (IB) in which R 1 is an acid-labile group and m2 R 2 are *-OR 1 can be produced, for example, by the following method. First, a compound represented by formula (IA) and a compound (IS-1) capable of inducing an acid-labile group are reacted in a solvent containing a base. TIFF0007712130000024.tif20103 For (IA) used in the above reaction, compounds represented by, for example, formula (I-12), formula (I-15), formula (I-16), formula (I-30), formula (I-40), formula (I-75), formula (I-76), formula (I-77), formula (I-78), etc. can be used. The solvent used in the above reaction is, for example, dimethylformamide, etc. Further, as the base used in the above reaction, a known base is used, for example, diisopropylethylamine, etc. In addition, as (IS-1) used in the above reaction, commercially available and easily obtainable compounds can be used. Specifically, the following compounds can be mentioned. The chlorine atoms contained in the compounds shown below may be replaced with halogen atoms such as bromine atoms and iodine atoms. By appropriately adjusting the reaction time of the above reaction or the reaction amount of (IS-1), some of the hydroxy groups contained in compound (IA) can be left unreacted, and the ratio of *-OR 1 to *-OH contained in compound (I) can be appropriately adjusted. TIFF0007712130000025.tif1189 Further, among compounds (I), when R 1 is an acid-labile group represented by formula (1a), it can also be produced according to the production method described in JP-A-2013-035764. For example, formula (I-44) to formula (I-60), etc. are preferably produced by the production method described in JP-A-2013-035764.

[0029] <Resin (A)> Resin (A) has a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"), and is at least one selected from the group consisting of a structural unit represented by formula (a1-0) described later, a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2), and includes a structural unit represented by formula (a3-4). Resin (A) preferably further includes a structural unit other than structural unit (a1) and structural unit (a3-4). Examples of the structural unit other than structural unit (a1) and structural unit (a3-4) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than structural unit (a1) and structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit having a non-leaving hydrocarbon group described later (hereinafter sometimes referred to as "structural unit (a5)"), and structural units derived from other monomers known in the art, etc.).

[0030] 〈Structural unit (a1)〉 Structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)"). The acid-labile group contained in resin (A) is preferably 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)). TIFF0007712130000026.tif1988 [In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, or R a1 and R a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bonding site.] TIFF0007712130000027.tif2171 [In formula (2), Ra1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’ are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and the —CH2— contained in the hydrocarbon group and the heterocyclic ring may be replaced by —O— or —S—. X represents an oxygen atom or a sulfur atom. na’ represents 0 or 1. * represents a bonding site.]

[0031] R a1 、R a2 and R a3 Examples of the alkyl group in R, R, and R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. R a1 、R a2 and R a3 Examples of the alkenyl group in R, R, and R include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, and a nonenyl group. R a1 、R a2 and R a3 The alicyclic hydrocarbon group in R, R, and R may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bonding site.). The carbon number of the alicyclic hydrocarbon group of R, R, and R is preferably 3 to 16. a1 、R a2 and R a3 The carbon number of the alicyclic hydrocarbon group of R, R, and R is preferably 3 to 16. TIFF0007712130000028.tif10150R a1 、R a2 and R a3Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl group or cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, and the like. Preferably, ma is 0 and na is 1. R a1 and R a2 When -C(R a1 )(R a2 )(R a3 ) is formed by R TIFF0007712130000029.tif30138R a1’ , R a2’ and R a3’ combining with each other to form a non-aromatic hydrocarbon ring, examples thereof include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * represents the bonding site with -O-. Examples of the hydrocarbon group in R a1 , R a2 and R a3 include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, and phenanthryl group. As the combined group, there are groups combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, alkylcycloalkyl group or cycloalkylalkyl group), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups such as phenylcyclohexyl group, etc. R a2’ and R a3’ When they are bonded to each other to form a heterocyclic ring together with the carbon atom to which they are bonded and X, -C(R a1’ )(R a2’ )-X-R a3’ includes the following rings. * represents the bonding site. TIFF0007712130000030.tif18130R a1’ and R a2’ Among them, at least one is preferably a hydrogen atom. na’ is preferably 0.

[0032] Examples of the group (1) include the following groups. In formula (1), a group where R a1 , R a2 and R a3 are alkyl groups, ma = 0, and na = 1. As such a group, a tert-butoxycarbonyl group is preferred. In formula (1), a group where R a1 , R a2 together with the carbon atom to which they are bonded form an adamantyl group, R a3 is an alkyl group, ma = 0, and na = 1. In formula (1), a group where R a1 and R a2 are each independently an alkyl group, R a3 is an adamantyl group, ma = 0, and na = 1. Examples of the group (1) specifically include the following groups. * represents the bonding site. JPEG0007712130000031.jpg154163

[0033] Specific examples of the group (2) include the following groups. * represents the bonding site. TIFF0007712130000032.tif55153

[0034] The monomer (a1) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer having an acid-labile group.

[0035] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are preferable. If a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

[0036] Examples of the structural unit derived from the (meth)acrylic monomer having the group (1) include a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as the structural unit (a1-0)), a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as the structural unit (a1-1)), or a structural unit represented by the formula (a1-2) (hereinafter sometimes referred to as the structural unit (a1-2)). Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more. TIFF0007712130000033.tif46149[In the formula (a1-0), the formula (a1-1), and the formula (a1-2), L a01 、L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -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 formed by combining these. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3.

[0037] R a01 、R a4 and R a5 are preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 、L a1 and L a2 are preferably an oxygen atom or *-O-(CH2) k01 -CO-O- (wherein k01 is preferably any integer from 1 to 4, more preferably 1), more preferably an oxygen atom. R a02 、R a03 and R a04 Examples of the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group formed by combining these in a1 、R a2 and R a3 include the same groups as those exemplified for R R a6 and R a7Examples of the alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and groups combining these include R in formula (1) a1 , R a2 , and R a3 . The groups are the same as those exemplified for R , R a02 , R a03 , and R a04 . The alkyl group in R , R a6 , and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. , R a02 , and R a03 , R a04 , R a6 , and R a7 . The number of carbon atoms of the alicyclic hydrocarbon group of R , R a02 , R a03 , R a04 , R a6 , and R a7 is preferably 5 to 12, and more preferably 5 to 10. . For the group combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms of the combined alkyl group and alicyclic hydrocarbon group is 18 or less. . For the group combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms of the combined alkyl group and aromatic hydrocarbon group is 18 or less. , R a02 , and R a03 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group. , R a04is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group. m1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1’ is preferably 0 or 1.

[0038] Examples of the structural unit (a1-0) include structural units represented by any of formulas (a1-0-1) to (a1-0-18) and structural units in which the methyl group corresponding to R a01 in the structural unit (a1-0) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group. Structural units represented by any of formulas (a1-0-1) to (a1-0-10), formula (a1-0-13) and formula (a1-0-14) are preferred. TIFF0007712130000034.tif97165

[0039] Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Among them, structural units represented by any of formulas (a1-1-1) to (a1-1-7) and structural units in which the methyl group corresponding to R a4 in the structural unit (a1-1) is replaced with a hydrogen atom are preferred, and structural units represented by any of formulas (a1-1-1) to (a1-1-4) are more preferred. TIFF0007712130000035.tif39167

[0040] As the structural unit (a1-2), there are a structural unit represented by any of formula (a1-2-1) to formula (a1-2-14) and a structural unit in which the methyl group corresponding to R in the structural unit (a1-2) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group. Among them, the structural units represented by formula (a1-2-2), formula (a1-2-5), formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-14) are preferable. a5 When the resin (A) contains the structural unit (a1-0), its content is usually 5 to 80 mol%, preferably 5 to 75 mol%, more preferably 10 to 70 mol% with respect to all the structural units of the resin (A). TIFF0007712130000036.tif67163

[0041] When the resin (A) contains the structural unit (a1-0), its content is usually 5 to 80 mol%, preferably 5 to 75 mol%, more preferably 10 to 70 mol% with respect to all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol%, still more preferably 20 to 75 mol%, and even more preferably 20 to 70 mol% with respect to all the structural units of the resin (A).

[0042] Examples of the structural unit having the group (2) in the structural unit (a1) include a structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF0007712130000037.tif3854[In formula (a1-4), R a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a33 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a30is a single bond or * -X a31 -(A a32 -X a32 ) nc - stands for -R. a32 represents the bonding site with the carbon atom to which it is bonded. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O-, or -O-CO-. nc represents 0 or 1. la represents an integer of 0 to 4. When la is an integer of 2 or more, a plurality of R 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 bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.]

[0043] R a32 and R a33 Examples of the halogen atom in include a fluorine atom, a chlorine atom, and a bromine atom. R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in the formula (I) include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group. R a33 Examples of the alkyl group in R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. R a33 Examples of the alkoxy group in R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group. R a33 Examples of the alkoxyalkyl group in R include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and still more preferably a methoxymethyl group. R a33 Examples of the alkoxyalkoxy group in R include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethyl group or an ethoxyethyl group. R a33 Examples of the alkylcarbonyl group in R include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a33Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a33 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxyethoxy group. An ethoxymethoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0044] *-X a31 -(A a32 -X a32 ) nc - includes *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a32 -CO-O-, *-O-CO-A a32 -O-, *-O-A a32 -CO-O-, *-CO-O-A a32 -O-CO-, *-O-CO-A a32 -O-CO-, etc. Among them, *-CO-O-, *-CO-O-A a32 -CO-O- or *-O-A a32 -CO-O- is preferred.

[0045] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[0046] A a30is a single bond, *-CO-O- or *-CO-O-A a32 -CO-O- is preferred, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0047] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 、R a35 and R a36 Examples of the hydrocarbon group in include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents the bonding site), etc. TIFF0007712130000038.tif10151 Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, etc. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., cycloalkylalkyl group), an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, etc. In particular, R a36Examples include an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups.

[0048] R a34 is preferably a hydrogen atom. R a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group of R is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R a36 The alkyl group and the alicyclic hydrocarbon group in are preferably unsubstituted. R a36 The aromatic hydrocarbon group in preferably has an aromatic ring having an aryloxy group having 6 to 10 carbon atoms. -OC(R a34 )(R a35 )-O-R a36 is eliminated by contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

[0049] Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, the structural units represented by formula (a1-4-1) to formula (a1-4-18) and R in the structural unit (a1-4) a32Examples of the structural unit in which the hydrogen atom corresponding to is replaced with a methyl group include, more preferably, the structural units represented by Formula (a1-4-1) to Formula (a1-4-5), Formula (a1-4-10), Formula (a1-4-13), and Formula (a1-4-14). TIFF0007712130000039.tif92156

[0050] When the resin (A) contains the structural unit (a1-4), its content is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, still more preferably 7 to 70 mol%, even more preferably 7 to 65 mol%, and particularly preferably 10 to 60 mol% based on the total of all the structural units of the resin (A).

[0051] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) include the structural unit represented by Formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007712130000040.tif4658In Formula (a1-5), R a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom. Z a1 represents a single bond or *-(CH2) h3 -CO-L 54 -, h3 represents an integer of 1 to 4, and * represents the bonding site with L 51 . 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.

[0052] Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group and trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferable that one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably any integer from 0 to 2. Z a1 is preferably a single bond or *-CH2-CO-O-.

[0053] Examples of the structural unit (a1-5) include structural units derived from the monomers described in JP-A-2010-61117. Among them, the structural units represented by formula (a1-5-1) to formula (a1-5-4) are preferable, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferable. TIFF0007712130000041.tif33133

[0054] When the resin (A) contains the structural unit (a1-5), its content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, still more preferably 5 to 40 mol%, and still more preferably 5 to 30 mol% based on all the structural units of the resin (A).

[0055] Examples of the structural unit (a1) also include the following structural units. TIFF0007712130000042.tif31162

[0056] When the resin (A) contains structural units such as the above (a1-3-1) to (a1-3-7), the content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, even more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol% based on all the structural units of the resin (A).

[0057] In addition, examples of the structural unit (a1) include the following structural units. TIFF0007712130000043.tif5295 When the resin (A) contains structural units such as the above (a1-6-1) to (a1-6-3), the content is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, still more preferably 20 to 50 mol%, even more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol% based on all the structural units of the resin (A).

[0058] 〈Structural unit (s)〉 The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer (s)"). As the monomer that leads to the structural unit (s), a monomer having no acid-labile group known in the resist field can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. When a resin having a structural unit having a hydroxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0059] 〈Structural unit (a2)〉 The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, when using a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet light) as the exposure light source, as the structural unit (a2), a structural unit (a2) having a phenolic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-A) described later. Further, when using an ArF excimer laser (193 nm) or the like, as the structural unit (a2), a structural unit (a2) having an alcoholic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-1) described later. The structural unit (a2) may be included alone by 1 type, or may be included by 2 or more types.

[0060] Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). TIFF0007712130000044.tif4551[In the formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or *-X a51 -(A a52 -X a52 ) nb -, where * represents the bonding position with the carbon atom to which -R a50 is bonded. A a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.]

[0061] R a50 and R a51 Examples of the halogen atom in R and R include a fluorine atom, a chlorine atom, and a bromine atom. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a51 Examples of the alkyl group in R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a51 Examples of the alkoxy group in R include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a51Examples of the alkoxyalkyl group in [context] include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group in [context] include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, and more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group in [context] include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a51 Examples of the alkylcarbonyloxy group in [context] include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group, and even more preferably a fluorine atom, an iodine atom, a hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0062] *-X a51 -(A a52 -X a52 ) nb- include, among others, *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a52 -CO-O-, *-O-CO-A a52 -O-, *-O-A a52 -CO-O-, *-CO-O-A a52 -O-CO-, *-O-CO-A a52 -O-CO- is included. Among them, *-CO-O-, *-CO-O-A a52 -CO-O- or *-O-A a52 -CO-O- is preferred.

[0063] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group.

[0064] A a50 is preferably a single bond, *-CO-O- or *-CO-O-A a52 -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0065] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

[0066] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577.

[0067] Examples of the structural unit (a2-A) include the structural units represented by Formula (a2-2-1) to Formula (a2-2-16), and the structural units represented by Formula (a2-2-1) to Formula (a2-2-16) in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. The structural unit (a2-A) is preferably a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom in the structural unit represented by Formula (a2-2-1), the structural unit represented by Formula (a2-2-3), the structural unit represented by Formula (a2-2-6), the structural unit represented by Formula (a2-2-8), the structural units represented by Formula (a2-2-12) to Formula (a2-2-14), and the structural unit represented by Formula (a2-2-1), the structural unit represented by Formula (a2-2-3), the structural unit represented by Formula (a2-2-6), the structural unit represented by Formula (a2-2-8), the structural units represented by Formula (a2-2-12) to Formula (a2-2-14). a50 More preferably, it is a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom in the structural unit represented by Formula (a2-2-3), the structural unit represented by Formula (a2-2-8), the structural units represented by Formula (a2-2-12) to Formula (a2-2-14), and the structural unit represented by Formula (a2-2-3) or the structural unit represented by Formula (a2-2-8), the structural units represented by Formula (a2-2-12) to Formula (a2-2-14). a50 Even more preferably, it is a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom in the structural unit represented by Formula (a2-2-8) and the structural unit represented by Formula (a2-2-8). a50 Even more preferably, it is a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom in the structural unit represented by Formula (a2-2-8) and the structural unit represented by Formula (a2-2-8). a50 Most preferably, it is a structural unit in which the methyl group corresponding to R in the structural unit (a2-A) is replaced with a hydrogen atom in the structural unit represented by Formula (a2-2-8) and the structural unit represented by Formula (a2-2-8). JPEG0007712130000045.jpg54169

[0068] When the resin (A) contains the structural unit (a2-A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol% based on all the structural units. The structural unit (a2-A) can be incorporated into the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Also, after polymerizing using acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide, the structural unit (a2-A) can be incorporated into the resin (A).

[0069] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include the structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). In the formula (a2-1) in TIFF0007712130000046.tif4258, L a3 represents -O- or *-O-(CH2) k2 -CO-O-, k2 represents any integer from 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 any integer from 0 to 10.

[0070] In the formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents any integer from 1 to 4), and more preferably -O-. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably any integer from 0 to 3, and more preferably 0 or 1.

[0071] Examples of the structural unit (a2-1) include structural units derived from monomers described in JP 2010-204646 A. A structural unit represented by any one of formulas (a2-1-1) to (a2-1-6) is preferred, a structural unit represented by any one of formulas (a2-1-1) to (a2-1-4) is more preferred, and a structural unit represented by formula (a2-1-1) or formula (a2-1-3) is even more preferred. TIFF0007712130000047.tif50140

[0072] When the resin (A) contains the structural unit (a2-1), the content thereof is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably 1 to 35 mol %, even more preferably 1 to 20 mol %, and still more preferably 1 to 10 mol %, based on all structural units in the resin (A).

[0073] <Structural unit (a3)> The lactone ring of the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or may be a condensed ring of a monocyclic lactone ring and another ring. Preferred examples include a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)).

[0074] The structural unit (a3) is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3) or formula (a3-4). One of these may be contained alone, or two or more of them may be contained. TIFF0007712130000048.tif52157 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH2) k3 It represents a group represented by -CO-O- (k3 represents an integer of any of 1 to 7). L a7 , -O-, *-OLa8 -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. * represents 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 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 each independently represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 is 2 or more, a plurality of R a21 , R a22 , R a23 and / or R a25 may be the same as or different from each other.

[0075] R a21 , R a22 , R a23 and R a25Examples of the aliphatic hydrocarbon group in [[ ]] include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, and tert-butyl group. R a24 Examples of the halogen atom in [[ ]] include fluorine atom, chlorine atom, bromine atom, and iodine atom. R a24 Examples of the alkyl group in [[ ]] include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Preferably, an alkyl group having 1 to 4 carbon atoms is mentioned, and more preferably, a methyl group or an ethyl group is mentioned. R a24 Examples of the alkyl group having a halogen atom in [[ ]] include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, etc.

[0076] L a8 and L a9 Examples of the alkanediyl group in [[ ]] and [[ ]] include 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, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group, etc.

[0077] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably -O- or, *-O-(CH2) k3 -CO-O- wherein k3 is an integer of 1 to 4, more preferably -O- and, *-O-CH2-CO-O-, and even more preferably an oxygen atom. R a18 ~Ra21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group or a methyl group. p1, q1 and r1 are each independently preferably any integer from 0 to 2, more preferably 0 or 1.

[0078] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably -O- or *-O-L a8 -CO-O-, more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably any integer from 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)'. TIFF0007712130000049.tif3848 (wherein R a24 , L a7 represent the same meaning as above.)

[0079] Examples of the structural unit (a3) include structural units derived from the monomers described in JP-A-2010-204646, the monomers described in JP-A-2000-122294, and the monomers described in JP-A-2012-41274. Examples of the structural unit (a3) include structural units represented by any of 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 (a3-4-12), and in the above structural units, R a18 , R a19 , R a20 and Ra24 A structural unit in which the methyl group corresponding thereto is replaced by a hydrogen atom is preferred.

[0080] TIFF0007712130000050.tif115165

[0081] When the resin (A) contains the structural unit (a3), the total content is usually 1 to 70 mol%, preferably 3 to 65 mol%, more preferably 5 to 60 mol% with respect to all the structural units of the resin (A). In addition, the content of the structural unit (a3-1), the structural unit (a3-2) or the structural unit (a3-3) is preferably 1 to 60 mol%, more preferably 3 to 50 mol%, and even more preferably 5 to 50 mol% with respect to all the structural units of the resin (A). The content of the structural unit (a3-4) is preferably 1 to 70 mol%, more preferably 3 to 60 mol%, and even more preferably 5 to 55 mol% with respect to all the structural units of the resin (A).

[0082] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007712130000051.tif2861[In the formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having a halogen atom with 1 to 24 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. R 42 The saturated hydrocarbon group represented by includes a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

[0083] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents the bonding site). Examples of the group formed by the combination of include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, and the like.

[0084] Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), and a structural unit represented by the formula (a4-4). TIFF0007712130000053.tif4247[In the 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 represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms. R 64 represents a hydrogen atom or a fluorine atom.]

[0085] L 4a Examples of the alkanediyl group in

[0086] L 3aExamples of the perfluoroalkanediyl group in [the compound] include a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluorohexane-2,2-diyl group, a perfluorohexane-3,3-diyl group, a perfluoroheptane-1,7-diyl group, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group, a perfluorooctane-1,8-diyl group, a perfluorooctane-2,2-diyl group, a perfluorooctane-3,3-diyl group, a perfluorooctane-4,4-diyl group, and the like. L 3a Examples of the perfluorocycloalkanediyl group in [the compound] include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

[0087] L 4a is preferably a single bond, a methylene group, or an ethylene group, and more preferably a single bond or a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0088] Examples of the structural unit (a4-0) include the structural units shown below and the structural units in which the methyl group corresponding to R in the following structural units is replaced with a hydrogen atom in the structural unit (a4-0). 54 include the structural units in which the methyl group corresponding to R in the following structural units is replaced with a hydrogen atom in the structural unit (a4-0). JPEG0007712130000054.jpg95166

[0089] TIFF0007712130000055.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, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g1). However, at least one of A a41 and R a42 has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007712130000056.tif1488[In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 each independently represent -O-, -CO-, -CO-O- or -O-CO-. However, the total number of carbon atoms of A a42 , A a43 , A a44 , X a41 and X a42 is 7 or less. ] * represents a bonding site, and the * on the right side is the bonding site with -O-CO-R a42 . ]

[0090] R a42 Examples of the saturated hydrocarbon group in R include a chain hydrocarbon group, a monocyclic or polycyclic saturated alicyclic hydrocarbon group, and a group formed by combining these.

[0091] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and the like. Examples of the monocyclic or polycyclic saturated alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bonding site). Examples of the group formed by the combination of TIFF0007712130000057.tif10160 include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, and the like.

[0092] R a42 Examples of the substituent that R has include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. TIFF0007712130000058.tif855[In the 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. * is the bonding site with R a42 .] However, in R a42 -X a43 -A a45 , when R a42 does not have a halogen atom, A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which has at least one halogen atom.

[0093] A a45 Examples of the saturated hydrocarbon group in include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group and the following group (* represents the bonding site). Examples of the group formed by the combination of TIFF0007712130000059.tif10160 combinations include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0094] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3). R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group and perfluorooctyl group. Examples of the perfluorocycloalkyl group include perfluorocyclohexyl group. R a42When R is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the number of carbon atoms contained in the group represented by the formula (a-g3), a42 the total number of carbon atoms is preferably 15 or less, more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent, the number thereof is preferably 1.

[0095] R a42 When being a saturated hydrocarbon group having a group represented by the formula (a-g3), R a42 is more preferably a group represented by the formula (a-g2). TIFF0007712130000060.tif872[In the formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents **-O-CO- or **-CO-O- (** represents the bonding site with A a46 ).). A a47 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, the total number of carbon atoms of A a46 , A a47 and X a44 is 18 or less, and at least one of A a46 and A a47 has at least one halogen atom. * represents the bonding site with the carbonyl group.]

[0096] A a46 The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 6, more preferably 1 to 3. A a47 The number of carbon atoms of the saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 12, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0097] A preferred structure of the group represented by the formula (a-g2) is the following structure (* is the bonding site with the carbonyl group). TIFF0007712130000061.tif14160

[0098] A a41 Examples of the alkanediyl group in the formula (I) include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group; and branched alkanediyl groups such as a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a 1-methylbutane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a41 Examples of the substituent in the alkanediyl group represented by the formula (I) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and further preferably an ethylene group.

[0099] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Examples of the divalent saturated hydrocarbon group represented by include a linear or branched alkanediyl group, a monocyclic divalent alicyclic saturated hydrocarbon group, and a divalent saturated hydrocarbon group formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group, etc. Specific examples include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, etc. A a42 , A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by the formula (1) include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. It is preferred that s is 0.

[0100] In the group represented by formula (a-g1), X a42Examples of the group being -O-, -CO-, -CO-O- or -O-CO- include the following groups and the like. In the following examples, * and ** each represent a bonding site, and ** is -O-CO-R a42 is the bonding site with. TIFF0007712130000062.tif47140

[0101] Examples of the structural unit represented by formula (a4-1) include the structural units shown below and the structural units in the following structural units where the methyl group corresponding to R a41 in the structural unit represented by formula (a4-1) is replaced by a hydrogen atom. TIFF0007712130000063.tif103152

[0102] TIFF0007712130000064.tif132149

[0103] Examples of the structural unit represented by formula (a4-1) include the structural unit represented by formula (a4-2) and the structural unit represented by formula (a4-3). TIFF0007712130000065.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 -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and having a fluorine atom. However, the upper limit of the total carbon number of L 44 and R f6 is 21.]

[0104] L 44 The alkanediyl group having 1 to 6 carbon atoms of is the same as the groups exemplified by A a41 and the like. R f6 The saturated hydrocarbon group of is the same as the groups exemplified by R 42 and the like. L44 As the alkanediyl group in 44 , an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.

[0105] Examples of the structural unit represented by formula (a4-2) include structural units represented by formulas (a4-1-1) to (a4-1-11), respectively. The methyl group corresponding to R in structural unit (a4-2) f5 The structural unit in which the methyl group is replaced by a hydrogen atom is also included as the structural unit represented by formula (a4-2).

[0106] TIFF0007712130000066.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. X f12 represents *-O-CO- or *-CO-O- (* represents the bonding site with A f13 ).). A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, at least one of A f13 and A f14 has a fluorine atom, and the upper limit of the total number of carbon atoms of L 5 , A f13 and A f14 is 20.]

[0107] L 5 Examples of the alkanediyl group in 5 include the same groups as those exemplified for the alkanediyl group of A a41 .

[0108] A f13The divalent saturated hydrocarbon group which may have a fluorine atom is preferably a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of the divalent chain saturated hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group. The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexanediyl group and perfluorocyclohexanediyl group. Examples of the polycyclic group include adamantanediyl group, norbornanediyl group, perfluoroadamantanediyl group.

[0109] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom of a42Groups similar to those exemplified above can be mentioned. Among them, alkyl fluoride groups such as trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantylmethyl group, etc. are preferred.

[0110] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group of is preferably a group containing a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain saturated hydrocarbon group having 2 to 3 carbon atoms. A f14 The saturated hydrocarbon group of is preferably a group containing a chain saturated hydrocarbon group having 3 to 12 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group containing a chain saturated hydrocarbon group having 3 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. Among them, A f14 is preferably a group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group.

[0111] Examples of the structural unit represented by formula (a4-3) include structural units represented by formulas (a4-1'-1) to (a4-1'-11), respectively. In the structural unit (a4-3), R f7 A structural unit in which the methyl group corresponding to is replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-3).

[0112] Examples of the structural unit (a4) also include a structural unit represented by formula (a4-4). TIFF0007712130000067.tif4466 [In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 - or -(CH2) j4 -CO-O-(CH2) j5 -. j1 to j5 each independently represent an integer from 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom.]

[0113] The saturated hydrocarbon group of R f22 is the same as the saturated hydrocarbon group represented by R a42 . R f22 is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, and even more preferably an alkyl group having 1 to 6 carbon atoms and having a fluorine atom.

[0114] In formula (a4-4), A f21 is preferably -(CH2) j1 -, more preferably an ethylene group or a methylene group, and even more preferably a methylene group.

[0115] Examples of the structural unit represented by formula (a4-4) include structural units represented by the following structural units and the following formulas, in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom. f21 Examples include structural units in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom. TIFF0007712130000068.tif86160

[0116] When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol% based on all the structural units of the resin (A).

[0117] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group in the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably has a group having an alicyclic hydrocarbon group. Examples of the structural unit (a5) include a structural unit represented by formula (a5-1). TIFF0007712130000069.tif3351[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.]

[0118] R 52 The alicyclic hydrocarbon group in R may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group, etc. The aliphatic hydrocarbon groups having 1 to 8 carbon atoms include, for example, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include 3-methyladamantyl group. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

[0119] L 55 Examples of the divalent saturated hydrocarbon group in L include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably a divalent chain saturated hydrocarbon group. Examples of the divalent chain saturated hydrocarbon group include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adamantanediyl group and norbornanediyl group.

[0120] L 55 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by L is replaced by -O- or -CO- include the groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. In formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents a bonding site with 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, the total number of carbon atoms in L x1 and L x2 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, the total number of carbon atoms in L x3 and L x4 is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each independently represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, the total number of carbon atoms in L x5 , L x6 and L x7 is 15 or less. In formula (L1-4), L x8 and L x9 each represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, the total number of carbon atoms in L x8 , L x9 and W x1 is 15 or less.

[0121] L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond. L x3is 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 a methylene group or an ethylene group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0122] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF0007712130000071.tif53136

[0123] Examples of the group represented by the formula (L1-2) include the following divalent groups. TIFF0007712130000072.tif23130

[0124] Examples of the group represented by the formula (L1-3) include the following divalent groups. TIFF0007712130000073.tif15162

[0125] Examples of the group represented by formula (L1-4) include, for example, the following divalent groups. TIFF0007712130000074.tif26114

[0126] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0127] Examples of the structural unit (a5-1) include the following structural units and structural units in which the methyl group corresponding to R in the following structural unit (a5-1) is replaced by a hydrogen atom. 51 When the resin (A) has the structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 3 to 15 mol% based on all the structural units of the resin (A). TIFF0007712130000075.tif110150 〈Structural unit (a6)〉 The structural unit (a6) is a structural unit having a -SO2- group, and preferably has a -SO2- group in the side chain. The structural unit having a -SO2- group may have a linear structure having a -SO2- group, a branched structure having a -SO2- group, or a cyclic structure (monocyclic and polycyclic structures) having a -SO2- group. Preferably, it is a structural unit having a cyclic structure having a -SO2- group, and more preferably, it is a structural unit having a cyclic structure (sultone ring) containing -SO2-O-.

[0128] Examples of the sultone ring include rings represented by the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 -4). The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. The polycyclic sultone ring means a bridged ring containing -SO2-O- as an atomic group constituting the ring, and formula (T 1 -1) and formula (T 1Examples of the ring represented by the formula (T 1 -2) include a ring in which, in addition to -SO2-O- as an atomic group constituting the ring, a heteroatom may further be included as in the ring represented by the formula (T TIFF0007712130000076.tif3187

[0129] The sultone ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyl group having 2 to 4 carbon atoms.

[0130] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. Preferably, it is an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group. Preferably, a trifluoromethyl group is included. Examples of the alkyl group having a hydroxy group include a hydroxymethyl group and a hydroxyalkyl group such as a 2-hydroxyethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. Examples of the aryl group include a phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, and 2-methyl-6-ethylphenyl group. Examples of the aralkyl group include a benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group. Examples of the alkoxycarbonyl group include a group in which an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or fewer carbon atoms, and more preferably a methoxycarbonyl group. Examples of the alkylcarbonyl group include an acetyl group, propionyl group, and butyryl group.

[0131] From the viewpoint that the production of the monomer leading to the structural unit (a6) is easy, a sultone ring having no substituent is preferred. As the sultone ring, a ring represented by the following formula (T1') is preferred. TIFF0007712130000077.tif3172[In the formula (T1'), X 11 represents an oxygen atom, sulfur atom, or methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. The bonding site is at an arbitrary position.] X 11 is preferably an oxygen atom or a methylene group, and more preferably a methylene group. R41 Examples thereof include the same as the substituents of the sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferable.

[0132] As the sultone ring, a ring represented by the formula (T1) is more preferable. TIFF0007712130000078.tif3149[In the formula (T1), R 8 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. m represents any integer from 0 to 9. When m is 2 or more, a plurality of R 8 may be the same or different. The bonding site is at an arbitrary position.]

[0133] R 8 is the same as R 41 Examples thereof include the same as those of R. ma in the formula (T1') and m in the formula (T1) are preferably 0 or 1, and more preferably 0.

[0134] Examples of the ring represented by the formula (T1') and the ring represented by the formula (T1) include the following rings. The bonding site is at an arbitrary position. TIFF0007712130000079.tif52161

[0135] The structural unit having a sultone ring preferably has the following group. * in the following group represents the bonding site. TIFF0007712130000080.tif51161

[0136] The structural unit having a -SO2- group preferably further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group, and the like. Among them, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer.

[0137] The structural unit (a6) is preferably a structural unit represented by the formula (Ix). TIFF0007712130000081.tif4956[In the formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. A xx represents 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- contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -N(R d )-. X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. R c and R d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0138] R x Examples of the halogen atom of R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R x Examples of the alkyl group of R include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group, etc. Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. R x Examples of the alkyl group having a halogen atom of R include, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group, etc. R x R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.

[0139] A x Examples of the divalent saturated hydrocarbon group of A include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and those obtained by combining two or more of these groups may also be used. Specifically, linear alkanediyl groups such as 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, tridecane-1,13-diyl group, tetradecane-1,14-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-diyl group and propane-2,2-diyl group; Branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; Monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Examples thereof include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group.

[0140] R 41 、X 11 And ma are the same as those in formula (T1’). Examples of the sultone ring include those described above, and among them, those described above with the bonding position specified are preferred.

[0141] Examples of the structural unit (a6) include the following structural units. TIFF0007712130000082.tif100159

[0142] Among them, the structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8) and formula (a6-12) are preferred, and the structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferred. When the resin (A) has the structural unit (a6), its content is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and still more preferably 3 to 30 mol% based on all the structural units of the resin (A).

[0143] <Structural unit (II)> The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter sometimes referred to as "structural unit (II)"). Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and a structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain or a structural unit having a sulfonio group and an organic anion in the side chain is preferred.

[0144] The 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'). TIFF0007712130000083.tif3089[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be replaced by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA - represents a sulfonate group or a carboxylate group. R III3represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.

[0145] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. R III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R. a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted on A include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, and the like.

[0146] X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations thereof may also be possible. Specifically, linear alkanediyl groups such as 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; branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; divalent monocyclic alicyclic saturated hydrocarbon groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Examples include divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group.

[0147] Examples of those in which -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- include divalent groups represented by formula (X1) to formula (X53). However, the number of carbon atoms before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less respectively. In the following formulae, * and ** represent bonding sites, and * represents the bonding site with A x1 and represents the bonding site with A. JPEG0007712130000084.jpg145161

[0148] 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.

[0149] ZA in formula (II-2-A’) + is the same as the cation Z1 in the salt represented by formula (B1). + Examples thereof include the same ones.

[0150] The structural unit represented by formula (II-2-A’) is preferably the structural unit represented by formula (II-2-A). JPEG0007712130000085.jpg37109 [In formula (II-2-A), R III3 , X III3 and ZA + have the same meanings as described above. z represents any integer from 0 to 6. R III2 and R III4 each independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. When z is 2 or more, a plurality of R III2 and R III4 may be the same as or different from each other. Q a and Q b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.]

[0151] R III2 , R III4 , Q a and Q b Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by b1 are the same as those of the perfluoroalkyl group having 1 to 6 carbon atoms represented by Q

[0152] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF0007712130000086.tif5676In formula (II-2-A-1), R III2 、R III3 、R III4 、Q a 、Q b 、z and ZA + have the same meanings as described above. 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, wherein -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom or a hydroxy group.

[0153] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. X I2 Examples of the divalent saturated hydrocarbon group represented by include the same as those of the divalent saturated hydrocarbon group represented by X III3 .

[0154] As the structural unit represented by formula (II-2-A-1), the structural unit represented by formula (II-2-A-2) is preferable. TIFF0007712130000087.tif5287In formula (II-2-A-2), R III3 、R III5 and ZA + have the same meanings as described above. m and nA each independently represent 1 or 2.

[0155] Examples of the structural unit represented by formula (II-2-A') include, for example, the following structural unit, R III3A structural unit in which a group corresponding to the methyl group is replaced with 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 (e.g., a trifluoromethyl group), and a structural unit described in International Publication No. 2012 / 050015 may be mentioned. ZA + represents an organic cation. JPEG0007712130000088.jpg86163

[0156] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1). TIFF0007712130000089.tif3381[In the formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R II2 and R II3 may combine with each other to form a ring together with the sulfur atom to which they are attached. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A - represents an organic anion. ] R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R include a phenylene group and a naphthylene group. R II2 and R II3 Examples of the hydrocarbon group represented by include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those described above. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group combining the above-described alkyl group and alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as a phenylcyclohexyl group, and the like. R II4 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. R II4 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R A II1 Examples of the divalent linking group represented by A include, for example, a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. Specifically, examples include the same ones as the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X III3 Examples of the divalent saturated hydrocarbon group represented by X include the same ones as the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X

[0157] Examples of the structural unit containing a cation in formula (II-1-1) include a structural unit represented by the following, a group corresponding to the methyl group of R II4 Examples of the structural unit in which the group corresponding to the methyl group of R is replaced by a hydrogen atom, a halogen atom (for example, a fluorine atom) or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (for example, a trifluoromethyl group, etc.) and the like. JPEG0007712130000090.jpg84130

[0158] A - Examples of the organic anion represented by A include a sulfonate anion, a sulfonylimide anion, a sulfonylmethide anion, a carboxylate anion, and the like. A -The organic anion represented by is preferably a sulfonate anion. Examples of the sulfonate anion include those similar to the anion represented by the following formula (B1). A - Examples of the sulfonylimide anion represented by include the following. TIFF0007712130000091.tif33136 Examples of the sulfonylmethide anion include the following. TIFF0007712130000092.tif29123 Examples of the carboxylate anion include the following. JPEG0007712130000093.jpg42154

[0159] Examples of the structural unit represented by the formula (II-1-1) include the structural units represented below. JPEG0007712130000094.jpg88149

[0160] When the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% with respect to all the structural units of the resin (A).

[0161] The resin (A) may have structural units other than the above-described structural units. Examples of such structural units include structural units well-known in the art.

[0162] The resin (A) preferably comprises a structural unit (a1) (wherein, including at least one selected from the group consisting of the structural unit represented by the formula (a1-0), the structural unit (a1-1) and the structural unit (a1-2)) and a structural unit (s) (wherein, including the structural unit represented by the formula (a3-4)), that is, a copolymer of the monomer (a1) and the monomer (s). The structural unit (a1) is preferably at least two selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2). The structural unit(s) is preferably structural unit (a2) and structural unit (a3-4). The structural unit (a2) is preferably a structural unit represented by formula (a2-1) or a structural unit represented by formula (a2-A).

[0163] Each structural unit constituting the resin (A) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using monomers that lead to these structural units. The content of each structural unit of the resin (A) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more), and 50,000 or less (more preferably 30,000 or less, still more preferably 15,000 or less). In this specification, the weight average molecular weight is a value determined by gel permeation chromatography under the conditions described in the examples.

[0164] <Resin other than resin (A)> The resist composition of the present invention may contain a resin other than the resin (A). Examples of the resin other than the resin (A) include resins containing structural unit (a4) or structural unit (a5) (hereinafter sometimes referred to as resin (X)).

[0165] Among them, the resin containing structural unit (a4) is preferable as the resin (X). In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 45 mol% or more, based on the total of all structural units of the resin (X). Examples of the structural unit that the resin (X) may further have include structural unit (a2), structural unit (a3), and structural units derived from other known monomers. Among them, the resin (X) is preferably a resin composed of only structural unit (a4) and / or structural unit (a5), and more preferably a resin composed of only structural unit (a4). Each structural unit constituting the resin (X) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using the monomers that induce these structural units. The content of each structural unit of the resin (X) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The measuring means for the weight average molecular weight of the resin (X) is the same as that of the resin (A). When the resist composition contains the resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and particularly preferably 1 to 8 parts by mass with respect to 100 parts by mass of the resin (A).

[0166] The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. When the resist composition contains a resin other than the resin (A), the total content of the resin (A) and the resin other than the resin (A) is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. The solid content of the resist composition and the content of the resin relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0167] <Acid generator (B)> The acid generator (B) may be either nonionic or ionic. Examples of nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, oxime sulfonates, N-sulfonyloxyimides, sulfonyloxy ketones, diazonaphthoquinone 4-sulfonates), sulfones (e.g., disulfones, ketosulfones, sulfonyldiazomethane), and the like. Representative examples of ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of anions of onium salts include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, and the like. As the acid generator (B), compounds that generate acid upon irradiation, as described in, for example, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., can be used. Further, compounds produced by known methods may also be used. The acid generator (B) may be used in combination of two or more.

[0168] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007712130000095.tif2958[In the formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, wherein -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-. Z + represents an organic cation.

[0169] Q b1 and Q b2 Examples of the perfluoroalkyl group represented by Q and Q include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group and the like. Q b1 and Q b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0170] L b1 Examples of the divalent saturated hydrocarbon group in L include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a group formed by combining two or more of these groups may also be used. Specifically, linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group and a heptadecane-1,17-diyl group; Branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; Monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group and the like can be mentioned.

[0171] L b1 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO- include groups represented by any of formula (b1-1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent bonding sites, and * represents a bond to -Y.

[0172] TIFF0007712130000096.tif26118[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. However, b2 the total carbon number of b3 and In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon 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, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, b4 the total carbon number of b5 L and In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon 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, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, b6 the total carbon number of b7 L and

[0173] In the groups represented by formula (b1-1) to formula (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced with -O- or -CO-, the carbon number before replacement is regarded as the carbon number of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include the same ones as the divalent saturated hydrocarbon group of b1 L.

[0174] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.

[0175] L b1 As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferable. Examples of the group represented by formula (b1-1) include the groups represented by formulas (b1-4) to (b1-8), respectively. TIFF0007712130000097.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be 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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, the total number of carbon atoms of b11 L b12 and In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated 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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, the total number of carbon atoms of b13 L b15 to In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced 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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. However, the total number of carbon atoms of b16 L b18 to

[0176] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. Lb9 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 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 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 a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0177] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11), respectively. TIFF0007712130000098.tif23140 [In the formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b20represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b19 and L b20 have a total carbon number of 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, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 have a total carbon number of 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. 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, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, L b24 , L b25 and L b26 have a total carbon number of 21 or less.

[0178] In the group represented by the formula (b1-9) to the group represented by the formula (b1-11), when the hydrogen atoms contained in the saturated hydrocarbon group are substituted with alkylcarbonyloxy groups, the carbon number before replacement is taken as the carbon number of the saturated hydrocarbon group. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

[0179] Examples of the group represented by the formula (b1-4) include the following. TIFF0007712130000099.tif16154

[0180] Examples of the group represented by the formula (b1-5) include the following. TIFF0007712130000100.tif68152

[0181] Examples of the group represented by the formula (b1-6) include the following. TIFF0007712130000101.tif29151

[0182] Examples of the group represented by the formula (b1-7) include the following. TIFF0007712130000102.tif57146

[0183] Examples of the group represented by formula (b1-8) include the following. TIFF0007712130000103.tif23150

[0184] Examples of the group represented by formula (b1-2) include the following. TIFF0007712130000104.tif31161

[0185] Examples of the group represented by formula (b1-9) include the following. TIFF0007712130000105.tif44137

[0186] Examples of the group represented by formula (b1-10) include the following. TIFF0007712130000106.tif92165

[0187] Examples of the group represented by formula (b1-11) include the following. TIFF0007712130000107.tif84164

[0188] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38). When -CH2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO2- or -CO-, the number thereof may be one or two or more. Examples of such groups include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43).

[0189] The alicyclic hydrocarbon group represented by TIFF0007712130000108.tif83166Y is preferably a group represented by any of formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43), more preferably a group represented by formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43), and even more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43). When the alicyclic hydrocarbon group represented by Y is a spiro ring having an oxygen atom such as formula (Y28) to formula (Y35), formula (Y39), formula (Y40), formula (Y42), formula (Y43), etc., the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom preferably has no fluorine atom substituted thereon.

[0190] Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these, and -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom. ja represents any integer from 0 to 4.). etc. are mentioned. Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted with a hydroxy group (wherein -CH2- contained in the alkyl group may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these, and -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom. ja represents an integer of 0 to 4.).

[0191] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, and examples thereof include a methylcyclohexyl group and a dimethylcyclohexyl group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group with 1 to 18 carbon atoms (such as tolyl group, xylyl group, cumenyl group, mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and an aromatic hydrocarbon group having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (such as p-adamantylphenyl group, p-cyclohexylphenyl group, etc.) are preferred. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as hydroxymethyl group, hydroxyethyl group, etc. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, etc. Examples of the group in which -CH2- contained in the alkyl group is replaced by -O-, -SO2- or -CO- etc. include alkoxy group, alkylsulfonyl group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group or a group combining these. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, dodecyloxy group, etc. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The number of carbon atoms in the sulfonyl group is preferably from 1 to 12, more preferably from 1 to 6, and still more preferably from 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. The number of carbon atoms in the alkoxycarbonyl group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 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 from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the combined group include a group formed by combining an alkoxy group and an alkyl group, a group formed by combining an alkoxy group and an alkoxy group, a group formed by combining an alkoxy group and an alkylcarbonyl group, and a group formed by combining an alkoxy group and an alkylcarbonyloxy group. Examples of the group formed by combining an alkoxy group and an alkyl group include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and an ethoxymethyl group. The number of carbon atoms in the alkoxyalkyl group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the group formed by combining an alkoxy group and an alkoxy group include an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group. The number of carbon atoms in the alkoxyalkoxy group is preferably from 2 to 12, more preferably from 2 to 6, and still more preferably from 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, and an ethoxypropionyl group. The number of carbon atoms in the alkoxyalkylcarbonyl group is preferably from 3 to 13, more preferably from 3 to 7, and still more preferably from 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, and an ethoxypropionyloxy group. The number of carbon atoms in the alkoxyalkylcarbonyloxy group is preferably from 3 to 13, more preferably from 3 to 7, and still more preferably from 3 to 5. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2- or -CO- etc. include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43).

[0192] Examples of Y include the following. JPEG0007712130000109.jpg149158

[0193] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, still more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and even more preferably an adamantyl group which may have a substituent, and -CH2- constituting the alicyclic hydrocarbon group or adamantyl group may be replaced by -CO-, -S(O)2- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by formula (Y42), formula (Y100) to formula (Y114).

[0194] As the anion in the salt represented by formula (B1), anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter, may be referred to as "anion (B1-A-1)" etc. according to the formula number.] are preferable, and an anion represented by any of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), and formula (B1-A-47) to formula (B1-A-59) is more preferable. JPEG0007712130000110.jpg231164

[0195] JPEG0007712130000111.jpg238165

[0196] JPEG0007712130000112.jpg168159Here, R i2 ~R i7 are, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. L A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 represent the same meaning as described above. Specific examples of the anion in the salt represented by formula (B1) include the anions described in JP-A-2010-204646.

[0197] Preferably, as the anion in the salt represented by formula (B1), anions represented by formula (B1a-1) to formula (B1a-38) are exemplified. JPEG0007712130000113.jpg238158

[0198] TIFF0007712130000114.tif129154

[0199] Among them, anions represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19), and formula (B1a-22) to formula (B1a-38) are preferable.

[0200] Z + Examples of the organic cation of Z include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferable, and arylsulfonium cations are more preferable. Specifically, cations represented by any of formula (b2-1) to formula (b2-4) (hereinafter, may be referred to as "cation (b2-1)" etc. according to the formula number) are included.

[0201] In formula (b2-1) to formula (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the hydrogen atom contained in the chain hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b7 and R b8 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent any integer from 0 to 5. When m2 is 2 or more, the plurality of Rs b7 may be the same or different, and when n2 is 2 or more, the plurality of Rs b8 may be the same or different. R b9 and R b10 each independently represent a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b11 represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the chain hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 may be bonded to each other to form a ring including the -CH-CO- to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18 each independently represents a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. L b31represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer from 0 to 5. q2 and r2 each independently represent an integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, the plurality of Rs b13 are the same or different, and when p2 is 2 or more, the plurality of Rs b14 are the same or different, and when q2 is 2 or more, the plurality of Rs b15 are the same or different, and when r2 is 2 or more, the plurality of Rs b16 are the same or different, and when s2 is 2 or more, the plurality of Rs b17 are the same or different, and when t2 is 2 or more, the plurality of Rs b18 are the same or different. The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. In particular, the chain hydrocarbon group of R b9 ~R b12 is preferably a chain hydrocarbon group having 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups. TIFF0007712130000116.tif10158 In particular, the alicyclic hydrocarbon group of R b9 ~R b12 is preferably a group having 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms. Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, a 2-isopropyladamantan-2-yl group, a methylnorbornil group, an isobornyl group, and the like. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms and having a fluorine atom, and examples thereof include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a perfluorobutyl group. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4.

[0202] Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples of the aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms include a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group, and examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group having 3 to 18 carbon atoms include a p-cyclohexylphenyl group and a p-adamantylphenyl group. When the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, and the like. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butyryl group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, a 2-ethylhexylcarbonyloxy group, and the like. R b4 and R b5 The ring formed by R and R being bonded to each other together with the sulfur atom to which they are bonded may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated ring. Examples of this ring include rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. Further, examples of the ring containing a sulfur atom include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. For example, the following rings can be mentioned. * represents a bonding site. TIFF0007712130000117.tif23144R b9 and R b10 The ring formed by R and R together may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated, and unsaturated ring. Examples of this ring include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. For example, a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, a 1,4-oxathian-4-ium ring, and the like can be mentioned. R b11 and R b12The ring formed by combining them may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes 3-membered rings to 12-membered rings, preferably 3-membered rings to 7-membered rings. Examples include oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring, oxoadamantane ring, etc.

[0203] Among cations (b2-1) to (b2-4), preferably, it is cation (b2-1). Examples of cation (b2-1) include the following cations. JPEG0007712130000118.jpg79158

[0204] JPEG0007712130000119.jpg110165

[0205] Examples of cation (b2-2) include the following cations. TIFF0007712130000120.tif18150

[0206] Examples of cation (b2-3) include the following cations. TIFF0007712130000121.tif26140

[0207] Examples of cation (b2-4) include the following cations. TIFF0007712130000122.tif127165

[0208] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), preferably, an anion represented by any of formula (B1a-1) to formula (B1a-3), formula (B1a-7) to formula (B1a-16), formula (B1a-18), formula (B1a-19), formula (B1a-22) to formula (B1a-38) and a combination with cation (b2-1), cation (b2-3) or cation (b2-4) are mentioned.

[0209] As the acid generator (B), those represented by formula (B1-1) to formula (B1-56) are preferable. Among them, those containing an arylsulfonium cation are preferable, and those represented by formula (B1-1) to formula (B1-3), formula (B1-5) to formula (B1-7), formula (B1-11) to formula (B1-14), formula (B1-20) to formula (B1-26), formula (B1-29), formula (B1-31) to formula (B1-56) are particularly preferable. JPEG0007712130000123.jpg214166

[0210] JPEG0007712130000124.jpg235160

[0211] JPEG0007712130000125.jpg205162

[0212] In the resist composition of the present invention, the content of the acid generator is preferably 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, still more preferably 3 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin (A). The resist composition of the present invention may contain one kind of the acid generator (B) alone or a plurality of kinds thereof.

[0213] <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, preferably 92% by mass or more and 99% by mass or less, more preferably 94% by mass or more and 99% by mass or less. The content of the solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography. Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used.

[0214] <Quencher (C)> Examples of the quencher (C) include salts that generate an acid having a lower acidity than the acid generated from the acid generator (B), and basic nitrogen-containing organic compounds. The content of the quencher (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, still more preferably about 0.1 to 5% by mass, and still more preferably about 0.1 to 3% by mass, based on the solid content of the resist composition.

[0215] The acidity of the salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is represented by the acid dissociation constant (pKa). The salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is usually a salt having an acid dissociation constant of the acid generated from the salt of -3 < pKa, preferably a salt of -1 < pKa < 7, and more preferably a salt of 0 < pKa < 5. Examples of salts that generate an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, 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, it is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably, it is the weak acid inner salt (D). JPEG0007712130000126.jpg89167

[0216] As the weak acid inner salt (D), a diphenyliodonium salt having an iodonium cation in which one of the two aryl groups has a carboxylic acid anion and the two aryl groups are bonded is preferable, and examples thereof include the following salts. TIFF0007712130000127.tif72166

[0217] Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of the amines include aliphatic amines and aromatic amines. Examples of the aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 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'-dipyridylsulfide, 4,4'-dipyridyldisulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Aromatic amines such as diisopropylaniline are preferable, and 2,6-diisopropylaniline is more preferable. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, and choline.

[0218] <Other Components> The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes referred to as "other components (F)"). There is no particular limitation on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used.

[0219] <Preparation of Resist Composition> The resist composition of the present invention can be prepared by mixing the resin (A) of the present invention, the acid generator (B), a salt that generates an acid having a lower acidity than the acid generated from the acid generator, and, if necessary, the resin (A2), the resin (X), the quencher (C), the solvent (E), and the other components (F). The mixing order is arbitrary and is not particularly limited. The temperature during mixing can be appropriately selected from 10 to 40°C according to the type of resin, etc. and the solubility of the resin, etc. in the solvent (E). The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. Note that the mixing means is also not particularly limited, and stirring and mixing, etc. can be used. After mixing the respective components, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

[0220] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention is (1) a step of applying the resist composition of the present invention onto a substrate, (2) a step of drying the applied composition to form a composition layer, (3) Exposing the composition layer, (4) Heating the exposed composition layer, and (5) Developing the heated composition layer.

[0221] To apply the resist composition onto a substrate, it can usually be done by using an apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers, and organic substrates having a resist film or the like formed on the surface. Before applying the resist composition, the substrate may be cleaned, or an antireflection film or the like may be formed on the substrate. By drying the applied composition, the solvent is removed to form a composition layer. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake), or by using a decompression device. The heating temperature is preferably 50 to 200 °C, and the heating time is preferably 10 to 180 seconds. Also, the pressure during decompression drying is preferably about 1 to 1.0×10 5 Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, those that emit laser light in the ultraviolet region such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), those that convert laser light from a solid laser light source (such as a YAG or semiconductor laser) to emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams, extreme ultraviolet light (EUV), etc. can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure" in some cases. During exposure, exposure is usually performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is heat-treated (so-called post-exposure bake) to promote the deprotection reaction at the acid-labile groups. The heating temperature is usually about 50 to 200°C, preferably about 70 to 150°C. Chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating. Also, before development, the steps of coating, drying, exposing, and heating the resist composition may be repeated on the composition layer after exposure. The composition layer after heating is usually developed using a developing solution with a developing apparatus. Examples of the developing method include dip method, paddle method, spray method, dynamic dispense method, etc. The developing temperature is preferably, for example, 5 to 60°C, and the developing time is preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as follows, a positive resist pattern or a negative resist pattern can be manufactured. When manufacturing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developing solution. The alkaline developer may be various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly called choline) etc. may be mentioned. The alkaline developer may contain a surfactant. It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern. When manufacturing a negative resist pattern from the resist composition of the present invention, a developing solution containing an organic solvent (hereinafter sometimes referred to as "organic-based developing solution") is used as the developing solution. Examples of the organic solvent contained in the organic-based developing solution include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole, etc. In the organic developing solution, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and still more preferably substantially only the organic solvent. Among them, as the organic developing solution, a developing solution containing butyl acetate and / or 2-heptanone is preferable. In the organic developing solution, the total content of butyl acetate and 2-heptanone is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and still more preferably substantially only butyl acetate and / or 2-heptanone. The organic developing solution may contain a surfactant. Further, the organic developing solution may contain a trace amount of water. During development, development may be stopped by substituting with a solvent of a type different from the organic developing solution. It is preferable to wash the resist pattern after development with a rinse solution. The rinse solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, preferably an alcohol solvent or an ester solvent. After washing, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

[0222] <Usage> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, and is useful for fine processing of semiconductors.

Examples

[0223] The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or the amount used are based on mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions. Apparatus: Model HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector Column temperature: 40 °C Injection volume: 100 μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)

[0224] Also, the structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC is Agilent model 1100, MASS is Agilent LC / MSD model). In the following examples, the value of this molecular ion peak is indicated as "MASS".

[0225] Synthesis Example 1: Synthesis of the compound represented by formula (I-5) 4 parts of the compound represented by formula (I-12), 40 parts of acetone, and 23.78 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the obtained mixture, 33.33 parts of the compound represented by formula (I-5-b) was added dropwise, and then stirred at 23 °C for 1 hour. To the obtained mixture, 100 parts of chloroform and 50 parts of ion-exchanged water were added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. To the obtained organic layer, 50 parts of 5% aqueous oxalic acid solution was added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. To the obtained organic layer, 50 parts of ion-exchanged water was added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. This washing operation was performed 5 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 1.19 parts of the compound represented by formula (I-5). MASS (mass spectrometry): 369.2 [M+H] +

[0226] Synthesis Example 2: Synthesis of the compound represented by formula (I-21) 4 parts of the compound represented by formula (I-26), 40 parts of dimethylformamide, and 6.76 parts of triethylamine were mixed and stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, 6.31 parts of the compound represented by formula (I-5-b) was added dropwise, and then the mixture was stirred at 23°C for 1 hour. To the resulting mixture, 100 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. To the obtained organic layer, 50 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. This water-washing operation was performed 5 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by a column (silica gel 60N (spherical, neutral), 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 1.66 parts of the compound represented by formula (I-21). MASS (mass spectrometry): 307.2 [M+H] +

[0227] Synthesis Example 3: Synthesis of the compound represented by formula (I-1) 3.52 parts of the compound represented by TIFF0007712130000130 (I-16), 40 parts of dimethylformamide, and 4.51 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. After dropping 4.21 parts of the compound represented by the formula (I-5-b) into the obtained mixture, the mixture was stirred at 23 °C for 1 hour. 100 parts of chloroform and 50 parts of ion-exchanged water were added to the obtained mixture, and the mixture was stirred at 23 °C for 30 minutes and separated to obtain an organic layer. 50 parts of a 5% aqueous oxalic acid solution was added to the obtained organic layer, and the mixture was stirred at 23 °C for 30 minutes and separated to obtain an organic layer. 50 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 °C for 30 minutes and separated to obtain an organic layer. This washing operation was performed 5 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 1.23 parts of the compound represented by the formula (I-1). MASS (Mass spectrometry): 233.2 [M+H] +

[0228] Synthesis Example 4: Synthesis of the compound represented by the formula (I-27) 4 parts of the compound represented by TIFF0007712130000131.tif39126 (I-30), 40 parts of dimethylformamide, and 6.76 parts of triethylamine were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the resulting mixture, 6.31 parts of the compound represented by formula (I-5-b) was added dropwise, and then stirred at 23 °C for 1 hour. To the resulting mixture, 100 parts of chloroform and 50 parts of ion-exchanged water were added, stirred at 23 °C for 30 minutes, and separated to obtain an organic layer. To the obtained organic layer, 50 parts of a 5% aqueous oxalic acid solution was added, stirred at 23 °C for 30 minutes, and separated to obtain an organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added, stirred at 23 °C for 30 minutes, and separated to obtain an organic layer. This washing operation with water was carried out 5 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 1.89 parts of the compound represented by formula (I-27). MASS (Mass spectrometry): 307.2 [M + H] +

[0229] Synthesis Example 5: Synthesis of the compound represented by formula (I-6) 2.47 parts of the compound represented by TIFF0007712130000132.tif47152 (I-12), 0.91 part of the compound represented by formula (I-6-c), 50 parts of ethyl acetate, and 5 parts of tetrahydrofuran were mixed and stirred at 23 °C for 30 minutes, and then cooled to 10 °C. To the resulting mixed solution, 2.62 parts of the compound represented by formula (I-6-b) was added dropwise at 10 °C, and after warming to 23 °C, stirred at 23 °C for 2 hours. To the resulting mixture, 30 parts of ion-exchanged water was added and stirred at 23 °C for 30 minutes, and then separated to take out the organic layer. This washing operation with water was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 3 / 1) to obtain 1.02 parts of the compound represented by formula (I-6). MASS (Mass spectrometry): 425.3 [M + H] +

[0230] Synthesis Example 6: Synthesis of the compound represented by formula (I-46) TIFF0007712130000133.tif331192 - 30 parts of 3 - hydroxy - 2 - methyladamantane, 210 parts of chloroform, and 32 parts of carbonyldiimidazole were mixed, and then the temperature was raised to 60°C and stirred at 60°C for 20 hours. After cooling the obtained mixed solution to 23°C, 80 parts of ion - exchanged water was added and stirred at 23°C for 30 minutes, and then liquid - separated to take out the organic layer. By concentrating the recovered organic layer, 44 parts of the compound represented by formula (I - 46 - a) was obtained. TIFF0007712130000134.tif521542 parts of the compound represented by formula (I - 15), 40 parts of acetone, and 16 parts of the compound represented by formula (I - 46 - a) were mixed, and further 0.2 part of potassium carbonate was added. Then, the temperature was raised to 60°C and stirred at 60°C for 20 hours. After cooling to 23°C, 100 parts of chloroform and 30 parts of ion - exchanged water were added to the reaction solution, stirred, allowed to stand, and liquid - separated to recover the organic layer. To the recovered organic layer, 30 parts of 1% aqueous oxalic acid solution was added, stirred, allowed to stand, and liquid - separated to recover the organic layer. Further, 30 parts of ion - exchanged water was added to the recovered organic layer, liquid - separated, and the organic layer was washed with water. After washing with water, the organic layer was concentrated, 100 parts of acetonitrile was added, dissolved, and then further concentrated. 60 parts of methanol was added to the concentrate, stirred, and then filtered to obtain 8.70 parts of the compound represented by formula (I - 46). MASS (Mass spectrometry): 697.4 [M + H] +

[0231] Synthesis Example 7: Synthesis of the compound represented by formula (I - 61) 5 parts of the compound represented by TIFF0007712130000135 (I-75), 50 parts of dimethylformamide, and 14.98 parts of diisopropylethylamine were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the resulting mixture, 8.43 parts of the compound represented by the formula (I-5-b) was added dropwise, and then stirred at 23 °C for 1 hour. To the resulting mixture, 100 parts of chloroform and 50 parts of ion-exchanged water were added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. To the obtained organic layer, 50 parts of 5% aqueous oxalic acid solution was added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. To the obtained organic layer, 50 parts of ion-exchanged water was added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. This washing operation with water was carried out 5 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 8.13 parts of the compound represented by the formula (I-61). MASS (Mass spectrometry): 285.2 [M+H] +

[0232] Synthesis Example 8: Synthesis of the compound represented by the formula (I-62) 5 parts of the compound represented by formula (I-75), 50 parts of dimethylformamide and 14.98 parts of diisopropylethylamine were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the resulting mixture, 2.81 parts of the compound represented by formula (I-5-b) was added dropwise, and then the mixture was stirred at 23 °C for 1 hour. To the resulting mixture, 100 parts of chloroform and 50 parts of ion-exchanged water were added, and the mixture was stirred at 23 °C for 30 minutes and then separated to obtain an organic layer. To the obtained organic layer, 50 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23 °C for 30 minutes and then separated to obtain an organic layer. To the obtained organic layer, 50 parts of ion-exchanged water was added, and the mixture was stirred at 23 °C for 30 minutes and then separated to obtain an organic layer. This washing operation with water was carried out 5 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by a column (silica gel 60N (spherical, neutral), 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain 4.28 parts of the compound represented by formula (I-62). MASS (Mass spectrometry): 227.2 [M+H] +

[0233] Synthesis Example 9: Synthesis of the compound represented by formula (I-63) 5 parts of the compound represented by formula (I-76), 50 parts of dimethylformamide and 18.24 parts of diisopropylethylamine were mixed and stirred at 23 °C for 30 minutes, and then cooled to 5 °C. To the resulting mixture, 10.26 parts of the compound represented by formula (I-5-b) was added dropwise, and then stirred at 23 °C for 1 hour. To the resulting mixture, 100 parts of chloroform and 50 parts of ion-exchanged water were added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. To the obtained organic layer, 50 parts of 5% aqueous oxalic acid solution was added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. To the obtained organic layer, 50 parts of ion-exchanged water was added, stirred at 23 °C for 30 minutes, and the organic layer was obtained by liquid separation. This washing operation with water was carried out 5 times. The obtained organic layer was concentrated, and the concentrated mass was fractionated by a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 6.12 parts of the compound represented by formula (I-63). MASS (Mass spectrometry): 359.2 [M+H] +

[0234] Synthesis of resin The compounds (monomers) used for the synthesis of resin (A) are shown below. Hereinafter, these compounds are referred to as "monomer (a1-1-1a)" etc. according to their formula numbers. TIFF0007712130000138.tif78160

[0235] Synthesis Example 10 [Synthesis of Resin A1] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer (a2-1-1) and monomer (a3-4-2) were used and mixed so that the molar ratio [monomer (a1-1-3): monomer (a1-2-6): monomer (a2-1-1): monomer (a3-4-2)] was 20:25:6:49. Propylene glycol monomethyl ether acetate 1.5 times the amount of all monomers by mass was added to make a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in amounts of 1 mol% and 3 mol%, respectively, based on the total monomer amount, and these were heated at 75 °C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered. This reprecipitation operation was performed twice, and resin A1 (copolymer) with a weight average molecular weight of 8.9×10 3 was obtained in a yield of 80%. This resin A1 has the following structural units. TIFF0007712130000139.tif44144

[0236] Synthesis Example 11 [Synthesis of Resin X1] As monomers, monomer (a5-1-1) and monomer (a4-0-12) were used and mixed so that the molar ratio [monomer (a5-1-1): monomer (a4-0-12)] was 50:50. Methyl isobutyl ketone 1.2 times the amount of all monomers by mass was added to make a solution. To this solution, azobis(2,4-dimethylvaleronitrile) was added as an initiator in an amount of 3 mol% based on the total monomer amount, and it was heated at 70 °C for about 5 hours. The resulting reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered, and resin X1 (copolymer) with a weight average molecular weight of 1.0×10 4 was obtained in a yield of 91%. This resin X1 has the following structural units. TIFF0007712130000140.tif3582

[0237] Synthesis Example 12 [Synthesis of Resin A2] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a1-4-2) were used, and their molar ratio [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2)] was mixed at a ratio of 53:3:12:32. Further, 1.5 times the mass of methyl isobutyl ketone was mixed with this monomer mixture based on the total mass of all monomers. To the resulting mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total monomer amount, and these were heated at 73 °C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 12 hours, and then separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery. 3 Resin A2 having a weight average molecular weight of about 5.3×10 TIFF0007712130000141.tif38128

[0238] Synthesis Example 13 [Synthesis of Resin A3] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a4-1-13) were used, and their molar ratio [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a4-1-13)] was mixed so as to be in a ratio of 53:3:12:32. Further, to this monomer mixture, methyl isobutyl ketone 1.5 times the total mass of all monomers was mixed. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total monomer amount, and these were heated at 73 °C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was performed. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, with a weight average molecular weight of about 5.1×10 3 Resin A3 with this value was obtained at a yield of 79%. This resin A3 has the following structural units. TIFF0007712130000142.tif38128

[0239] Synthesis Example 14 [Synthesis of Resin A4] As monomers, acetoxystyrene, monomer (a1-1-2), monomer (a2-1-1), and monomer (a3-4-2) were used, and their molar ratio [acetoxystyrene: monomer (a1-1-2): monomer (a2-1-1): monomer (a3-4-2)] was mixed so as to be in a ratio of 48:30:10:12. Further, to this monomer mixture, methyl isobutyl ketone 1.5 times the total mass of all monomers was mixed. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, based on the total monomer amount, and these were heated at 73 °C for about 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was performed. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, with a weight average molecular weight of about 5.3×10 3Resin A4 was obtained in a yield of 69%. This resin A4 has the following structural units. TIFF0007712130000143.tif47147

[0240] Synthesis Example 15 [Synthesis of Resin A5] As monomers, monomer (a1-3-1), monomer (ax), monomer (a1-1-1a) and monomer (a3-4-2) were used, and they were mixed so that the molar ratio [monomer (a1-3-1): monomer (ax): monomer (a1-1-1a): monomer (a3-4-2)] was 18:23:34:25. Propylene glycol monomethyl ether acetate 1.5 times the mass of the total monomer amount was added to make a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol%, respectively, based on the total monomer amount, and these were heated at 75 °C for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered. This reprecipitation operation was performed twice, and a resin A5 (copolymer) with a weight average molecular weight of 8.8×10 3 was obtained in a yield of 69%. This resin A5 has the following structural units. TIFF0007712130000144.tif41152

[0241] Synthesis Example 16 [Synthesis of Resin AX1] As monomers, acetoxystyrene, monomer (a1-1-2), and monomer (a2-1-1) were used, and they were mixed so that the molar ratio [acetoxystyrene: monomer (a1-1-2): monomer (a2-1-1)] was 60:30:10. Further, 1.5 times the total mass of all the monomers of methyl isobutyl ketone was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol% respectively with respect to the total monomer amount, and these were heated at 73 °C for about 5 hours. Thereafter, an aqueous solution of 25% tetramethylammonium hydroxide was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was performed. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, and the weight average molecular weight was about 5.3×10 3 Resin AX1 having a yield of 69% was obtained. This resin AX1 has the following structural units. TIFF0007712130000145.tif33109

[0242] Synthesis Example 17 [Synthesis of Resin AX2] As monomers, monomer (a1-3-1), monomer (ax), monomer (a1-1-1a), and monomer (a3-2-1a) were used, and they were mixed so that the molar ratio [monomer (a1-3-1): monomer (ax): monomer (a1-1-1a): monomer (a3-2-1a)] was 18:23:34:25. 1.5 times the total monomer amount of propylene glycol monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1 mol% and 3 mol% respectively with respect to the total monomer amount, and these were heated at 75 °C for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The reprecipitation operation was performed twice, and the weight average molecular weight was 8.9×10 3The resin AX2 (copolymer) was obtained in a yield of 66%. This resin AX2 has the following structural units. TIFF0007712130000146.tif30156

[0243] <Preparation of Resist Composition> As shown in Table 1, each of the following components was mixed, and the resulting mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

Table 1

[0244] <Resin> A1, A5, X1, AX2: Resin A1, Resin A5, Resin X1, Resin AX2 <Acid Generator> B1-21: Salt represented by formula (B1-21) (synthesized according to the examples in JP-A-2012-224611) B1-22: Salt represented by formula (B1-22) (synthesized according to the examples in JP-A-2012-224611) B1-49: Salt represented by formula (B1-49) (synthesized according to the examples in JP-A-2018-048106) JPEG0007712130000148.jpg38163<Compound (I)> I-1: Compound represented by formula (I-1) I-5: Compound represented by formula (I-5) I-6: Compound represented by formula (I-6) I-12: Compound represented by formula (I-12) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-15: Compound represented by formula (I-15) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-16: Compound represented by formula (I-16) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-21: Compound represented by formula (I-21) I-26: Compound represented by formula (I-26) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-27: Compound represented by formula (I-27) I-30: Compound represented by formula (I-30) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-46: Compound represented by formula (I-46) I-61: Compound represented by formula (I-61) I-62: Compound represented by formula (I-62) I-63: Compound represented by formula (I-63) I-75: Compound represented by formula (I-75) (manufactured by Tokyo Chemical Industry Co., Ltd.) TIFF0007712130000149.tif29142I-76: Compound represented by formula (I-76) (manufactured by Mitsubishi Gas Chemical Company, Inc.) <Quencher (C)> D1: (manufactured by Tokyo Chemical Industry Co., Ltd.) TIFF0007712130000150.tif1932<Solvent> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-Heptanone 20 parts γ-Butyrolactone 3.5 parts

[0245] <Manufacture and Evaluation of Resist Pattern> An organic antireflection film composition (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an organic antireflection film with a film thickness of 78 nm on the wafer. Next, the above resist composition was applied (spin-coated) on the organic antireflection film so that the film thickness after drying was 85 nm. After application, the silicon wafer was prebaked on a direct hot plate at the temperature described in the "PB" column of Table 1 for 60 seconds to form a composition layer. The silicon wafer with the composition layer formed was exposed using an ArF excimer stepper for immersion lithography (XT: 1900Gi; manufactured by ASML, NA = 1.35, 3 / 4 Annular X-Y polarization) with a mask for forming a contact hole pattern (hole pitch 90 nm / hole diameter 55 nm), and the exposure dose was changed stepwise for exposure. Note that ultrapure water was used as the immersion medium. After exposure, post-exposure baking was performed on a hot plate at the temperature described in the "PEB" column of Table 1 for 60 seconds. Subsequently, the composition layer on this silicon wafer was developed by the dynamic dispense method at 23°C for 20 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as the developer to produce a negative resist pattern.

[0246] In the resist pattern obtained after development, the exposure dose at which the hole diameter formed using the mask was 50 nm was defined as the effective sensitivity.

[0247] <CD Uniformity (CDU) Evaluation> At the 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 defined as the average hole diameter of one hole. Using the average hole diameters of the patterns formed with a mask having a hole diameter of 55 nm measured at 400 locations within the same wafer as the population, the standard deviation was determined. The results are shown in Table 2. The numerical values in the table indicate the standard deviation (nm).

Table 2

[0248] <Preparation of Resist Composition> As shown in Table 3, 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.

[0249]

Table 3

[0250] <Resin> A2, A3, A4, AX1: Resin A2, Resin A3, Resin A4, Resin AX1 <Acid Generator> B1-43: Salt represented by formula (B1-43) (synthesized according to the examples of JP 2016-47815 A) TIFF0007712130000153.tif4281<Compound (I)> I-1: Compound represented by formula (I-1) I-5: Compound represented by formula (I-5) I-6: Compound represented by formula (I-6) I-12: Compound represented by formula (I-12) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-15: Compound represented by formula (I-15) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-16: Compound represented by formula (I-16) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-21: Compound represented by formula (I-21) I-26: Compound represented by formula (I-26) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-27: Compound represented by formula (I-27) I-30: Compound represented by formula (I-30) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-46: Compound represented by formula (I-46) I-61: Compound represented by formula (I-61) I-62: Compound represented by formula (I-62) I-63: Compound represented by formula (I-63) I-75: Compound represented by formula (I-75) (manufactured by Tokyo Chemical Industry Co., Ltd.) I-76: Compound represented by formula (I-76) (manufactured by Mitsubishi Gas Chemical Company, Inc.) <Quencher (C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF0007712130000154.tif4247<Solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0251] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer was treated with hexamethyldisilazane on a direct hot plate at 90°C for 60 seconds. A resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, it was pre-baked for 60 seconds at the temperature shown in the "PB" column of Table 3 on a direct hot plate to form a composition layer. Using an electron beam lithography machine ["ELS-F125 125keV" manufactured by Elionix, Inc.], a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn on the composition layer formed on the wafer by gradually changing the exposure dose. After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 3 on a hot plate. Next, the composition layer on this silicon wafer was developed using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer by the dynamic dispense method at 23°C for 20 seconds to obtain a resist pattern.

[0252] In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was defined as the effective sensitivity.

[0253] <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 taken as the average hole diameter of one hole. Using as the population the measurement of the average hole diameters of 400 patterns formed with a hole diameter of 17 nm within the same wafer, the standard deviation was obtained. The results are shown in Table 4. The numerical values in the table indicate the standard deviation (nm).

Table 4

Industrial Applicability

[0254] The resist composition containing the compound of the present invention is suitable for semiconductor microfabrication and is extremely useful industrially because a resist pattern having good CD uniformity (CDU) can be obtained.

Claims

1. A resist composition containing a compound represented by formula (I), a resin having an acid-labile group, an acid generator, and a salt that generates an acid with a lower acidity than the acid generated from the acid generator, wherein the resin having the acid-labile group comprises 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), and a structural unit represented by formula (a3-4). [In formula (I), L 1 represents an (m2 + 1)-valent aliphatic hydrocarbon group having 1 to 24 carbon atoms, which may have a substituent. R １ represents a hydrogen atom or an acid-labile group. R ２ represents a hydrogen atom, *-OH or *-O-R １ , where * represents the bonding site with 1 L. R １ and R ２ or two Rs ２ may together form a group having an acetal ring structure. m2 represents any integer from 1 to 7, and when m2 is 2 or more, the plurality of Rs ２ may be the same as or different from each other.] [In formula (a1-0), formula (a1-1), and formula (a1-2), L ａ０１ , L ａ１ and L ａ２ each independently represents -O- or *-O-(CH ２ ), ｋ１ -CO-O-, k1 represents any integer from 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 groups. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3.] [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. * represents the bonding position with the carbonyl group. R ａ２４ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or 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 any integer from 0 to 8. When w1 is 2 or more, the plurality of Rs ａ２５ may be the same as or different from each other.]

2. L １ The resist composition according to claim 1, wherein L is a (m2 + 1)-valent chain hydrocarbon group having 1 to 8 carbon atoms, a (m2 + 1)-valent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a (m2 + 1)-valent group combining these.

3. L １ is a chain hydrocarbon group having (m2 + 1) valences and 1 to 8 carbon atoms, The resist composition according to claim 2, wherein m2 is 1 to 3.

4. L １ is an (m2 + 1)-valent alicyclic hydrocarbon group having 3 to 10 carbon atoms or an (m2 + 1)-valent group combining a chain hydrocarbon group having 1 to 8 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms, The resist composition according to claim 2, wherein m2 is 1 to 3.

5. R ２ represents -OR １ and R １ represents an acid-labile group. The resist composition according to any one of claims 1 to 4

6. R １ The resist composition according to any one of claims 1 to 5, wherein R is a group represented by formula (1a) or a group represented by formula (2a). [In formula (1a), R aa1 , R aa2 and R aa3 each independently represents an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 2 to 8 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or R aa1 and R aa2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. naa represents 0 or 1. * represents a bond.] [In formula (2a), R aa1’ and R aa2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R aa3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R aa2’ and R aa3’ are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the -C-X ａ - to which they are bonded, and the -CH ２ - contained in the hydrocarbon group and the heterocyclic group may be replaced by -O- or -S-. X a represents an oxygen atom or a sulfur atom. * represents a bond.]

7. The resist composition according to any one of claims 1 to 6, wherein the acid generator contains 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 the -CH ２ - in the divalent saturated hydrocarbon group 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 a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and -CH contained in the alicyclic hydrocarbon group ２ - may be replaced by -O-, -SO ２ - or -CO-. Z ＋ represents an organic cation.]

8. (1) A step of applying the resist composition according to any one of claims 1 to 7 onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, A method for manufacturing a resist pattern including these steps.

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