salt

Abstract

To provide a salt which allows a resist pattern to be produced with good line edge roughness.SOLUTION: The salt is represented by formula (IA) [where R1A and R2A each represent a hydrogen atom or a C1-6 alkyl group; R3A represents a hydrogen atom; R4A and R5A each represent a halogen atom, a C1-6 fluorinated alkyl group or a C1-12 alkyl group; and AI- represents an organic anion.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a salt for an acid generator used in the microfabrication of semiconductors. [Background technology]

[0002] Patent Document 1 describes a salt represented by the following formula: TIFF0007791275000001.tif1750 Patent Document 2 describes a salt represented by the following formula: TIFF0007791275000002.tif3572 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Unexamined Patent Publication No. 49-123860 [Patent Document 2] Japanese Patent Application Publication No. 2018-030830 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a resist pattern that is better than a resist pattern formed from a resist composition containing the above salt. The present invention provides a salt that can produce resist patterns with good line edge roughness (LER). The purpose is to provide [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] Resin containing a structural unit represented by formula (a2-A) and a structural unit having an acid labile group and a resist composition containing the salt represented by formula (I). TIFF0007791275000003.tif4653[In formula (a2-A), R a50is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: R a51 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or * -X a51 -(A a52 -X a52 ) nb - represents -R a50 is combined represents the bond to the carbon atom. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, multiple R in Numbers a51 may be the same or different from each other.] TIFF0007791275000004.tif4897 [In formula (I), R 1a and R 2a each independently represents a carbon number which may have a hydrogen atom or a fluorine atom, 1 to 18 hydrocarbon groups (-CH2- contained in the hydrocarbon groups is not limited to -O-, -S-, -CO - or -SO2- may be replaced.) or R 1a and R 2a and are connected to each other a ring (or rings) having 3 to 36 carbon atoms which may be bonded to one another and which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms; -CH2- contained in the alkyl group may be replaced with -O- or -CO-, -CH2- contained in the ring is replaced by -O-, -S-, -CO- or -SO2- It may be formed. R 3a represents a hydrogen atom or R 1a and R 2a and R 3a and bond to each other, and the fluorine atom or a ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms (including the alkyl group -CH2- contained in the ring may be replaced by -O- or -CO-, and - contained in the ring CH2- may be replaced by -O-, -S-, -CO- or -SO2-. Form. R 4 is a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. The fluorinated alkyl group and the —CH2— contained in the alkyl group are each independently —O— or It may be replaced by -CO-. R 5 represents a halogen atom, a fluoroalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, group or -O-CO-CR 1b R 2b R 3b and the fluorinated alkyl group and the alkyl group The -CH2- contained in the formula may be replaced by -O- or -CO-. R 1b and R 2b each independently represents a carbon number which may have a hydrogen atom or a fluorine atom, 1 to 18 hydrocarbon groups (-CH2- contained in the hydrocarbon groups is not limited to -O-, -S-, -CO - or -SO2- may be replaced.) or R 1b and R 2b and are connected to each other a ring (or rings) having 3 to 36 carbon atoms which may be bonded to one another and which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms; -CH2- contained in the alkyl group may be replaced with -O- or -CO-, -CH2- contained in the ring is replaced by -O-, -S-, -CO- or -SO2- It may be formed. R 3b represents a hydrogen atom or R 1b and R 2b and R 3b and bond to each other, and the fluorine atom or a ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms (including the alkyl group -CH2- contained in the ring may be replaced by -O- or -CO-, and - contained in the ring CH2- may be replaced by -O-, -S-, -CO- or -SO2-. Form. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R 4 are the same as each other They may be the same or different. m5 represents an integer of 0 to 5, and when m5 is 2 or more, a plurality of R 5 are the same as each other They may be the same or different. AI - represents an organic anion. [2] AI - However, sulfonate anion, sulfonylimide anion, sulfonylmethide The resist composition according to [1], wherein the anion is an anion or a carboxylate anion. [3] AI - is a sulfonate anion, and the sulfonate anion is represented by the formula (IA): [2] The resist composition according to [2], wherein the anion is represented by the formula: TIFF0007791275000005.tif2965[In formula (IA), Q 1 and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents a methyl group. L 1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH 2- may be replaced by -O- or -CO-, and the water contained in the saturated hydrocarbon group The hydrogen atom may be substituted with a fluorine atom or a hydroxy group. Y 1 is a methyl group which may have a substituent or a methyl group having 3 to 4 carbon atoms which may have a substituent. 18 represents an alicyclic hydrocarbon group, and -CH2- contained in the alicyclic hydrocarbon group is -O-, may be replaced by -SO2- or -CO-.] [4] The resin having an acid labile group is a resin having a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1- 2) is a resin containing at least one structural unit represented by [1] to [3] The resist composition described above. TIFF0007791275000006.tif46102 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or -O-(CH2) k1 -CO-O represents -, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 are each independently an alkyl group having 1 to 8 carbon atoms, a It represents an alicyclic hydrocarbon group or a group formed by combining these groups. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. [5] The composition further contains a salt that generates an acid that is weaker in acidity than the acid generated from the acid generator. The resist composition according to any one of items 1] to [4]. [6] (1) A process for applying the resist composition according to any one of [1] to [5] onto a substrate. The course, (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) developing the composition layer after heating; A method for producing a resist pattern comprising: [7] A salt represented by formula (IA). TIFF0007791275000007.tif51102[In formula (IA), R 1A and R 2A are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (the alkyl -CH2- contained in the alkyl group may be replaced by -O- or -CO-. represent. R 3A represents a hydrogen atom. R 4A and R 5A are each independently a halogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms. or an alkyl group having 1 to 12 carbon atoms, and the fluorinated alkyl group and the alkyl group The -CH2- may be replaced by -O- or -CO-. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R 4A are mutually They may be the same or different. m5 represents an integer of 0 to 5, and when m5 is 2 or more, a plurality of R 5A are mutually They may be the same or different. AI - represents an organic anion. [Effects of the Invention]

[0006] By using a resist composition that uses the salt of the present invention, it is possible to obtain good line edge roughness. Resist patterns can be produced using laser elimination (LER). DETAILED DESCRIPTION OF THE INVENTION

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

[0008] [Resist Composition] The resist composition of the present invention comprises a compound having a structural unit represented by formula (a2-A) and an acid labile group. A resin containing a structural unit represented by formula (I) (hereinafter, sometimes referred to as resin (A)) It contains a salt (hereinafter sometimes referred to as "salt (I)") that is The resist composition may also contain a quencher (hereinafter referred to as "quencher (C)"). It is preferable that the liquid contains a solvent (hereinafter sometimes referred to as "solvent (E)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). .

[0009] <Resin (A)> Resin (A) is a structural unit represented by formula (a2-A) (hereinafter referred to as "structural unit (a2-A)"). (sometimes referred to as "inventory"). <Structural unit (a2-A)> In formula (a2-A), R a50 and R a51 The halogen atom in , 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 include: Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, phenyl group 2,2,3,3-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2, 3,3,4,4-octafluorobutyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 2,2,3,3,4,4-hexafluoro 2,2,3,3,4,4,4-Heptafluorobutyl group, butyl group, pentafluorobutyl group fluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropane butyl group, 2-(perfluorobutyl)ethyl group, 2,2,3,3,4,4,5,5,5- Nonafluoropentyl group, pentyl group, hexyl group, 1,1,2,2,3,3,4,4, 5,5-decafluorohexyl group, 2,2,3,3,4,4,5,5,6,6-decafluoro Orohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohe Examples of the alkyl group include a perfluorohexyl group and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is more preferably an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a51 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, or the like. Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. can be done. R a51 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an isopropyl ... Examples include a propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methyl group is more preferred. A hydroxy group is more preferred. R a51 The alkylcarbonyl group in the formula (I) includes an acetyl group, a propionyl group, and a butyl group. Examples thereof include an aryl group. R a51 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, or Examples of such groups include an aryloxy group and a butyryloxy group. R a51 is preferably a methyl group.

[0010] * -X a51 -(A a52 -X a52 ) nb -As * -O-, * -CO-O-,* -OC O-, * -CO-OA a52 -CO-O-, * -O-CO-A a52 -O-, * -OA a52 -CO-O-, * -CO-OA a52 -O-CO-, * -O-CO-A a52 -O-CO-, Among them, * -CO-O-, * -CO-OA a52 -CO-O- or * - Office Automation a52 -CO-O- is preferred.

[0011] Examples of the alkanediyl group include a methylene group, an ethylene group, and a propane-1,3-diyl group. Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and and 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group.

[0012] A a50 is a single bond, * -CO-O- or * -CO-OA a52 -CO-O- Preferably, a single bond, * -CO-O- or * -CO-O-CH2-CO-O- More preferably, a single bond or * More preferably, it is —CO—O—.

[0013] 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- or p-position of the benzene ring, and more preferably to the p-position. It is more preferable to combine them.

[0014] The structural unit (a2-A) is represented by the formulas (a2-2-1) to (a2-2-6). The structural units and the structural units represented by formulas (a2-2-1) to (a2-2-6) R in structural unit (a2-A) a50 The structure in which the methyl group corresponding to The structural unit (a2-A) is a structural unit represented by the formula (a2-2-1): A structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), and a structural unit represented by formula (a2-2-7) A structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), or a structural unit represented by formula ( In the structural unit represented by a2-2-6), R in the structural unit (a2-A) a50 to Preferably, the structural unit has a corresponding methyl group substituted for a hydrogen atom. TIFF0007791275000008.tif42166

[0015] The content of the structural unit (a2-A) in the resin (A) is preferably 5% by weight based on the total amount of the structural units. The content is preferably from 10 to 80 mol %, more preferably from 10 to 70 mol %, and even more preferably from 15 to 180 mol %. 65 mol %, and even more preferably 20 to 65 mol %. The structural unit (a2-A) can be prepared by, for example, polymerizing the structural unit (a1-4) and then reacting the polymer with p-toluenesulfonyl ether. It can be incorporated into the resin (A) by treating it with an acid such as enesulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0016] The resin (A) contains a structural unit having an acid labile group (hereinafter, sometimes referred to as "structural unit (a1)"). Here, the acid labile group includes a group having a leaving group, which is released upon contact with an acid. By "hydrophilic group" is meant a group that forms a hydrophilic group (for example, a hydroxy group or a carboxy group).

[0017] <Structural unit (a1)> The structural unit (a1) is a monomer having an acid labile group (hereinafter referred to as "monomer (a1)"). (in some cases). The acid labile group contained in the resin (A) is a group represented by formula (1) (hereinafter also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF0007791275000009.tif1986 [In formula (1), R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 8 carbon atoms. R represents a cyclic group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group combining these groups; a1 Reach BiR a2 are bonded to each other and, together with the carbon atoms to which they are bonded, are non-aromatic carbon atoms having 3 to 20 carbon atoms. Forms a hydrogen chloride ring. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.] TIFF0007791275000010.tif2275[In formula (2), R a1’ and R a2’ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms, represents a hydrocarbon group of 2, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ Reach BiR a3’ are bonded to each other and together with the carbon atoms to which they are bonded and X, form a group having 3 to 20 carbon atoms. A heterocyclic ring is formed, and -CH2- contained in the hydrocarbon group and the heterocyclic ring is -O- or -S- may be replaced by . X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.]

[0018] R a1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, or a propyl group. Examples of the alkyl group include an alkyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, ... Examples of cycloalkyl groups include cycloheptyl and cyclooctyl groups. Examples of the hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups: (* indicates a bonding site.) a1 , R a2 and R a3 Alicyclic carbonization of The hydrogen group preferably has 3 to 16 carbon atoms. TIFF0007791275000011.tif10150 Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexane. xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group , adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. do. Preferably, ma is 0 and na is 1. Ra1 and R a2 -C(R a1 ) (R a2 )(R a3 ) includes the following rings. The non-aromatic hydrocarbon ring is preferably It has 3 to 12 carbon atoms. * indicates the bonding site with -O-. TIFF0007791275000012.tif30139

[0019] R a1’ , R a2’ and R a3’ The hydrocarbon group in the Examples of the alkyl group include a hydroxyl group, an aromatic hydrocarbon group, and a group formed by combining these groups. can be done. The alkyl group and the alicyclic hydrocarbon group are represented by R a1 , R a2 and R a3 The same groups as those listed in Examples include: Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples include aryl groups such as a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, alkyl groups Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups with alicyclic hydrocarbon groups (p-cyclohexane adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. An aryl-cycloalkyl group is exemplified. R a1’ and R a2’are bonded to each other and together with the carbon atoms to which they are bonded and X, When forming a ring, -C(R a1’ )(R a2’ )-XR a3’ Examples of rings include the following: * indicates a binding site. TIFF0007791275000013.tif19130R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0020] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and n A group where a=1. As the group, a tert-butoxycarbonyl group is preferred. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamannes Forms a methyl group, R a3 is an alkyl group, ma=0, and na=1. In formula (1), R a1 and R a2 are each independently an alkyl group, and R a3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following: * represents a binding site. TIFF0007791275000014.tif78168

[0021] Specific examples of group (2) include the following groups: * represents a bond. TIFF0007791275000015.tif68162

[0022] The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond. More preferably, it is a (meth)acrylic monomer having an acid labile group.

[0023] Among the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of the compound having a bulky structure such as an alicyclic hydrocarbon group include: A resin (A) having a structural unit derived from a monomer (a1) having the above structure is used in a resist composition. This can improve the resolution of the resist pattern.

[0024] As a structural unit derived from a (meth)acrylic monomer having the group (1), 0) (hereinafter, may be referred to as structural unit (a1-0)), -1) (hereinafter, may be referred to as structural unit (a1-1)) or a structural unit represented by the formula ( a1-2) (hereinafter, sometimes referred to as structural unit (a1-2)) Preferably, the structural unit (a1-1) is selected from the group consisting of the structural unit (a1-2): These may be used alone or in combination of two or more. They may be used in combination. TIFF0007791275000016.tif43141 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or * -O-(CH2) k1 - represents CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. vinegar. R a01 , R a4 and R a5each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 are each independently an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups or groups combining these groups. R a6 and R a7 are each independently an alkyl group having 1 to 8 carbon atoms, a It represents an alicyclic hydrocarbon group or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0025] R a01 , R a4 and R a5 is preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or —O—(CH2) k01 -C OO- (wherein k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 alkyl groups, alicyclic hydrocarbon groups, and As a group combining these, R in formula (1) a1 , R a2 and R a3 Similar to the groups listed in Examples include groups. R a02 , R a03 , and R a04 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. A group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. do. R a6 and R a7 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, it is a methyl group, an ethyl group, or an isopropyl group, and even more preferably, it is an ethyl group. The alkyl group is an isopropyl group or an isopropyl group. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably It is 5 to 12, and more preferably 5 to 10. The group in which an alkyl group and an alicyclic hydrocarbon group are combined is The total number of carbon atoms in combination with the group is preferably 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl The alkyl group is an alkyl group or an ethyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. be. R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group. , an ethyl group, or an isopropyl group, and more preferably an ethyl group or an isopropyl group. be. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0026] Examples of the structural unit (a1-0) include those represented by the formulae (a1-0-1) to (a1-0-12): and R in the structural unit (a1-0) a01 Methionine equivalent The structural units of the formula (a1-0-1) to the formula (a1-0) are exemplified by those in which a methyl group is replaced with a hydrogen atom. -10) is preferred. TIFF0007791275000017.tif65159

[0027] Examples of the structural unit (a1-1) include those described in JP-A-2010-204646. Among them, structural units derived from the monomers of formula (a1-1-1) to formula (a1 -1-4) and R in the structural unit (a1-1) a4 In accordance with Structural units in which the corresponding methyl group is replaced with a hydrogen atom are preferred, and those represented by the formulae (a1-1-1) to (a1-1-2) are A structural unit represented by any one of (a1-1-4) is more preferred. JPEG0007791275000018.jpg39107

[0028] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to formula (a1-2-6). and R in the structural unit (a1-2) a5 The methyl group corresponding to Examples of structural units in which atoms are replaced include those represented by formula (a1-2-2), formula (a1-2-5), and A structural unit represented by any one of the formulas (a1-2-6) is preferred. TIFF0007791275000019.tif31142

[0029] When the resin (A) contains the structural unit (a1-0), its content is determined based on the total structural units of the resin (A). It is usually 5 to 60 mol %, preferably 5 to 50 mol %, more preferably The content is usually 10 to 40 mol %. When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), The total content of these is usually 10 to 95 mol % based on the total structural units of the resin (A), and preferably It is preferably 15 to 90 mol %, more preferably 20 to 85 mol %, and even more preferably Preferably, it is 25 to 80 mol %, and even more preferably, it is 30 to 75 mol %.

[0030] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of such structural units include those (hereinafter, may be referred to as "structural unit (a1-4)"). TIFF0007791275000020.tif4070[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1 group optionally having a halogen atom Represents an alkyl group of 1 to 6. R a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of R a33 are mutual may be the same or different. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH2- contained in the alkyl group and the divalent hydrocarbon group is replaced by -O- or -S-. That's fine.]

[0031] R a32 and R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an iso ... Examples of the alkyl group include a propyl group, a butyl group, a pentyl group, and a hexyl group. An alkyl group having 1 to 4 prime numbers is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even more preferable. R a32 and R a33 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl. ethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoromethyl group perfluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group propyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluoropropyl group butyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluorobutyl group 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, Examples of the alkyl group include an ethyl group, a hexyl group, and a perfluorohexyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. Among them, alkoxy groups having 1 to 4 carbon atoms are particularly preferred. A methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. . Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a bromide group, and a bromine group. Examples thereof include a thyryloxy group. R a34 , R a35 and R a36 The hydrocarbon group in the formula (I) may be an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups combining these. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a methyl group. Examples include a sil group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the cyclopentyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, butyl group, adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include: TIFF0007791275000021.tif10151Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples include aryl groups such as a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, alkyl groups Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups with alicyclic hydrocarbon groups (p-cyclohexane adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36As for carbon number 1 to 18, alkyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Examples of groups include groups formed by combining these.

[0032] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred, and a methoxy group and an ethoxy group are also preferred. is more preferred, and a methoxy group is even more preferred. la is preferably 0 or 1, and more preferably 0. R a34 is preferably a hydrogen atom. R a35 is preferably an alkyl group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms, more preferably More preferably, it is a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, a Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is a group formed by an alkyl group having 1 to 18 carbon atoms, a group formed by an alkyl group having 3 to 1 carbon atoms, R is an alicyclic aliphatic hydrocarbon group having 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. a36 in The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 Fragrance in The aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0033] -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid), it is eliminated to form a hydroxy group.

[0034] Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a1-4-1) to formula (a1-4-2) are preferred. -4-12) and R in the structural unit (a1-4) a32 In accordance with A structural unit in which the corresponding hydrogen atom is replaced by a methyl group is preferred, and a structural unit represented by the formula (a 1-4-1) to (a1-4-5), and structural units represented by formula (a1-4-10) Examples include: TIFF0007791275000022.tif68157

[0035] When the resin (A) contains the structural unit (a1-4), the content thereof is determined based on the total structure of the resin (A). It is preferably 10 to 95 mol %, more preferably 15 to 90 mol %, based on the total of the units. It is more preferable that the content is 20 to 85 mol %, and even more preferable that the content is 20 to 70 mol %. It is even more preferable that the content is 20 to 60 mol %, and it is particularly preferable that the content is 20 to 60 mol %.

[0036] The structural unit derived from a (meth)acrylic monomer having the group (2) includes a structural unit represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can be. TIFF0007791275000023.tif3849 formula (a1-5), R a8 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. represents a halogen atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, and h3 is 1 to 4 represents an integer, and * represents L 51 Represents a bond with . L51 , 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.

[0037] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, and an ethyl group. group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoro group Examples of such groups include a trifluoromethyl group and a trifluoromethyl group. In formula (a1-5), R a8 is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 is preferably an oxygen atom. L 52 and L 53 Among these, it is preferred that one is —O— and the other is —S—. s1 is preferably 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or —CH2—CO—O—.

[0038] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers of formula (a1-5-1) to formula (a1-5- 4), and the structural units represented by formula (a1-5-1) or formula (a1-5-2) are preferred. ) is more preferred. TIFF0007791275000024.tif33135

[0039] When the resin (A) contains the structural unit (a1-5), the content thereof is determined based on the total structure of the resin (A). The content is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %, based on the unit. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0040] Further, examples of the structural unit (a1) include the following structural units. TIFF0007791275000025.tif31162

[0041] When the resin (A) contains structural units such as those of the formulae (a1-3-1) to (a1-3-7), In this case, the content thereof is preferably 10 to 95 mol % based on the total structural units of the resin (A), and 5 to 90 mol% is more preferable, 20 to 85 mol% is even more preferable, and 20 to 70 mol% is still more preferable. is even more preferable, and 20 to 60 mol % is particularly preferable.

[0042] Resin (A) is a copolymer consisting of only structural units (a2-A) and structural units (a1). or may contain one or more structural units other than the structural unit (a2-A) and the structural unit (a1). The structural unit other than the structural unit (a2-A) and the structural unit (a1) may be a copolymer. The structural unit may be a structural unit having a halogen atom other than a structural unit having an acid labile group. structural unit (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit not having an acid labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit having a non-leaving hydrocarbon group (hereinafter (hereinafter sometimes referred to as "structural unit (a5)"), a structural unit that decomposes upon exposure to generate acid (hereinafter sometimes referred to as "structural unit (II)"), and other monomers known in the art. Examples include structural units derived from When the resin (A) contains a structural unit represented by the formula (a4) and / or (a5) described below ( Hereinafter, this may be referred to as "resin (AX)"). The content of I) is preferably 5 to 75% by weight based on the total amount of all structural units of the resin (X) of the present invention. % by mole, more preferably 10 to 70 mol %, and further preferably 10 to 65 mol %. % by mole, and particularly preferably 10 to 60 mol %.

[0043] <Structural unit(s)> The structural unit (s) is a monomer that does not have an acid labile group (hereinafter referred to as "monomer (s)"). The monomer from which the structural unit (s) is derived is an acid-inhibiting monomer known in the resist field. Monomers without stabilizing groups can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. A structural unit having an oxy group and not having an acid labile group (hereinafter referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid labile group (hereinafter referred to as "structural unit"). When a resin having the structural unit (a3) ​​is used in the resist composition of the present invention, This can improve the resolution of the resist pattern and the adhesion to the substrate.

[0044] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may also be a hydroxyl group. When a resist pattern is produced from the resist composition of the present invention, KrF is used as the exposure light source. High energy rays such as excimer laser (248 nm), electron beam, or EUV (extreme ultraviolet) are used. In this case, the structural unit (a2) may be a structural unit having a phenolic hydroxy group ( It is preferable to use a2). In addition, it is also preferable to use an ArF excimer laser (193 nm) or the like. In this case, the structural unit (a2) may be a structural unit (a2) having an alcoholic hydroxy group. ) is preferred, and it is more preferred to use the structural unit (a2-1) described below. As a2), one kind may be contained alone, or two or more kinds may be contained.

[0045] The structural unit (a2) having an alcoholic hydroxy group includes a structural unit represented by the formula ( a2-1) (hereinafter referred to as "structural unit (a2-1)") Examples include: TIFF0007791275000026.tif4057 formula (a2-1), L a3 is -O- or * -O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents a bond to —CO—. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer of 0 to 10.

[0046] In equation (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0047] Examples of the structural unit (a2-1) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a2-1-1) to formula (a2-1-6) are examples. ) is preferred, and a structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) The structural unit represented by formula (a2-1-1) or formula (a2-1- The structural unit represented by 3) is more preferred. TIFF0007791275000027.tif54149

[0048] When the resin (A) contains the structural unit (a2-1), its content is determined based on the total amount of all structural units in the resin (A). It is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably It is preferably 1 to 35 mol %, more preferably 1 to 20 mol %, and even more preferably The content is usually 1 to 10 mol %.

[0049] <Structural unit (a3)> The lactone ring contained in the structural unit (a3) ​​is a β-propiolactone ring, a γ-butyrolactone ring, or It may be a monocyclic ring such as a lactone ring or a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring with another ring. Preferably, the ring is a γ-butyrolactone ring, an adamantane lactone ring, or a γ -Bridged ring containing a butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) Examples include:

[0050] The structural unit (a3) ​​is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or a structural unit represented by formula (a3-4). One of these may be contained alone, Two or more types may be contained. TIFF0007791275000028.tif51160 [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 1 to 7). L a7 -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- vinegar. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or represents a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 are each independently a carboxy group, a cyano group or a carbon atom. It represents an aliphatic hydrocarbon group having 1 to 4 prime numbers. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , Ra22 , R a2 3 and / or R a25 may be the same or different.]

[0051] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in butyl, sec-butyl and tert-butyl groups. Examples include alkyl groups such as t-butyl groups. R a24 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine. Examples include atoms. R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Preferably, the alkyl group has 1 to 4 carbon atoms, and more preferably, the methyl group. or an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group Examples include a methyl group and a triiodomethyl group.

[0052] L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane group, or a methyl group. Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pe hexane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentaerythritol Examples include 2-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

[0053] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferred or -O- or *-O-(CH2) k3 In -CO-O-, k3 is any of 1 to 4 groups each of which is an integer, more preferably -O- and *-O-CH2-CO-O-, and An oxygen atom is preferred. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group or a methyl group. It is a methyl group. p1, q1, and r1 each independently represent an integer of preferably 0 to 2, More preferably, it is 0 or 1.

[0054] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a It is a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably -O- or *-OL a8 -CO-O-, more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF0007791275000029.tif4326 (in the formula, R a24 , L a7 has the same meaning as above.)

[0055] The structural unit (a3) ​​may be a monomer described in JP-A-2010-204646. , the monomers described in JP-A-2000-122294, and JP-A-2012-41274 Examples of the structural unit (a3) ​​include structural units derived from the monomers described in the above publication. , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-1 2), and in the structural unit, the structural unit represented by formula (a3-1) to formula (a3-2) R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to Structural units that replace elementary atoms are preferred.

[0056] TIFF0007791275000030.tif115165

[0057] When the resin (A) contains the structural unit (a3), the total content of the structural unit (a3) ​​is the total content of all structural units of the resin (A). It is usually 5 to 70 mol %, preferably 10 to 65 mol %, more preferably The content is preferably 10 to 60 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) The content of the units (a3-4) is 5 to 60 moles per total structural units of the resin (A). % by mole, more preferably 5 to 50 mol %, and even more preferably 10 to 50 mol %.

[0058] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF0007791275000031.tif3169[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, The —CH2— contained in the group may be replaced with —O— or —CO—. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain hydrocarbon group and a monocyclic or polycyclic alicyclic hydrocarbon group. groups, and groups formed by combining these groups.

[0059] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include decyl, heptadecyl, and octadecyl groups. The hydrogen group includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and cycloalkyl groups such as methyl group; decahydronaphthyl group, adamantyl group, norbornyl group and polycyclic and alicyclic hydrocarbon groups such as the following groups (* represents a bond): TIFF0007791275000032.tif11158 The group formed by the combination may include one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0060] The structural unit (a4) includes the formula (a4-0), the formula (a4-1), the formula (a4-2), the formula (a4-3), the formula (a4-4), the formula (a4-5), the formula (a4-6), the formula (a4-7), the formula (a4-8), the formula (a4-9), the formula (a4-10), the formula (a4-11), the formula (a4-12), the formula (a4-13), the formula ( a4-3) and a structure represented by at least one selected from the group consisting of formula (a4-4) Units include: TIFF0007791275000033.tif4552[In formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. represents a fluorocycloalkanediyl group. R 64 represents a hydrogen atom or a fluorine atom.

[0061] L 4a The alkanediyl group in the formula (I) includes a methylene group, an ethylene group, a propane-1, linear alkanediyl groups such as butane-1,3-diyl and butane-1,4-diyl; -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane Branched alkanes such as pan-1,3-diyl and 2-methylpropane-1,2-diyl groups An example is a diyl group.

[0062] L 3a The perfluoroalkanediyl group in Fluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane- 1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane- 2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2, 2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5 -diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3 -diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2 -diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4 -diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8 -diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3 -diyl group, perfluorooctane-4,4-diyl group, and the like. L 3a The perfluorocycloalkanediyl group in perfluorocyclopentanediyl group, perfluorocycloheptanediyl group yl group, perfluoroadamantanediyl group, and the like.

[0063] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond, bond, a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably or a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0064] The structural unit (a4-0) may be the following structural unit or a structural unit ( a4-0) in R 54 The structural unit in which the methyl group corresponding to can be. TIFF0007791275000034.tif95166

[0065] TIFF0007791275000035.tif4466[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, or a group represented by the formula (ag 1), where A a41 and R a42 At least one of the The group has a halogen atom (preferably a fluorine atom). TIFF0007791275000036.tif20123 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 are each independently a divalent group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 is a single bond or a divalent aliphatic hydrocarbon having 1 to 5 carbon atoms which may have a substituent. Represents a group. X a41 and X a42 are each independently -O-, -CO-, -CO-O- or -O-CO - represents. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * is a bond, and the * on the right is -O-CO-R a42 It is a combination with .]

[0066] R a42 The saturated hydrocarbon group in the formula (I) includes a chain hydrocarbon group and a monocyclic or polycyclic alicyclic hydrocarbon group. Examples of the groups include hydride groups, and groups formed by combining these groups.

[0067] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include decyl, heptadecyl, and octadecyl groups. The hydrogen group includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and cycloalkyl groups such as methyl group; decahydronaphthyl group, adamantyl group, norbornyl group and polycyclic and alicyclic hydrocarbon groups such as the following groups (* represents a bond): TIFF0007791275000037.tif11158 The group formed by the combination may include one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0068] R a42 The substituents of the formula (a-g3) include halogen atoms and groups represented by the formula (a-g3). The halogen atom may be at least one selected from the group consisting of fluorine atom, Examples include a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom. TIFF0007791275000038.tif965[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . * denotes R a42 represents a bond with .] However, R a42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a4 5 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom .

[0069] A a45 The aliphatic hydrocarbon group in group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, penta Alkyl groups such as decyl, hexadecyl, heptadecyl and octadecyl groups; cyclo Monocyclic alicyclic groups such as pentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups hydrocarbon groups of the formula: and decahydronaphthyl, adamantyl, norbornyl, and the following groups: and polycyclic alicyclic hydrocarbon groups such as the group (where * represents a bond). TIFF0007791275000039.tif11158 The group formed by the combination may include one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0070] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and / or a saturated hydrocarbon group having a group represented by formula (a-g3) More preferable. R a42When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom. It is preferably a saturated hydrocarbon group having a fluorocarbon group, more preferably a perfluoroalkyl group or a perfluorosilyl group. Preferably, the alkyl group is a chloroalkyl group, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the fluoro groups include perfluoromethyl, perfluoroethyl, and perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples of perfluorocycloalkyl groups include perfluoroheptyl and perfluorooctyl groups. Examples of the cyclohexyl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3) and the number of carbon atoms contained in the group represented by R a42 The total number of carbon atoms is preferably 15 or less. When the alkyl group has a group represented by formula (a-g3) as a substituent, The number is preferably one.

[0071] R a42 is a saturated hydrocarbon having a group represented by formula (a-g3), R a42 Ha, further Of these, a group represented by formula (a-g2) is preferred. TIFF0007791275000040.tif879[In formula (a-g2), A a46 represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. Represents. X a44 represents **-O-CO- or **-CO-O- (** represents A a46 Shows the bond with vinegar.). A a47represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 of At least one of them has at least one halogen atom. * indicates a bond to the carbonyl group.

[0072] A a46 The aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. A a47 The aliphatic hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0073] A preferred structure of the group represented by formula (a-g2) is the following structure (* indicates a carbonyl group): (It is a combination with ). TIFF0007791275000041.tif14160

[0074] A a41 The alkanediyl group in the formula (I) includes a methylene group, an ethylene group, a propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 linear alkanediyl groups such as propane-1,2-diyl, butane-1,6-diyl; ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- and branched alkanediyl groups such as 2-methylbutane-1,4-diyl and 2-methylbutane-1,4-diyl. do. A a41 The substituents in the alkanediyl group represented by the formula (I) include a hydroxy group and an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkoxy group include alkoxy groups of formula 6. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably It is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

[0075] A in the group represented by formula (a-g1) a42 , A a43 and A a44 The bivalent saturated The saturated hydrocarbon group includes a linear or branched alkanediyl group and a monocyclic divalent saturated hydrocarbon group. By combining a hydroxyl group with an alkanediyl group and a divalent saturated alicyclic hydrocarbon group, Specifically, a methylene group, an ethylene group, a divalent saturated hydrocarbon group formed by propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group yl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group group, and 2-methylpropane-1,2-diyl group. A a42 , A a43 and A a44 The substituent of the divalent saturated hydrocarbon group represented by is hydroxyl. Examples of the alkoxy group include an alkoxy group and an alkoxy group having 1 to 6 carbon atoms. Preferably, s is 0.

[0076] In the group represented by formula (a-g1), X a42 is -O-, -CO-, -CO-O- or Examples of the -O-CO- group include the following groups: ** indicates the binding site, and ** indicates -O-CO-R a42 This is the binding site for TIFF0007791275000042.tif51161

[0077] The structural unit represented by formula (a4-1) includes the following structural units and R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to Examples of structural units that have been replaced include: TIFF0007791275000043.tif104151

[0078] TIFF0007791275000044.tif135152

[0079] The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2). I wish. TIFF0007791275000045.tif4371[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and —C H2- may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The maximum total carbon number is 21.]

[0080] L 44 The alkanediyl group having 1 to 6 carbon atoms is A a41 The same groups as those exemplified in can be. R f6 The saturated hydrocarbon group of R a42 Examples of the groups include the same groups as those exemplified in L 44 The alkanediyl group having 1 to 6 carbon atoms is preferably an alkanediyl group having 2 to 4 carbon atoms. A methyl group is preferred, and an ethylene group is more preferred.

[0081] Examples of the structural unit represented by formula (a4-2) include those represented by formula (a4-1-1) to formula (a4 -1-11) are structural units represented by the structural unit (a4-2). R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It is one of the structural units.

[0082] TIFF0007791275000046.tif5672[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. vinegar. X f12 represents *-O-CO- or *-CO-O- (* represents A f13 ) . A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may contain a fluorine atom. However, A f13 and A f14 At least one of L has a fluorine atom, 5 , A f13 and A f14 The total number of carbon atoms in a molecule is limited to 20.

[0083] L 5 The alkanediyl group in a41 The alkanediyl group in The same groups as those mentioned above are exemplified.

[0084] A f13 The divalent saturated hydrocarbon group optionally having a fluorine atom in or a divalent aliphatic saturated hydrocarbon group which may have a fluorine atom and a It is a divalent alicyclic saturated hydrocarbon group which may be present, and more preferably a perfluoroalkanedi group. It is a yl group. The divalent aliphatic hydrocarbon group which may have a fluorine atom includes a methylene group, an ethylene group, alkanediyl groups such as an alkanediyl group, a propanediyl group, a butanediyl group, and a pentanediyl group; Difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, per Perfluoroalkanediyl groups such as fluorobutanediyl and perfluoropentanediyl groups Examples of the aryl group include aryl groups. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexyl group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and the like. diyl group, perfluoroadamantanediyl group, and the like.

[0085] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 in The same groups as those exemplified above can be mentioned. Among them, trifluoromethyl group, difluoromethyl group, ethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorohexyl group. Fluorinated alkyl groups such as fluorooctyl groups, cyclopropylmethyl groups, cyclopropyl groups , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantine A methyl group is preferred.

[0086] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group is a chain hydrocarbon group having 1 to 6 carbon atoms and a chain hydrocarbon group having 3 to 12 carbon atoms. A group containing an alicyclic hydrocarbon group such as the above is preferred, and a chain hydrocarbon group having 2 to 3 carbon atoms is more preferred. stomach. A f14 The saturated hydrocarbon group is a chain hydrocarbon group having 3 to 12 carbon atoms and an aliphatic hydrocarbon group having 3 to 12 carbon atoms. Groups containing cyclic hydrocarbon groups are preferred, and chain hydrocarbon groups having 3 to 10 carbon atoms and groups having 3 to 1 carbon atoms are also preferred. A group containing an alicyclic hydrocarbon group of A is more preferred. f14 is preferably carbon It is a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably, cyclopropylmethyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups.

[0087] Examples of the structural unit represented by formula (a4-3) include those represented by formula (a4-1'-1) to formula (a 4-1'-11) are structural units represented by the following formulas. KerR f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-3). It is one of the structural units that can be mentioned.

[0088] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF0007791275000047.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -or-(CH2) j4 - CO-O-(CH2) j5 - represents. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0089] R f22 The saturated hydrocarbon group of R a42 The saturated hydrocarbon group may be the same as the saturated hydrocarbon group represented by the following formula: R f22 represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or a carbon atom having a fluorine atom An alicyclic hydrocarbon group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms and a fluorine atom is preferred. A fluorine atom-containing alkyl group having 1 to 6 carbon atoms is more preferred.

[0090] In formula (a4-4), A f21 As -(CH2) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0091] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by R in the structural unit (a4-4) f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced. TIFF0007791275000048.tif80147

[0092] When the resin (A) has the structural unit (a4), its content is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and more preferably 3 to 10 mol % is more preferred.

[0093] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) may be a straight-chain, branched or cyclic hydrocarbon group. Among these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The group is preferred. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1): . JPEG0007791275000049.jpg3563 [In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in the alicyclic hydrocarbon group The atom may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The —CH2— contained in the formula may be replaced with —O— or —CO—.

[0094] R 52 The alicyclic hydrocarbon group in may be either a monocyclic or polycyclic group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclopentyl group. Examples of the polycyclic alicyclic hydrocarbon group include: , adamantyl group, and norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an isopropyl group. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group Examples of alkyl groups include an octyl group and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. do. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably Examples thereof include an adamantyl group, a norbornyl group, and a cyclohexyl group.

[0095] L 55 The divalent saturated hydrocarbon group in the above is a divalent chain saturated hydrocarbon group and a divalent fatty acid group. Examples include cyclic saturated hydrocarbon groups, and preferably divalent chain saturated hydrocarbon groups. Examples of the divalent chain saturated hydrocarbon group include a methylene group, an ethylene group, and a propanediol group. alkanediyl groups such as butanediyl, pentanediyl, and the like. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adatom group. Examples include a mantanediyl group and a norbornanediyl group.

[0096] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * represents a bond to an oxygen atom. TIFF0007791275000050.tif17155 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1) . L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 are each independently a single bond or a divalent aliphatic saturated carbon atom having 1 to 14 carbon atoms. Represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less. L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a methylene group or an ethylene group. L x2is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond. L x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a methylene group or an ethylene group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably , a cyclohexanediyl group, or an adamantanediyl group.

[0097] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF0007791275000051.tif53136

[0098] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF0007791275000052.tif23130

[0099] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF0007791275000053.tif17154

[0100] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF0007791275000054.tif29130

[0101] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0102] The structural unit (a5-1) includes the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to can be. JPEG0007791275000055.jpg115158 When the resin (A) has the structural unit (a5), its content is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and more preferably 3 to 15 mol % is more preferred.

[0103] <Structural unit (II)> The resin (A) further contains a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit”). The structural unit (II) may include, for example, Examples of the structural units include those described in JP-A-2016-79235, and those having a sulfonyl group in the side chain. A structural unit having a carboxylate group or a carboxylate group and an organic cation, or a sulfonate group in a side chain A structural unit having an aryl group and an organic anion is preferred.

[0104] A structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007791275000056.tif3089 [In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- contained in the saturated carbon may be replaced by -O-, -S- or -CO-. The hydrogen atom contained in the hydrogen hydride group is a halogen atom, a carbon number which may have a halogen atom It may be substituted with 1 to 6 alkyl groups or hydroxy groups. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the water contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. stomach. RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a group having 1 carbon atom which may have a halogen atom Represents an alkyl group of 1 to 6. ZA + represents an organic cation.

[0105] R III3 The halogen atom represented by the formula (I) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples include uran atoms. R III3 The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom is represented by the formula: R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by Examples include the same things. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, and the like. , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples thereof include a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. do. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include trifluoroalkyl groups. Fluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroiso Propyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group Examples of the alkyl group include a perfluoropentyl group, a perfluorohexyl group, and the like.

[0106] X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched hydrocarbon group. and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. It may be a combination of the above. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group linear alkanediyl groups such as decane-1,12-diyl; butane-1,3-diyl; 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentaerythritol Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohetane-1,3-diyl group, Cycloalkanediyl groups such as cyclohexan-1,4-diyl group and cyclooctane-1,5-diyl group norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane Divalent polycyclic saturated hydrocarbons such as benzophenone-1,5-diyl group and adamantane-2,6-diyl group groups, etc.

[0107] -CH2- in saturated hydrocarbon groups is replaced with -O-, -S- or -CO- Examples of the divalent groups include those represented by the formulae (X1) to (X53). The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-. The number of carbon atoms in each of the preceding groups is 17 or less. In the following formula, * and ** represent binding sites. * is A x1 Represents a bond with . TIFF0007791275000057.tif145161

[0108] 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.

[0109] ZA + The organic cation represented by the formula (B1) below is a cation represented by the formula (B2) below. The same as thione can be mentioned.

[0110] The structural unit represented by formula (II-2-A') is a structural unit represented by formula (II-2-A) It is preferable that: JPEG0007791275000058.jpg38108 [In formula (II-2-A), R III3 , X III3 and ZA + has the same meaning as above. zx represents an integer of 0 to 6. R III2 and R III4 are each independently a hydrogen atom, a fluorine atom, or a group having 1 carbon atom represents a perfluoroalkyl group having a number of 1 to 6, and when zx is 2 or more, multiple R III2 and R I II4 may be the same as or different from each other. Q a and Q b are each independently a fluorine atom or a perfluoroalkane having 1 to 6 carbon atoms. represents a alkyl group.]

[0111] R III2 , R III4 , Q a and Q b Perfluoroalkyl groups having 1 to 6 carbon atoms, represented by As the aryl group, the Q b1 The same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by Examples include:

[0112] The structural unit represented by formula (II-2-A) is a structural unit represented by formula (II-2-A-1). It is preferable that the position is . TIFF0007791275000059.tif6489 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b , zx and ZA+ has the same meaning as above Represents. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and the saturated hydrocarbon group -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon The hydrogen atoms contained in the alkyl group may be substituted with halogen atoms or hydroxy groups.

[0113] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula include a methyl group, an ethyl group, and , propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and and dodecyl groups. X I2 As the divalent saturated hydrocarbon group represented by X III3 Divalent saturated carbon represented by The same as the hydrogen chloride group can be mentioned.

[0114] The structural unit represented by formula (II-2-A) is represented by formula (II-2-A-2): Structural units are more preferred. TIFF0007791275000060.tif4577 [In formula (II-2-A-2), R III3 , R III5 and ZA + has the same meaning as above. mx and nx each independently represent 1 or 2.

[0115] Examples of the structural unit represented by formula (II-2-A') include the following structural units, R III3 The group corresponding to the methyl group is a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a halogen atom an alkyl group having 1 to 6 carbon atoms which may have one or more atoms (for example, a trifluoromethyl group, etc.); and structural units described in WO 2012 / 050015. ZA + represents an organic cation. TIFF0007791275000061.tif86163

[0116] The structural unit having a sulfonio group and an organic anion in the side chain is represented by formula (II-1-1): It is preferable that the structural unit is a structural unit that can be formed by the above-mentioned method. TIFF0007791275000062.tif3279 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 and R II3 are bonded to each other to form a ring with the sulfur atom to which they are attached. That's fine. R II4 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I) include a phenylene group. and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group and an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups formed by combining these groups. R II4Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodide atom. Examples include elementary atoms. R II4 As an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by is R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by Some examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated carbon atom having 1 to 18 carbon atoms. The -CH2- contained in the divalent saturated hydrocarbon group may be -O-, -S- or may be replaced by -CO-. Specifically, X III3 The number of carbon atoms is 1 to 1 Examples thereof include the same divalent saturated hydrocarbon groups as those of 8.

[0117] The structural unit containing a cation in formula (II-1-1) includes the structural units represented by the following formulas: BiR II4 The group corresponding to the methyl group in the formula (1) is a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. Examples include replaced structural units. TIFF0007791275000063.tif84130

[0118] A - Examples of the organic anion represented by the formula include a sulfonate anion, a sulfonylimide anion, and Examples include sulfonylmethide anions, carboxylic acid anions, and the like. - is expressed as The organic anion is preferably a sulfonate anion, and examples of the sulfonate anion include those described below. It is more preferable that the anion is an anion represented by formula (IA). The anion A in formula (I) is a methyl anion, a sulfonylmethide anion, and a carboxylate anion. I - The same can be mentioned.

[0119] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. JPEG0007791275000064.jpg161142

[0120] When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 30 mol %, based on the total structural units of the fat (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0121] The resin (A) may have structural units other than the above-mentioned structural units. The moieties include structural units known in the art.

[0122] The resin (A) is preferably a resin composed of the structural unit (a2-A) and the structural unit (a1). , that is, a copolymer of the monomer (a2-A) and the monomer (a1) and the structural unit (a2 -A) and the structural unit (a1) and the structural unit (s), that is, a resin comprising the monomer (a2 -A) and a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably a cyclohexyl group and a structural unit having a cyclopentyl group) The structural unit (a1) is preferably at least one selected from the group consisting of -1) and structural unit (a1-2) (preferably a cyclohexyl group and a cyclopentyl group) and more preferably, There are at least two types. The structural unit (s) is preferably selected from the group consisting of the structural unit (a2) and the structural unit (a3): The structural unit (a2) is preferably at least one selected from the structural unit (a2-1). The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), a structural unit represented by formula (a3 -2) and a structural unit represented by formula (a3-4), At least one of these is

[0123] The structural units constituting the resin (A) may be used singly or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (for example, radical polymerization methods). The content of each structural unit contained in the resin (A) can be determined by the following procedure. It can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more). 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 In this specification, the weight average molecular weight is 1,000 or less, and more preferably 15,000 or less. The molecular weight is determined by gel permeation chromatography under the conditions described in the examples. is.

[0124] <Resins other than Resin (A)> The resist composition of the present invention may contain a resin other than the resin (A) in combination. Examples of resins other than the resin (A) include those containing the structural unit (a4) or the structural unit (a5). a resin (hereinafter sometimes referred to as resin (X)) having a structural unit represented by formula (a2-A): and a resin containing a structural unit having an acid labile group (hereinafter referred to as resin (AY) (There are some examples.) As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In resin (X), the content of structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. The structural units that the resin (X) and the resin (AY) may further have include the structural unit ( a1), structural unit (a2), structural unit (a3) ​​and structures derived from other known monomers Among them, the resin (X) contains the structural unit (a4) and / or the structural unit (a It is preferable that the resin consists of only 5). The structural units constituting the resin (X) and the resin (AY) may be of one type or a combination of two or more types. The monomers from which these structural units are derived may be used in the form of a copolymer, and the copolymer may be polymerized by a known polymerization method (e.g., polymerization of a copolymer). The content of each structural unit in resin (X) is can be adjusted by the amount of monomer used in the polymerization. The weight average molecular weight of the resin (X) and the resin (AY) is preferably 6, 000 or more (more preferably 7,000 or more), 80,000 or less (more preferably 60 The weight average molecular weight of the resin (X) and the resin (AY) is measured by The same as in the case of fat (A). When the resist composition of the present invention contains resin (AY), the content thereof is 10% by weight of resin (A). 0 parts by mass, usually 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) is. Furthermore, when the resist composition contains resin (X), the content of resin (X) is 100 mass % of resin (A). parts, preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, It is more preferably 1 to 40 parts by mass, and particularly preferably 1 to 30 parts by mass. The amount is preferably 1 to 8 parts by mass.

[0125] The content of resin (A) in the resist composition is 8% by weight based on the solid content of the resist composition. It is preferably 0% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. In addition, when a resin other than the resin (A) is contained, the resin (A) and the resin other than the resin (A) are preferably mixed. The total content of the resin is 80% by mass or more and 99% by mass or less of the solid content of the resist composition. The content is preferably 90% by mass or more and more preferably 99% by mass or less. The solid content of the product and the resin content relative to it are measured by liquid chromatography or gas chromatography. It can be measured by known analytical means such as graphy.

[0126] <Salt represented by formula (I)> The resist composition of the present invention contains a salt represented by formula (I) (hereinafter, sometimes referred to as "salt (I)"). containing In salt (I), the side with a negative charge is called an anion (I), and the side with a positive charge is called a cationic It is sometimes called "On(I)". TIFF0007791275000065.tif5192 [wherein all symbols have the same meanings as defined above.]

[0127] R 1a , R 1b , R 2a and R 2b The hydrocarbon group may be a chain hydrocarbon such as an alkyl group. Aromatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof Examples of such groups include: Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 12 carbon atoms. Preferably, it is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. It is even more preferably 1 to 2. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spirocyclic groups, and may be saturated or unsaturated. The alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, ... Cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group group, monocyclic cycloalkyl groups such as cyclododecyl group, norbornyl group, adamantyl group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 100. It is preferably 18, more preferably 3 to 16, and even more preferably 3 to 12. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. The number of carbon atoms in the group is preferably 6 to 18, more preferably 6 to 14, and even more preferably Usually it is 6 to 10. Examples of groups formed by combining these include cyclopentylmethyl. adamantylmethyl group, etc., which are a combination of an alicyclic hydrocarbon group and a chain hydrocarbon group Aromatic hydrocarbon groups and chain hydrocarbon groups such as aryl groups, benzyl groups, and phenethyl groups are combined. Examples include groups such as In the case of a group formed by combining the above groups, groups with different valences (2 containing valent or trivalent groups (chain hydrocarbon groups, alicyclic saturated hydrocarbon groups, aromatic hydrocarbon groups, etc.) It may be included. R 1a , R 2a , R 1b and R 2b a hydrocarbon group represented by R 1a and R 2a , R 1b and R 2b , R 1a and R2a and R 3a or R 1b and R 2b and R 3b are bonded together to form -CH2- in the ring is replaced by -O-, -S-, -CO- or -SO2- In this case, the number of carbon atoms before substitution is the total number of carbon atoms in the hydrocarbon group or ring. 1a and R 2a , R 1a and R 2a and R 3a , R 1b and R 2b or R 1b and R 2b and R 3b and When the ring formed by bonding to each other has an alkyl group, the number of carbon atoms excluding the number of carbon atoms of the alkyl group is The prime number is the total number of carbon atoms in the ring. R 1a , R 2a , R 1b or R 2b When is a hydrocarbon group, the number of carbon atoms in the hydrocarbon group is and each independently is preferably 1 to 18, more preferably 1 to 14. More preferably, R is 1 to 12. 1a and R 2a , R 1b and R 2b , R 1a and R 2a and R 3a or R 1b and R 2b and R 3b When they are bonded to each other to form a ring, the carbon atoms of the ring The prime numbers are each independently preferably 3 to 24, and more preferably 3 to 18. It is preferable that the number of carbon atoms is 3 to 16, and more preferable that the number of carbon atoms is 3 to 16. R 1a and R 2a , R 1a and R 2a and R 3a , R 1b and R 2bor R 1b and R 2b and R 3 b and may be bonded to each other to form a ring, the alkyl group that may be included therein is, for example, the above-mentioned Similar groups are mentioned.

[0128] Examples of alkyl groups in which -CH2- is replaced with -O- or -CO- include: Hydroxy group (a group in which -CH2- in a methyl group is replaced with -O-), carbo an oxy group (an ethyl group in which -CH2-CH2- is replaced with -O-CO-); Alkoxy group having 1 to 11 carbon atoms (-CH2- contained in alkyl group having 2 to 12 carbon atoms) , -O- substituted), alkoxycarbonyl group having 2 to 11 carbon atoms (groups having 3 to 1 (a group in which -CH2-CH2- in the alkyl group of 2 is replaced with -O-CO-), Alkylcarbonyl groups with 2 to 12 carbon atoms (-CH contained in alkyl groups with 2 to 12 carbon atoms) 2- is replaced by -CO-), alkylcarbonyloxy group having 2 to 11 carbon atoms ( -CH2-CH2- in the alkyl group having 3 to 12 carbon atoms is replaced with -CO-O- Examples include groups such as The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy Examples thereof include a siloxy group, a nonyloxy group, a decyloxy group, and an undecyloxy group. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group are A carbonyl group or a carbonyloxy group is bonded to the alkyl group or the alkoxy group. Represents a group. The alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group, a bromine group, a methyl ... Examples of the alkylcarbonyl group include an acetyl group, a propyl group, and the like. The alkylcarbonyloxy group includes acetyl, ... Examples thereof include an oxy group, a propionyloxy group, and a butyryloxy group.

[0129] R 1a and R 2a , R 1a and R 2a and R 3a , R 1b and R 2b or R 1b and R 2b and R 3 b and bond to each other to form a ring, -C(R 1a )(R 2a )(R 3a ) or -C (R 1b )(R 2b )(R 3b ) includes the following groups. * indicates a carbonyl group. Represents the bonding site with the carbon atom. TIFF0007791275000066.tif86163R 1a , R 2a , R 1b and R 2b are each independently a hydrogen atom or a fluorine atom. A hydrocarbon group having 1 to 14 carbon atoms which may have a substituent (-CH2- contained in the hydrocarbon group is -O-, -S-, -CO- or -SO2- may be substituted, or R 1 a and R 2a , R 1b and R 2b and are bonded to each other, and are each a fluorine atom or an alkyl group having 1 to 12 carbon atoms. a ring having 3 to 24 carbon atoms which may have a methyl group (the —CH2— contained in the alkyl group is —O— or -CO-, and -CH2- contained in the ring may be replaced by -O-, -S- , -CO- or -SO2- may be replaced by each independently being a hydrogen atom or a carbon atom having 1 to 12 carbon atoms which may have a fluorine atom; A hydrogen group (the -CH2- contained in the hydrocarbon group is -O-, -S-, -CO- or -SO2 - may be replaced by ) or R 1a and R 2a , R 1b and R 2b and each other a ring ( -CH2- contained in the alkyl group may be replaced with -O- or -CO-, -CH2- contained in the ring is replaced by -O-, -S-, -CO- or -SO2- It is more preferable to form Each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 12 carbon atoms, or a fluorine atom. an adamantyl group optionally having a nitrogen atom (the —CH— contained in the adamantyl group is —O -, -S-, -CO- or -SO2-) or a fluorine atom A spiro ring containing an adamantyl group (the adamantyl group and the spiro ring -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. or R 1a and R 2a , R 1b and R 2b and bonded to each other, and an adamantyl group optionally having up to 6 alkyl groups (wherein the —CH2— contained in the alkyl group is , -O- or -CO-, and -CH2 contained in the adamantyl group - may be replaced by -O-, -S-, -CO- or -SO2-), fluorine A spiro ring containing an adamantyl group which may have an atom or an alkyl group having 1 to 6 carbon atoms (the adamantyl group The —CH2— contained in the alkyl group may be replaced by —O— or —CO—, The damantyl group and the —CH2— contained in the spiro ring are each independently selected from —O—, —S—, —CO—, and — It is more preferable to form a cyclohexane-2-sulfonyl group, in which the cyclohexane-2-sulfonyl group may be replaced by SO2-. Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom an adamantyl group optionally having -CH2- in the adamantyl group; may be replaced by -S-, -CO- or -SO2-, or R 1a and R 2a , R 1b and R 2b and bonded to each other, and have a fluorine atom or an alkyl group having 1 to 6 carbon atoms. an adamantyl group (wherein the —CH2— contained in the alkyl group is substituted with —O— or —CO—) The —CH2— contained in the adamantyl group may be replaced by —O—, —S—, — It is even more preferable to form a methyl group. .

[0130] R 3a and R 3b are each independently a hydrogen atom or R 1a and R 2a and R 3a also is R 1b and R 2b and R 3b and are bonded to each other, and A ring having 3 to 24 carbon atoms which may have a group (-CH2- contained in the alkyl group is -O- or may be replaced by -CO-, and -CH2- contained in the ring may be replaced by -O-, -S-, It is preferable to form a cycloalkyl group, in which the cycloalkyl group may be replaced by —CO— or —SO—, hydrogen atom or R 1a and R 2a and R 3a or R 1b and R 2b and R 3b and are connected to each other a ring having 3 to 16 carbon atoms which may be bonded to a ring having 3 to 16 carbon atoms and which may have a fluorine atom or an alkyl group having 1 to 6 carbon atoms (the The —CH2— contained in the alkyl group may be replaced by —O— or —CO—. -CH2- in the ring is replaced by -O-, -S-, -CO- or -SO2-. It is more preferable to form hydrogen atom or R 1a and R 2a and R 3a or R 1b and R 2b and R 3b and are connected to each other an adamantyl group optionally having a fluorine atom or an alkyl group having 1 to 6 carbon atoms (the alkyl group The -CH2- contained in the alkyl group may be replaced by -O- or -CO-, and the -CH2- in the manthyl group is replaced by -O-, -S-, -CO- or -SO2-. adamantane which may have a fluorine atom or an alkyl group having 1 to 6 carbon atoms; Spiro ring containing a butyl group (-CH2- contained in the alkyl group is -O- or -CO-) The —CH2— contained in the adamantyl group and the spiro ring may be replaced by — may be replaced by -O-, -S-, -CO- or -SO2-. More preferably, hydrogen atom or R 1a and R 2a and R 3a or R 1b and R 2b and R 3b and are connected to each other an adamantyl group optionally having a fluorine atom or an alkyl group having 1 to 6 carbon atoms (the alkyl group The -CH2- contained in the alkyl group may be replaced by -O- or -CO-, and the -CH2- in the manthyl group is replaced by -O-, -S-, -CO- or -SO2-. It is even more preferable to form a

[0131] R 4 and R 5 The halogen atoms include fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms. Examples include children. R 4 and R 5 Examples of the fluorinated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a difluoromethyl group, Fluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group Perfluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octyl Perfluorobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5 fluorinated alkyl groups such as -nonafluoropentyl and perfluorohexyl groups; The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 4, more preferably 1 to 3. . R 4 and R 5 Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group Examples of alkyl groups include a silyl group, an octyl group, and a nonyl group. The number of carbon atoms in the alkyl group is preferably Preferably, it is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. R 4 and R 5 The -CH2- contained in the fluorinated alkyl group and the alkyl group represented by the formula When the fluorinated alkyl group is substituted with O- or -CO-, the number of carbon atoms before the substitution is and the total number of carbon atoms in the alkyl group. R 4 and R 5 The -CH2- contained in the alkyl group represented by the formula (I) is substituted with -O- or -CO-. The substituted group is a hydroxy group (-CH2- contained in a methyl group is replaced with -O-). carboxyl group (the -CH2-CH2- in the ethyl group is replaced by -O-CO -substituted), alkoxy groups having 1 to 11 carbon atoms (among alkyl groups having 2 to 12 carbon atoms (groups in which -CH2- in the above is replaced with -O-), alkoxycarbonyl groups having 2 to 11 carbon atoms A hydroxyl group (-CH2-CH2- contained in an alkyl group having 3 to 12 carbon atoms) is replaced with -O-CO- alkylcarbonyl groups having 2 to 12 carbon atoms (groups substituted with alkylcarbonyl groups having 2 to 12 carbon atoms) alkyl groups having 2 to 11 carbon atoms, a carbonyloxy group (-CH2-CH2- contained in an alkyl group having 3 to 12 carbon atoms) -CO-O- is substituted). R 4 and R 5 -CH2- contained in the fluorinated alkyl group represented by the formula: The group substituted with - includes a fluorinated alkoxy group having 1 to 5 carbon atoms (a fluorinated alkoxy group having 2 to 6 carbon atoms). a group in which -CH2- in a substituted alkyl group is replaced with -O-, a fluoroalkyl group having 2 to 5 carbon atoms Fluorinated alkoxycarbonyl group (-CH2- contained in fluorinated alkyl group having 3 to 6 carbon atoms) (a group in which -CH2- is replaced by -O-CO-), a fluorinated alkylcarbonyl group having 2 to 6 carbon atoms A fluoroalkyl group (a fluoroalkyl group having 2 to 6 carbon atoms in which -CH2- is replaced with -CO-) fluorinated alkylcarbonyloxy groups having 2 to 5 carbon atoms (fluorinated alkyl groups having 3 to 6 carbon atoms), (a group in which -CH2-CH2- in an alkyl group is replaced with -CO-O-) can be. Alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups and alkylcarbonyl groups Examples of the oxy group include the same groups as those mentioned above. Fluorinated alkoxy groups, fluorinated alkoxycarbonyl groups, fluorinated alkylcarbonyl groups, and The fluorinated alkylcarbonyloxy group is a group in which one or more hydrogen atoms of the groups exemplified above are substituted. It can be replaced with a fluorine atom. R 4 and R 5 is -O-CO-C(R 1a )(R 2a )(R 3a ) even if it is the same group They may be different groups. m4 and m5 each independently represent preferably 0, 1, 2 or 3, and more preferably 0, 1 or 2. is preferred, and 0 or 1 is more preferred. R 4 represents a fluorine atom, a fluorinated alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. (The -CH2- contained in the fluorinated alkyl group and the alkyl group is -O- or -CO-. It is preferable that the aryl group is substituted with aryl. R 5 is a fluorine atom, a fluorinated alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 6 carbon atoms ( The fluorinated alkyl group and the —CH2— contained in the alkyl group are replaced with —O— or —CO—. may be replaced) or -O-CO-C(R 1b )(R 2b )(R 3b ) is more preferred.

[0132] -O-CO-C(R 1a )(R 2a)(R 3a ) is the bond position of the iodine atom. The amino acid may be in any of the m-, p-, or p-positions, but the p-position is preferred. R 4 and R 5 The bonding position of the iodine atom can be either the o-position, m-position, or p-position. In particular, R 5 is the bond position of the iodine atom, -O-CO-C(R 1a )( R 2a )(R 3a ) is preferably bonded at the same position as

[0133] Examples of the cation (I) include the following cations: TIFF0007791275000067.tif168146

[0134] AI - Examples of the organic anion represented by the formula (I) include a sulfonate anion, a sulfonylimide anion, and the like. Examples include anion, sulfonylmethide anion, and carboxylic acid anion. - Represented by The organic anion is preferably a sulfonate anion, and the anion is represented by the formula (IA): It is more preferable that: TIFF0007791275000068.tif2965[In formula (IA), Q 1 and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents a methyl group. L 1 represents a saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH 2- may be replaced by -O- or -CO-, and the water contained in the saturated hydrocarbon group The hydrogen atom may be substituted with a fluorine atom or a hydroxy group. Y 1is a methyl group which may have a substituent or a methyl group having 3 to 4 carbon atoms which may have a substituent. 18 represents an alicyclic hydrocarbon group, and -CH2- contained in the alicyclic hydrocarbon group is -O-, may be replaced by -SO2- or -CO-.]

[0135] In formula (IA), -CH2- contained in the saturated hydrocarbon group is -O- or -C(=O )-, the number of carbon atoms before the substitution is the number of carbon atoms of the saturated hydrocarbon group. In addition, -CH2- contained in the alicyclic hydrocarbon group is -O-, -SO2- or -C(=O). When substituted with -, the number of carbon atoms before substitution is regarded as the number of carbon atoms of the alicyclic hydrocarbon group. .

[0136] Q 1 and Q 2 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, Perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group , perfluoropentyl group, and perfluorohexyl group. Q 1 and Q 2 are each independently a fluorine atom or a trifluoromethyl group. It is preferable that both are fluorine atoms.

[0137] L 1 The divalent saturated hydrocarbon group in and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A group formed by combining two or more of these may also be used. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- linear alkanediyl groups such as diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group branched alkanediyl groups such as 2-methylbutane-1,4-diyl groups; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa cycloalkanediyl groups such as cyclohexene-1,4-diyl and cyclooctane-1,5-diyl a monocyclic divalent alicyclic saturated hydrocarbon group; Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Examples include a hydrogen group.

[0138] L 1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group may be, for example, a group represented by any one of formulas (b1-1) to (b1-3). In addition, the groups represented by formulae (b1-1) to (b1-3) and their specific examples are In the examples of groups represented by formulae (b1-4) to (b1-11), * and ** represent bonding sites. represents the place, and * represents -Y 1 represents the binding site with

[0139] TIFF0007791275000069.tif26118[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0140] As the divalent saturated hydrocarbon group, L b1 The divalent saturated hydrocarbon groups are the same as those mentioned above. can be.

[0141] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the divalent saturated hydrocarbon The hydrogen atoms contained in the hydrogen group may be substituted with fluorine atoms. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. The —CH2— contained in the divalent saturated hydrocarbon group is replaced with —O— or —CO—. That's fine.

[0142] L 1The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group is preferably a group represented by formula (b1-1) or formula (b1-3).

[0143] The group represented by formula (b1-1) includes those represented by formulas (b1-4) to (b1-8), respectively. Examples of such groups include: TIFF0007791275000070.tif49120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the divalent saturated hydrocarbon group The contained -CH2- may be replaced by -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the formula may be replaced with -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b16 ~L b18 The total number of carbon atoms is 19 or less.

[0144] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0145] The group represented by formula (b1-3) includes the groups represented by formulas (b1-9) to (b1-11), respectively. Examples include groups represented by the following formula: TIFF0007791275000071.tif23140 formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atom may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atom may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atom may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0146] In addition, in the groups represented by formula (b1-9) to formula (b1-11), saturated When a hydrogen atom contained in a mono- or di-hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is the number of carbon atoms of the saturated hydrocarbon group.

[0147] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a bromide group, and a bromine group. Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0148] Examples of the group represented by formula (b1-4) include the following. TIFF0007791275000072.tif16153

[0149] Examples of the group represented by formula (b1-5) include the following. TIFF0007791275000073.tif71163

[0150] Examples of the group represented by formula (b1-6) include the following. TIFF0007791275000074.tif44149

[0151] Examples of the group represented by formula (b1-7) include the following. TIFF0007791275000075.tif62153

[0152] Examples of the group represented by formula (b1-8) include the following. TIFF0007791275000076.tif23150

[0153] Examples of the group represented by formula (b1-2) include the following. JPEG0007791275000077.jpg31161

[0154] Examples of the group represented by formula (b1-9) include the following. TIFF0007791275000078.tif44137

[0155] Examples of the group represented by formula (b1-10) include the following. TIFF0007791275000079.tif92165

[0156] Examples of the group represented by formula (b1-11) include the following. TIFF0007791275000080.tif84164

[0157] Y 1 Examples of the alicyclic hydrocarbon group represented by the formula (Y1) to the formula (Y11) and the formula (Y36) -A group represented by formula (Y38) is exemplified. Y 1 -CH2- contained in the alicyclic hydrocarbon group represented by the formula: When it is replaced by -CO-, the number of the replaced groups may be one or more. Examples include groups represented by formulae (Y12) to (Y35) and (Y39) to (Y41). * is L 1 represents the binding site with

[0158] TIFF0007791275000081.tif82161

[0159] Y 1 The alicyclic hydrocarbon group represented by the formula (Y1) to the formula (Y20), the formula (Y26), Formula (Y27), Formula (Y30), Formula (Y31), Formula (Y39) ~ Formula (Y41) and more preferably a group represented by formula (Y11), formula (Y15), or formula (Y1 6), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula ( Y39) or (Y40), and more preferably a group represented by formula (Y11), formula (Y 15), Formula (Y20), Formula (Y26), Formula (Y27), Formula (Y30), Formula (Y31), Formula (Y39) or a group represented by formula (Y40). Y 1 The alicyclic hydrocarbon groups represented by the formulae (Y28) to (Y35), (Y39) to (Y40) In the case of a spiro ring containing an oxygen atom, such as Y40), the alkanediyl group between the two oxygen atoms is The alkyl group preferably has one or more fluorine atoms. In the glycandiyl group, the methylene group adjacent to the oxygen atom is substituted with a fluorine atom. Preferably not.

[0160] Y 1 The substituent of the methyl group represented by the formula (I) is a halogen atom, a hydroxy group, a methyl group having 3 to 4 carbon atoms, or 16 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, - (CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 group (in the formula , R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group in which these groups are combined; The —CH2— contained in the alkyl group and the alicyclic hydrocarbon group represents any one of the integers. -, -S(O)2- or -CO-, and the alkyl group, the alicyclic carbon The hydrogen atoms contained in the hydrocarbon group and the aromatic hydrocarbon group are substituted with hydroxy groups or fluorine atoms. It may be replaced.) Y 1 The substituent of the alicyclic hydrocarbon group represented by the formula (I) is a halogen atom, a hydroxy group, a hydroxyl ... an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group; an alicyclic group having 3 to 16 carbon atoms; hydrocarbon groups, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, Aralkyl groups with 7 to 21 prime numbers, alkylcarbonyl groups with 2 to 4 carbon atoms, glycidyloxy Group, -(CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 base (In the formula, R b1 represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, represents an aromatic hydrocarbon group having 6 to 18 carbon atoms or a group combining these; The —CH2— contained in the alkyl group and the alicyclic hydrocarbon group represents any one of the integers , -O-, -S(O)2- or -CO-, and the alkyl group, the fatty acid The hydrogen atoms contained in the cyclic hydrocarbon group and the aromatic hydrocarbon group are substituted with hydroxy groups or fluorine groups. The atom may be substituted.

[0161] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclohexyl group. cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, Examples of the alicyclic hydrocarbon group include a carboxyl group, a carboxyl group, and an adamantyl group. Examples of the cyclohexyl group include a methylcyclohexyl group and a dimethylcyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthyl group. The aromatic hydrocarbon group may be a chain hydrocarbon group or an aliphatic hydrocarbon group. An aromatic carbon having a chain hydrocarbon group having 1 to 18 carbon atoms, which may have a cyclic hydrocarbon group. Hydrogen hydride groups include tolyl, xylyl, cumenyl, mesityl, and p-ethylphenyl. group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6- ethylphenyl group, etc., and aromatic hydrocarbons having an alicyclic hydrocarbon group having 3 to 18 carbon atoms. Examples of hydrogen groups include a p-cyclohexylphenyl group and a p-adamantylphenyl group. can be. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromine group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group etc. Examples of alkyl groups substituted with hydroxy groups include hydroxymethyl groups, hydroxy Examples include hydroxyalkyl groups such as an ethyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hydroxyl group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy groups. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and the like. Examples include an ethyl group and a naphthylethyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. etc.

[0162] Y 1 Examples include the following: TIFF0007791275000082.tif151153

[0163] Y 1 is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. An adamantyl group which may have a substituent is more preferred, and the alicyclic hydrocarbon group Or, -CH2- constituting the adamantyl group is replaced with -CO-, -S(O)2- or -CO-. It may be replaced. Y 1 is more preferably an adamantyl group, a hydroxyadamantyl group, adamantyl group, oxoadamantyl group, or a group represented by the following formula: TIFF0007791275000083.tif60162

[0164] The anions represented by formula (IA) include those represented by formulas (IA-1) to (IA-55). The anion represented by the formula (hereinafter, it may be referred to as "anion (IA-1)" or the like depending on the formula number) Formula (IA-1) to Formula (IA-4), Formula (IA-9), Formula (I- A-10), formula (IA-24) to formula (IA-33), formula (IA-36) to formula (I- A-40), an anion represented by any one of formulas (IA-47) to (IA-55) More preferable.

[0165] TIFF0007791275000084.tif79143

[0166] TIFF0007791275000085.tif95153

[0167] TIFF0007791275000086.tif129158

[0168] TIFF0007791275000087.tif184156

[0169] TIFF0007791275000088.tif50141 TIFF0007791275000089.tif113161

[0170] where R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 is, for example, a chain hydrocarbon having 1 to 12 carbon atoms. a group, 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 is more preferred, and a methyl group, an ethyl group, a cyclohexyl group, It is a silyl group or an adamantyl group. A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q is a 1 and Q 2 has the same meaning as above. Specific examples of the anion represented by formula (IA) include those described in JP 2010-204646 A Examples of anions include those described in the publication No.

[0171] The anion represented by formula (IA) is preferably an anion represented by formula (Ia-1) to formula (Ia- 34) are examples of anions represented by the formula: TIFF0007791275000090.tif89154

[0172] TIFF0007791275000091.tif140144

[0173] TIFF0007791275000092.tif160166

[0174] Among them, the compounds represented by formula (Ia-1) to formula (Ia-3) and formula (Ia-7) to formula (Ia- 19), and anions represented by any one of formulas (Ia-22) to (Ia-34) are preferred. It's nice.

[0175] AI - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF0007791275000093.tif41131

[0176] Examples of sulfonylmethide anions include the following: TIFF0007791275000094.tif29128

[0177] Examples of carboxylate anions include the following: TIFF0007791275000095.tif51153

[0178] Specific examples of the salt (I) include salts of any combination of the above-mentioned cations and anions. Specific examples of the salt (I) are shown in the table below. In the table below, each symbol represents the symbol attached to the structure representing the anion or cation described above. For example, salt (I-1) is a compound obtained by combining an anion represented by formula (Ia-1) and a compound represented by formula (Ic-1) and a cation represented by the following formula: TIFF0007791275000096.tif17108

[0179] [Table 1] TIFF0007791275000098.tif223154 TIFF0007791275000099.tif223154 TIFF0007791275000100.tif223154 TIFF0007791275000101.tif223154 TIFF0007791275000102.tif223154 TIFF0007791275000103.tif223154 TIFF0007791275000104.tif223154 TIFF0007791275000105.tif223154 TIFF0007791275000106.tif223154 TIFF0007791275000107.tif223154 TIFF0007791275000108.tif140152

[0180] Among them, salt (I) is salt (I-1) to salt (I-5), salt (I-13) to salt (I-25) , Salt (I-30) ~ Salt (I-34), Salt (I-42) ~ Salt (I-54), Salt (I-59) ~Salt (I-63), Salt (I-71) ~Salt (I-83), Salt (I-88) ~Salt (I-92) , Salt (I-100) ~ Salt (I-112), Salt (I-117) ~ Salt (I-121), Salt (I -129) ~ Salt (I-141), Salt (I-146) ~ Salt (I-150), Salt (I-158 ) ~ Salt (I-170), Salt (I-175) ~ Salt (I-179), Salt (I-187) ~ Salt ( I-199), Salt (I-204) ~ Salt (I-208), Salt (I-216) ~ Salt (I-22 8), Salt (I-233) ~ Salt (I-237), Salt (I-245) ~ Salt (I-257), Salt (I-262) ~ Salt (I-266), Salt (I-274) ~ Salt (I-286), Salt (I-2 91) ~ Salt (I-295), Salt (I-303) ~ Salt (I-315), Salt (I-320) ~ Salt (I-324), Salt (I-332) ~ Salt (I-344), Salt (I-349) ~ Salt (I- 353), Salt (I-361) ~ Salt (I-373), Salt (I-378) ~ Salt (I-382) , Salt (I-390) ~ Salt (I-402), Salt (I-407) ~ Salt (I-411), Salt (I -419) to salt (I-431).

[0181] The salt represented by formula (I) may be a salt represented by formula (IA). TIFF0007791275000109.tif4997 [wherein all symbols have the same meanings as defined above.] In addition, R 5A At least one of the following is -O-CO-CR 1B R 2B R 3B may also represent , R 1B , R 2B and R 3B is R 1A , R 2A and R 3A It has the same meaning as:

[0182] <Method for producing salt (I) and salt (IA)> The salt (I), particularly the salt (IA), is a salt represented by the formula (IA-a) and a salt represented by the formula (IA-b). The compound can be produced by reacting the compound with a salt thereof in a solvent. TIFF0007791275000110.tif53161 [wherein all symbols have the same meanings as defined above.] X represents a chlorine atom, a bromine atom, or an iodine atom. R A , R B and R C each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or R A , R B and R C may combine to form an aromatic ring. D is a hydrogen atom or a carbon atom represents a hydrocarbon group of 1 to 12.] Examples of solvents used in this reaction include chloroform, acetonitrile, and ion-exchanged water. It can be obtained. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0183] Examples of the salt represented by formula (IA-b) include the salt represented by the following formula: They are readily available and can be easily synthesized by known methods. TIFF0007791275000111.tif75131

[0184] The salt represented by formula (IA-a) is a compound represented by formula (IA-c) and a compound represented by formula (IA-d) and a compound represented by the formula (I) in a solvent in the presence of a catalyst. Cut. TIFF0007791275000112.tif46134 [wherein all symbols have the same meanings as defined above.] Catalysts include potassium peroxymonosulfate (Oxone®), sulfuric acid, p-toluenesulfonyl ether, and the like. enesulfonic acid and the like. Examples of the solvent include chloroform, monochlorobenzene, and acetonitrile. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0185] The compound represented by formula (IA-c) includes compounds represented by the following formula: It can be easily obtained from the market and can be easily produced by known methods. do. TIFF0007791275000113.tif52146

[0186] The compound represented by formula (IA-d) includes compounds represented by the following formula: It can be easily obtained from the market. TIFF0007791275000114.tif1417

[0187] The salt represented by the following formula (IA-a1) is prepared by reacting a compound represented by formula (IA-e) with iodic acid. Reacting with potassium in a solvent in the presence of a sulfuric acid catalyst, followed by treatment with sodium bromide It can be produced by TIFF0007791275000115.tif48140 [wherein all symbols have the same meanings as defined above.] Solvents include acetic acid, acetic anhydride, chloroform, monochlorobenzene, and acetonitrile. etc. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0188] The compound represented by formula (IA-e) includes compounds represented by the following formula: It can be easily obtained from the market and can be easily produced by known methods. do. TIFF0007791275000116.tif52145

[0189] <Acid generator> The acid generator of the present invention is an acid generator containing one kind of salt (I). Alternatively, two or more types of salt (I) may be contained. In addition to the salt (I), the acid generator of the present invention may also include acid generators known in the resist field (hereinafter referred to as "acid generators"). The acid generator (B) may be used alone. Alternatively, two or more of them may be used in combination.

[0190] The acid generator (B) may be either a nonionic or ionic acid generator. Biocides include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, etc.). sulfonates, oximesulfonates, N-sulfonyloxyimides, sulfonyloxyketones ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfones, ketones Examples of ionic acid generators include ionic acid generators such as ionic acid generators (sulfones, sulfonyldiazomethanes, etc.). Onium salts containing ammonium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples of onium salts include sulfonate anions. anion, sulfonylimide anion, sulfonylmethide anion, etc.

[0191] Examples of the acid generator (B) include those disclosed in JP-A-63-26653 and JP-A-55-164824; JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP 62-153853 A, JP 63-146029 A, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate acids when exposed to radiation, such as those described in US Pat. No. 126,712, can be used. In addition, compounds produced by known methods may be used. The acid generator (B) may be a mixture of two or more compounds. They may also be used in combination.

[0192] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a compound represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)"). TIFF0007791275000117.tif2863[In formula (B1), Q b1 and Q b2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents an alkyl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the saturated hydrocarbon group The -CH2- may be replaced by -O- or -CO-, and the saturated hydrocarbon group The hydrogen atoms contained therein may be substituted with fluorine atoms or hydroxy groups. Y is a methyl group which may have a substituent or a C3-C1 8, and -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + represents an organic cation.

[0193] Q in formula (B1) b1 , Q b2 , L b1 and Y are each represented by the above formula (IA) Q in 1 , Q 2 , L 1 and Y 1 And similar things can be mentioned. The sulfonate anion in formula (B1) may be an anion represented by formula (IA) Similar examples include:

[0194] Z1 + Examples of the organic cation include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations, and Among these, organic sulfonium cations are Preferred are iodonium and organic iodonium cations, and more preferred are arylsulfonium cations. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter Below, depending on the formula number, it may be referred to as "cation (b2-1)" etc.)

[0195] TIFF0007791275000118.tif77115In equations (b2-1) to (b2-4), R b4 ~R b6are each independently a chain hydrocarbon group having 1 to 30 carbon atoms, a chain hydrocarbon group having 3 to 36 carbon atoms, It represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the chain hydrocarbon group The hydrogen atoms contained in the alkyl group are hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, and alkyl groups with 3 to 12 carbon atoms. It may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group are halogen atoms, aliphatic hydrocarbon groups having 1 to 18 carbon atoms, may be substituted with an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atoms contained in the aromatic hydrocarbon group are replaced by halogen atoms, hydroxy groups, or groups having 1 carbon atom. It may be substituted with up to 12 alkoxy groups. R b4 and R b5 are bonded to each other and form a ring with the sulfur atom to which they are attached. -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. good. R b7 and R b8 are each independently a hydroxy group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms. Or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5; When m2 is 2 or more, multiple R b7 may be the same or different, and when n2 is 2 or more, R in Numbers b8 may be the same or different. R b9 and R b10 are each independently a chain hydrocarbon group having 1 to 36 carbon atoms or a chain hydrocarbon group having 3 to 4 carbon atoms, Represents 36 alicyclic hydrocarbon groups. R b9 and R b10 are bonded to each other and form a ring with the sulfur atom to which they are attached -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. Good too. R b11 is a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, It represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the chain hydrocarbon group are It may be substituted with an aromatic hydrocarbon group having 6 to 18 prime numbers, and the aromatic hydrocarbon group The hydrogen atom is preferably an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group. R b11 and R b12 are bonded to each other to form a ring including the -CH-CO- to which they are attached. -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. It is also possible. R b13 ~R b18 are each independently a hydroxy group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms. Or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4; u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14 are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, r2 When is 2 or more, multiple R b16are the same or different, and when s2 is 2 or more, multiple R b17 teeth Identical or different, when t2 is 2 or more, multiple R b18 are the same or different.

[0196] The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and Examples of the alkyl group include a 2-ethylhexyl group. In particular, R b9 ~R b12 The chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and a monocyclic alicyclic hydrocarbon group may be The hydrogen group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclohexyl group. cycloalkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups; Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group and an adamantyl group. group, a norbornyl group, and the following groups. TIFF0007791275000119.tif10158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms.

[0197] Examples of alicyclic hydrocarbon groups in which hydrogen atoms are substituted with aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyl 2-Isopropyladamantan-2-yl group, methylnor Examples of the alkyl group include a bornyl group and an isobornyl group. In the alicyclic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 1. Preferably it is 20 or less.

[0198] Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group. The aromatic hydrocarbon group having a chain hydrocarbon group may have a tolyl group, Xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group Examples of the phenyl group include a 2,6-diethylphenyl group and a 2-methyl-6-ethylphenyl group. The aromatic hydrocarbon group having an alicyclic hydrocarbon group is a p-cyclohexylphenyl group. , p-adamantylphenyl group, etc. In addition, when the aromatic hydrocarbon group is a chain hydrocarbon group, When the alkyl group has a chain hydrocarbon group or an alicyclic hydrocarbon group, the alkyl group is a chain hydrocarbon group having 1 to 18 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms. Alicyclic hydrocarbon groups of 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples thereof include a methyl group. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include a benzyl group, a phenyl group, and a phenyl group. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples include an aralkyl group.

[0199] The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hydroxyl group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy groups. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be done. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group and an ethylcarbonyloxy group. Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group silyl group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include an oxy group and a 2-ethylhexylcarbonyloxy group.

[0200] R b4 and R b5 and bond together with the sulfur atom to which they are attached to form a ring The ring may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. The ring may have 3 to 18 carbon atoms, and preferably has 4 to 18 carbon atoms. The ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples include the rings shown below, where * represents a binding site. TIFF0007791275000120.tif23143

[0201] R b9 and R b10 The ring formed by combining and can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of the ring include a 3-membered ring to a 12-membered ring. Preferably, it is a 3- to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothio) thiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring, etc. It can be obtained. R b11 and R b12The ring formed by combining and can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of the ring include a 3-membered ring to a 12-membered ring. and preferably a 3- to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring , oxonorbornane ring, oxoadamantane ring, etc.

[0202] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF0007791275000121.tif75148

[0203] TIFF0007791275000122.tif74143

[0204] Examples of the cation (b2-2) include the following cations. TIFF0007791275000123.tif18140

[0205] Examples of the cation (b2-3) include the following cations. TIFF0007791275000124.tif31155

[0206] Examples of the cation (b2-4) include the following cations. TIFF0007791275000125.tif141154

[0207] The acid generator (B) is a combination of the above-mentioned sulfonate anion and the above-mentioned organic cation. These can be combined in any desired manner. The acid generator (B) is preferably a compound represented by the formula (B1 a-1) ~ formula (B1a-3), formula (B1a-7) ~ formula (B1a-16), formula (B1a-1) 8), formula (B1a-19), formula (B1a-22) to formula (B1a-34) and a combination of the anion (b2-1) or the cation (b2-3). do.

[0208] The acid generator (B) is preferably a compound represented by formula (B1-1) to formula (B1-48), Among them, those containing an arylsulfonium cation are preferred, Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B Those represented by formulas (1-31) to (B1-48) are particularly preferred. TIFF0007791275000126.tif119149

[0209] JPEG0007791275000127.jpg77148

[0210] JPEG0007791275000128.jpg147146

[0211] JPEG0007791275000129.jpg61154

[0212] TIFF0007791275000130.tif107143

[0213] When the acid generator contains a salt (I) and an acid generator (B), the salt (I) and the acid generator (B) The ratio of the salt (I):acid generator (B) content (mass ratio; salt (I):acid generator (B)) is usually 1:99 to 99:1. The ratio is preferably 2:98 to 98:2, and more preferably 5:95 to 95:5. , more preferably 10:90 to 90:10, and particularly preferably 15:85 to 85: It is 15.

[0214] In the resist composition of the present invention, the content of the acid generator is 100% by mass of the aforementioned resin (A). With respect to the amount of the hydroxybenzoate, the amount is preferably 1 part by mass or more and 40 parts by mass or less, and more preferably 3 parts by mass or more and 30 parts by mass or less. It is 5 parts by mass or less, and more preferably 10 parts by mass or more and 35 parts by mass or less.

[0215] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less. It is preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of the solvent (E) is 99% by mass or less. The content of the solvent (E) is measured by, for example, liquid chromatography or gas chromatography. It can be measured by known analytical means such as chromatography. The solvent (E) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate and ethyl pyruvate; acetone, methyl isobutyl esters; ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; γ-butyrolactone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0216] <Quencher (C)> The quencher (C) may be a basic nitrogen-containing organic compound or a compound generated from an acid generator (B). Examples of the acid generating salts include those that generate acids with weaker acidity than the acid generated by the resist composition. When the resist composition contains the quencher (C), the content of the quencher (C) is determined based on the solid content of the resist composition. Based on the standard, it is preferably about 0.01 to 15% by mass, and more preferably about 0.1 to 10% by mass. It is more preferable to do so. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary amines, Amines include secondary amines and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, and diisopropylamine. aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine , octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine amine, triethylamine, trimethylamine, tripropylamine, tributylamine, Tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine , methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine, Ethyldibutylamine diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexane xylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropylamine Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine amine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -Dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane N, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( (2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. are mentioned, preferably aromatic amines such as diisopropyl aniline are mentioned, more preferably 2,6-diisopropyl aniline is mentioned. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropyl ammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethyl ammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, etc. are mentioned. Examples include.

[0217] The acidity of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The acid that generates an acid with a lower acidity than the acid generated from the acid generator (B) The salt that generates is a salt with an acid dissociation constant of the acid generated from the salt usually -3 <pKa, preferably is a salt of -1 <pKa <7, more preferably a salt of 0 <pKa <5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include the following formula a salt represented by formula (D) described in JP-A-2015-147926 (hereinafter, Weak acid inner salt (D)" and JP 2012-229206 A , JP 2012-6908 A, JP 2012-72109 A, JP 2011-3 9502 and JP-A 2011-191745. The salt that generates an acid weaker in acidity than the acid generated from (B) is preferably an acid generator (B ) produces a carboxylic acid that is weaker in acidity than the acid produced from A weak acid inner salt (D) is more preferred. TIFF0007791275000131.tif113145

[0218] Examples of the weak acid inner salt (D) include the following salts. TIFF0007791275000132.tif95145

[0219] <Other ingredients> The resist composition of the present invention may contain components other than the above-mentioned components (hereinafter referred to as "other components") as needed. It may contain other ingredients (F). The resist composition may contain additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc. Agents, dyes, etc. can be used.

[0220] <Preparation of Resist Composition> The resist composition of the present invention comprises a salt (I) and a resin (A), and, if necessary, an acid generating Agent (B), resin other than resin (A), solvent (E), quencher (C) and other components ( F). The order of mixing is arbitrary and is not particularly limited. The temperature when mixing varies from 10 to 40°C depending on the type of resin, solvent, etc. The appropriate temperature can be selected depending on the solubility of the compound in E). Depending on the situation, an appropriate time can be selected from 0.5 to 24 hours. There is no limitation on the method, and stirring and mixing can be used. After mixing the components, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable that

[0221] <Method for producing a resist pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) applying the resist composition of the present invention onto a substrate; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating is included. To apply the resist composition to the substrate, a commonly used device such as a spin coater is used. The substrate can be an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be cleaned, and an anti-reflection film or the like may be formed on the substrate. It may be possible. The composition after coating is dried to remove the solvent and form a composition layer. For example, the solvent can be evaporated using a heating device such as a hot plate (prebaking). The heating temperature is 50 to 200°C. The heating time is preferably 10 to 180 seconds. The pressure during this process is 1 to 1.0 x 10 5 It is preferable that the pressure is about Pa. The resulting composition layer is usually exposed using an exposure machine. The exposure light source may be a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert wavelength and emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range, electron beams, Various types of light sources can be used, such as those that irradiate ultraviolet light (EUV). In this case, the irradiation of these radiations is sometimes collectively called "exposure". The exposure is usually carried out through a mask corresponding to the desired pattern. In the case of lines, exposure may be performed by direct writing without using a mask. The composition layer after exposure is subjected to a heat treatment (or The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150°C. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of methods include the dip method, paddle method, spray method, and dynamic dispense method. The development temperature is preferably, for example, 5 to 60°C, and the development time is, for example, 5 The time is preferably 300 seconds or less. By selecting the type of developer as follows: Either a positive resist pattern or a negative resist pattern can be produced. When a positive resist pattern is produced from the resist composition of the present invention, a developer An alkaline developer is used. The alkaline developer is a type of alkaline water used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include an aqueous solution of ethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is removed. It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, a developer A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers include ketones such as 2-hexanone and 2-heptanone. Glycol ether solvents such as propylene glycol monomethyl ether acetate Ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and aromatic hydrocarbon solvents such as the above. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, The content is more preferably 95% by mass or more and 100% by mass or less, and more preferably substantially only an organic solvent. More preferable. Among them, organic developers include developers containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass. Preferably, the content is 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. It is more preferable that the mixture is qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 100%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. After development, the resist pattern is preferably washed with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and solvents containing general organic solvents are also usable. A solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0222] <Application> The resist composition of the present invention is a resist composition for exposure to KrF excimer laser, ArF excimer laser, Resist composition for exposure to ultraviolet laser, resist composition for exposure to electron beam (EB) or EU It is preferred as a resist composition for ultraviolet (UV) exposure, particularly as a resist composition for ArF excimer laser exposure. It is suitable for semiconductor microfabrication. [Example]

[0223] The present invention will be explained in more detail with reference to examples. "%" and "parts" are by weight unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analytical conditions for gel permeation chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (Tosoh Corporation) Eluent: tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation) The structure of the compound was determined by mass spectrometry (LC: Agilent 1100, MASS: Agilent The molecular ion peak was measured using a LC / MSD (manufactured by ent). In the examples, the value of this molecular ion peak is indicated by "MASS."

[0224] Example 1: Synthesis of salt represented by formula (I-92) TIFF0007791275000133.tif37146 4.76 parts of the compound represented by formula (I-92-a) and 6.40 parts of Oxone (registered trademark) The mixture was mixed and stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture was added 23. After adding 56 parts of the compound represented by formula (I-92-b), the mixture was stirred at 5° C. for 30 minutes. A mixed solution of 4.15 parts of a compound represented by the formula (I) and 20.74 parts of chloroform was added, and the resulting mixture was stirred at 5° C. After stirring for 30 minutes, the mixture was further stirred for 2 hours at 23°C. The mixture was added to 20 parts of the ethanol and stirred at 23°C for 30 minutes, and then filtered. The recovered filtrate was concentrated and then To the concentrated residue, 125 parts of chloroform and 25 parts of acetonitrile were added, and the mixture was stirred at 23°C for 30 minutes. After stirring, 50 parts of 5% hydrochloric acid was added and stirred at 23°C for 30 minutes, and then the mixture was separated to remove the organic layer. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, followed by separation. The organic layer was washed with water and extracted. This water washing procedure was repeated three times. The obtained organic layer was concentrated. To the condensation mixture, 45 parts of tert-butyl methyl ether was added, and the mixture was stirred at 23°C for 30 minutes. Filtration gave 3.33 parts of the salt represented by formula (I-92-c). TIFF0007791275000134.tif56150 5.34 parts of the salt represented by formula (I-92-d), 30 parts of chloroform, and 5% oxalic acid solution 10 parts of the solution were mixed and stirred at 23° C. for 30 minutes. The resulting mixture was added with a compound of the formula (I-92-c 3.13 parts of a salt represented by the formula (1) was added, and the mixture was stirred at 23°C for 1 hour, and then the organic layer was separated. 10 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. After that, 40 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. After stirring, the supernatant was removed and the mixture was concentrated to give the salt 4.8 represented by formula (I-92). I got 8 copies. MASS(ESI(+)Spectrum):M + 395.1 MASS(ESI(-)Spectrum):M - 517.1

[0225] Example 2: Synthesis of salt represented by formula (I-179) TIFF0007791275000135.tif27139 9 parts of potassium iodate, 14.39 parts of the compound represented by formula (I-179-a), 2 parts of acetic acid 7 parts of acetic anhydride and 13.5 parts of acetic anhydride were mixed, stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, 9 parts of sulfuric acid was added over 10 minutes, and the mixture was stirred at 5°C for 3 hours. The mixture was stirred at 23° C. for 12 hours. To the resulting mixture, 27 parts of tert-butyl methyl ether was added. 27 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 2 hours, filtered, and the filtrate was collected. The resulting organic layer was separated and the organic layer was extracted. The mixture was added with 13.5 parts of water, stirred at 23°C for 2 hours, and then filtered. As a result, 2.59 parts of the salt represented by the formula (I-179-b) were obtained. TIFF0007791275000136.tif55145 3.39 parts of the salt represented by formula (I-92-d), 30 parts of chloroform, and 5% oxalic acid solution 27 parts of the solution was mixed with the compound of the formula (I-179- 1.87 parts of the salt represented by b) was added, and the mixture was stirred at 23°C for 1 hour, and then the organic layer was separated. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. After adding 30 parts of the mixture and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 3.48 parts of the salt represented by the formula (I-179) was obtained. MASS(ESI(+)Spectrum):M + 397.0 MASS(ESI(-)Spectrum):M - 517.1

[0226] Example 3: Synthesis of salt represented by formula (I-177) TIFF0007791275000137.tif32163 2.25 parts of the salt represented by formula (I-177-d), 30 parts of chloroform, and 5% oxalic acid 27 parts of an aqueous solution was mixed therewith, and the mixture was stirred at 23° C. for 30 minutes. The resulting mixture was added with a compound of the formula (I-179 1.87 parts of the salt represented by -b) was added, and the mixture was stirred at 23°C for 1 hour. Then, the organic layer was separated. The obtained organic layer was concentrated, and then tert-butyl methyl ether was added to the concentrated residue. After adding 30 parts of ethanol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 2.29 parts of the salt represented by the formula (I-177) was obtained. MASS(ESI(+)Spectrum):M + 397.0 MASS(ESI(-)Spectrum):M - 323.0

[0227] Synthesis Example 1: Synthesis of salt represented by formula (I-322) TIFF0007791275000138.tif26157 9 parts of potassium iodate, 27 parts of the compound represented by formula (I-322-a), 27 parts of acetic acid, and The mixture was stirred at 23°C for 30 minutes and then cooled to 5°C. To the resulting mixture, 9 parts of sulfuric acid was added over 10 minutes, and the mixture was stirred at 5°C for 3 hours. The mixture was stirred at rt for 12 hours. To the resulting mixture was added 27 parts of tert-butyl methyl ether and 27 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 2 hours, and then filtered. The recovered filtrate was separated. The organic layer was extracted by adding 4.5 parts of sodium bromide and ion-exchanged water. 13.5 parts of the mixed solution was added, and the mixture was stirred at 23°C for 2 hours, followed by filtration to obtain a product of the formula ( 4.68 parts of the salt designated I-322-b) were obtained. TIFF0007791275000139.tif52135 2.25 parts of the salt represented by formula (I-177-d), 30 parts of chloroform, and 5% oxalic acid 27 parts of an aqueous solution was mixed therewith, and the mixture was stirred at 23° C. for 30 minutes. The resulting mixture was added with a compound of the formula (I-322 2.81 parts of the salt represented by -b) was added, and the mixture was stirred at 23°C for 1 hour. Then, the organic layer was separated. The obtained organic layer was concentrated, and then tert-butyl methyl ether was added to the concentrated residue. After adding 30 parts of ethanol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 2.29 parts of the salt represented by the formula (I-322) was obtained. MASS(ESI(+)Spectrum):M + 637.2 MASS(ESI(-)Spectrum):M - 323.0

[0228] Example 4: Synthesis of salt represented by formula (I-89) TIFF0007791275000140.tif59154 1.84 parts of the salt represented by formula (I-89-d), 30 parts of chloroform, and 5% oxalic acid solution 10 parts of the solution were mixed and stirred at 23° C. for 30 minutes. The resulting mixture was added with a compound of the formula (I-92-c ) was added, and the mixture was stirred at 23°C for 1 hour, followed by separation to remove the organic layer. 10 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. After that, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. After stirring, the supernatant was removed and the mixture was concentrated to give 1.8% of the salt represented by formula (I-89). I got 9 copies. MASS(ESI(+)Spectrum):M + 395.1 MASS(ESI(-)Spectrum):M - 339.1

[0229] Example 5: Synthesis of salt represented by formula (I-90) TIFF0007791275000141.tif64150 1.77 parts of the salt represented by formula (I-177-d), 30 parts of chloroform, and 5% oxalic acid The resulting mixture was stirred at 23° C. for 30 minutes. A compound of the formula (I-92- 1.71 parts of the salt represented by c) was added, and the mixture was stirred at 23°C for 1 hour, and then the organic layer was separated. 10 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and washed with water five times. After that, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. After stirring, the supernatant was removed and the mixture was concentrated to give the salt 2. We received 02 copies. MASS(ESI(+)Spectrum):M + 395.1 MASS(ESI(-)Spectrum):M - 323.0

[0230] Example 6: Synthesis of salt represented by formula (I-100) TIFF0007791275000142.tif58168 2.37 parts of the salt represented by formula (I-100-d), 30 parts of chloroform, and 5% oxalic acid The resulting mixture was stirred at 23° C. for 30 minutes. A compound of the formula (I-92- 1.71 parts of the salt represented by c) was added, and the mixture was stirred at 23°C for 1 hour, and then the organic layer was separated. 10 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and washed with water five times. After that, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. After stirring, the supernatant was removed and the mixture was concentrated to obtain a salt 2 represented by formula (I-100). It sold 0.29 copies. MASS(ESI(+)Spectrum):M + 395.1 MASS(ESI(-)Spectrum):M - 467.1

[0231] Example 7: Synthesis of salt represented by formula (I-187) TIFF0007791275000143.tif52164 3.01 parts of the salt represented by formula (I-100-d), 30 parts of chloroform, and 5% oxalic acid 27 parts of an aqueous solution was mixed therewith, and the mixture was stirred at 23° C. for 30 minutes. The resulting mixture was added with a compound of the formula (I-179 1.87 parts of the salt represented by -b) was added, and the mixture was stirred at 23°C for 1 hour. Then, the organic layer was separated. The obtained organic layer was concentrated, and then tert-butyl methyl ether was added to the concentrated residue. After adding 30 parts of ethanol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 3.43 parts of the salt represented by the formula (I-187) was obtained. MASS(ESI(+)Spectrum):M + 397.0 MASS(ESI(-)Spectrum):M - 467.1

[0232] Example 8: Synthesis of salt represented by formula (I-176) TIFF0007791275000144.tif50155 2.33 parts of the salt represented by formula (I-89-d), 30 parts of chloroform, and 5% oxalic acid solution 27 parts of the solution was mixed with the compound of the formula (I-179- 1.87 parts of the salt represented by b) was added, and the mixture was stirred at 23°C for 1 hour, and then the organic layer was separated. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. After adding 30 parts of the mixture and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 2.25 parts of the salt represented by the formula (I-176) was obtained. MASS(ESI(+)Spectrum):M + 397.0 MASS(ESI(-)Spectrum):M - 339.1

[0233] Example 9: Synthesis of salt represented by formula (I-129) TIFF0007791275000145.tif37145 5.01 parts of the compound represented by formula (I-129-a) and 6.40 parts of Oxone (registered trademark) The mixture was mixed and stirred at 23°C for 30 minutes, and then cooled to 5°C. After adding 0.56 parts, the mixture was stirred at 5°C for 30 minutes. A mixed solution of 4.15 parts of a compound represented by the formula (1) and 20.74 parts of chloroform was added, and the mixture was heated at 5°C. The mixture was stirred at 4°C for 30 minutes and then further stirred at 23°C for 2 hours. The mixture was added to 120 parts of the ethanol and stirred at 23°C for 30 minutes, and then filtered. The collected filtrate was concentrated. To the concentrated residue, 125 parts of chloroform and 25 parts of acetonitrile were added, and the mixture was stirred at 23°C for 30 minutes. After stirring for 30 minutes, 50 parts of 5% hydrochloric acid was added and the mixture was stirred at 23°C for 30 minutes. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated three times. The obtained organic layer was concentrated. To the concentrated mixture was added 45 parts of tert-butyl methyl ether, and the mixture was stirred at 23°C for 30 minutes. The mixture was filtered to obtain 3.48 parts of a salt represented by the formula (I-129-c). TIFF0007791275000146.tif58168 2.37 parts of the salt represented by formula (I-100-d), 30 parts of chloroform, and 5% oxalic acid The resulting mixture was stirred at 23° C. for 30 minutes. A compound of the formula (I-129) 1.77 parts of the salt represented by -c) was added, and the mixture was stirred at 23°C for 1 hour. Then, the organic layer was separated. 10 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. After that, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. After stirring for 1 hour, the supernatant was removed and the mixture was concentrated to obtain a salt represented by formula (I-129). It sold 2.12 copies. MASS(ESI(+)Spectrum):M + 409.1 MASS(ESI(-)Spectrum):M - 467.1

[0234] Example 10: Synthesis of salt represented by formula (I-158) TIFF0007791275000147.tif41152 5.26 parts of the compound represented by formula (I-158-a) and 6.40 parts of Oxone (registered trademark) The mixture was mixed and stirred at 23°C for 30 minutes, and then cooled to 5°C. After adding 0.56 parts, the mixture was stirred at 5°C for 30 minutes. A mixed solution of 4.15 parts of a compound represented by the formula (1) and 20.74 parts of chloroform was added, and the mixture was heated at 5°C. The mixture was stirred at 4°C for 30 minutes and then further stirred at 23°C for 2 hours. The mixture was added to 120 parts of the ethanol and stirred at 23°C for 30 minutes, and then filtered. The collected filtrate was concentrated. To the concentrated residue, 125 parts of chloroform and 25 parts of acetonitrile were added, and the mixture was stirred at 23°C for 30 minutes. After stirring for 30 minutes, 50 parts of 5% hydrochloric acid was added and the mixture was stirred at 23°C for 30 minutes. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated three times. The obtained organic layer was concentrated. To the concentrated mixture was added 45 parts of tert-butyl methyl ether, and the mixture was stirred at 23°C for 30 minutes. The mixture was filtered to obtain 3.13 parts of a salt represented by the formula (I-158-c). TIFF0007791275000148.tif58168 2.37 parts of the salt represented by formula (I-100-d), 30 parts of chloroform, and 5% oxalic acid The resulting mixture was stirred at 23° C. for 30 minutes. A compound of the formula (I-158) was added to the resulting mixture. 1.83 parts of the salt represented by -c) was added, and the mixture was stirred at 23°C for 1 hour. Then, the organic layer was separated. 10 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. After that, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. After stirring for 1 hour, the supernatant was removed and the mixture was concentrated to obtain a salt represented by formula (I-158). It yielded 1.98 copies. MASS(ESI(+)Spectrum):M + 423.1 MASS(ESI(-)Spectrum):M - 467.1

[0235] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-3)" etc. according to their formula numbers. TIFF0007791275000149.tif4179

[0236] Synthesis Example 2 [Synthesis of Resin A1] As the monomers, the monomer (a1-4-2), the monomer (a1-1-3) and the monomer (a1-2-6) was used, and the molar ratio [monomer (a1-4-2):monomer (a1-1 -3):monomer (a1-2-6) in a ratio of 38:24:38, Furthermore, this monomer mixture was mixed with 1.5 times by mass of methyl methyl ester based on the total mass of all monomers. Isobutyl ketone was mixed in the resulting mixture, and azobisisobutyronite was added as an initiator. The amount of methyl acrylate was 7 mol % based on the total number of moles of all monomers. The polymerization was carried out by heating at 40°C for about 5 hours. An aqueous acid solution was added, and the mixture was stirred for 6 hours, followed by separation. The obtained organic layer was diluted with a large amount of n-heptane The resin was precipitated by pouring it into a flask, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.3 × 10 3 Resin A1 (copolymer) having the following structural units was obtained in a yield of 78%. This is what we do. TIFF0007791275000150.tif29126

[0237] Synthesis Example 3 [Synthesis of Resin A2] As the monomers, the monomer (a1-4-2) and the monomer (a1-2-6) were used. The molar ratio of monomer (a1-4-2):monomer (a1-2-6) was 38:62. Further, to this monomer mixture, 1.5 times by mass of methyl isobutyl ketone was mixed with the resulting mixture. Azobisisobutyronitrile was added at 7 mol% relative to the total moles of all monomers. The mixture was then heated at 85°C for approximately 5 hours to carry out polymerization. An aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 6 hours, followed by separation of the resulting organic layer. The resin was poured into a large amount of n-heptane to precipitate, and then filtered and recovered to obtain a weight average The molecular weight is approximately 5.4 x 10 3 Resin A2 (copolymer) was obtained in a yield of 89%. has the following structural unit: TIFF0007791275000151.tif2886

[0238] <Preparation of Resist Composition> As shown in Table 2, the following components were mixed, and the resulting mixture was passed through a fluorine-containing filter with a pore size of 0.2 μm. The mixture was filtered through a resin filter to prepare a resist composition.

[0239] [Table 2]

[0240] <Resin> A1, A2: Resin A1, Resin A2 <Salt (I)> I-89: A salt represented by formula (I-89) I-90: A salt represented by formula (I-90) I-92: A salt represented by formula (I-92) I-100: A salt represented by formula (I-100) I-129: A salt represented by the formula (I-129) I-158: A salt represented by the formula (I-158) I-176: A salt represented by formula (I-176) I-177: A salt represented by the formula (I-177) I-179: A salt represented by the formula (I-179) I-187: A salt represented by formula (I-187) I-322: A salt represented by the formula (I-322) <Acid generator> IX-1: TIFF0007791275000153.tif1750IX-2: TIFF0007791275000154.tif21113<Quencher (C)> C1: TIFF0007791275000155.tif3546<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-butyrolactone 5 parts

[0241] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer is heated on a direct hot plate with hexamethyldisilazane. The silicon wafer was treated at 90°C for 60 seconds using a resist composition. The layer was spin-coated to a thickness of 0.04 μm. The substrate was prebaked on the sheet for 60 seconds at the temperature shown in the "PB" column of Table 2 to form a composition layer. The composition layer formed on the wafer was subjected to an electron beam lithography machine (HL-800D manufactured by Hitachi, Ltd.). 50 keV] and gradually change the exposure dose to create a line and space pattern. Directly painted. After exposure, the film was post-exposed on a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 2. The mixture was then baked in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. A resist pattern was obtained by puddle development with a solution for 60 seconds. The resulting resist pattern (line and space pattern) was observed with a scanning electron microscope. Therefore, the line width and space width of the 60 nm line and space pattern are 1:1. The exposure amount was taken as the effective sensitivity.

[0242] Line Edge Roughness Evaluation (LER): Sidewall of resist pattern manufactured with effective sensitivity The amplitude of the unevenness of the surface was measured using a scanning electron microscope to determine the line edge roughness. The results are shown in Table 3.

[0243] [Table 3]

[0244] From the above results, it can be seen that the salt of the present invention and the resist composition containing the salt can effectively prevent line edge roughness. It can be seen that the LER is good. [Industrial Applicability]

[0245] The salt of the present invention and the resist composition containing said salt exhibit good line edge roughness, and It is useful for microfabrication of conductors.

Claims

[Claim 1] A salt represented by formula (IA): [In formula (IA), R １Ａ and R ２Ａ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (a —CH ２ - may be replaced by -O- or -CO-. R ３Ａ represents a hydrogen atom. R ４Ａ and R ５Ａ each independently represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and —CH 2 - may be replaced by -O- or -CO-. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R ４Ａ may be the same or different from each other. m5 represents an integer of 0 to 5, and when m5 is 2 or more, a plurality of R ５Ａ may be the same or different from each other. AI － represents an anion represented by formula (IA). [In formula (IA), Q 1 and Q 2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L 1 represents a group represented by any one of formulas (b1-1) to (b1-3). Y 1 represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and one —CH 2 — contained in the alicyclic hydrocarbon group may be replaced by —O—, —SO 2 — or —CO—.] [In formula (b1-1), L b2 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 b3 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 or a hydroxy group, and a —CH 2 — contained in the saturated hydrocarbon group may be substituted with —O— or —CO—. However, the total number of carbon atoms in L b2 and L b3 is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, 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, in which a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and a —CH 2 — contained in the saturated hydrocarbon group may be substituted with —O— or —CO—. However, the total number of carbon atoms in L b4 and L b5 is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, 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, in which a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and a —CH 2 — contained in the saturated hydrocarbon group may be substituted with —O— or —CO—. However, the total number of carbon atoms in L b6 and L b7 is 23 or less. * and ** represent bonding sites, and * represents a bonding site with -Y 1 .]

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