Method for manufacturing resist compositions and resist patterns

Abstract

To provide a resist composition from which a resist pattern having good LER can be produced.SOLUTION: The resist composition contains: a carboxylic acid generator containing a carboxylate represented by formula (IA) or formula (IB); an acid generator other than the carboxylic acid generator; and a resin containing a structural unit having an acid-labile group and a structural unit represented by formula (a2-A).SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Patent Document 1 contains a salt represented by the following formula, and a resist set containing the salt as an acid generator. The product is described. Patent Document 2 (TIFF0007879325000001.tif30104) contains a carboxylic acid salt represented by the following formula as a carboxylic acid generator. A dystrophy composition is described. TIFF0007879325000002.tif2641 Patent Document 3 contains a carboxylic acid salt represented by the following formula as a carboxylic acid generator. A dystrophy composition is described. TIFF0007879325000003.tif2643 [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] WO2003 / 040090 pamphlet [Patent Document 2] Japanese Patent Publication No. 2011-39502 [Patent Document 3] Japanese Patent Publication No. 2014-88367 [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention provides a better resist pattern than one formed from a resist composition containing the above-mentioned salt. We offer a salt that can produce resist patterns with desirable line edge roughness (LER). It is intended for use in the public. [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A carboxylate represented by formula (IA) or formula (IB). TIFF0007879325000004.tif69144 [In formula (IA) and formula (IB), R 1 、R 2 、R 3 and R 4 each independently represents a hydrocarbon group having 1 to 24 carbon atoms, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -C O- or -SO2-. R 1 and R 2 , and R 3 and R 4 may each combine with each other to form a ring having 3 to 24 carbon atoms together with the sulfur atom to which they are attached, and -CH2- contained in the ring may be replaced by -O-, -S- or -CO- . R 5 、R 6 、R 7 、R 8 and R 9 each independently represents a halogen atom, a hydroxy group, a perfluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkyl group may be replaced by -O- or -CO-. m5 represents any integer from 0 to 4, and when m5 is 2 or more, a plurality of R 5 may be the same or different from each other. m6 represents any integer from 0 to 4, and when m6 is 2 or more, a plurality of R 6 may be the same or different from each other. m7 represents any integer from 0 to 4, and when m7 is 2 or more, a plurality of R 7They are the same It can be one or different. m8 represents an integer between 0 and 4, and when m8 is 2 or greater, multiple R 8 They are the same It can be one or different. X 1 and X 2 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or an atom with 1 to 6 carbon atoms. The alkanediyl group is represented, and the -CH2- contained in the alkanediyl group is either -O- or -CO - may be used as a substitute. X 01 , X 02 and X 03 Each of these independently has 1 to 72 carbon atoms, which may have substituents. The hydrocarbon group is represented, and the -CH2- contained in the hydrocarbon group is -O-, -S-, -CO- Alternatively, it may be replaced with -SO2-. [2]R 1 , R 2 , R 3 and R 4 However, each may independently have substituents. A carboxylate salt described in [1], which has a nyl group. [3]X 01 , X 02 and X 03 However, each may independently have substituents, C1 ~72 aliphatic hydrocarbon groups (however, the -CH2- contained in the aliphatic hydrocarbon group is -O- , -S-, -CO- or -SO2- may be substituted. ) or even if substituents are present. A carboxylate salt according to [1] or [2], which is a good aromatic hydrocarbon group having 6 to 36 carbon atoms. [4]X 01 , X 02 and X 03 However, each independently of the fluorine atom or hydroxyl Alicyclic hydrocarbon groups which may have a group (the -CH2- contained in the alicyclic hydrocarbon group is -O -It may be replaced by -CO-. ), alicyclic hydrocarbon groups and chain hydrocarbon groups The combined group (the -CH2- contained in the alicyclic hydrocarbon group and the chain hydrocarbon group is - It may be replaced by O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group It may have a fluorine atom or a hydroxyl group. The carboxylic acid described in any of [1] to [3] is an aromatic hydrocarbon group which may have a group. salt. A carboxylic acid generator containing a carboxylic acid salt as described in any of [5][1] to [4]. [6][5] The carboxylic acid generators described therein, acid generators other than the carboxylic acid generators, and acid generators A resist composition containing a resin having a stable group. [7] Resins having acid-unstable groups are structural units represented by formula (a1-1) and formula (a1- The register described in [6] includes at least one selected from the group consisting of structural units represented in (2). Stress composition. TIFF0007879325000005.tif46102[In formulas (a1-1) and (a1-2), L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents k1 represents an integer from 1 to 7, and * represents the association with -CO-. R a4 and R a5 Each of these independently represents either a hydrogen atom or a methyl group. R a6 and R a7 These are, independently, an alkyl group with 1 to 8 carbon atoms and an alicyclic group with 3 to 18 carbon atoms. This represents a hydrocarbon group or a group formed by combining these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3. [8] The resin having an acid-labile group contains a structural unit represented by the formula (a2-A) [6] and is the resist composition described in [7]. TIFF0007879325000006.tif4459 [In the formula (a2-A), R a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a50 represents a single bond or * -X a51 -(A a52 -X a52 ) nb - and * represents the bonding position to the carbon atom to which -R a50 is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. <000,0904>X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, plural Rs may be the same as or different from each other. ] a51 [9] (1) The step of applying the resist composition according to any one of [6] to [8] onto a substrate, (2) The step of drying the applied composition to form a composition layer, (3) The step of exposing the composition layer, (4) The step of heating the exposed composition layer, and (5) A method for manufacturing a resist pattern, comprising the step of developing the composition layer after heating. [Effects of the Invention]

[0006] By using the resist composition containing the salt of the present invention, good line edge roughness can be achieved. Resist patterns can be manufactured using LER. [Modes for carrying out the invention]

[0007] In this specification, "(meth)acrylic monomer" means "acrylic monomer and This means "at least one methacrylate monomer." "(meth)acrylate" and " The notation "(meth)acrylic acid," etc., also has the same meaning. For those that can take both a linear and branched structure, either is acceptable. A "combined group" refers to a group formed by combining two or more of the exemplified groups, with their valencies appropriately changed. To taste. "Derived from" or "induced from" refers to polymerizable C=C bonds contained in the molecule. This refers to the formation of a -CC- group through polymerization. If stereoisomers exist, all stereoisomers are formed. Includes isomers. In this specification, "solid content of the resist composition" means the amount of solids of the resist composition that is added to the total amount of solids of the resist composition. This refers to the sum of the components excluding the solvent (E) described above.

[0008] <Carboxylate salts represented by formula (IA) or formula (IB)> The present invention relates to a carboxylate salt represented by formula (IA) (hereinafter referred to as "carboxylate salt (IA)"). (In some cases) and salts represented by formula (IB) (hereinafter referred to as "carboxylate salt (IB)") Regarding a certain Of the carboxylate salts (IA) and carboxylate salts (IB), the side with the negative charge is called "anio The side with the positive charge is called "cation (I)" or "cation (IB)". It can happen. TIFF0007879325000007.tif69144[In formulas (IA) and (IB), all symbols have the same meanings as defined above.] Carboxylate salts (IA) and carboxylate salts (IB) can also be represented as shown in the following equations. TIFF0007879325000008.tif84162[In formulas (IA) and (IB), all symbols have the same meanings as defined above.]

[0009] R 1 , R 2 , R 3 and R 4 The hydrocarbon group in this context is an aliphatic hydrocarbon group (alkyl group). Chain hydrocarbon groups such as alkenyl groups and alkynyl groups, and alicyclic hydrocarbon groups, aromatic carbon Hydrogen groups, as well as chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and alicyclic groups Examples include groups that combine hydrocarbon groups and aromatic hydrocarbon groups. R 1 , R 2 , R 3 and R 4 The -CH2- contained in the hydrocarbon group in this case is -O-, -S If replaced by -, -CO- or -SO2-, the number of carbon atoms before replacement in the carbonized water This is the total number of carbon atoms in the elementary group. Alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, and butyl group. Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. Examples include alkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably The range is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. be. Examples of alkenyl groups include ethenyl group, propenyl group, isopropenyl group, butenyl group, Isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples include octynyl group, isooctynyl group, nonenyl group. Examples of the alkynyl group include ethynyl group, propynyl group, isopropynyl group, butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, Examples include nonynyl group and the like. When -CH2- contained in the chain hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-, the total carbon number of the chain hydrocarbon group is the carbon number before replacement. For example, groups in which any -CH2- contained in the alkyl group is replaced by -O- or -CO- include hydroxy group (a group in which any -CH2- contained in the methyl group is replaced by -O- -), carboxy group (a group in which any -CH2-CH2- contained in the ethyl group is replaced by -O-CO- -), alkoxy group (a group in which any -CH2- contained in the alkyl group is replaced by -O- -), alkoxycarbonyl group (a group in which any -CH2-CH2- contained in the alkyl group is replaced by -O-CO- -), alkylcarbonyl group (a group in which any -CH2- contained in the alkyl group is replaced by -CO- -), alkylcarbonyloxy group (a group in which any -CH2-CH2- contained in the alkyl group is replaced by -CO-O- -), etc. Examples include groups in which any -CH2-CH2- contained in the alkyl group is replaced by -CO-O- In addition, the replacement in the alkenyl group and alkynyl group may be any example of the replacement in the above-mentioned alkyl group as long as it contains a carbon-carbon double bond or a carbon-carbon triple bond at an arbitrary position. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyl hydroxyl group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, noni Examples include the ruoxy group, decyloxy group, undecyloxy group, and dodecyloxy group. The number of carbon atoms in the alkoxy group can be 1 to 11, preferably 1 to 6, and more preferably The values ​​are 1 to 4. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups are A carbonyl group or carbonyloxy group is bonded to the alkyl group or alkoxy group mentioned above. It represents a group. Examples of alkoxycarbonyl groups include the methoxycarbonyl group and the ethoxycarbonyl group. Examples include the acetyl group and the butoxycarbonyl group, while alkylcarbonyl groups include the acetyl group. Examples include propionyl groups and butyryl groups, and alkylcarbonyloxy groups include Examples include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The carbon number of carbon atoms in the cycarbonyl group can range from 2 to 11, preferably 2 to 6. Preferably, it is 2 to 4. The number of carbon atoms in the alkylcarbonyl group can be 2 to 12. Preferably 2 to 6, more preferably 2 to 4. Alkylcarbonyloxy group The number of carbon atoms can range from 2 to 11, preferably 2 to 6, and more preferably 2 to 11. The answer is 4. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and may be saturated or unsaturated. Any of the following may be used. Examples of alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, and cyclopropyl group. Clopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl Monocyclic cycloalkyl groups such as cyclododecyl groups, norbornyl groups, adamantyl groups, etc. Examples include polycyclic cycloalkyl groups. Specifically, alicyclic hydrocarbon groups include formulas (Y1) to (Y11), and formulas (Y36) to (Y11). Examples include the group represented by (Y38). Also, -CH2- contained in alicyclic hydrocarbon groups. However, the groups replaced by -O-, -CO-, or -SO2- are given by equations (Y12) to (Y 35) Examples include groups represented by formulas (Y39) to (Y43). * indicates a bonding site. . Among them, alicyclic hydrocarbon groups include formulas (Y1) to (Y20), formula (Y26), and ( It can be expressed by any of the following equations: Y27), (Y30), (Y31), (Y39) to (Y43) It is preferable that the group is one of the following: formula (Y3), (Y4), formula (Y9), formula (Y11), formula ( Y14), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), Formula (Y30), Formula (Y31), Formula (Y39), Formula (Y40), Formula (Y42), or Formula (Y4 It is more preferable that the group is represented by 3). The number of carbon atoms in the alicyclic hydrocarbon group is preferably The range is 3 to 18, more preferably 3 to 16, and even more preferably 3 to 12. TIFF0007879325000009.tif83168

[0010] Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl and fluorenyl groups, as well as phenyl and naphthyl groups. and anthryl groups are preferred, phenyl groups and naphthyl groups are more preferred, and phenyl groups are Even more preferable, the number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, and more preferably The value of k is 6 to 14, and more preferably 6 to 10.

[0011] The combined bases are, Alicyclic hydrocarbon groups and chain hydrocarbon groups (alkyl groups, alkenyl groups and / or alkynyl groups) Groups combined with (such as the chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group)) The -CH2- contained in the group (etc.) and the alicyclic hydrocarbon group is -O-, -S-, -CO- or (It may be replaced with -SO2-) A group that combines an alicyclic hydrocarbon group and an aromatic hydrocarbon group (the alicyclic hydrocarbon group contains The -CH2- group may be replaced with -O-, -S-, -CO-, or -SO2-. ), and Aromatic hydrocarbon groups and chain hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups, etc.) A group that combines (the chain-like hydrocarbon group (alkyl group, alkenyl group, alkynyl group, etc.) Even if the contained -CH2- is replaced by -O-, -S-, -CO- or -SO2- (Good) are listed. In addition, in combinations, alicyclic hydrocarbon groups and chain hydrocarbon groups (alkyl groups, alke groups) are used. Even when two or more types of groups (such as nyl groups and alkynyl groups) and aromatic hydrocarbon groups are combined, Good. Also, groups with different valencies (divalent or trivalent groups (chain hydrocarbon groups, lipids)) are good. It may contain cyclic saturated hydrocarbon groups, aromatic hydrocarbon groups, etc. Also, any of the groups It may be bonded to a sulfur atom. Specific examples of combined elements include: Alicyclic hydrocarbon groups such as adamantylmethyl group and cyclohexylmethyl group - chain hydrocarbons Group -*(The -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group are -O-, - (May be replaced by S-, -CO-, or -SO2-) Chain-type hydrocarbon group such as methyladamantyl group - alicyclic hydrocarbon group - *(the chain-type hydrocarbon group And the -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO (It may be replaced with 2.) Chain-type hydrocarbon groups such as tolyl groups and xylyl groups - aromatic hydrocarbon groups - *(the chain-type hydrocarbon group) The -CH2- contained in is replaced by -O-, -S-, -CO- or -SO2-. (Also good), Methylcyclohexylmethyl group and other chain hydrocarbon groups - alicyclic hydrocarbon groups - chain hydrocarbon groups Group -*(The -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group are -O-, - (May be replaced by S-, -CO-, or -SO2-) Aromatic hydrocarbon groups such as benzyl groups - chain hydrocarbon groups - * (contained in the chain hydrocarbon group) (-CH2- may be replaced by -O-, -S-, -CO- or -SO2-), Chain-type hydrocarbon group such as tolylmethyl group - aromatic hydrocarbon group - chain-type hydrocarbon group - *(the chain-type The -CH2- group in the hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2-. (It's okay if you already know this.) Aromatic hydrocarbon group - alicyclic hydrocarbon group - *(the alicyclic carbon The -CH2- contained in the hydrogenated group is replaced by -O-, -S-, -CO-, or -SO2-. (It's okay if it's not), Alicyclic hydrocarbon groups such as cyclohexylphenyl and adamantylphenyl groups - aromatic Hydrocarbon group -*(The -CH2- contained in this alicyclic hydrocarbon group is -O-, -S-, -CO Examples include - (which may be replaced with -SO2-), etc. Here, * represents the bonding position with the sulfur atom.

[0012] R 1 , R 2 , R 3 and R 4 The substituents on the hydrocarbon group include halogen atoms and shea atoms. A group, a perfluoroalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms (the alkyl group Examples include the fact that the -CH2- group may be replaced by -O- or -CO-. It can be done. 1 , R 2 , R 3 and R 4 If the hydrocarbon group in has substituents, substitute The number of carbon atoms in the preceding carbon group is taken as the total number of carbon atoms in the hydrocarbon group. Groups in which the -CH2- group in an alkyl group is replaced by -O- or -CO- include: Hydroxyl group (a group in which the -CH2- contained in a methyl group is replaced by -O-), Carbo Xy group (a group in which the -CH2-CH2- contained in the ethyl group is replaced with -O-CO-), An alkoxy group (where any -CH2- in an alkyl group is replaced by -O-) (a group), alkoxycarbonyl group (a -CH2-CH2 group at any position within an alkyl group) -A group that has been replaced by -O-CO-), an alkylcarbonyl group (contained within the alkyl group) (A group in which -CH2- at any position is replaced by -CO-), alkylcarbonyloxy The group (where any -CH2-CH2- in the alkyl group is replaced by -CO-O-) Examples include the following:

[0013] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of perfluoroalkyl groups include trifluoromethyl group, perfluoroethyl group, and perfluoroalkyl group. Perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoropropyl group Orosec-butyl group, perfluorotert-butyl group, perfluoropentyl group and Examples include perfluorohexyl groups. The number of carbon atoms in the perfluoroalkyl group is preferably The range is 1 to 4, and more preferably 1 to 3. Alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, and butyl group. Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. Examples of alkyl groups include the alkyl group having 1 to 9 carbon atoms, and more preferably the alkyl group having 1 to 9 carbon atoms. More preferably 1 to 6, and even more preferably 1 to 4. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. hydroxyl group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, noni Examples include the ruoxy group, decyloxy group, undecyloxy group, and dodecyloxy group. The number of carbon atoms in the alkoxy group can be 1 to 11, preferably 1 to 6, and more preferably The values ​​are 1 to 4. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups are A carbonyl group or carbonyloxy group is bonded to the alkyl group or alkoxy group mentioned above. It represents a group. Examples of alkoxycarbonyl groups include the methoxycarbonyl group and the ethoxycarbonyl group. Examples include the acetyl group and the butoxycarbonyl group, while alkylcarbonyl groups include the acetyl group. Examples include propionyl groups and butyryl groups, and alkylcarbonyloxy groups include Examples include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The carbon number of carbon atoms in the cycarbonyl group can range from 2 to 11, preferably 2 to 6. Preferably, it is 2 to 4. The number of carbon atoms in the alkylcarbonyl group can be 2 to 12. Preferably 2 to 6, more preferably 2 to 4. Alkylcarbonyloxy group The number of carbon atoms can range from 2 to 11, preferably 2 to 6, and more preferably 2 to 11. The answer is 4.

[0014] R 1 , R 2 , R 3 and R 4 These are, independently, alkyl groups with 1 to 6 carbon atoms and alkyl groups with 3 carbon atoms. R 1 and R 2 , and also, R 3 and R 4 However, they combine with each other and form sulfurous Together with the child, it forms a ring with 3 to 12 carbon atoms (the -CH2- contained in the ring is -O-, -S- or It is preferable that the group forms a methyl group, cyclohexyl group (which may be replaced by -CO-), It is more preferable that the group is a phenyl group which may have substituents. It is more preferably a phenyl group which may contain a halogen atom and a phenyl group with 1 to 3 carbon atoms. Fluoroalkyl groups, alkyl groups with 1 to 6 carbon atoms (the alkyl group contains -CH2- The phenyl group may have -O- or -CO- (which may be replaced by -O- or -CO-). More preferably, a phenyl group which may have a halogen atom is even more preferable. Phenyl groups that may have an oxyatom are particularly preferred.

[0015] R 5 , R 6 , R 7 , R 8 and R 9 As perfluoroalkyl groups having 1 to 6 carbon atoms, Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Isopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluoro Examples include tert-butyl groups, perfluoropentyl groups, and perfluorohexyl groups. It is. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 4, more preferably 1 to 3. R 5 、R 6 、R 7 、R 8 and R 9 Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group , a pentyl group, a hexyl group, an octyl group, a nonyl group and other alkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. R 5 、R 6 、R 7 、R 8 and R 9 When -CH2- contained in the alkyl group in R 、R 、R 5 、R 6 、R 7 and R 8 is replaced by -O- or -CO-, the total number of carbon atoms before replacement is taken as the total number of carbon atoms of the alkyl group . Examples of the group in which -CH2- contained in the alkyl group in R 、R 、R 、R 、R and R Groups in which -CH2- is replaced by -CO-O-, etc. can be mentioned. Specific examples thereof are the same as those described above. R 5 R 6 R 7 and R 8 are each independently preferably a halogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms, more preferably a fluorine atom, a hydroxy group or a methyl group, and even more preferably a fluorine atom or a hydroxy group. m5, m6, m7 and m8 are each independently preferably any integer from 0 to 2, and more preferably 0 or 1. R 9 is preferably a halogen atom, a hydroxy group or a perfluoroalkyl group having 1 to 6 carbon atoms, more preferably a halogen atom or a hydroxy group, and even more preferably a fluorine atom or a hydroxy group.

[0016] X 1 and X 2 as the alkane diyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group , a linear alkane diyl group such as a hexane-1,6-diyl group; an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a branched alkane diyl group such as a 2-methylbutane-1,4-diyl group, etc. can be mentioned. The carbon number of the alkane diyl group is preferably 1 to 4, and more preferably 1 to 3. ​ X 1 and X 2 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, a methylene group, or an ethyl group. It is preferably a len group, more preferably an oxygen atom or a sulfur atom, and oxygen atom Being a child is even more preferable. X 1 and X 2 The bond position is I + The bond position can be any of the ortho, m, or p positions. Yes. In particular, + It is preferable that the bond is located at the p-position or m-position relative to the bonding site, It is more preferable that they be coupled to the position.

[0017] Examples of cations (IA) include the following: TIFF0007879325000010.tif205169

[0018] TIFF0007879325000011.tif140168

[0019] Examples of cations (IB) include the following: TIFF0007879325000012.tif84153

[0020] TIFF0007879325000013.tif227166

[0021] In equation (I), X 01 , X 02 and X 03 As for hydrocarbon groups represented by aliphatic groups, Hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups, and alicyclic hydrocarbon groups) Examples include hydrogenated groups, aromatic hydrocarbon groups, and groups combining these. Aliphatic carbon The -CH2- contained in the hydrogen group is replaced by -O-, -S-, -CO-, or -SO2-. It's fine if you do that. Alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, and butyl group. Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. Examples of alkyl groups include the alkyl group having 1 to 18 carbon atoms, and more preferably the alkyl group having 1 to 18 carbon atoms. The range is 1 to 12, more preferably 1 to 9, and even more preferably 1 to 6. Yes, and more preferably 1 to 4. Examples of alkenyl groups include ethenyl group, propenyl group, isopropenyl group, butenyl group, Isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples include the octinyl group, isooctinyl group, and nonenyl group. Examples of alkynyl groups include ethynyl group, propynyl group, isopropynyl group, butynyl group, Isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octinyl group, Examples include noninyl groups. The -CH2- contained in the chain hydrocarbon group is converted to -O-, -S-, -CO-, or -SO2-. The replaced group is the hydroxyl group (the -CH2- contained in the methyl group is replaced by -O-). (Replaced group), carboxyl group (the -CH2-CH2- contained in the ethyl group, -OC Groups replaced by O-, alkoxy groups (-CH2 at any position within an alkyl group) -A group that has been replaced by -O-), an alkoxycarbonyl group (a group contained within an alkyl group) (A group in which the -CH2-CH2- at the right position is replaced by -O-CO-), alkylcarbonyl A group (a group in which any -CH2- at any position within an alkyl group is replaced by -CO-), Alkylcarbonyloxy group (the -CH2-CH2- at any position within the alkyl group) , a group replaced by -CO-O-, alkylthio group (any position contained within the alkyl group) Examples include groups in which the -CH2- group is replaced by -S-. Alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyl Oxy groups include, for example, alkoxy groups with 1 to 17 carbon atoms and alkoxycal groups with 2 to 17 carbon atoms. Bonyl group, alkylcarbonyl group having 2 to 18 carbon atoms, and alkylcarbonyl group having 2 to 17 carbon atoms. Examples include the yloxy group, and the same groups as above. Examples of alkylthio groups include carbon Examples of alkylthio groups include 1 to 17 alkylthio groups, such as methylthio group, ethylthio group, and propionic group. Examples include the luthio group. Furthermore, the substitution of alkenyl and alkynyl groups is as described above for alkyl groups. In the example of substitution, a carbon-carbon double bond or carbon-carbon triple bond can be placed at any position. Anything that includes it is acceptable. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and may be saturated or unsaturated. Any of the following may be used. Examples of alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, and cyclopropyl group. Clopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl Monocyclic cycloalkyl groups such as cyclododecyl groups, norbornyl groups, adamantyl groups, etc. Examples include polycyclic cycloalkyl groups. Alicyclic hydrocarbon groups and the -CH2- contained in alicyclic hydrocarbon groups are -O-, -S-, - Examples of groups that have been replaced by CO- or -SO2- include the following groups: The connection point can be at any position. TIFF0007879325000014.tif130161 Alicyclic hydrocarbon group or -CH2- contained in alicyclic hydrocarbon group is -O-, -S-, - The groups that have been replaced by CO- or -SO2- are the groups represented by formulas (y1) to (y71). This is preferable, and equations (y1) to (y20), (y26), (y27), (y30), A group represented by any of formulas (y31), (y39) to (y71) is more preferred, (y3), (y4), formula (y9), formula (y11), formula (y14), formula (y15), formula (y 16), formula (y20), formula (y26), formula (y27), formula (y30), formula (y31), formula (y39), formula (y40), formula (y42), formula (y43), formula (y49)~formula (y58) Groups represented by formulas (y62) to (y71) are even more preferred. Carbon of the alicyclic hydrocarbon group The number is preferably 3 to 36, more preferably 3 to 24, and even more preferably 3 It is ~18, and more preferably 3~16.

[0022] Aromatic hydrocarbon groups include phenyl group, naphthyl group, biphenyl group, anthryl group, Examples include aryl groups such as phenanthryl groups and binaphthyl groups. Carbon of aromatic hydrocarbon groups The prime numbers are preferably 6 to 36, more preferably 6 to 24, and even more preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. be. In the case of combined groups, the groups with different valencies (alkanediyl group, alkanediyl group) are mentioned above. ¹triyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkane It may also contain (such as a cycloalkanetetrayl group, cycloalkanetetrayl group, etc.).

[0023] The combined bases are, A group that combines an alicyclic hydrocarbon group and a chain hydrocarbon group (the chain hydrocarbon group and the alicyclic hydrocarbon group) The -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2-. (It may be replaced), A group that combines a chain hydrocarbon group and an aromatic hydrocarbon group (the chain hydrocarbon group contains (-CH2- may be replaced by -O-, -S-, -CO- or -SO2-), and A group that combines an alicyclic hydrocarbon group and an aromatic hydrocarbon group (the alicyclic hydrocarbon group contains The -CH2- group may be replaced with -O-, -S-, -CO-, or -SO2-. ) represents. In addition, the combinations include alicyclic hydrocarbon groups, chain hydrocarbon groups, and aromatic hydrocarbon groups. Each of these may be combined in combination of two or more types. Specifically, the combined bases are: Alicyclic hydrocarbon groups such as adamantylmethylene groups and cyclohexylmethylene groups - chain carbon Hydrogen group-*, (alicyclic hydrocarbon group) 2-chain hydrocarbon group-* (the chain hydrocarbon group and the alicyclic hydrocarbon group) The -CH2- contained in the cyclic hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2-. (It may be replaced), Chain-type hydrocarbon groups such as methyladamantyl group and dimethyladamantyl group - alicyclic hydrocarbons Group-*, (chain hydrocarbon group) 2-alicyclic hydrocarbon group-* (the chain hydrocarbon group and the alicyclic The -CH2- group in the hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2-. (It's okay if you already know this.) Chain-type hydrocarbon groups such as tolyl groups and xylyl groups - aromatic hydrocarbon groups - *(the chain-type hydrocarbon group) The -CH2- contained in is replaced by -O-, -S-, -CO- or -SO2-. (Also good), Methylcyclohexylmethylene group and other chain-type hydrocarbon groups - alicyclic hydrocarbon groups - chain-type carbonized water Elemental group-*, (chain hydrocarbon group) 2-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain carbide Hydrogen group - alicyclic hydrocarbon group) 2 - chain hydrocarbon group - * (the chain hydrocarbon group and the alicyclic hydrocarbon group) The -CH2- contained in the hydrogenated group is replaced by -O-, -S-, -CO-, or -SO2-. (It's okay if it's not), Aromatic hydrocarbon groups such as benzyl groups - chain hydrocarbon groups - * (contained in the chain hydrocarbon group) (-CH2- may be replaced by -O-, -S-, -CO- or -SO2-), Chain-type hydrocarbon group such as tolylmethyl group - aromatic hydrocarbon group - chain-type hydrocarbon group - *(the chain-type The -CH2- group in the hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2-. (It's okay if you already know this.) Methyladamantanemethyleneadamantyl group, di(methyladamantanemethylene)ada Chain hydrocarbon group such as mantyl group - alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group -*, (chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group) 2-alicyclic hydrocarbon group - *, (chain hydrocarbon group - alicyclic hydrocarbon group) 2-chain hydrocarbon group - alicyclic hydrocarbon group - * , (chain hydrocarbon group) 2-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-*( The -CH2- contained in the chain-like hydrocarbon group and the alicyclic hydrocarbon group are -O-, -S-, - (May be replaced by CO- or -SO2-), Alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group - *, (alicyclic (Hydrogen group) 2-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic Hydrocarbon group - chain hydrocarbon group) 2 - alicyclic hydrocarbon group - chain hydrocarbon group - *, (alicyclic carbon Hydrogenated group - Chain hydrocarbon group - Alicyclic hydrocarbon group) 2 - Chain hydrocarbon group - * (The chain hydrocarbon group) The -CH2- contained in the elementary group and the alicyclic hydrocarbon group is -O-, -S-, -CO- or - (It may be replaced with SO2-) Chain hydrocarbon group - Alicyclic hydrocarbon group - Chain hydrocarbon group - Alicyclic hydrocarbon group - Chain carbonized water Elemental group - *, (chain hydrocarbon group) 2-alicyclic hydrocarbon group - chain hydrocarbon group - alicyclic hydrocarbon group Base-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group)2-chain hydrocarbon group- Alicyclic hydrocarbon group - chain hydrocarbon group - *, (chain hydrocarbon group - alicyclic hydrocarbon group - chain hydrocarbon group) Hydrogenated group) 2-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic carbon Hydrogen group - Chain hydrocarbon group - Alicyclic hydrocarbon group) 2 - Chain hydrocarbon group - * (Same chain hydrocarbon group) The -CH2- contained in the group and the alicyclic hydrocarbon group is -O-, -S-, -CO- or -S (It may be replaced with O2-) Examples include the following. Here, * represents the bonding position of the carbonyl group to the carbon atom.

[0024] X 01 , X 02 and X 03 The -CH2- contained in the hydrocarbon group represented by -O-, - If replaced by S-, -CO-, or -SO2-, the number of carbon atoms before replacement is determined by the carbonization. This is the total number of carbon atoms in the hydrogen group. Also, X 01 , X 02 and X 03 Substituted with hydrocarbon groups represented by When a group is bonded, the number of carbon atoms before substitution is considered to be the total number of carbon atoms in the hydrocarbon group. X 01 , X 02 and X 03 The hydrocarbon group represented by has one or more substituents. That's good too. Substituents include hydroxyl groups, halogen atoms, cyano groups, and alkyl groups with 1 to 12 carbon atoms. Group, alkoxy group with 1 to 12 carbon atoms, alkoxycarbonyl group with 2 to 13 carbon atoms, carbon number 2-13 alkylcarbonyl group, 2-13 alkylcarbonyloxy group, carbon Alicyclic hydrocarbon groups with 3 to 12 carbon atoms, aromatic hydrocarbon groups with 6 to 10 carbon atoms, or combinations thereof Examples include combined groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkyl groups with 1 to 12 carbon atoms include methyl, ethyl, propyl, and isopropyl groups. butyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl Examples include the yl group and the nonyl group. Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, and b Toxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group These are some examples. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and The alkylcarbonyloxy group having 2 to 13 carbon atoms is the alkyl or alkoxy group described above. This represents a group to which a carbonyl group or a carbonyloxy group is bonded. Examples of alkoxycarbonyl groups with 2 to 13 carbon atoms include the methoxycarbonyl group and the ethoxycarbonyl group. Examples include carbonyl groups and butoxycarbonyl groups, which are alkylcarbonyl groups with 2 to 13 carbon atoms. Examples of acetyl groups include acetyl groups, propionyl groups, and butyryl groups, with 2 to 1 carbon atoms. 3. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, Examples include butyryloxy groups. Examples of alicyclic hydrocarbon groups having 3 to 12 carbon atoms are listed below. ** represents X 0 This represents the bonding position with [the specified element]. TIFF0007879325000015.tif17162 Aromatic hydrocarbon groups with 6 to 10 carbon atoms include aryl groups such as phenyl and naphthyl groups. These are some examples. The combined groups include a hydroxyl group and an alkyl group with 1 to 12 carbon atoms. A combination of alkyl groups with 1 to 12 carbon atoms and aromatic hydrocarbon groups with 6 to 10 carbon atoms. The group combines an alicyclic hydrocarbon group with 3 to 12 carbon atoms and an aromatic hydrocarbon group with 6 to 10 carbon atoms. Examples include combined bases, etc. Groups that combine a hydroxyl group with an alkyl group having 1 to 12 carbon atoms include: Examples include methyl groups, hydroxyethyl groups, and other hydroxyalkyl groups having 1 to 12 carbon atoms. ru. A group combining an alkyl group with 1 to 12 carbon atoms and an aromatic hydrocarbon group with 6 to 10 carbon atoms. Examples include aralkyl groups with 7 to 22 carbon atoms, such as benzyl groups, tolyl groups, xylyl groups, and other carbon atoms. Examples include alkylaryl groups with prime numbers between 7 and 22. Combining alicyclic hydrocarbon groups with 3 to 12 carbon atoms and aromatic hydrocarbon groups with 6 to 10 carbon atoms Examples of such groups include the cyclohexylphenyl group.

[0025] X 0 The hydrocarbon group represented is preferably a C1-C7 group which may have substituents. 2 aliphatic hydrocarbon groups (the -CH2- contained in the aliphatic hydrocarbon group is -O-, -S-, It may be replaced by -CO- or -SO2-, and may have substituents, having 6 carbon atoms. ~36 aromatic hydrocarbon groups, groups represented by formula (aa) or groups represented by formula (bb) , More preferably, an alicyclic hydrocarbon group which may have a hydroxyl group or a fluorine atom ( The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO-, or -SO2- It may be replaced by: ), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group. (The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO2 - may be replaced by -CH2- contained in the chain hydrocarbon group, -O- or - It may be replaced by CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group are fluorine It may have an atom or a hydroxyl group. ), it may also have a fluorine atom or a hydroxyl group. A good aromatic hydrocarbon group, a group represented by formula (aa) or a group represented by formula (bb), More preferably, *-alicyclic hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group) may be replaced by -O-, -S-, -CO- or -SO2-, and the alicyclic carbon The hydrogen group may have a hydroxyl group or a fluorine atom. * is -COO - carbon atoms This indicates the bonding position with the alicyclic hydrocarbon group. ) *-alicyclic hydrocarbon group-chain hydrocarbon group (the alicyclic hydrocarbon group Even if the contained -CH2- is replaced by -O-, -S-, -CO- or -SO2- Often, the -CH2- contained in the chain-like hydrocarbon group is replaced by -O- or -CO-. The alicyclic hydrocarbon group and the chain hydrocarbon group may also have a fluorine atom or a hydroxyl group. It may be included. * indicates COO - This represents the bonding position with the carbon atom. ) *-chain hydrocarbon group- Alicyclic hydrocarbon group (the -CH2- contained in the chain hydrocarbon group is replaced with -O- or -CO-) It may be replaced, and the -CH2- contained in the alicyclic hydrocarbon group may be -O-, -S-, -CO- or -SO2- may be replaced, and the chain hydrocarbon group and the alicyclic carbon The hydrogen group may have a fluorine atom or a hydroxyl group. * is -COO - With carbon atoms Represents the bond position.), an aromatic hydrocarbon group which may have a fluorine atom or a hydroxyl group, The group is represented by formula (aa) or formula (bb), More preferably, a polycyclic alicyclic hydrocarbon group (the polycyclic alicyclic hydrocarbon group Even if the contained -CH2- is replaced by -O-, -S-, -CO- or -SO2- Often, the polycyclic alicyclic hydrocarbon group may have a hydroxyl group or a fluorine atom. Ha - COO - This represents the bonding position with the carbon atom. ) *-Polycyclic alicyclic hydrocarbon group-chain carbon Hydrogenated group (the -CH2- contained in the polycyclic alicyclic hydrocarbon group is -O-, -S-, -C It may be replaced by O- or -SO2-, and the -CH2- contained in the chain hydrocarbon group may be replaced by -O- or -CO-, and the polycyclic alicyclic hydrocarbon group and the The chain-like hydrocarbon group may have a fluorine atom or a hydroxyl group. * is -COO - carbon Represents the bonding position with an atom. ), *-chain hydrocarbon group-polycyclic alicyclic hydrocarbon group (the chain hydrocarbon group) The -CH2- contained in the hydrogenated group may be replaced with -O- or -CO-, and the majority The -CH2- group in a cyclic alicyclic hydrocarbon group is either -O-, -S-, -CO-, or -SO 2- may be replaced, and the chain-like hydrocarbon group and the polycyclic alicyclic hydrocarbon group are It may have a fluorine atom or a hydroxyl group. * is -COO - The bond positions with carbon atoms are shown. (aa) Aromatic hydrocarbon group which may have a fluorine atom or a hydroxyl group. The group is represented by formula (bb), Particularly preferred are an adamantanone group, a hydroxyadamantyl group, and an adamantyl group. A group combined with a lukyl group (the -CH2- contained in the alkyl group is -O- or -CO - May be replaced by: ), a group represented by formula (Y30F), having a hydroxyl group It is a phenyl group, a group represented by formula (aa), or a group represented by formula (bb). In the above group, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 36, and more preferably The range is 3 to 24, more preferably 3 to 18, and even more preferably 3 to 1 The number of carbon atoms in the chain hydrocarbon group is preferably 6, and more preferably 3 to 12. is 1 to 18, more preferably 1 to 12, and even more preferably 1 to 9, More preferably 1 to 6, and even more preferably 1 to 4. Aromatic hydrocarbon group The number of carbon atoms is preferably 6 to 36, more preferably 6 to 24, and even more preferably The value is 6 to 18, more preferably 6 to 14, and even more preferably 6 to 1 It is 0. TIFF0007879325000016.tif26125[In formula (aa), X a and X b These represent either -O- or -S- independently. X 1a This represents a hydrocarbon group having 1 to 24 carbon atoms, which may have substituents, and contains The -CH2- group may be replaced by -O-, -S-, -CO-, or -SO2-. stomach. X 2a This represents a hydrocarbon group having 1 to 48 carbon atoms, which may have substituents, and contains The -CH2- group may be replaced by -O-, -S-, -CO-, or -SO2-. stomach. * indicates the bonding position of the carbonyl group to the carbon atom. [In formula (bb), L A This represents an alkanediyl group having 1 to 6 carbon atoms, which may contain a fluorine atom. LB This represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, and the alkanediyl group contains The -CH2- group may be replaced by -O-, -S-, -CO-, or -SO2-. stomach. R A This represents a hydrocarbon group having 1 to 36 carbon atoms, which may have substituents, and contains The -CH2- group may be replaced by -O-, -S-, -CO-, or -SO2-. stomach. * indicates the bonding position of the carbonyl group to the carbon atom.

[0026] X a and X b It is preferable that they are the same atom, and more preferably that they are both oxygen atoms. It's nice.

[0027] X 1a and X 2a The hydrocarbon groups represented include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and Examples include groups formed by combining two or more of these groups. Note that these hydrocarbon groups have substituents. They may also contain -CH2-, -O-, -S-, It may be replaced with -CO- or -SO2-. Here, the number of carbon atoms in the hydrocarbon group is This refers to the number of carbon atoms in a hydrocarbon group that does not have substitution or replacement.

[0028] X 1a Examples of aliphatic hydrocarbon groups include chain hydrocarbon groups such as alkanetriyl groups and alicyclic hydrocarbon groups. Examples include hydrogenated groups or groups combining these. Examples of alkanetriyl groups include methine, ethanetriyl, and propanetriyl groups. Lyyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group Iyl group, octantriyl group, nonantriyl group, decantriyl group, undecantryyl Examples include the yl group and the dodecantryyl group.

[0029] The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include the cyclobutanetriyl group and the cyclopentanetriyl group. Examples include the triyl group, cyclohexanetriyl group, and cyclooctanetriyl group. Examples of polycyclic alicyclic hydrocarbon groups include norbornanetriyl groups and norbornanetriyl Examples include the adamantane triyl group. Aromatic hydrocarbon groups include benzenetriyl group, naphthalenetriyl group, and anthracete Examples include nitryl groups. In the case of combined groups, groups with different valencies (alkyl groups, alkanedies) among the above-mentioned groups chloro group, alkanetetrayl group, cycloalkyl group, cycloalkanediyl group, cycloal It may contain (cantetrayl group, etc.).

[0030] X 1a The hydrocarbon group represented by has 1 to 24 carbon atoms, and further comprises one or more substituents. They may have. The substituents include a hydroxyl group, a halogen atom, a cyano group, and a number of carbon atoms. 1-12 alkyl groups, alkoxy groups with 1-12 carbon atoms, alkoxy groups with 2-13 carbon atoms Carbonyl group, alkylcarbonyl group having 2 to 13 carbon atoms, alkylcarbonyl group having 2 to 13 carbon atoms Nyloxy group, alicyclic hydrocarbon group with 3 to 12 carbon atoms, aromatic hydrocarbon group with 6 to 10 carbon atoms Alternatively, combinations of these can be used. Halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbon Nyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group and these The groups that combine these elements are the same as those mentioned above.

[0031] X 1a The hydrocarbon group represented by this is an alkane having 1 to 6 carbon atoms, which may have substituents. It is preferably a lyyl group or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents. Furthermore, alkanetriyl groups with 1 to 6 carbon atoms are represented by formulas (w1-1) to (w1-11). It is more preferable that the group be a carbon-1 to carbon-6 alkanetriyl group, formula (w1-1) Polycyclic hydrocarbon groups such as the group represented by formula (w1-3) or the group represented by formula (w1-2) It is more preferable that the group is a monocyclic hydrocarbon group such as the group represented by formula (w1-6). It's nice. TIFF0007879325000017.tif53143 [Formula (w1-1) to formula (w1-11), The ring consists of a hydroxyl group, a halogen atom, a cyano group, an alkyl group with 1 to 12 carbon atoms, and a carbon number 1-12 alkoxy groups, 2-13 alkoxycarbonyl groups, 2-13 carbon atoms Alkylcarbonyl group, alkylcarbonyloxy group with 2-13 carbon atoms, C3-12 carbon atoms Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 10 carbon atoms, or groups combining these. It is acceptable to have it. * indicates a bond position.

[0032] X 2a The number of carbon atoms in the hydrocarbon group represented is preferably 2 to 48, and is 4 to 48. It is more preferable that it be 6 to 44, and even more preferable that it be 8 to 40. It is even more preferable that the value be between 10 and 38. Here, the carbon number of the hydrocarbon group is the carbon of an unsubstituted hydrocarbon group that does not have substituents. It means prime number.

[0033] X 2aThe substituents that the hydrocarbon group in the hydrocarbon group may have include a hydroxyl group and a halogen. Atom, cyano group, alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, carbon number 2-13 alkoxycarbonyl groups, C2-13 alkylcarbonyl groups, C2 ~13 alkylcarbonyloxy groups, alicyclic hydrocarbon groups with 3-12 carbon atoms, C6- Examples include 10 aromatic hydrocarbon groups or groups formed by combining these groups. Halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbon Nyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group and these The groups that combine these elements are the same as those mentioned above. X 2a A hydrocarbon group having 1 to 48 carbon atoms, represented by , has one substituent or multiple substituents. It's fine if you do that.

[0034] X 2a The hydrocarbon group in this context is a linear or branched chain hydrocarbon group (for example, aluminum Examples include candiyl groups, monocyclic or polycyclic alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. A combination of two or more of these groups is also acceptable. 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 Linear alkanediyl groups such as ,7-diyl groups and octane-1,8-diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Monocyclic cycloalkanes such as n-1,4-diyl groups and cyclooctane-1,5-diyl groups A monocyclic alicyclic hydrocarbon group that is an yl group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic cycloalkanediyl groups such as 1,5-diyl groups and adamantane-2,6-diyl groups A polycyclic alicyclic hydrocarbon group; Phenylene group, naphthylene group, biphenylene group, anthrylene group, phenanthrylene group Examples include aromatic hydrocarbon groups such as binaphthylene groups. In the case of combined groups, groups with different valencies (alkyl groups, alkanet groups) are included in the above group. Iyl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cyclo It may contain (such as an alkanetetrayl group). The combined groups include a group that combines a chain-like hydrocarbon group and an alicyclic hydrocarbon group, and a chain-like group. A group combining a hydrocarbon group and an aromatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group Examples include groups that combine these, specifically, a chain hydrocarbon group with one or more alicyclic hydrocarbon groups. A group to which a chain hydrocarbon group is bonded (for example, a chain hydrocarbon group - alicyclic hydrocarbon group, a chain hydrocarbon group - alicyclic hydrocarbon group) (Examples) Cyclic hydrocarbon group (2nd class), group in which one or more chain hydrocarbon groups are bonded to an alicyclic hydrocarbon group. For example, -alicyclic hydrocarbon group-chain hydrocarbon group, -alicyclic hydrocarbon group-(chain hydrocarbon group) (2nd class), a group in which one or more alicyclic hydrocarbon groups and a chain hydrocarbon group are bonded to a chain hydrocarbon group (e.g.) For example, -chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group, -chain hydrocarbon group-(alicyclic hydrocarbon group) Examples include cyclic hydrocarbon groups and chain hydrocarbon groups (2, etc.).

[0035] X 2a As for hydrocarbon groups in this context, A chain-like hydrocarbon group having 2 to 18 carbon atoms (the -CH2- contained in this chain-like hydrocarbon group is -O- Alternatively, it may be replaced with -CO-, and the chain-like hydrocarbon group may have substituents. stomach.), Alicyclic hydrocarbon groups having 3 to 18 carbon atoms (the -CH2- contained in the alicyclic hydrocarbon group is - The alicyclic hydrocarbon group may be replaced by O-, -S-, -CO- or -SO2-. It may have substituents. ), or, A chain-like hydrocarbon group having 1 to 12 carbon atoms (the -CH2- contained in the chain-like hydrocarbon group is -O- Alternatively, it may be replaced with -CO-.) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon group) The -CH2- contained in the cyclic hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2-. A group that is a combination of (which may have substituents) (which may be replaced) It is preferable that there be such a thing. A chain-like hydrocarbon group having 4 to 18 carbon atoms (the -CH2- contained in this chain-like hydrocarbon group is -O- Alternatively, it may be replaced with -CO-, and the chain-like hydrocarbon group may have substituents. i. ), or, A chain-like hydrocarbon group having 1 to 12 carbon atoms (the -CH2- contained in the chain-like hydrocarbon group is -O- Alternatively, it may be replaced with -CO-.) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (the alicyclic hydrocarbon group) The -CH2- contained in the cyclic hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2-. A group that is a combination of (which may have substituents) (which may be replaced) It is preferable that there be such a thing. A chain-like hydrocarbon group having 6 to 14 carbon atoms (the -CH2- contained in this chain-like hydrocarbon group is -O- Alternatively, it may be replaced with -CO-, and the chain-like hydrocarbon group may have substituents. i. ), or, A chain-like hydrocarbon group having 1 to 12 carbon atoms (the -CH2- contained in the chain-like hydrocarbon group is -O- Alternatively, it may be replaced with -CO-.) and an alicyclic hydrocarbon group having 5 to 14 carbon atoms (the alicyclic hydrocarbon group) The -CH2- contained in the cyclic hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2-. A group that is a combination of (which may have substituents) (which may be replaced) It would be even better if it were a certain way.

[0036] Specifically, X 2a As for hydrocarbon groups in this context, Alkanediyl groups having 2 to 18 carbon atoms (the -CH2- contained in the alkanediyl group is - It may be replaced by O- or -CO-, and the alkanediyl group may have substituents. (That's fine.) Alicyclic hydrocarbon groups having 3 to 18 carbon atoms (the -CH2- contained in the alicyclic hydrocarbon group is - The alicyclic hydrocarbon group may be replaced by O-, -S-, -CO- or -SO2-. (It may have substituents.) Alkanediyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkanediyl group is - It may be replaced by O- or -CO-.) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms ( The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO-, or -SO2- A group consisting of (which may have substituents), or Alkanediyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkanediyl group is - (May be replaced by O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms Alkyl alkyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkyl group is -O- or -CO -May be replaced by ) and a group consisting of (the group may have substituents). It is preferable that this be the case. Alkanediyl groups having 4 to 18 carbon atoms (the -CH2- contained in the alkanediyl group is - It may be replaced by O- or -CO-, and the alkanediyl group may have substituents. (That's fine.) Alkanediyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkanediyl group is - It may be replaced by O- or -CO-.) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms ( The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO-, or -SO2- A group consisting of (which may have substituents), or Alkanediyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkanediyl group is - (May be replaced by O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms Alkyl alkyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkyl group is -O- or -CO -May be replaced by ) and a group consisting of (the group may have substituents). It is more preferable that, Alkanediyl groups having 6 to 14 carbon atoms (the -CH2- contained in the alkanediyl group is - It may be replaced by O- or -CO-, and the alkanediyl group may have substituents. (That's fine.) Alkanediyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkanediyl group is - It may be replaced by O- or -CO-.) and adamantanediyl group (the adamanta The -CH2- group in the nucleotide group may be replaced by -O- or -CO-. A group consisting of (the group may have substituents), or Alkanediyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkanediyl group is - It may be replaced by O- or -CO-. ) and an adamantanediyl group and a carbon number of 1 to 1 2 alkyl groups (the -CH2- contained in the alkyl group is replaced by -O- or -CO-) It may be a group consisting of (the group may have substituents). Even better.

[0037] Specifically, X 2a is the equation (X 2 The base represented by (X -1), formula (X 2 (2) the base, formula (X 2 (X) is represented by a base or formula (X 2 It is preferable that the group is represented by (-4). TIFF0007879325000018.tif34157[In the formula, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x These are, independently, A with 1 to 6 carbon atoms. Lukyl groups, alicyclic hydrocarbon groups with 5 to 12 carbon atoms, or combinations of two or more of these groups. The group is represented, and the -CH2- contained in the alkyl group and the alicyclic hydrocarbon group is -O-, -S -, -CO- or -SO2- may be replaced, and the alkyl group and the alicyclic carbon The hydrogen group may have substituents. * is X a and X b [This represents the bonding position with .] The combined group consists of one alkyl group and one alicyclic hydrocarbon group as described above. It may be a single object, or a base formed by combining two or more of either of them, or two or more of both. In this case, the combination The combined number of carbon atoms in the group is 39 or less, preferably 37 or less.

[0038] Among them, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x As for, A The alkyl group (the -CH2- contained in the alkyl group is replaced by -O- or -CO-) It may also be, and the alkyl group may have substituents. ), alicyclic carbon having 5 to 12 carbon atoms Hydrogenated group (the -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or It may be replaced by -SO2-, and the alicyclic hydrocarbon group may have substituents. i. ) or an alkyl group having 1 to 6 carbon atoms (the -CH2- contained in the alkyl group is -O- or (The alicyclic hydrocarbon group may be replaced with -CO-.) and a alicyclic hydrocarbon group having 5 to 12 carbon atoms (the alicyclic The -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2-. A group that is a combination of (which may have substituents) (which may be substituted) Preferably, a methoxy group, an adamantyl group (containing -CH) is present in the adamantyl group. 2- may be replaced with -O- or -CO-, and the adamantyl group has substituents ) or an alkyl group having 1 to 6 carbon atoms (the alkyl group contains -CH2 - may be replaced with -O- or -CO-.) and the adamantyl group are combined It is more preferable that the group is a set group (which may have substituents).

[0039] In equation (bb), L A and L B As for the alkanediyl group having 1 to 6 carbon atoms: For example, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group. Linear alkanes such as yl groups, pentane-1,5-diyl groups, and hexane-1,6-diyl groups. Diyl group; propane-1,2-diyl group, 1-methylpropane-1,3-diyl group, 2- Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methyl Branched alkanes such as louboutan-1,4-diyl group and 2-methylbutane-1,4-diyl group Examples include diyl groups. The number of carbon atoms in the alkanediyl group is preferably 1 to 4, and more Preferably, it is 1 to 3. Examples of alkanediyl groups that may contain a fluorine atom include difluoromethylene groups and phenyl Perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and Examples include perfluoroalkanediyl groups such as perfluoropentanediyl groups. The -CH2- group in the alkanediyl group is replaced by -O- or -CO-. In addition, the number of carbon atoms before replacement is defined as the total number of carbon atoms in the alkanediyl group. , hydroxyl group (a group in which the -CH2- contained in the methyl group is replaced by -O-), A boxy group (a group in which the -CH2-CH2- contained in an ethyl group is replaced with -O-CO-). , an alkoxy group (where -CH2- at any position within an alkyl group is replaced by -O-) (a group that has been added), an alkoxycarbonyl group (a -CH2-C group at any position within an alkyl group) A group in which H2- is replaced by -O-CO-), an alkylcarbonyl group (containing within the alkyl group) (A group in which -CH2- at any position is replaced by -CO-), alkylcarbonyl group Xy group (where any -CH2-CH2- in the alkyl group is replaced by -CO-O-) (alternated group), alkanediyloxy group (any position contained within the alkanediyl group) CH2- is replaced by -O- in the group, alkanediyloxycarbonyl group (alkane A group in which any -CH2-CH2- at any position in the diyl group is replaced by -O-CO-. ), alkanediyl carbonyl group (-CH2 at any position contained within the alkanediyl group) - (a group replaced by -CO-), alkanediylcarbonyloxy group (alkanediyl A group in which any -CH2-CH2- at any position in the group is replaced by -CO-O- It is acceptable to have it. Examples of alkanediyloxy groups include methyleneoxy group, ethyleneoxy group, and p Examples include ropanediyloxy groups, butanediyloxy groups, and pentanediyloxy groups. . Examples of alkanediyloxycarbonyl groups include the methyleneoxycarbonyl group. Ethyleneoxycarbonyl group, propanediyloxycarbonyl group, butanediyloxy Examples include carbonyl groups. Examples of alkanediylcarbonyl groups include methylenecarbonyl groups and ethylenecarbonyl groups. Bonyl group, propanediyl carbonyl group, butanediyl carbonyl group, pentanediyl Examples include the rubonyl group. Examples of alkanediylcarbonyloxy groups include methylenecarbonyloxy groups. Ethylene carbonyloxy group, propanediyl carbonyloxy group, butanediylcarbon Examples include the yloxy group. L A This is an alkanediyl group having 1 to 4 carbon atoms, which may contain a fluorine atom. Preferably, it is an alkanediyl group having 1 to 3 carbon atoms and containing a fluorine atom. stomach. L BThis refers to a single bond or an alkanediyl group having 1 to 3 carbon atoms (the alkanediyl group contains It is preferable that -CH2- may be replaced with -O- or -CO-. It is more preferable that the group is a single bond, a methylene group, or an ethylene group.

[0040] R A The hydrocarbon groups in this context include aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, etc.). Chain hydrocarbon groups such as lukinyl groups and alicyclic hydrocarbon groups), aromatic hydrocarbon groups and these Examples of groups formed by combining them include: Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, and n-propyl group. butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -Heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, Examples include n-undecyl groups and n-dodecyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 9, more More preferably 1 to 6, and even more preferably 1 to 4. Examples of alkenyl groups include ethenyl group, propenyl group, isopropenyl group, butenyl group, Isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples include the octinyl group, isooctinyl group, and nonenyl group. Examples of alkynyl groups include ethynyl group, propynyl group, isopropynyl group, butynyl group, Isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octinyl group, Examples include noninyl groups. The -CH2- contained in the chain hydrocarbon group is converted to -O-, -S-, -CO-, or -SO2-. The replaced groups include hydroxyl groups, carboxyl groups, alkoxy groups, and alkoxycal groups. Examples include vonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, and alkylthio groups. It can be done. Alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyl Examples of oxy groups and alkylthio groups include alkoxy groups having 1 to 17 carbon atoms, and carbon atoms 2-17 alkoxycarbonyl groups, 2-18 alkylcarbonyl groups, 2 carbon atoms Examples include alkylcarbonyloxy groups with up to 17 carbon atoms and alkylthio groups with 1 to 17 carbon atoms. Similar groups to those mentioned above can be cited. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and saturated and It can be either unsaturated or unsaturated. Examples of monocyclic or alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo Monocyclic cycloal groups such as octyl, cyclononyl, cyclodecyl, and cyclododecyl groups Examples include the chyl group. Polycyclic alicyclic hydrocarbon groups include, for example, decahydronaphthyl. Examples include polycyclic cycloalkyl groups such as adamantyl groups and norbornyl groups. Alicyclic hydrocarbon groups and the -CH2- contained in alicyclic hydrocarbon groups are -O-, -S-, - Specifically, the groups that have been replaced by CO- or -SO2- are those in the above equations (y1) to (y7) Examples include the group represented in 1). The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 36. Yes, more preferably 3 to 24, even more preferably 3 to 18, even more preferably More preferably 3 to 16, and even more preferably 3 to 12. Aromatic hydrocarbon groups include phenyl group, naphthyl group, biphenyl group, anthryl group, Examples include aryl groups such as phenanthryl groups and binaphthyl groups. Carbon of aromatic hydrocarbon groups The prime numbers are preferably 6 to 36, more preferably 6 to 24, and even more preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. be. In the case of combined groups, the groups with different valencies (alkanediyl group, alkanediyl group) are mentioned above. It contains (such as cycloalkanediyl groups, cycloalkanetriyl groups, etc.) That's good too. The groups formed by combining them include aromatic hydrocarbon groups and chain hydrocarbon groups. Groups that combine (for example, aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic) Aromatic hydrocarbon groups (*), groups combining alicyclic hydrocarbon groups and chain hydrocarbon groups (for example) , alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), fragrance A group that combines a fragrant hydrocarbon group and an alicyclic hydrocarbon group (for example, an aromatic hydrocarbon group - alicyclic hydrocarbon group) Examples include cyclic hydrocarbon groups (*) and alicyclic hydrocarbon groups (*) (aromatic hydrocarbon groups). This indicates the joining point. Aromatic hydrocarbon groups - alkanediyl groups - * include benzyl groups, phenethyl groups, etc. One example is the larchyl group. Examples of alkyl-aromatic hydrocarbon groups include tolyl, xylyl, and coumenyl groups. It can be listed. Examples of alicyclic hydrocarbon groups - alkanediyl groups -* include cyclohexylmethyl group, cyclo Hexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 Examples include cycloalkylalkyl groups such as -yl-1-methylethyl. Examples of alkyl-alicyclic hydrocarbon groups include methylcyclohexyl group and dimethylcyclohexyl group. Cyclohexyl group, 2-alkyladamantan-2-yl group, and other alkyl groups Examples include the lukil group. Examples of aromatic hydrocarbon groups (alicyclic hydrocarbon groups) include the phenyladamantyl group. It is possible. Examples of alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include the adamantylphenyl group. It is possible. In terms of combinations, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups are Each of these may be combined with two or more other types. Also, any of the groups may be L B Even if you're home stomach. The -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2-. In addition to the groups mentioned above, the other groups that have been replaced include cycloalkoxy groups and cycloalkylalkoxy groups. C group, alkoxycarbonyloxy group, aromatic hydrocarbon group-carbonyloxy group, these Examples include groups that combine two or more of these groups. Examples of cycloalkoxy groups include cycloalkoxy groups with 3 to 17 carbon atoms, for example Examples include cyclohexyloxy groups. Examples of cycloalkylalkoxy groups include carbon Examples include cycloalkylalkoxy groups with prime numbers 4 to 17, for example, cyclohexylmethyl Examples include alkoxycarbonyloxy groups, which have 2 to 16 carbon atoms. Examples include xycarbonyloxy groups, such as the butoxycarbonyloxy group. Aromatic hydrocarbon groups - carbonyloxy groups include aromatic hydrocarbons with 7 to 17 carbon atoms. Examples include carbonyloxy groups, such as the benzoyloxy group. The -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -SO2-, or -CO-. If a substitution has occurred, the number of carbon atoms before the substitution shall be considered the total number of carbon atoms in the hydrocarbon group. The number can be one, or two or more.

[0041] R A The substituents that the hydrocarbon group may have include a halogen atom, a cyano group, and a carbon atom. Alkyl groups number 1 to 12 (the -CH2- contained in the alkyl group is -O-, -S-, -C Examples include those that may be replaced by O- or -SO2-. Examples of halogen atoms include the same groups as those described above. Examples of alkyl groups having 1 to 12 carbon atoms include the same groups as those described above. Groups in which the -CH2- group in an alkyl group is replaced by -O- or -CO- include: Hydroxy group, carboxyl group, alkoxy group, alkoxycarbonyl group, alkylcarbon Examples include the nyl group and the alkylcarbonyloxy group. Alkoxy group, alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyl Examples of alkoxy groups include alkoxy groups with 1 to 11 carbon atoms and alkoxycal groups with 2 to 11 carbon atoms. Bonyl group, alkylcarbonyl group with 2 to 12 carbon atoms, alkylcarbonyl group with 2 to 11 carbon atoms Examples include luoxy groups, such as the same groups as those mentioned above. R A The hydrocarbon group in may have one substituent or multiple substituents.

[0042] R A The hydrocarbon group in this is an alkyl group having 1 to 12 carbon atoms, which may have substituents. (However, the -CH2- contained in the alkyl group is -O-, -S-, -CO- or -SO2 -May be replaced by ) or cyclic carbonized water having 3 to 18 carbon atoms which may have substituents Elementary group (however, the -CH2- contained in the cyclic hydrocarbon group is -O-, -S-, -CO- or It may be replaced by -SO2-.) Preferably, it is a fluorine atom, a hydroxyl A cyclic hydrocarbon group having 3 to 18 carbon atoms may have a C1-C6 alkyl group (however Furthermore, the -CH2- contained in the cyclic hydrocarbon group is -O-, -S-, -CO-, or -SO2 - may be replaced with this. ) is preferable.

[0043] As for cyclic hydrocarbon groups, monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms and Cyclic hydrocarbon groups such as aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof. These are some examples. As for alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combined groups, they are the same as the groups mentioned above. Some examples can be listed. In addition, in the combination, there may be no more than two types of alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The above can be combined. Also, any of the bases is L B They may be bound together.

[0044] A cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may contain a fluorine atom, a hydroxyl group, or The alicyclic hydrocarbon group may have an alkyl group with 1 to 6 carbon atoms, and the -CH2- (This may be replaced by -O-, -S-, -CO-, or -SO2-.) A C3-C1 alkyl group which may have a fluorine atom, a hydroxyl group, or a C1-C4 alkyl group. 8 alicyclic hydrocarbon groups (the -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, (May be replaced by -CO- or -SO2-), or, A C6-C1 atom which may have a fluorine atom, a hydroxyl group, or a C1-C4 alkyl group. It is preferably an aromatic hydrocarbon group of 8. A C3-C1 alkyl group which may have a fluorine atom, a hydroxyl group, or a C1-C4 alkyl group. 8. Alicyclic hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group is -O- or -CO It is more preferable that it be replaced by -. Examples of alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, and cyclopentyl group. Cyclohexyl group, norbornyl group, adamantyl group, and the following groups (bonding site is at any position) (is preferred), and as aromatic hydrocarbon groups, phenyl groups and naphthyl groups are preferred. TIFF0007879325000019.tif1687

[0045] Examples of anion (I) include carboxylic acid anions listed below. TIFF0007879325000020.tif98162

[0046] TIFF0007879325000021.tif118134

[0047] TIFF0007879325000022.tif126139

[0048] TIFF0007879325000023.tif124154

[0049] TIFF0007879325000024.tif155143

[0050] TIFF0007879325000025.tif218160

[0051] TIFF0007879325000026.tif192163

[0052] Specific examples of carboxylate salts (IA) and carboxylate salts (IB) include the cations mentioned above and Examples include salts formed by any combination of anions. Carboxylate salts (IA) and carboxylic acids. Specific examples of salts (IB) 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, the carboxylate salt (IA-1) is formed from the anion represented by formula (Ia-1) and formula ( A salt consisting of the cation represented by IA-c-1), and the carboxylate salt (IB-1) is It consists of an anion represented by formula (Ia-1) and a cation represented by formula (IB-c-1). It is a salt, and represents the following salts. TIFF0007879325000027.tif62129 [Table 1] TIFF0007879325000029.tif223166 TIFF0007879325000030.tif223166 TIFF0007879325000031.tif223166 TIFF0007879325000032.tif223166 TIFF0007879325000033.tif223166 TIFF0007879325000034.tif223166 TIFF0007879325000035.tif125165

[0053] [Table 2] TIFF0007879325000037.tif223165 TIFF0007879325000038.tif223165 TIFF0007879325000039.tif223165 TIFF0007879325000040.tif223165 TIFF0007879325000041.tif47155

[0054] In particular, carboxylate salts (IA) are carboxylate salts (IA-1) ~ carboxylate salts (IA- 5) Carboxylate salts (IA-30) to carboxylate salts (IA-34), carboxylate salts (IA -59) ~Carboxylate (IA-63), Carboxylate (IA-88) ~Carboxylate ( IA-92), carboxylate (IA-117) ~ carboxylate (IA-121), carb Carboxylate (IA-146) ~ Carboxylate (IA-150), Carboxylate (IA-187 )~Carboxylate (IA-257), Carboxylate (IA-282)~Carboxylate (I It is preferable that it be A-292), and the carboxylate salt (IB) is carboxylate salt (IB-1 )~Carboxylate (IB-5), Carboxylate (IB-30)~Carboxylate (IB-3 4) Carboxylate (IB-59) ~ Carboxylate (IB-63), Carboxylate (IB -88) Carboxylate (IB-92), Carboxylate (IB-125) Carboxylate (IB-173), carboxylate salt (IB-198) ~ carboxylate salt (IB-208) It is preferable to do so.

[0055] <Method for producing carboxylate salts (IA)> Carboxylate salts (IA) include salts represented by formula (Ia) and salts represented by formula (Ib). It can be produced by reacting it in a solvent in the presence of a base catalyst. TIFF0007879325000042.tif75152[In this formula, all symbols have the same meaning as described above.] Examples of bases include potassium carbonate. Examples of solvents include chloroform, dimethylformamide, and acetonitrile. ru. The reaction temperature is typically between 15°C and 140°C, and the reaction time is typically between 0.5 and 24 hours. .

[0056] Examples of salts represented by formula (Ia) include compounds represented by the following formula, and are available from the market. These salts are readily available. Furthermore, these salts are described in Japanese Patent Publication No. 2011-39502. Refer to the methods described in Japanese Patent Publication No. 2014-88367 and Japanese Patent Publication No. 2013-200561. You can also gain something from thinking about it. TIFF0007879325000043.tif184151

[0057] Examples of salts represented by formula (Ib) include those represented by the following formula, which are readily available on the market. These salts can be obtained from Japanese Patent Publication No. 2011-39502, Japanese Patent Publication No. Japanese Patent Publication No. 2012-224611, Japanese Patent Publication No. 2014-88367, Japanese Patent Publication No. 2013-20 This can also be obtained by referring to the method described in Publication No. 0561. TIFF0007879325000044.tif167145

[0058] Carboxylate salts (IA) include salts represented by formula (Ic) and salts represented by formula (Id). It can also be produced by reacting it in a solvent in the presence of a base catalyst. TIFF0007879325000045.tif71150[In this formula, all symbols have the same meaning as described above.] Examples of bases include potassium carbonate. Examples of solvents include chloroform, dimethylformamide, and acetonitrile. ru. The reaction temperature is typically between 15°C and 140°C, and the reaction time is typically between 0.5 and 24 hours. .

[0059] Examples of salts represented by formula (Ic) include compounds represented by the following formula, and are available from the market. These salts are readily available. Furthermore, these salts are described in Japanese Patent Publication No. 2011-39502. Refer to the methods described in Japanese Patent Publication No. 2014-88367 and Japanese Patent Publication No. 2013-200561. You can also gain something from thinking about it. TIFF0007879325000046.tif209167

[0060] Examples of salts represented by formula (Id) include those represented by the following formula, which are readily available on the market. These salts can be obtained from Japanese Patent Publication No. 2011-39502, Japanese Patent Publication No. Japanese Patent Publication No. 2012-224611, Japanese Patent Publication No. 2014-88367, Japanese Patent Publication No. 2013-20 This can also be obtained by referring to the method described in Publication No. 0561. TIFF0007879325000047.tif223165

[0061] <Method for producing carboxylate salts (IB)> Carboxylate salts (IB) include the salt represented by formula (Ia) and the salt represented by formula (I-b1). By reacting the salt represented by formula (I-a1) with a base catalyst in a solvent, It can be manufactured. TIFF0007879325000048.tif79166[In this formula, all symbols have the same meaning as described above.] Examples of bases include potassium carbonate. Examples of solvents include chloroform, dimethylformamide, and acetonitrile. ru. The reaction temperature is typically between 15°C and 140°C, and the reaction time is typically between 0.5 and 24 hours. .

[0062] Examples of salts represented by formula (I-a1) include compounds represented by the following formula, and are available on the market. These salts are readily available. Furthermore, these salts are described in Japanese Patent Publication No. 2011-39502. The methods described in Japanese Patent Publication No. 2014-88367 and Japanese Patent Publication No. 2013-200561 You can also learn from it. TIFF0007879325000049.tif208163

[0063] Examples of salts represented by formula (I-b1) include salts represented by the following formula, and are available in larger quantities on the market. These salts are readily available. Furthermore, these salts are described in Japanese Patent Publication No. 2011-39502, Japanese Patent Publication No. 2012-224611, Japanese Patent Publication No. 2014-88367, Japanese Patent Publication No. 2013-2 This can also be obtained by referring to the method described in Public Notice No. 00561. TIFF0007879325000050.tif178165

[0064] Carboxylate salts (IB) include salts represented by formula (Ic) and salts represented by formula (I-d1). By reacting the salt represented by formula (I-c1) with a base catalyst in a solvent, It can also be manufactured. TIFF0007879325000051.tif76165[In this formula, all symbols have the same meaning as described above.] Examples of bases include potassium carbonate. Examples of solvents include chloroform, dimethylformamide, and acetonitrile. ru. The reaction temperature is typically between 15°C and 140°C, and the reaction time is typically between 0.5 and 24 hours. .

[0065] Examples of salts represented by formula (I-c1) include compounds represented by the following formula, and are available on the market. These salts are readily available. Furthermore, these salts are described in Japanese Patent Publication No. 2011-39502. The methods described in Japanese Patent Publication No. 2014-88367 and Japanese Patent Publication No. 2013-200561 You can also learn from it. TIFF0007879325000052.tif203164

[0066] Examples of salts represented by formula (I-d1) include the salt represented by the following formula, and are available in larger quantities on the market. These salts are readily available. Furthermore, these salts are described in Japanese Patent Publication No. 2011-39502, Japanese Patent Publication No. 2012-224611, Japanese Patent Publication No. 2014-88367, Japanese Patent Publication No. 2013-2 This can also be obtained by referring to the method described in Public Notice No. 00561. TIFF0007879325000053.tif219170

[0067] [Carboxylic acid generator] The carboxylic acid generator of the present invention is an acid generator containing a carboxylic acid salt (I). The acid generating agent may contain only one type or two or more types of carboxylate (I) salts. The carboxylate salt (I) of the present invention acts as an acid generator in a resist composition. It is possible. The carboxylic acid generator of the present invention is a carboxylate other than carboxylate salt (I) known in the resist field. It may contain carboxylates. In this case, carboxylates other than carboxylates (I) may be included. The ratio (mass ratio) of the carboxylate content to the carboxylate is usually 1:99 to 100:0, preferably 1 :99~99:1, more preferably 2:98~98:2, even more preferably 5:95~9 It's 5:5.

[0068] [Resist composition] The resist composition contains a carboxylic acid generator containing the carboxylic acid salt (I) of the present invention, and Acid generators other than vonite (I) (B) and resins having acid-unstable groups (hereinafter referred to as "resin (A)") (There are cases where this occurs) and contains. Here, "acid-unstable group" refers to a group that has a leaving group and comes into contact with an acid. Upon contact, the leaving group is removed, forming a hydrophilic group (e.g., a hydroxyl group or a carboxyl group). It means the basis for doing something. The resist composition further includes a quencher (hereinafter referred to as "quencher (C)") It may contain (a) and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). In the resist composition of the present invention, the content of carboxylate salt (I) is the resist composition Preferably, the amount is 0.1% by mass or more and 35% by mass or less relative to the solid content, and 0.5% by mass or more and 30% by mass or less. It is more preferable that the amount be less than or equal to % by mass, and even more preferable that it be between 1% by mass and 25% by mass.

[0069] <Acid Generator (B)> If the resist composition of the present invention contains an acid generator (B), etc., then a carboxylate salt (I) and The ratio of the content of acid generator (B) to carboxylate (I): acid generator (B), etc., is: Typically, the ratio is 1:99 to 100:0, preferably 1:99 to 99:1, and more preferably 2:98. ~98:2, and more preferably 5:95~95:5. Furthermore, if the resist composition of the present invention contains an acid generator (B), etc., a carboxylate (I The total content of the acid generator (B), etc., is preferably per 100 parts by mass of resin (A). 1 part by mass or more (more preferably 3 parts by mass or more), preferably 55 parts by mass or less (more preferably (The amount is 50 parts by mass or less, more preferably 45 parts by mass or less)

[0070] The acid generator (B) may be either nonionic or ionic. As herbal preparations, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate ester) are used. Sulfonate, oximesulfonate, N-sulfonyloxiimide, sulfonyloxyke Ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, keto Examples include sulfones, sulfonyl diazomethanes, etc. Ionic acid generators include onions. Onium salts containing um cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples include salts (iodonium salts). An anion of anium salts is aniodonium sulfonate. Examples include sulfonylimide anions, sulfonylmethide anions, and others.

[0071] As for the acid generating agent (B), see Japanese Patent Publication No. 63-26653, Japanese Patent Publication No. 55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 Japanese Patent Publication No. 62-153853, Japanese Patent Publication No. 63-146029, U.S. Patent No. 3,779, Patent No. 778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate acid when exposed to radiation, as described in publications No. 126, 712, etc., can be used. Compounds manufactured by known methods may also be used. The acid generator (B) may consist of two or more types. They may be used in combination.

[0072] The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a fluorine-containing acid generator of formula (B1). This is a salt represented by (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007879325000054.tif2962[In formula (B1), Q b1 and Q b2 Each of these independently contains a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. It represents the 'L' group. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the saturated hydrocarbon group contains -CH2- may be replaced by -O- or -CO-, and the saturated hydrocarbon group is contained The hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups. Y is a methyl group which may have substituents or a C3-C2 group which may have substituents 4 represents an alicyclic hydrocarbon group, and the -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + This represents an organic cation.

[0073] Q b1 and Q b2 The perfluoroalkyl group represented by is a trifluoromethyl group, perfluoro Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro Butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perflu Examples include the olopentyl group and the perfluorohexyl group. Q b1 and Q b2 Each of these independently consists of a fluorine atom or a trifluoromethyl group. Preferably, both are fluorine atoms, and more preferably, both are fluorine atoms.

[0074] L b1 Examples of divalent saturated hydrocarbon groups in this context include linear alkanediyl groups and branched alkanediyl groups. Examples include dipropyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these groups It may also be a group formed by combining two or more of these types. 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, 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 Branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as n-1,4-diyl group and cyclooctane-1,5-diyl group A monocyclic, divalent, alicyclic saturated hydrocarbon group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic saturated carbon such as 1,5-diyl group and adamantane-2,6-diyl group Examples include hydrogen groups.

[0075] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The substituted base can be represented, for example, by any of the following equations: (b1-1) to (b1-3). The bases are listed. Furthermore, the bases represented by formulas (b1-1) to (b1-3) and their specific examples are In the example groups represented by formulas (b1-4) to (b1-11), * and ** are bond positions. This represents the bond position with -Y.

[0076] TIFF0007879325000055.tif26117 [In formula (b1-1), L b2 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms. L b3 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms. L b5 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. L b7 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0077] In the groups represented by formulas (b1-1) to (b1-3), the saturated hydrocarbon group is included. If -CH2- is replaced by -O- or -CO-, the number of carbon atoms before replacement is... This is the number of carbon atoms in the hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups. ru. L b2 The bond is preferably a single bond. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 Preferably, the divalent saturated hydrocarbon group has 1 to 8 carbon atoms, and the divalent saturated hydrocarbon water The hydrogen atoms in the elementary group may be substituted with fluorine atoms. L b5 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 The saturated hydrocarbon group is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms. L b7 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. The -CH2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO-. That's good too. L 1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The replaced group is preferably the group represented by formula (b1-1) or formula (b1-3).

[0078] The base represented by equation (b1-1) is shown in equations (b1-4) to (b1-8), respectively. The basis for this is listed below. TIFF0007879325000056.tif48120[In formula (b1-4), L b8 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. In formula (b1-5), L b9 This represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and contains The -CH2- group may be replaced by -O- or -CO-. L b10 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b12 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 This represents a divalent saturated hydrocarbon group with 1 to 19 carbon atoms. L b14 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. L b15 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and this divalent saturated hydrocarbon group The -CH2- group may be replaced by -O- or -CO-. L b17 This represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. L b18 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. L b8 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14This is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 This is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0079] The base represented by equation (b1-3) is given by equations (b1-9) to (b1-11), respectively. The bases that can be represented are listed below. TIFF0007879325000057.tif23139 [In formula (b1-9), L b19 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b20 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b22 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b25 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b26 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0080] Furthermore, between the group represented by formula (b1-9) and the group represented by formula (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before replacement is defined as the number of carbon atoms in the saturated hydrocarbon group.

[0081] Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, and b thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group These are some examples.

[0082] The following are examples of bases represented by formula (b1-4): TIFF0007879325000058.tif16153

[0083] The following are examples of bases represented by formula (b1-5): TIFF0007879325000059.tif68151

[0084] The following are examples of bases represented by formula (b1-6): TIFF0007879325000060.tif31164

[0085] The following are examples of bases represented by formula (b1-7): TIFF0007879325000061.tif57145

[0086] The following are examples of bases represented by formula (b1-8): TIFF0007879325000062.tif23150

[0087] The following are examples of bases represented by formula (b1-2): JPEG0007879325000063.jpg31161

[0088] The following are examples of bases represented by formula (b1-9): TIFF0007879325000064.tif44137

[0089] The following are examples of bases represented by formula (b1-10): TIFF0007879325000065.tif92165

[0090] The following are examples of bases represented by formula (b1-11): TIFF0007879325000066.tif84164

[0091] Examples of alicyclic hydrocarbon groups represented by Y include formulas (Y1) to (Y11), formula (Y36) to (Y36). Examples of groups represented by formula (Y38) include those shown. The -CH2- contained in the alicyclic hydrocarbon group represented by Y is either -O-, -S(O)2-, or - When replaced by CO-, the number of replacements may be one or two or more. For example, the bases represented by equations (Y12) to (Y35) and (Y39) to (Y43) are listed. * is L b1 This represents the bonding position with [the specified element]. TIFF0007879325000067.tif83168

[0092] The alicyclic hydrocarbon group represented by Y is preferably formula (Y1) to formula (Y20), formula ( Y26), equation (Y27), equation (Y30), equation (Y31), equation (Y39) to equation (Y43) A group represented by any of the following, more preferably by formula (Y11), formula (Y15), or formula (Y16) ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39) A group represented by formula (Y40), formula (Y42), or formula (Y43), more preferably Alternatively, see equation (Y11), equation (Y15), equation (Y20), equation (Y26), equation (Y27), equation ( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43) It is a base represented by . The alicyclic hydrocarbon group represented by Y is given by formulas (Y28) to (Y35), (Y39), and (Y 40) If it is a spiro ring containing an oxygen atom, such as formula (Y42) or formula (Y43), 2 The alkanediyl group between the oxygen atoms preferably has one or more fluorine atoms. Furthermore, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom It is preferable that the fluorine atom is not substituted.

[0093] The substituents of the methyl group represented by Y include halogen atoms, hydroxyl groups, and groups with 3 to 1 carbon atoms. 6 alicyclic hydrocarbon groups, C6-C18 aromatic hydrocarbon groups, glycidyloxy groups, -( CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 teeth, Alkyl groups with 1 to 16 carbon atoms, alicyclic hydrocarbon groups with 3 to 16 carbon atoms, and aromatic groups with 6 to 18 carbon atoms. This represents a fragrant hydrocarbon group or a group formed by combining these groups, and the alkyl group and the alicyclic hydrocarbon. The -CH2- group may be replaced by -O-, -SO2-, or -CO-. The hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are It may be replaced by a droxy group or a fluorine atom. ja is an integer from 0 to 4. Examples include: ) which represent... The substituents of the alicyclic hydrocarbon group represented by Y include halogen atoms, hydroxyl groups, and hydroxyl groups. A C1-C16 alkyl group which may be substituted with a roxy group (the alkyl group contains -CH2- may be replaced by -O- or -CO-. ), lipids with 3 to 16 carbon atoms. Cyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, aralkyl groups with 7 to 21 carbon atoms, Glycidyloxy group, -(CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO -R b1 group (in the formula, R b1 This refers to alkyl groups with 1 to 16 carbon atoms and alicyclic carbonized water with 3 to 16 carbon atoms. The alkyl group represents an elemental group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. The -CH2- contained in the alicyclic hydrocarbon group and the alicyclic hydrocarbon group is -O-, -SO2-, or -CO- The alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group The hydrogen atoms contained in may be replaced by hydroxyl groups or fluorine atoms. Examples include: , representing an integer between 0 and 4.

[0094] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, and methyl cyclohexyl groups. Chlohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, no Examples include the rubornyl group and the adamantyl group. Alicyclic hydrocarbon groups are chain hydrocarbon groups. They may also contain, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. be. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, and biphenyl groups. Examples include aryl groups such as nyl groups and phenanthryl groups. Aromatic hydrocarbon groups are chain carbon It may have a hydrogenated group or an alicyclic hydrocarbon group, and a chain hydrocarbon group having 1 to 18 carbon atoms. The aromatic hydrocarbon groups it possesses include tolyl, xylyl, cumenyl, mesityl, and p- Ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2 Examples include the -methyl-6-ethylphenyl group, and it has an alicyclic hydrocarbon group with 3 to 18 carbon atoms. As aromatic hydrocarbon groups, p-cyclohexylphenyl group, p-adamantylphenyl group Examples include groups such as the 'L' group. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14, and more preferably The answer is 6-10. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, and b Tyl 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 Examples include the following. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 It is ~9, more preferably 1~6, and even more preferably 1~4. Alkyl groups substituted with hydroxyl groups include hydroxymethyl groups and hydroxy Examples include hydroxyalkyl groups such as ethyl groups. Examples of aralkyl groups include benzyl group, phenethyl group, phenylpropyl group, and naphthyl group. Examples include tyl groups and naphthylethyl groups. The -CH2- group in the alkyl group is replaced by -O-, -S(O)2-, or -CO-, etc. Examples of such groups include alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, and alkoxycarbonyl groups. Examples include chlorocarbonyloxy groups or groups combining these. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 12. Yes, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups. Examples include alkoxycarbonyl groups and butoxycarbonyl groups. The number of carbon atoms in the alkoxycarbonyl group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples include the following. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably The value is between 2 and 6, and more preferably between 2 and 4. Examples of alkylcarbonyloxy groups include acetyloxy groups and propionyloxy groups. Examples include the cy group and the butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of combined groups include groups that combine an alkoxy group and an alkyl group, and A group combining a lucoxy group and an alkoxy group, or a group combining an alkoxy group and an alkylcarbonyl group. Groups combining these, groups combining an alkoxy group and an alkylcarbonyloxy group, etc. It can be listed. Examples of groups combining an alkoxy group and an alkyl group include the methoxymethyl group. Alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, and ethoxymethyl group For example, the number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, and more preferably k is 2 to 6, and more preferably 2 to 4. Groups that combine alkoxy groups include methoxymethoxy groups and metoxy groups. Alkoxyalkoxy groups such as xyethoxy group, ethoxymethoxy group, and ethoxyethoxy group Examples include the following. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, and more Preferably, it is 2 to 6, and more preferably 2 to 4. Examples of groups combining an alkoxy group and an alkylcarbonyl group include methoxyacetyl. Alco groups such as methoxypropionyl group, ethoxyacetyl group, and ethoxypropionyl group Examples include xyalkylcarbonyl groups. The number of carbon atoms in an alkoxyalkylcarbonyl group is... Preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. be. Groups that combine an alkoxy group and an alkylcarbonyloxy group include methoxya Cetyloxy group, Methoxypropionyloxy group, Ethoxyacetyloxy group, Ethoxy Examples include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the coxyalkylcarbonyloxy group is preferably 3 to 13, and more preferably The value of k is between 3 and 7, and more preferably between 3 and 5. The -CH2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S(O)2-, or -CO-, etc. The substituted bases are expressed in equations (Y12) to (Y35) and (Y39) to (Y43). Examples of such bases include:

[0095] The following are examples of Y: JPEG0007879325000068.jpg156170

[0096] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms, which may have substituents. More preferably, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, which may have substituents. More preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents. More preferably, the adamantyl group may have substituents, and the alicyclic hydrocarbon The -CH2- group that constitutes the group or adamantyl group is -CO-, -S(O)2-, or -CO- It may be replaced. Specifically, Y is preferably an adamantyl group, hydroxyadamantine thyl group, oxoadamantyl group or formula (Y42), formula (Y100) to formula (Y114) It is the base that is represented.

[0097] The anions in the salt represented by formula (B1) are given by formula (B1-A-1) ~ formula (B1- Anions represented by A-59) (hereinafter referred to as "anion (B1-A-1)" etc. depending on the formula number) In some cases, this is preferable, and formulas (B1-A-1) to (B1-A-4), formula (B1 -A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 An anion represented by any of 9) is more preferred.

[0098] TIFF0007879325000069.tif111143

[0099] TIFF0007879325000070.tif128167

[0100] TIFF0007879325000071.tif93145

[0101] TIFF0007879325000072.tif137140

[0102] TIFF0007879325000073.tif84163

[0103] JPEG0007879325000074.jpg90150 Here R i2 ~R i7 Each of these is independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 For example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, Preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or the same Groups formed by combination, more preferably methyl group, ethyl group, cyclohexyl It is a group or an adamantyl group. A4 These are single bonds or alkanediyl groups having 1 to 4 carbon atoms. ru. Q b1 and Q b2 This expresses the same meaning as above. Specifically, the anion in the salt represented by formula (B1) is as described in Japanese Patent Publication No. 2010-20. Anions listed in Public Gazette No. 4646 are examples.

[0104] The preferred anions in the salt represented by formula (B1) are formulas (B1a-1) to formula ( The anions represented by B1a-38 are listed below. TIFF0007879325000075.tif122158

[0105] TIFF0007879325000076.tif95145

[0106] TIFF0007879325000077.tif167156

[0107] In particular, equations (B1a-1) to (B1a-3), and equations (B1a-7) to (B1a-1) 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a-3) An anion represented by any of 8) is preferred.

[0108] Z1 + Examples of organic cations include organic onium cations and organic sulfonium cations. Organic iodium cation, organic ammonium cation, benzothiazolium cation and Examples include organic phosphonium cations. Among these, organic sulfonium cationic cations are particularly noteworthy. N and organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) ( Below, depending on the formula number, it may be referred to as "cation (b2-1)," etc. ) is an example. In formulas (b2-1) to (b2-4) of TIFF0007879325000078.tif48169, R b4 ~R b6 These are, independently, chain hydrocarbon groups with 1 to 30 carbon atoms and groups with 3 to 36 carbon atoms. This term represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and is contained in the chain-like hydrocarbon group. The hydrogen atoms present are found in hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, and lipid groups with 3 to 12 carbon atoms. The alicyclic hydrocarbon group 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 and aliphatic hydrocarbon groups with 1 to 18 carbon atoms. They may also be substituted with an alkylcarbonyl group or glycidyloxy group having 2 to 4 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group are halogen atoms, hydroxyl groups, or C1 groups. It may be substituted with ~12 alkoxy groups. R b4 and R b5 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. Even if the -CH2- contained in the ring is replaced by -O-, -S-, or -CO- good. Rb7 and R b8 These are, independently, a halogen atom, a hydroxyl group, and a lipid with 1 to 12 carbon atoms. This represents a fatty hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer between 0 and 5. When m2 is 2 or more, multiple R b7 They may be the same or different, and when n2 is 2 or more, multiple Number R b8 They may be the same or different. R b9 and R b10 Each of these is independently a chain-like hydrocarbon group having 1 to 36 carbon atoms or a group having 3 to 3 carbon atoms. It represents 36 alicyclic hydrocarbon groups. R b9 and R b10 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. It may be done, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. That's good too. R b11 This consists of a hydrogen atom, a chain hydrocarbon group with 1 to 36 carbon atoms, and an alicyclic carbon group with 3 to 36 carbon atoms. This represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 This refers to a chain-type hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or This represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in this chain-like hydrocarbon group are carbon It may be substituted with an aromatic hydrocarbon group having prime numbers 6 to 18, and the aromatic hydrocarbon group contains The hydrogen atom is a carbon-1 to carbon-12 alkoxy group or a carbon-1 to carbon-12 alkyl carbonyl group. It may be substituted with an oxy group. R b11 and R b12 These molecules bond to each other, forming a ring including the -CH-CO- groups to which they are joined. It is also possible that the -CH2- contained in the ring is replaced by -O-, -S-, or -CO-. That's fine. R b13 ~R b18 These are, independently, a hydroxyl group and an aliphatic hydrocarbon group having 1 to 12 carbon atoms. Alternatively, it represents an alkoxy group having 1 to 12 carbon atoms. L b31 This represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer between 0 and 5. q2 and r2 each independently represent an integer between 0 and 4. u2 represents either 0 or 1. When o2 is 2 or more, multiple R b13 They are the same or different, and when p2 is 2 or more, multiple R b14 They are the same or different, and when q2 is 2 or more, multiple R b15 They are the same or different, r2 When there are 2 or more R b16 They are the same or different, and when s2 is 2 or more, multiple R b17 teeth If the same or different, and t2 is 2 or more, multiple R b18 They are either the same or different. Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, and butyl groups. Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and Examples include alkyl groups with a 2-ethylhexyl group. In particular, R b9 ~R b12 The chain-like hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and monocyclic alicyclic carbon Examples of hydrogen groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of cycloalkyl groups include cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include the decahydronaphthyl group and the adamantyl group. Examples include norbornyl groups and the following groups. TIFF0007879325000079.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably These have 4 to 12 carbon atoms. As an example of an alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, methylcyclohex xyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyl Ruadamantan-2-yl group, 2-isopropyladamantan-2-yl group, methyl nor Examples include bornyl groups and isobornyl groups. Hydrogen atoms are substituted with aliphatic hydrocarbon groups. In alicyclic hydrocarbon groups, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferable. The number is 20 or less. Aromatic hydrocarbon groups include phenyl, biphenylyl, naphthyl, and phenantyl groups. Examples include aryl groups such as aryl groups. Aromatic hydrocarbon groups are chain hydrocarbon groups or alicyclic hydrocarbon groups. It may have a hydrogen group, and as an aromatic hydrocarbon group having a chain-like hydrocarbon group, a tolyl group xylyl group, coumenyl group, mesityl group, p-ethylphenyl group, p-tert-butyl Examples include phenyl groups, 2,6-diethylphenyl groups, and 2-methyl-6-ethylphenyl groups. Aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p -Examples include adamantylphenyl group. Furthermore, aromatic hydrocarbon groups may have chain-like hydrocarbon groups. Alternatively, if alicyclic hydrocarbon groups are included, chain hydrocarbon groups with 1 to 18 carbon atoms and 3 carbon atoms. ~18 alicyclic hydrocarbon groups are preferred. As an aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group, p-methoxyphenyl Examples include the 'L' group. Examples of chain hydrocarbon groups in which hydrogen atoms are substituted with aromatic hydrocarbon groups include the benzyl group and the ferrous hydrocarbon group. Netyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. An example is the aralkyl group. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups, etc. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It is possible. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkylcarbonyloxy groups include methylcarbonyloxy group and ethylcarbonyl Oxy group, propyl carbonyloxy group, isopropyl carbonyloxy group, butylcarbon Bonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy C group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include oxy groups and 2-ethylhexylcarbonyloxy groups. R b4 and R b5 The ring formed when these atoms bond to each other and together with the sulfur atom they bond to is The rings may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may have 3 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Furthermore, the ring containing the sulfur atom can be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. For example, the following ring can be cited. * represents a bond position. TIFF0007879325000080.tif23143Rb9 and R b10 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothi Examples include the ophenium ring, thian-1-ium ring, and 1,4-oxatian-4-ium ring. It can be done. R b11 and R b12 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring Examples include oxonorbornane rings and oxoadamantane rings.

[0109] Among cations (b2-1) to (b2-4), preferably cation (b2 -1) The following cations can be considered as cations (b2-1): TIFF0007879325000081.tif38158

[0110] TIFF0007879325000082.tif140154

[0111] The following cations can be considered as cations (b2-2): TIFF0007879325000083.tif18150

[0112] The following cations can be considered as cations (b2-3): TIFF0007879325000084.tif26139

[0113] The following cations can be considered as cations (b2-4): TIFF0007879325000085.tif85169

[0114] The acid generator (B) is a combination of the anion and the organic cation described above, and these are They can be combined in any way. The acid generator (B) is preferably of formula (B1a-1)~ Equations (B1a-3) and (B1a-7) to (B1a-16), (B1a-18), and Animates expressed by (B1a-19), or any of the formulas (B1a-22) to (B1a-38) Examples include combinations of ON and cation (b2-1) or cation (b2-3).

[0115] The acid generator (B) is preferably represented by formulas (B1-1) to (B1-56), respectively. Examples include those that are used. Among them, those containing arylsulfonium cations 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 1-31) The form represented by formula (B1-56) is particularly preferred. TIFF0007879325000086.tif119149

[0116] JPEG0007879325000087.jpg77147

[0117] JPEG0007879325000088.jpg147146

[0118] JPEG0007879325000089.jpg64163

[0119] TIFF0007879325000090.tif168168

[0120] <Resin (A)> Resin (A) is a structural unit having an acid-unstable group (hereinafter referred to as "structural unit (a1)"). The resin (A) may further contain structural units other than structural unit (a1). Preferred. Structural units other than structural unit (a1) include structural units that do not have acid-unstable groups ( (Hereinafter referred to as "structural unit (s)"), structural unit (a1), and other structural units (s) Structural units (for example, structural units having halogen atoms as described later (hereinafter referred to as "structural unit (a4)") In some cases, this may be referred to as "structural unit ( a5) In some cases, this refers to structural units derived from monomers known in the art. These are some examples.

[0121] <Structural unit (a1)> Structural unit (a1) is a monomer having an acid-unstable group (hereinafter referred to as "monomer (a1)"). It is derived from (in some cases). The acid-unstable group contained in resin (A) is the 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. TIFF0007879325000091.tif2397 [In formula (1), R a1 , R a2 and R a3 Each of these is an alkyl group having 1 to 8 carbon atoms, independently of the others. , represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms or a group combining these, or R a1 and R a2 These are alicyclic hydrocarbons with 3 to 20 carbon atoms, bonded together with the carbon atoms to which they are bonded. Forms a base. ma and na each independently represent 0 or 1, and at least one of ma and na This represents 1. * indicates a bond position. TIFF0007879325000092.tif2379 [In formula (2), R a1’ and R a2’ Each of these is independently a hydrogen atom or a carbon atom with 1 to 1 carbon atoms. Represents two hydrocarbon groups, R a3’ R represents a hydrocarbon group with 1 to 20 carbon atoms. a2’ Reach biR a3’ They bond with each other, and together with the carbon atoms and X they bond to, they have 3 to 20 carbon atoms. A heterocycle is formed, and the hydrocarbon group and the -CH2- contained in the heterocycle are -O- or -S- It can be replaced with this. X represents either an oxygen atom or a sulfur atom. 'na' represents either 0 or 1. * indicates a bond position.

[0122] R a1 , R a2 and R a3 Examples of alkyl groups in this context include methyl group, ethyl group, and propyl group. Examples include the hydroxyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group. R a1 , R a2 and R a3 In this context, the alicyclic hydrocarbon group is either monocyclic or polycyclic. This is also acceptable. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, and cyclopentyl group. Examples include cycloalkyl groups such as chloroheptyl and cyclooctyl groups. Polycyclic and alicyclic groups. The hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following: Examples include the group (* indicates a bonding position). a1 , R a2 and R a3 Alicyclic carbonized water The number of carbon atoms in the elemental group is preferably 3 to 16. TIFF0007879325000093.tif10150 Examples of groups combining alkyl groups and alicyclic hydrocarbon groups include methylcyclohexyl Xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group Examples include adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. ru. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 ) (R a2 )(R a3 Examples of such rings include the following. The non-aromatic hydrocarbon ring is preferably The carbon atoms range from 3 to 12. * indicates the bond position with -O-. TIFF0007879325000094.tif30139

[0123] R a1’ , R a2’ and R a3’ Examples of hydrocarbon groups in this context include alkyl groups and alicyclic carbon groups. Examples include hydrogenated groups, aromatic hydrocarbon groups, and groups formed by combining these. It is possible. Alkyl and alicyclic hydrocarbon groups are R a1 , R a2 and R a3 Similar to the base mentioned above This is one example. Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclophenyl group) Xylphenyl group, p-adamantylphenyl group, etc., phenylcyclohexyl group, etc. Examples include reel-cycloalkyl groups. R a2’ and R a3’ These atoms bond to each other, forming a heterocycle with the carbon atoms and X to which they bond. When forming -C(R a1’ )(R a2’ )-XR a3’ The following rings can be cited as examples. * indicates a bonding position. TIFF0007879325000095.tif19130R a1’ and R a2’ Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0124] The following are examples of base (1): In equation (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and n A group where a=1. A tert-butoxycarbonyl group is preferred as this group. In equation (1), R a1 , R a2 However, together with the carbon atoms to which these bond, adamant Forms a chill group, R a3 A group that is an alkyl group, with ma=0 and na=1. In equation (1), R a1 and R a2 Each of them is an alkyl group independently, and R a3 Adama A methyl group with ma=0 and na=1. The following are specific examples of group (1). * indicates the bonding position. TIFF0007879325000096.tif78168

[0125] The following are specific examples of group (2). * indicates the bonding position. TIFF0007879325000097.tif74154

[0126] The monomer (a1) preferably has an acid-unstable group and an ethylenically unsaturated bond. Mer, more preferably a (meth)acrylic monomer having an acid-unstable group.

[0127] Among (meth)acrylic monomers having an acid-unstable group, preferably those having 5 to 20 carbon atoms. Examples include those having alicyclic hydrocarbon groups. A resin (A) having structural units derived from monomer (a1) is used in the resist composition. This allows for an improvement in the resolution of the resist pattern.

[0128] As a structural unit derived from a (meth)acrylic monomer having group (1), formula (a1- A structural unit represented by (0) (hereinafter sometimes referred to as structural unit (a1-0)), formula (a1 A structural unit represented by -1) (hereinafter sometimes referred to as structural unit (a1-1)) or formula ( The structural units represented by a1-2) (hereinafter sometimes referred to as structural units (a1-2)) are listed below. Preferably, from the group consisting of structural unit (a1-1) and structural unit (a1-2) These are at least one selected structural unit. These may be used individually or in combination of two or more. They can be used together. TIFF0007879325000098.tif43145[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or * -O-(CH2) k1 - CO-O- represents a bond, k1 is an integer from 1 to 7, and * represents the bond position with -CO-. vinegar. R a01 , R a4 and R a5 Each of these independently represents either a hydrogen atom or a methyl group. R a02 , R a03 and R a04 These are, independently, alkyl groups with 1 to 8 carbon atoms and alkyl groups with 3 to 8 carbon atoms. This represents 18 alicyclic hydrocarbon groups or groups formed by combining these groups. R a6 and R a7 These are, independently, alkyl groups with 1 to 8 carbon atoms and alkyl groups with 3 to 18 carbon atoms. This term represents an alicyclic hydrocarbon group or a group formed by combining these groups. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

[0129] R a01 , R a4 and R a5 The group is preferably a methyl group. L a01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 -C OO- (where k01 is preferably an integer from 1 to 4, more preferably It is 1, more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 Alkyl groups, alicyclic hydrocarbon groups and The base formed by combining these is R in equation (1). a1 , R a2 and R a3 Similar to the bases mentioned above. The basis is cited. R a02 , R a03 , and R a04 The alkyl group in this case is preferably an alkyl group having 1 to 6 carbon atoms. It is a group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. ru. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. , more preferably a methyl group, an ethyl group or an isopropyl group, and even more preferably ethyl It is either an isopropyl group or an isopropyl group. R a02 , R a03 and R a04 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 5 to 12. More preferably, it is 5 to 10. Groups that combine alkyl groups and alicyclic hydrocarbon groups are formed by combining these alkyl groups and alicyclic hydrocarbon groups. It is preferable that the total number of carbon atoms in the combined group is 18 or less. R a02 and R a03 The alkyl group is preferably a C1-C6 alkyl group, and more preferably a methyl group. It is either an ethyl group or an ethyl group. R a04 Preferably, an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. The group is a methyl group, more preferably an ethyl group, a cyclohexyl group, or an adamantyl group. be. R a6 and R a7 The alkyl group is preferably a C1-C6 alkyl group, and more preferably a C6 alkyl group. The group is a ethyl group, an ethyl group, or an isopropyl group, and more preferably an ethyl group or an isopropyl group. It is a lu group. m1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0130] Examples of structural units (a1-0) are given by equations (a1-0-1) to (a1-0-12). A structural unit represented by one of the following and R in the structural unit (a1-0) a01 Methi equivalent to Examples of structural units in which the ∫ group is replaced by a hydrogen atom include equations (a1-0-1) to (a1-0 A structural unit represented by any of the following (-10) is preferred. TIFF0007879325000099.tif66158

[0131] As for the structural unit (a1-1), for example, as described in Japanese Patent Publication No. 2010-204646 Examples of structural units derived from monomers include those from formula (a1-1-1) to formula (a1 -1-4) A structural unit represented by any of the above and R in the structural unit (a1-1) a4 Equivalent to A structural unit in which the methyl group is replaced by a hydrogen atom is preferred, and formulas (a1-1-1) to ( A structural unit represented by any of a1-1-4) is more preferable. TIFF0007879325000100.tif44114

[0132] The structural unit (a1-2) is one of the following equations: (a1-2-1) to (a1-2-6). Structural units represented by and R in structural units (a1-2) a5 The methyl group corresponding to the hydrogen source Examples of structural units that have been replaced by children are given by equations (a1-2-2), (a1-2-5), and equation A structural unit represented by any of (a1-2-6) is preferred. TIFF0007879325000101.tif36161

[0133] If resin (A) contains structural unit (a1-0), its content is the total structural unit of resin (A). For each position, it is usually 5-60 mol%, preferably 5-50 mol%, and more preferably The percentage is between 10 and 40 mol%. If resin (A) contains structural unit (a1-1) and / or structural unit (a1-2), The total content of these is typically 10 to 95 mol% relative to the total structural units of resin (A), and is preferable. More preferably 15-85 mol%, more preferably 15-80 mol%, and even more preferably More preferably, it is 20-80 mol%, and even more preferably 20-75 mol%.

[0134] A structural unit having a base (2) in structural unit (a1) is represented by formula (a1-4). Examples of structural units (hereinafter sometimes referred to as "structural units (a1-4)") include the following. TIFF0007879325000102.tif3867[In formula (a1-4), R a32 This is a hydrogen atom, a halogen atom, or a C1-C6 atom which may have a halogen atom. It represents the alkyl group. R a33 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyl This represents a luoxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer between 0 and 4. If la is 2 or greater, multiple R a33 They are intertwined They may be the same or different. R a34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R a36 R represents a hydrocarbon group with 1 to 20 carbon atoms. a35 and R a36 they combine with each other and Together with the -CO- to which they bond, they form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the carbonized water The -CH2- contained in the elementary group and the divalent hydrocarbon group is replaced by -O- or -S- That's good too.

[0135] R a32 and R a33 The alkyl groups in this context are methyl, ethyl, propyl, and iso. Examples include propyl groups, butyl groups, pentyl groups, and hexyl groups. The alkyl group is carbon A alkyl group with prime numbers 1 to 4 is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even better. R a32 and R a33 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. These are some examples. Examples of C1-C6 alkyl groups that may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoro Ethyl 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, perfluor Lopentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl Examples include the hexyl group, perfluorohexyl group, etc. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. Examples include oxy groups and hexyloxy groups. In particular, alkoxy groups having 1 to 4 carbon atoms. A group is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred. . Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It can be done. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, and b Examples include thyryloxy groups. R a34 , R a35 and R a36 Examples of hydrocarbon groups in this context include alkyl groups and alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups and groups formed by combining these. Alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples include syl groups, heptyl groups, and octyl groups. The alicyclic hydrocarbon group may be monocyclic or polycyclic. Monocyclic alicyclic hydrocarbon group Examples include cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups. Examples of cycloalkyl groups include decahydrona. Phthyl groups, adamantyl groups, norbornyl groups, and the following groups (* indicates a bonding site), etc. It can be listed. TIFF0007879325000103.tif10151 Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclophenyl group) Xylphenyl group, p-adamantylphenyl group, etc., phenylcyclohexyl group, etc. Examples include reel-cycloalkyl groups. In particular, R a36 As for, A Lukyl group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms or Examples of groups formed by combining these include

[0136] In equation (a1-4), R a32 A hydrogen atom is preferred as the element. R a33 Preferably, the group is an alkoxy group having 1 to 4 carbon atoms, and also includes methoxy and ethoxy groups. A methoxy group is more preferable, and a methoxy group is even more preferable. For la, 0 or 1 is preferred, and 0 is more preferred. R a34 Preferably, it is a hydrogen atom. R a35 Preferably, it is an alkyl group or alicyclic hydrocarbon group having 1 to 12 carbon atoms. 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, or a C3 to 18 carbon atom Alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof The group formed is more preferably an alkyl group having 1 to 18 carbon atoms, or a group having 3 to 1 carbon atoms. It is an 8-cell alicyclic hydrocarbon group or an aralkyl group having 7 to 18 carbon atoms. a36 Alki in The rico group and alicyclic hydrocarbon group are preferably unsubstituted. a36 Aromatic carbonization in The hydrogen group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.

[0137] -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36is an acid (for example) It is eliminated upon contact with p-toluenesulfonic acid, forming a hydroxyl group. As for structural units (a1-4), for example, see Japanese Patent Publication No. 2010-204646. Examples include monomer-derived structural units. Preferably, formulas (a1-4-1) to (a1 -4-12) Structural units and R a32 The hydrogen atom corresponding to this is placed on the methyl group. Examples of replaced structural units include, more preferably, formulas (a1-4-1) to (a1-4- 5) Examples of structural units can be found in equations (a1-4-10). TIFF0007879325000104.tif68157 If resin (A) has structural units (a1-4), the content thereof is the total structural unit of resin (A). Preferably, the amount is 5 to 60 mol% of the total production units, and preferably 5 to 50 mol%. This is more preferable, and even more preferable is 10 to 40 mol%.

[0138] As structural units derived from (meth)acrylic monomers having group (2), formula (a1 Structural units represented by -5) (hereinafter sometimes referred to as "structural units (a1-5)") are also mentioned. It can be done. TIFF0007879325000105.tif4354 formula (a1-5), R a8 This may have a halogen atom, an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom. It represents an atom. Z a1 This is a single bond or *-(CH2) h3 -CO-L 54 - represents a value, and h3 is one of 1 to 4. Represents an integer of L, where * is L 51 This represents the bonding position with [the specified element]. L 51 , L 52 , L 53 and L 54These represent either -O- or -S- independently. s1 represents an integer between 1 and 3. s1' represents an integer between 0 and 3.

[0139] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. C1-C6 alkyl groups that may have a halogen atom include methyl group, ethyl group, Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group Examples include tyl groups and trifluoromethyl groups. In equation (a1-5), R a8 This is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 A single bond or *-CH2-CO-O- is preferred.

[0140] Examples of structural units (a1-5) are described in Japanese Patent Publication No. 2010-61117. Examples of monomer-derived structural units include those from formula (a1-5-1) to formula (a1-5- 4) The structural units represented by formula (a1-5-1) or formula (a1-5-2 A structural unit represented by ) is more preferable. TIFF0007879325000106.tif34138 If resin (A) has structural units (a1-5), the content thereof is the total structural unit of resin (A). The amount is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and 5 to 40 mol% relative to the production unit. A mol% is more preferable, and 5 to 30 mol% is even more preferable.

[0141] As for structural units (a1), for example, a structural unit represented by formula (a1-0X) (hereinafter referred to as structural unit (a1-0X) It is sometimes referred to as a manufacturing unit (a1-0X). TIFF0007879325000107.tif3961[In formula (a1-0X), R x1 represents a hydrogen atom or a methyl group. R x2 and R x3 Each of these independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms. Ar x1 This represents an aromatic hydrocarbon group with 6 to 36 carbon atoms.

[0142] R x2 and R x3 Examples of saturated hydrocarbon groups include alkyl groups, alicyclic hydrocarbon groups, and so Examples of groups formed by combining these include: Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, and n-propyl group. Examples include butyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups. ru. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and monocyclic alicyclic hydrocarbon group Examples include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, and cyclohexyl groups. These are some examples. Ar x1 Aromatic hydrocarbon groups include phenyl groups, naphthyl groups, anthryl groups, etc. Examples include aryl groups with prime numbers between 6 and 36. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, and more preferably has 6 to 1 carbon atoms. It is 8, and more preferably a phenyl group. Ar x1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, and more preferably a It is a phenyl group or a naphthyl group, and more preferably a phenyl group. R x1 , R x2 and R x3 These are preferably methyl or ethyl groups, respectively. It is preferable that the group be a methyl group.

[0143] The structural units (a1-0X) are as follows: In R x1 Examples include compounds in which the corresponding methyl group is replaced by a hydrogen atom. Structure The unit (a1-0X) is a structural unit (a1-0X-1) to structural unit (a1-0X-3). It is preferable to do so. TIFF0007879325000108.tif34161 If resin (A) has structural unit (a1-0X), its content is as follows: The amount is preferably 5 to 60 mol% and 5 to 50 mol% relative to the total monomer. It is more preferable that the amount is 10 to 40 mol%, and even more preferable that it is 10 to 40 mol%. Resin (A) may contain two or more structural units (a1-0X).

[0144] In addition, the following structural units (a1) can also be listed. TIFF0007879325000109.tif26161 If resin (A) contains the above structural units, the content of these units is, relative to the total structural units of resin (A). Preferably, 5-60 mol%, more preferably 5-50 mol%, and 10-40 mol%. It is preferable.

[0145] <Structural unit (s)> A structural unit (s) is a monomer that does not have an acid-unstable group (hereinafter referred to as "monomer (s)"). It is derived from (there is a combination). The monomer that derives the structural unit (s) is an acid-resistant monomer known in the field of resists. Monomers without a stable group can be used. The structural unit (s) preferably has a hydroxyl group or a lactone ring. A structural unit having a xyl group and not having an acid-unstable group (hereinafter referred to as "structural unit (a2)") A structural unit having a lactone ring and / or not having an acid-unstable group (hereinafter referred to as "structural unit") If a resin having a "production unit (a3)" is used in the resist composition of the present invention, This improves the resolution of the resist pattern and its adhesion to the substrate.

[0146] <Structural Unit (a2)> The hydroxyl group in structural unit (a2) can be an alcoholic hydroxyl group or a phenolic group. A hydroxyl group may also be used. When manufacturing a resist pattern from the resist composition of the present invention, KrF is used as the exposure light source. High-energy beams such as excimer lasers (248 nm), electron beams, or EUV (ultra-ultraviolet light) are used. If present, the structural unit (a2) is a structural unit having a phenolic hydroxyl group ( a2) is preferred, and it is even more preferable to use the structural unit (a2-A) described later. When using an ArF excimer laser (193 nm), the structural unit (a2) is A A structural unit (a2) having a hydroxyl group is preferred, and the structural unit (a2) described later -1) is more preferable. The structural unit (a2) contains one type alone. It is acceptable to include two or more types.

[0147] Structural units having a phenolic hydroxyl group in structural unit (a2) include those of formula (a Examples of structural units represented by 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") include It is possible. TIFF0007879325000110.tif4551[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 atom which may have a halogen atom. This represents a luquill group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyl This represents a luoxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 -(A a52 -X a52 ) nb - represents -R a50 they combine This indicates the bonding position with the carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, Number R a51 They may be identical or different from one another.

[0148] R a50 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. It can be done. R a50 Examples of C1-C6 alkyl groups that may have a halogen atom include: Fluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2 -Trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pelf Luoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, pel Fluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropene Examples include tyl groups, pentyl groups, hexyl groups, and perfluorohexyl groups. R a50 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable. R a51 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Examples include the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. It is possible. R a51 The alkoxy groups in this context include methoxy, ethoxy, propoxy, and iso Examples include propoxy groups, butoxy groups, sec-butoxy groups, and tert-butoxy groups. A carbon-1 to carbon-4 alkoxy group is preferred, and a methoxy group or ethoxy group is more preferred. A toxic group is even more preferable. R a51 The alkylcarbonyl groups in this context include acetyl, propionyl, and butyric groups. Examples include the lyl group. R a51 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups and propionyl groups. Examples include the luoxy group and the butyryloxy group. R a51 A methyl group is preferred.

[0149] *-X a51 -(A a52 -X a52 ) nb - for example, *-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-, These include *-CO-O- and *-CO-OA. a52 -CO-O- or *- OA a52 -CO-O- is preferred. Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and Examples include 2-methylbutane-1,4-diyl groups. A a52 It is preferable that this is a methylene group or an ethylene group. A a50 These are single bonds, *-CO-O- or *-CO-OA a52 Being a CO-O Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. More preferably, the bond is a single bond or even more preferably *-CO-O-. mb is preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxyl group is preferably bonded to the ortho or para position of the benzene ring, and the para position It is more preferable for them to bond.

[0150] As for the structural unit (a2-A), see Japanese Patent Publication No. 2010-204634, Japanese Patent Publication No. 2012- Examples include monomer-derived structural units described in Publication No. 12577. The structural unit (a2-A) is represented by equations (a2-2-1) to (a2-2-6). In structural units and structural units represented by formulas (a2-2-1) to (a2-2-6), R in the manufacturing unit (a2-A) a50 A structural unit in which the methyl group equivalent to a hydrogen atom is replaced by a hydrogen atom. The following can be listed. The structural unit (a2-A) is the structural unit represented by formula (a2-2-1), formula Structural units represented by (a2-2-3), structural units represented by formula (a2-2-6), and formula ( a2-2-1) Structural unit represented by formula (a2-2-3) or formula (a In the structural unit represented in 2-2-6), R in structural unit (a2-A) a50 Equivalent to It is preferable that the structural unit is one in which the methyl group is replaced by a hydrogen atom. TIFF0007879325000111.tif42166 Content of structural unit (a2-A) when structural unit (a2-A) is present in resin (A) This is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, relative to the total structural units. It is mol%, more preferably 15-65 mol%, and even more preferably 20- The percentage is 65 mol%, and is particularly preferably 25-55 mol%. Structural unit (a2-A) is polymerized using structural unit (a1-4), for example, and then p-Tol It can be incorporated into resin (A) by treating it with an acid such as ene sulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0151] Structural units having an alcoholic hydroxyl group in structural unit (a2) include those with the formula ( The structural unit represented by a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") It can be listed. TIFF0007879325000112.tif3957 formula (a2-1), L a3 is -O- or * -O-(CH2) k2 -CO-O- represents, k2 represents an integer between 1 and 7. * represents the associative position with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 Each of these independently represents a hydrogen atom, a methyl group, or a hydroxyl group. o1 represents an integer between 0 and 10.

[0152] In equation (a2-1), L a3 Preferably, -O-, -O-(CH2) f1 -CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-. R a14 The group is preferably a methyl group. R a15 Preferably, it is a hydrogen atom. R a16 This is preferably a hydrogen atom or a hydroxyl group. o1 is preferably an integer between 0 and 3, more preferably 0 or 1.

[0153] As for the structural unit (a2-1), for example, see Japanese Patent Publication No. 2010-204646. Examples of structural units derived from monomers are given by equations (a2-1-1) to (a2-1-6). A structural unit represented by any of the following formulas is preferred, from formula (a2-1-1) to formula (a2-1-4) A structural unit represented by either formula (a2-1-1) or formula (a2-1- The structural unit represented in 3) is even more preferable. TIFF0007879325000113.tif50138 If resin (A) contains structural unit (a2-1), its content is the total structural unit of resin (A). For each position, it is usually 1 to 45 mol%, preferably 1 to 40 mol%, and more preferably The amount is 1 to 35 mol%, more preferably 1 to 20 mol%, and even more preferably The percentage is between 1 and 10 mol%.

[0154] <Structural unit (a3)> The lactone rings of structural unit (a3) ​​are a β-propiolactone ring and a γ-butyrolactone ring. It can be a monocyclic ring such as a δ-valerolactone ring, and the contraction of a monocyclic lactone ring with other rings. A ring compound is also acceptable. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or γ - A bridged ring containing a butyrolactone ring structure (e.g., a structural unit represented by the following formula (a3-2)) These are some examples. The structural unit (a3) ​​is preferably formula (a3-1), formula (a3-2), formula (a3-3) Alternatively, it is a structural unit represented by formula (a3-4). These may be contained individually. It may contain two or more types. TIFF0007879325000114.tif51162[In formulas (a3-1), (a3-2), (a3-3), and (a3-4), L a4 , L a5 and L a6 These are, independently, -O- or *-O-(CH2) k3 - This represents a base represented by CO-O-(where k3 is an integer from 1 to 7). L a7 is -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8-O-CO-L a9 -O- represents vinegar. L a8 and L a9 Each of these independently represents an alkanediyl group with 1 to 6 carbon atoms. * indicates the bonding position with the carbonyl group. R a18 , R a19 and R a20 Each of these independently represents either a hydrogen atom or a methyl group. R a24 This includes an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, a hydrogen atom, or This represents a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 This represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. R a22 , R a23 and R a25 Each of these independently comprises a carboxyl group, a cyano group, or a carbon Represents aliphatic hydrocarbon groups with prime numbers 1 through 4. p1 represents an integer between 0 and 5. q1 represents an integer between 0 and 3. r1 represents an integer between 0 and 3. w1 represents an integer between 0 and 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 They may be the same or different from each other.

[0155] R a21 , R a22 , R a23 and R a25 As for aliphatic hydrocarbon groups in this context, methyl ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and ter Examples include alkyl groups such as t-butyl groups. R a24 The halogen atoms in this include fluorine, chlorine, bromine, and iodine. Atoms are one example. R a24 The alkyl groups in this context include methyl, ethyl, propyl, and isopropyl groups. butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Examples include alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups. Alternatively, an ethyl group may be used. R a24 Examples of alkyl groups having a halogen atom include the trifluoromethyl group. Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perf Perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Lufluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl Examples include the 14-3 group and the triiodomethyl group.

[0156] L a8 and L a9 Examples of alkanediyl groups in this context include methylene groups, ethylene groups, and pro groups. Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, tan-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, pen Examples include tan-1,4-diyl groups and 2-methylbutane-1,4-diyl groups.

[0157] In equations (a3-1) to (a3-3), L a4 ~L a6 Each is independently preferred Alternatively, -O- or *-O-(CH2) k3In -CO-O-, k3 is 1 to 4 A base that is any integer, more preferably -O- and *-O-CH2-CO-O-, and further Preferably, it is an oxygen atom. R a18 ~R a21 The group is preferably a methyl group. R a22 and R a23 Each of these is independently preferably a carboxyl group, a cyano group, or a melanin group. It is a chill group. p1, q1, and r1 are each independently, preferably integers between 0 and 2. More preferably, it is 0 or 1.

[0158] In equation (a3-4), R a24 Preferably, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is a group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a group of the same type. It is either a hydrogen atom or a methyl group. R a25 The group is preferably a carboxyl group, a cyano group, or a methyl group. L a7 Preferably -O- or *-OL a8 -CO-O- and, far It is -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably an integer between 0 and 2, and more preferably 0 or 1. In particular, formula (a3-4)' is preferred over formula (a3-4). TIFF0007879325000115.tif3845 (in the formula, R a24 , L a7 (This expresses the same meaning as above.)

[0159] The structural unit (a3) ​​is the monomer described in Japanese Patent Publication No. 2010-204646. , monomers described in Japanese Patent Publication No. 2000-122294, Japanese Patent Publication No. 2012-41274 Examples of structural units derived from monomers described in the publication are listed below. Structural unit (a3) ​​is , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , equation (a3-3-1), equation (a3-3-2), and equation (a3-4-1) ~ equation (a3-4-1 2) A structural unit represented by any of the above, and in the said structural unit, formula (a3-1) to formula ( R in a3-4) a18 , R a19 , R a20 and R a24 A methyl group corresponding to this is placed on the hydrogen atom. The altered structural units are preferable. TIFF0007879325000116.tif115165 If resin (A) contains structural unit (a3), the total content of the resin (A) is the total structural unit For each position, it is usually 1 to 70 mol%, preferably 1 to 65 mol%, and more preferably The percentage is between 1 and 60 mol%. Also, structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structure The content of units (a3-4) is 1 to 60 units relative to the total structural units of resin (A), respectively. % is preferred, 1 to 50 mol% is more preferred, and 1 to 50 mol% is even more preferred.

[0160] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF0007879325000117.tif3165[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 This represents a saturated hydrocarbon group having fluorine atoms with 1 to 24 carbon atoms, and the saturated hydrocarbon The -CH2- group in the group may be replaced by -O- or -CO-. R 42 The saturated hydrocarbon group represented by this term includes chain hydrocarbon groups and monocyclic or polycyclic alicyclic hydrocarbon groups. Examples include bases, and bases formed by combining them.

[0161] Chain hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include the decyl group, heptadecyl group, and octadecyl group. Monocyclic or polycyclic alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, and cyclopentyl groups. Cycloalkyl groups such as chloroheptyl and cyclooctyl groups; decahydronaphthyl groups, ada Polycyclic alicyclic carbons such as mantyl groups, norbornyl groups, and the following groups (* indicates bonding position). Hydrogenated groups are one example. TIFF0007879325000118.tif10160 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic hydrocarbon groups include -Alkanediyl group-alicyclic hydrocarbon group, -Alkanediyl group-alkyl group, -Al Examples include candiyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0162] As structural units (a4), equation (a4-0), equation (a4-1), equation (a4-2), equation ( Structures represented by at least one selected from the group consisting of a4-3) and formula (a4-4) The units are listed. TIFF0007879325000119.tif3953[In formula (a4-0), R 5a represents a hydrogen atom or a methyl group. L 4a This represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a This is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. This represents a luorocycloalkanediyl group. R 6a This represents a hydrogen atom or a fluorine atom.

[0163] L 4a The alkanediyl groups in this include methylene group, ethylene group, propane-1, Linear alkanediyl groups such as 3-diyl groups and butane-1,4-diyl groups, ethane-1,1 -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylprop Branched alkanes such as pan-1,3-diyl groups and 2-methylpropane-1,2-diyl groups A diyl group is one example.

[0164] L 3a In this context, perfluoroalkanediyl groups include difluoromethylene groups and per Fluoroethylene group, perfluoropropane-1,1-diyl 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, Examples include 3-diyl groups and perfluorooctane-4,4-diyl groups. L 3a As for the perfluorocycloalkanediyl group in this context, perfluorocyclo xandiyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl Examples include yl groups and perfluoroadamantanediyl groups.

[0165] L 4a The is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond. The bond is a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably Alternatively, it is a perfluoroalkanediyl group with 1 to 3 carbon atoms.

[0166] The structural units (a4-0) include the structural units shown below and the structural units within the following structural units ( a4-0) R 5a Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007879325000120.tif95165

[0167] TIFF0007879325000121.tif5170[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 This represents a saturated hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. A a41 This is an alkanediyl group having 1 to 6 carbon atoms, which may have substituents, or a compound of formula (ag 1) represents the base. However, A a41 and R a42 At least one of them is a substituent. It has a halogen atom (preferably a fluorine atom). TIFF0007879325000122.tif1383 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44 Each of these is independently a divalent carbon atom having 1 to 5 carbon atoms, which may have substituents. This represents a saturated hydrocarbon group. A a43 This is a divalent aliphatic hydrocarbon having 1 to 5 carbon atoms, which may have single bonds or substituents. It represents the base. X a41 and X a42 These are, 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. * represents a bond position, and the * on the right is -O-CO-R a42 This is the bonding position with [the other element].

[0168] R a42 The saturated hydrocarbon groups in this context include chain-type saturated hydrocarbon groups and monocyclic or polycyclic alicyclic groups. Examples include saturated hydrocarbon groups and groups formed by combining them. ru.

[0169] Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, and pentyl groups. Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, Examples include xadecyl groups, heptadecyl groups, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include cyclopentyl groups and cyclohexyl groups. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic alicyclic groups such as adamantyl groups, norbornyl groups, and the following groups (* indicates bonding position). Examples include saturated hydrocarbon groups. TIFF0007879325000123.tif10160 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic saturated hydrocarbon groups include -Alkanediyl group-alicyclic saturated hydrocarbon group, -Alkanediyl group-alkyl Examples include AL groups, -alkanediyl groups, -alicyclic saturated hydrocarbon groups, -alkyl groups, etc.

[0170] R a42 The substituents it possesses include halogen atoms and groups represented by formula (a-g3). At least one selected from the group is mentioned. Examples of halogen atoms include fluorine atoms, Examples include chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. TIFF0007879325000124.tif752[In formula (a-g3), X a43 **-O-CO- or **-CO-O-** represents an oxygen atom, a carbonyl group, or a carbonyl group. A a45 This represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. . * is R a42 [This represents the bonding position with .] However, R a42 -X a43 -A a45 In R a42 If it does not have a halogen atom, then A a4 5 This represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and containing at least one halogen atom. .

[0171] A a45The aliphatic hydrocarbon groups in this context include methyl, ethyl, propyl, and butyl groups. 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. Formula hydrocarbon groups; as well as decahydronaphthyl groups, adamantyl groups, norbornyl groups and the following Examples include polycyclic alicyclic hydrocarbon groups such as the group (* indicates a bonding position). TIFF0007879325000125.tif10160 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic hydrocarbon groups include -Alkanediyl group-alicyclic hydrocarbon group, -Alkanediyl group-alkyl group, -Al Examples include candiyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0172] R a42 The halogen atom is preferably a saturated hydrocarbon group which may have a halogen atom. Alkyl groups having and / or saturated hydrocarbon groups having a group represented by formula (a-g3) are suitable. It is preferable. R a42 If it is a saturated hydrocarbon group having a halogen atom, it preferably has a fluorine atom. A saturated hydrocarbon group, more preferably a perfluoroalkyl group or perfluoroalkyl group. It is a chloroalkyl group, and more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. The perfluoromethyl group, perfluoroethyl group, and perfluoropropyl group are examples of perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples include oroheptyl groups and perfluorooctyl groups. Examples of the 'l' group include the perfluorocyclohexyl group. R a42 However, if it is a saturated hydrocarbon group having a group represented by formula (a-g3), then formula (a- Including the number of carbon atoms in the group represented by g3), R a42 The total number of carbon atoms should preferably be 15 or less. Furthermore, 12 or less is more preferable. When the group represented by formula (a-g3) is used as a substituent, The number should preferably be one.

[0173] R a42 If is a saturated hydrocarbon group having a group represented by formula (a-g3), then R a42 is, More preferably, the group is represented by the formula (a-g2). TIFF0007879325000126.tif874[In formula (a-g2), A a46 This comprises a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, which may have a halogen atom. represent. X a44 This represents **-O-CO- or **-CO-O- (where ** is A a46 The bond position with vinegar.). A a47 This represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. . However, A a46 , A a47 and X a44 The total number of carbon atoms is 18 or less, A a46 and A a47 of Of these, at least one has at least one halogen atom. * indicates the bonding position with the carbonyl group.

[0174] Aa46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3. A a47 The number of carbon atoms in the aliphatic hydrocarbon group is preferably 4 to 15, more preferably 5 to 12. A a47 A cyclohexyl group or an adamantyl group is more preferable.

[0175] The preferred structure of the group represented by formula (a-g2) is as follows (* represents a carbonyl group) (This is the bonding position with [the other party].) TIFF0007879325000127.tif13161

[0176] A a41 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 Linear alkanediyl groups such as ,6-diyl groups; propane-1,2-diyl groups, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- Examples include branched alkanediyl groups such as diyl groups and 2-methylbutane-1,4-diyl groups. ru. A a41 The substituents in the alkanediyl group represented by are a hydroxyl group and a carbon 1- Examples include 6 alkoxy groups. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a carbon number The group is an alkanediyl group of type 2 to 4, and more preferably an ethylene group.

[0177] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Divalent saturated carbonized water The elemental groups include linear or branched alkanediyl groups and monocyclic or polycyclic divalent alicyclic water carbon. Formed by combining an elementary group with an alkanediyl group and a divalent alicyclic hydrocarbon group. Examples of such groups include methylene groups, ethylene groups, and propane-1,3-di Iyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane -1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1 Examples include 2-diyl groups. A a42 , A a43 and A a44 The substituents of the divalent saturated hydrocarbon group represented by are hydroxyl groups. Examples include alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0178] In the group represented by formula (a-g1), X a42 -O-, -CO-, -CO-O- or The following are examples of groups that are -O-CO-. In the following examples, * and ** represents the bond position, and ** is -O-CO-R a42 This is the bonding position with [the other party]. TIFF0007879325000128.tif48153

[0179] The structural units represented by formula (a4-1) are the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to this is placed on a hydrogen atom. Examples of replaced structural units include: TIFF0007879325000129.tif100142

[0180] TIFF0007879325000130.tif123140

[0181] As a structural unit represented by formula (a4-1), the structural unit represented by formula (a4-2) is preferable. It seems so. TIFF0007879325000131.tif3354[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 This represents an alkanediyl group having 1 to 6 carbon atoms, and the -C contained in the alkanediyl group H2- may be replaced by -O- or -CO-. R f6 This represents a saturated hydrocarbon group having 1 to 20 fluorine atoms. However, L 44 and R f6 The upper limit for the total number of carbon atoms is 21.

[0182] L 44 The alkanediyl group is A a41 Similar to the examples given earlier, the same types of bases can be cited. R f6 The saturated hydrocarbon group is R a42 Similar to the examples given earlier, the same types of bases can be cited. L 44 In this context, an alkanediyl group having 2 to 4 carbon atoms is preferred. An ethylene group is more preferable.

[0183] Examples of structural units represented by formula (a4-2) include formulas (a4-1-1) to (a4 The structural units represented in (a4-2) are as follows. 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 can be cited as a structural unit.

[0184] TIFF0007879325000132.tif5164[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 This represents an alkanediyl group with 1 to 6 carbon atoms. A f13This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, which may contain a fluorine atom. vinegar. X f12 is *-O-CO- or *-CO-O-(* is A f13 Represents the bonding position with. . A f14 This 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 them has a fluorine atom, L 5 , A f13 and A f14 The upper limit for the total number of carbon atoms is 20.

[0185] L 5 The alkanediyl group in A is a41 The same as the example with the alkanediyl group. The basis for this can be cited. A f13 A preferred divalent saturated hydrocarbon group which may have a fluorine atom is A divalent chain-type saturated hydrocarbon group which may have a fluorine atom and a fluorine atom A divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanedi It is a lu group. Examples of divalent chain hydrocarbon groups that may contain a fluorine atom include methylene groups and ethylene groups. Alkanediyl groups such as propanediyl, butanediyl and pentanediyl groups; di Fluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perf Perfluoroalkanediyl groups such as ruolobutanediyl and perfluoropentanediyl groups Examples include the 'L' group. A divalent alicyclic hydrocarbon group that may contain a fluorine atom can be monocyclic or polycyclic. But that's fine too. Examples of monocyclic groups include the cyclohexanediyl group and the perfluorocyclohexa Examples include the nucleotide group. Polycyclic groups include the adamantanediyl group and norbornane. Examples include diyl groups and perfluoroadamantanediyl groups.

[0186] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 in Similar groups to those exemplified can be cited. Among them, the trifluoromethyl group and the difluoromethyl group are particularly noteworthy. Tyl 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 per Fluoroctyl groups and other alkyl fluorides, cyclopropylmethyl groups, cyclopropyl groups Cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group Xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbol Nyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl A methyl group is preferred.

[0187] In equation (a4-3), L 5 An ethylene group is preferred. A f13 The divalent saturated hydrocarbon groups are divalent chain hydrocarbon groups with 1 to 6 carbon atoms and 3 carbon atoms. A group containing a divalent alicyclic hydrocarbon group of ~12 is preferred, and a divalent chain-type carbon dioxide group having 2 to 3 carbon atoms is preferred. A more preferable base material is available. A f14 The saturated hydrocarbon group consists of a chain-like hydrocarbon group with 3 to 12 carbon atoms and a lipid group with 3 to 12 carbon atoms. Groups containing cyclic hydrocarbon groups are preferred, including chain hydrocarbon groups having 3 to 10 carbon atoms and groups having 3 to 1 carbon atoms. Groups containing 0 alicyclic hydrocarbon groups are even more preferred. Among them, A f14 Preferably carbon The group contains 3 to 12 alicyclic hydrocarbon groups, and more preferably cyclopropylmethyl These are the cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group.

[0188] Examples of structural units represented by equation (a4-3) include equation (a4-1'-1) ~ equation (a The structural units represented in 4-1'-11) are listed below. Keru R f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also shown in formula (a4-3). It can be cited as a structural unit.

[0189] As a structural unit (a4), the structural unit represented by formula (a4-4) can also be cited. TIFF0007879325000133.tif4061[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 through j5 each independently represent an integer from 1 to 6. R f22 This represents a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom.

[0190] Rf22 The saturated hydrocarbon group is R a42 Examples include the same saturated hydrocarbon group represented by . R f22 This refers to an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom, or a carbon atom containing a fluorine atom. A cycloaliphatic 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 group is more preferred, and an alkyl group having 1 to 6 carbon atoms and containing a fluorine atom is even more preferred. In equation (a4-4), A f21 As for, -(CH2) j1 - is preferred, ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0191] Examples of structural units represented by formula (a4-4) include the following structural units and the following formula In the structural unit shown, R in structural unit (a4-4) f21 The methyl group corresponding to One example is a structural unit in which a hydrogen atom has been replaced. TIFF0007879325000134.tif86160 If resin (A) has structural units (a4), the content thereof is the total structural unit of resin (A). A percentage of the position is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and 3 to 10 mol%. A percentage is even more preferable.

[0192] <Structural Unit (a5)> The non-leaved hydrocarbon groups possessed by structural unit (a5) include linear, branched, or cyclic hydrocarbons. Groups having a group are examples. In particular, structural unit (a5) has an alicyclic hydrocarbon group. The base is preferable. Examples of structural units (a5) include the structural unit represented by formula (a5-1). . TIFF0007879325000135.tif3972[In formula (a5-1), R 51represents a hydrogen atom or a methyl group. R 52 This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in this alicyclic hydrocarbon group The elementary atoms may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- group contained in may be replaced by -O- or -CO-.

[0193] R 52 The alicyclic hydrocarbon group in this can be either monocyclic or polycyclic. Examples of alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, and cyclopene. Examples include chill groups and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include, for example, Examples include adamantyl groups and norbornyl groups. Aliphatic hydrocarbon groups with 1 to 8 carbon atoms include, for example, methyl, ethyl, propyl, and iso groups. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl Examples include alkyl groups such as the octyl group and the 2-ethylhexyl group. Examples of alicyclic hydrocarbon groups with substituents include the 3-methyladamantyl group. ru. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably k is an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0194] L 55 In this context, divalent saturated hydrocarbon groups include divalent chain saturated hydrocarbon groups and divalent lipids. Examples include cyclic saturated hydrocarbon groups, preferably divalent chain saturated hydrocarbon groups. Examples of divalent chain-type saturated hydrocarbon groups include methylene groups, ethylene groups, and propanedi groups. Examples include alkanediyl groups such as the yl group, butanediyl group, and pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl groups and cyclohexanediyl groups. Examples include the roalkanediyl group. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include ada Examples include mantanediyl groups and norbornanediyl groups.

[0195] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by can be replaced with -O- or -CO-. Examples of the replaced groups include those represented by formulas (L1-1) to (L1-4). In the following formula, * and ** represent bonding positions, with * representing the bonding position with the oxygen atom. TIFF0007879325000136.tif18165 formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is L x1 (Represents the bonding position with [another element].) L x1 This represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 This 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 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 This 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 x5This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 Each of these independently consists of a single bond or a divalent aliphatic saturated carbon with 1 to 14 carbon atoms. It 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 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 This represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0196] L x1 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x2 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a single bond. L x3 Preferably, it is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 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 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably The group is either a methylene group or an ethylene group. L x7Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. L x9 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. W x1 Preferably, a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably It is either a cyclohexanediyl group or an adamantanediyl group.

[0197] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF0007879325000137.tif55134

[0198] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF0007879325000138.tif24131

[0199] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF0007879325000139.tif15145

[0200] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF0007879325000140.tif26114L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0201] Structural units (a5-1) include the structural units shown below and the structural units within the following structural units ( a5-1) R 51 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007879325000141.tif110150 If resin (A) has structural units (a5), the content of these units is the total structural unit content of resin (A). A value of 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 3 to 15 mol% is preferred. A percentage is even more preferable.

[0202] <Structural Unit (II)> Resin (A) further decomposes upon exposure to generate acid, resulting in structural units (hereinafter referred to as "structural units") It may contain (II) (in some cases). Specifically, structural unit (II) is Examples include the structural unit described in Japanese Patent Publication No. 2016-79235, with a sulfonate group in the side chain. Alternatively, a structural unit having a carboxylate group and an organic cation, or a side chain with a sulfonio group. It is preferable that the structural unit has an organic anion.

[0203] Structural units having a sulfonate group or carboxylate group in the side chain are defined by formula (II-2 It is preferable that the structural unit is represented by -A'). TIFF0007879325000142.tif36104[In formula (II-2-A'), X III3 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and contains -CH2- may be replaced with -O-, -S-, or -CO- in the saturated carbonized water. The hydrogen atoms contained in the elementary group are halogen atoms, or C1-C2 atoms which may contain halogen atoms. It may be replaced by an alkyl group or hydroxyl group of 6. A x1 This represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen contained in the alkanediyl group The atoms may be substituted with fluorine atoms or perfluoroalkyl groups having 1 to 6 carbon atoms. . RA- This represents a sulfonate group or a carboxylate group. R III3 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents the alkyl group. ZA + This represents an organic cation.

[0204] R III3 The halogen atoms represented by include fluorine, chlorine, bromine, and iodine. Examples include atoms, etc. R III3 A C1-C6 alkyl group which may have a halogen atom represented by the following is: , R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by These are some examples. A x1 Examples of alkanediyl groups with 1 to 8 carbon atoms, represented by the following: methylene group, ethylene group, Propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group Iyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples include the group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. . A x1 Examples of perfluoroalkyl groups having 1 to 6 carbon atoms that may be substituted include truffles. Peromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl Ropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl Examples include the syl group, perfluoropentyl group, and perfluorohexyl group. XIII3 As a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, the following are examples: linear or branched a Examples include lucandiyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of these groups. They can be placed together. 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, do Linear alkanediyl groups such as decane-1,12-diyl groups; butane-1,3-diyl groups, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen Branched alkanedi such as tan-1,4-diyl group and 2-methylbutane-1,4-diyl group cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclo Cycloalkanes such as xane-1,4-diyl groups and cyclooctane-1,5-diyl groups Lu group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamanta Divalent polycyclic alicyclic saturated carbon such as n-1,5-diyl groups and adamantane-2,6-diyl groups Examples include hydrogenated groups. The -CH2- group in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. Examples include the divalent groups represented by equations (X1) to (X53). However, Furthermore, the -CH2- group contained in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. The number of carbon atoms in each preceding atom is 17 or less. In the following formula, * and ** represent bond positions, and * is A x1 This represents the bonding position with [the specified element]. TIFF0007879325000143.tif145161

[0205] X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6 This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 This represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0206] ZA in equation (II-2-A') + This refers to the cation Z1 in the acid generator (B1). + Similar Examples include:

[0207] The structural unit represented by formula (II-2-A') is the structural unit represented by formula (II-2-A) It is preferable that this be the case. TIFF0007879325000144.tif38109 [In formula (II-2-A), R III3 , X III3 and ZA + This expresses the same meaning as above. z2A represents an integer between 0 and 6. R III2 and R III4 Each of these is independently a hydrogen atom, a fluorine atom, or a carbon atom with 1 to 6 carbon atoms. Represents a fluoroalkyl group, and when z2A is 2 or more, multiple R III2 and R III4 they They may be the same, or they may be different. Q a and Q bEach is independently a fluorine atom or a perfluoroal with 1 to 6 carbon atoms. [Represents the kill group.] R III2 , R III4 Q a and Q b As a perfluoroalkyl group having 1 to 6 carbon atoms, So, the aforementioned Q b1 Examples include perfluoroalkyl groups with 1 to 6 carbon atoms, as shown below. It can be done.

[0208] The structural unit represented by formula (II-2-A) is the same as the structural unit represented by formula (II-2-A-1). It is preferable that it be in that position. TIFF0007879325000145.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 Q a Q b and ZA + This expresses the same meaning as above. R III5 This represents a saturated hydrocarbon group with 1 to 12 carbon atoms. z2A1 represents an integer between 0 and 6. X I2 This represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and the saturated hydrocarbon group contains -CH2- may be replaced by -O-, -S-, or -CO-, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with halogen atoms or hydroxyl groups. R III5 Examples of saturated hydrocarbon groups with 1 to 12 carbon atoms represented by these groups include methyl group, ethyl group, and propyl group. Ropyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentium hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and do Examples include linear or branched alkyl groups such as decyl groups. X I2As a divalent saturated hydrocarbon group represented by , X III3 Divalent saturated hydrocarbons represented by Similar examples can be given.

[0209] The structural unit represented by formula (II-2-A-1) is represented by formula (II-2-A-2). A structural unit that can be made is even more preferable. TIFF0007879325000146.tif5287 [In formula (II-2-A-2), R III3 , R III5 and ZA + This expresses the same meaning as above. m and n each independently represent either 1 or 2.

[0210] Examples of structural units represented by formula (II-2-A') include the following structural unit, R III3 The group corresponding to the methyl group is a hydrogen atom, a halogen atom (for example, a fluorine atom), or a halogen. A C1-C6 alkyl group that may contain atoms (e.g., a trifluoromethyl group). Examples of structural units that have been replaced by others, and structural units described in International Publication No. 2012 / 050015, include It can be done. ZA + This represents an organic cation. TIFF0007879325000147.tif85163

[0211] A structural unit having a sulfonio group and an organic anion in its side chain is represented by formula (II-1-1). It is preferable that the structural unit is such that it can be formed. TIFF0007879325000148.tif3791 [In formula (II-1-1), A II1 This represents a single bond or a divalent linking group. R II1 This represents a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms. R II2 and R II3Each of these independently represents a hydrocarbon group with 1 to 18 carbon atoms, and R II2 Reach biR II3 These atoms may bond to each other, forming a ring with the sulfur atom to which they are bonded. R II4 This is a hydrogen atom, a halogen atom, or a C1-C6 atom which may have a halogen atom. This represents a luquill group. A - This represents an organic anion. R II1 Divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, as represented by the phenylene group, Examples include naphthylene groups. R II2 and R II3 Examples of hydrocarbon groups represented include alkyl groups, alicyclic hydrocarbon groups, and aromatic groups. Examples include hydroxyl groups and groups formed by combining them. R II4 The halogen atoms represented by include fluorine, chlorine, bromine, and iodine. Examples include atoms, etc. R II4 A C1-C6 alkyl group which may have a halogen atom represented by the following is: , R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by These are some examples. A II1 Examples of divalent linking groups represented by this formula include divalent saturated carbon dioxide with 1 to 18 carbon atoms. Examples include the elemental group, and the -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or It may be replaced with -CO-. Specifically, X III3 Two carbon atoms represented by 1 to 18 carbon atoms Examples include the same saturated hydrocarbon groups as those with a valence.

[0212] The structural units containing cations in formula (II-1-1) are the structural units represented below and biR II4The group equivalent to the methyl group is a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. Examples include replaced structural units. JPEG0007879325000149.jpg85130

[0213] A - Examples of organic anions represented by this include sulfonic acid anions and sulfonylimido anions. Examples include sulfonylmethide anions and carboxylic acid anions. - It is represented The organic anion is preferably a sulfonate anion, and as for the sulfonate anion, as mentioned above. It is more preferable that the anion is contained in the salt represented by formula (B1).

[0214] A - Examples of sulfonylimid anions represented by the formula include the following: TIFF0007879325000150.tif38135

[0215] Examples of sulfonylmethide anions include the following: TIFF0007879325000151.tif29123

[0216] Examples of carboxylic acid anions include the following: TIFF0007879325000152.tif39136

[0217] Examples of structural units represented by formula (II-1-1) include the following structural units. It is possible. TIFF0007879325000153.tif99155 When resin (A) contains structural unit (II), the content of structural unit (II) is: The amount is preferably 1 to 20 mol%, and more preferably 2 to 1 mol%, relative to the total structural units of fat (A). The percentage is 15 mol%, and more preferably 3 to 10 mol%.

[0218] Resin (A) may have structural units other than those described above, and such structural units In terms of rank, well-known structural units in this field can be cited.

[0219] The resin (A) is preferably a resin consisting of structural unit (a1) and structural unit (s). . The structural unit (a1) is preferably structural unit (a1-0), structural unit (a1-1) and structural unit (a1-0) Manufacturing unit (a1-2) (preferably having a cyclohexyl group and a cyclopentyl group) At least one, more preferably at least two, selected from the group consisting of (production units). That is the case. The structural unit (s) is preferably from the group consisting of structural unit (a2) and structural unit (a3). It is at least one selected. The structural unit (a2) is preferably represented by formula (a2-A). It is a structural unit that is represented by formula (a2-1). The structural unit (a3) ​​is preferably Alternatively, structural units represented by formula (a3-1), structural units represented by formula (a3-2), and formula ( It is at least one selected from the group consisting of structural units represented in a3-4).

[0220] Each structural unit constituting resin (A) may be used individually or in combination of two or more types. Furthermore, using monomers that derive these structural units, known polymerization methods (e.g., radical polymerization) can be used. Therefore, it can be manufactured. The content of each structural unit in resin (A) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,5 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 (less than 15,000, more preferably less than 15,000). In this specification, weight average fraction The amount of molecules was determined by gel permeation chromatography under the conditions described in the examples. That is the case.

[0221] <Resins other than resin (A)> The resist composition of the present invention may also contain resins other than resin (A). Examples of resins other than resin (A) include structural unit (a4) or structural unit (a5). Examples include resins (hereinafter sometimes referred to as resin(X)). Among the resins (X), resins containing structural units (a4) are preferred. In resin (X), the content of structural unit (a4) is equal to the sum of all structural units in resin (X). In contrast, it is preferable that the amount be 30 mol% or more, and more preferably 40 mol% or more. Furthermore, it is more preferable that the amount be 45 mol% or more. The structural units that resin (X) may further possess include structural unit (a2) and structural unit (a3) and other structural units derived from known monomers are examples. Among them, resin ( X) is preferably a resin consisting only of structural unit (a4) and / or structural unit (a5). It is more preferable that the resin consists solely of structural units (a4). Each structural unit constituting the resin (X) may be used individually or in combination of two or more types. These monomers that induce structural units can be used in known polymerization methods (e.g., radical polymerization). Therefore, it can be manufactured. The content of each structural unit in resin (X) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000). The value is 0 or greater, and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight-average molecular weight is the same as in the case of resin (A). Furthermore, if the resist composition contains resin (X), its content is equal to 100 mass of resin (A). Preferably, the amount is 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, More preferably 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, and particularly preferred The amount is 1 to 8 parts by mass.

[0222] The content of resin (A) in the resist composition is 8 in relation to the solid content of the resist composition. Preferably, it is 0% by mass or more and 99% by mass or less, and preferably 90% by mass or more and 99% by mass or less. It is preferable. Also, if it contains resins other than resin (A), then resin (A) and resins other than resin (A) The total content of the resin is 80% by mass or more and 99% by mass or less relative to the solid content of the resist composition. The resist composition is preferably as follows: The solid content of a substance and the resin content thereto are determined by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as fluoroscopy.

[0223] <Solvent (E)> The solvent (E) content is typically 90% by mass or more and 99.9% by mass or less in the resist composition. Yes, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of solvent (E) is 99% by mass or less. The content of solvent (E) is determined, for example, by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as chromatography. The solvent (E) includes ethyl cellosolve acetate, methyl cellosolve acetate, and Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, vinegar Esters such as butyl acid, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl Ketones such as lucetone, 2-heptanone, and cyclohexanone; γ-butyrolactone, etc. Examples include cyclic esters; etc. One of the solvents (E) may be used alone. You may use two or more types.

[0224] <Quencher (C)> Quencher (C) is an acid generated from a basic nitrogen-containing organic compound or an acid generator (B). Salts that produce acids with weaker acidity than those of the compound (excluding carboxylate salts represented by formula (I)). Examples include: If the resist composition contains quencher (C), quencher (C The content of ) is approximately 0.01 to 15% by mass, based on the solid content of the resist composition. Preferably, it is about 0.1 to 10% by mass, and more preferably about 0.1 to 5% by mass. It is more preferable that the concentration is 0 degrees, and even more preferable that it is about 0.1 to 3% by mass. . Basic nitrogen-containing organic compounds include amines and ammonium salts. Examples include aliphatic amines and aromatic amines. Aliphatic amines include primary amines. Examples include amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, and diisopropylamine. Ruaniline, 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 mine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, methyldinonylamine, methylddecylamine, ethyl dibuty Luamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine Ethyl dioctylamine, ethyl dinonylamine, ethyl didecylamine, dicyclo Xylmethylamine, Tris[2-(2-methoxyethoxy)ethyl]amine, Triiso Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine Mine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmeth , 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridazole 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl (Lu)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-Pyridyl)ketone, 4,4'-dipyridylsulfide, 4,4'-dipyridyldisulfide Examples include phyto, 2,2'-dipyridylamine, 2,2'-dipicolylamine, and bipyridine. Aromatic amines such as diisopropylaniline are preferred, and more preferably One example is 2,6-diisopropylaniline. 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, and the like.

[0225] The acidity of a 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). A salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt with an acid dissociation constant of the acid generated from the salt usually being -3 < pKa, preferably a salt with -1 < pKa < 7, and more preferably a salt with 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as " intramolecular salt of weak acid (D)"), and salts described in JP-A-2012-229206 , JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. As the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B), preferably, a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion ), and more preferably, an intramolecular salt of weak acid (D). TIFF0007879325000154.tif85165

[0226] Examples of intramolecular salts (D) of weak acids include the following salts: TIFF0007879325000155.tif72165

[0227] <Other ingredients> The resist composition of the present invention may optionally include components other than those described above (hereinafter referred to as "other components"). It may be referred to as "F (F)". It may contain other components (F) in particular. There are no known additives in the resist field, such as sensitizers, dissolution inhibitors, surfactants, and stabilizers. Agents, dyes, etc. can be used.

[0228] <Preparation of resist composition> The resist composition of the present invention comprises a carboxylate (I) and a resin (A), an acid generator (B), and In addition, if necessary, resins other than resin (A), solvent (E), quencher (C) and their It can be prepared by mixing with other components (F). The mixing order is arbitrary, and in particular It is not limited to this. The mixing temperature can range from 10 to 40°C, depending on the type of resin, etc. An appropriate temperature can be selected depending on the solubility in solvents (E), etc. The mixing time is Depending on the mixing temperature, you can choose an appropriate time from 0.5 to 24 hours. There are no particular restrictions on the mixing method, and stirring and mixing can be used. After mixing each component, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable to do so.

[0229] <Method for manufacturing resist patterns> The method for manufacturing a resist pattern of the present invention is: (1) A step of applying the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) Includes a step of developing the composition layer after heating. To coat the resist composition onto the substrate, a commonly used device such as a spin coater is used. Therefore, it can be done. Examples of substrates include inorganic substrates such as silicon wafers. Before applying the Dist composition, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate. It's fine if you do that. By drying the applied composition, the solvent is removed and a composition layer is formed. Drying is performed. For example, evaporating a solvent using a heating device such as a hot plate (so-called private heating) This is done by (k) or by using a vacuum device. The heating temperature is 50-200°C. It is preferable that the heating time be 10 to 180 seconds. Also, vacuum drying The pressure used during this process is 1 to 1.0 × 10 5 It is preferable that the pressure be around Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine is an immersion exposure machine. This is also good. As exposure light sources, KrF excimer laser (wavelength 248nm), ArF excimer Ultraviolet lasers such as lasers (wavelength 193nm) and F2 excimer lasers (wavelength 157nm) Laser light is emitted from solid-state laser sources (such as YAG or semiconductor lasers). These devices emit high-harmonic laser light in the far-ultraviolet or vacuum-ultraviolet region by wavelength conversion, such as electron beams and ultra-high-frequency lasers. Various methods can be used, such as those that irradiate with ultraviolet light (EUV). In some cases, the act of irradiating with these radiations is collectively referred to as "exposure." Typically, exposure is performed through a mask corresponding to the desired pattern. The exposure light source is electron In the case of lines, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is heat-treated to promote the deprotection reaction at the acid-unstable groups. Perform a loose post-exposure bake. The heating temperature is usually around 50-200°C, or as preferred. The temperature is approximately 70-150°C. The heated composition layer is typically developed using a developing device and a developing solution. Examples include the dipping method, paddle method, spray method, and dynamic dispensing method. The development temperature is preferably, for example, 5 to 60°C, and the development time is, for example, 5 It is preferable that the developing time is ~300 seconds. By selecting the type of developer as follows: Positive-type resist patterns or negative-type resist patterns can be manufactured. When producing a positive-type resist pattern from the resist composition of the present invention, the developer is used as follows: An alkaline developer is used. The alkaline developer is a type of alkaline water used in this field. Any solution will do. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). Alkaline developers may contain surfactants. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is washed away. It is preferable to remove it. When manufacturing a negative-type resist pattern from the resist composition of the present invention, the developer is used as A developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used. Organic solvents contained in organic developers include ketosols such as 2-hexanone and 2-heptanone. Solvents; glycol ethers such as propylene glycol monomethyl ether acetate Sterling solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole Examples include aromatic hydrocarbon solvents such as the like. In organic developer solutions, the content of organic solvents is preferably 90% by mass or more and 100% by mass or less. It is more preferable that the concentration be 95% by mass or more and 100% by mass or less, and that it be substantially composed of only organic solvents. It is preferable. Among organic developers, those containing butyl acetate and / or 2-heptanone are Preferred. The total content of butyl acetate and 2-heptanone in the organic developer is 50% by mass. Preferably, the amount is 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the composition consists solely of butyl acetate and / or 2-heptanone. Organic developers may contain surfactants. Also, organic developers may contain trace amounts of surfactants. It may contain moisture. During development, by substituting a different type of solvent than the organic developer, development can be stopped. That's good too. It is preferable to wash the resist pattern with a rinsing solution after development. The rinsing solution can be: There are no particular restrictions as long as it does not dissolve the resist pattern, including general organic solvents. A liquid can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove any remaining rinse solution from the substrate and patterns.

[0230] <Application> The resist composition of the present invention is a resist composition for KrF excimer laser exposure, and ArF Resist compositions for Kishima laser exposure, resist compositions for electron beam (EB) exposure, or EU Resist compositions for V exposure, particularly resist compositions for electron beam (EB) exposure or EUV exposure It is suitable as a resist composition for use and is useful for semiconductor microfabrication. [Examples]

[0231] The present invention will be described in more detail with reference to examples. In the examples, the content or amount used is expressed Unless otherwise specified, "%" and "parts" refer to mass. The weight-average molecular weight is a value obtained by gel permuration chromatography. The analytical conditions for gel permuration chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The compound structure was determined by mass spectrometry (LC: Agilent 1100, MASS: Agil This was confirmed by measuring molecular ion peaks using an ent LC / MSD (manufactured by ent). In the examples, the value of this molecular ion peak is indicated by "MASS".

[0232] Example 1: Synthesis of the salt represented by formula (IA-31) TIFF0007879325000156.tif68127 4.72 parts of salt represented by formula (IA-31-a), 5 parts of salt represented by formula (IA-31-b) Mix 0.10 parts, 30 parts dimethylformamide, and 0.69 parts potassium carbonate, and heat at 120°C. After stirring for 4 hours, the mixture was cooled to 23°C. To the resulting reaction mixture, chloroform 60 Add 30 parts of the mixture and 30 parts of deionized water, stir at 23°C for 30 minutes, then separate to remove the organic layer. The organic layer was removed. 30 parts of deionized water were added to the recovered organic layer and stirred at 23°C for 30 minutes. Next, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated eight times. The resulting organic layer was concentrated. Shrinkage and concentration residue are processed in a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd.) (Manufactured by Gaku Co., Ltd., developing solvent: chloroform / methanol = 1 / 1) By fractionation, formula ( 0.48 parts of the salt represented by IA-31) were obtained. MASS(ESI(+)Spectrum):M 2+ 288.0 (M / 2) MASS(ESI(-)Spectrum):M - 193.1

[0233] Example 2: Synthesis of the salt represented by formula (IB-2) TIFF0007879325000157.tif68157 4.72 parts of salt represented by formula (IA-31-a), 2 parts of salt represented by formula (IA-31-b) Mix 0.55 parts, 30 parts dimethylformamide, and 1.38 parts potassium carbonate, and heat at 120°C. After stirring for 4 hours, the mixture was cooled to 23°C. To the resulting reaction mixture, chloroform 60 Add 30 parts of the mixture and 30 parts of deionized water, stir at 23°C for 30 minutes, then separate to remove the organic layer. The organic layer was removed. 30 parts of deionized water were added to the recovered organic layer and stirred at 23°C for 30 minutes. Next, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated eight times. The resulting organic layer was concentrated. Shrinkage and concentration residue are processed in a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd.) (Manufactured by Gaku Co., Ltd., developing solvent: chloroform / methanol = 1 / 1) By fractionation, formula ( 0.79 parts of the salt represented by IB-2) were obtained. MASS(ESI(+)Spectrum):M 3+ 278.4 (M / 3) MASS(ESI(-)Spectrum):M - 193.1

[0234] Example 3: Synthesis of the salt represented by formula (IA-33) TIFF0007879325000158.tif71127 6.16 parts of salt represented by formula (IA-33-a), 6 parts of salt represented by formula (IA-33-b) Mix 0.54 parts, 30 parts dimethylformamide, and 0.69 parts potassium carbonate, and heat at 120°C. After stirring for 4 hours, the mixture was cooled to 23°C. To the resulting reaction mixture, chloroform 60 Add 30 parts of the mixture and 30 parts of deionized water, stir at 23°C for 30 minutes, then separate to remove the organic layer. The organic layer was removed. 30 parts of deionized water were added to the recovered organic layer and stirred at 23°C for 30 minutes. Next, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated eight times. The resulting organic layer was concentrated. Shrinkage and concentration residue are processed in a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd.) (Manufactured by Gaku Co., Ltd., developing solvent: chloroform / methanol = 1 / 1) By fractionation, formula ( 0.51 parts of the salt represented by IA-33) were obtained. MASS(ESI(+)Spectrum):M 2+ 288.0 (M / 2) MASS(ESI(-)Spectrum):M - 337.1

[0235] Example 4: Synthesis of the salt represented by formula (IB-4) TIFF0007879325000159.tif77161 6.16 parts of salt represented by formula (IA-33-a), 3 parts of salt represented by formula (IA-33-b) Mix 0.27 parts, 30 parts dimethylformamide, and 1.38 parts potassium carbonate, and heat at 120°C. After stirring for 4 hours, the mixture was cooled to 23°C. To the resulting reaction mixture, chloroform 60 Add 30 parts of the mixture and 30 parts of deionized water, stir at 23°C for 30 minutes, then separate to remove the organic layer. The organic layer was removed. 30 parts of deionized water were added to the recovered organic layer and stirred at 23°C for 30 minutes. Next, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated eight times. The resulting organic layer was concentrated. Shrinkage and concentration residue are processed in a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd.) (Manufactured by Gaku Co., Ltd., developing solvent: chloroform / methanol = 1 / 1) By fractionation, formula ( 0.88 parts of the salt represented by IB-4) were obtained. MASS(ESI(+)Spectrum):M 3+ 278.4 (M / 3) MASS(ESI(-)Spectrum):M - 337.1

[0236] Example 5: Synthesis of the salt represented by formula (IA-201) TIFF0007879325000160.tif39149 contains 4.49 parts of pyridine and 14.67 parts of a compound represented by formula (IA-201-b), and A solution obtained by mixing 25 parts of trahydrofuran with compound 1 represented by formula (IA-201-a) To a solution prepared by mixing 0 parts of tetrahydrofuran with 10 parts of tetrahydrofuran, the mixture was added dropwise at 0°C. The resulting mixture The mixture was stirred at 23°C for 1 hour. 30 parts of deionized water were added to the reaction mixture, and ethyl acetate was added. Extraction was performed using [method / method]. The extracted organic layer was concentrated under reduced pressure, then n-heptane was added and stirred for 1 hour. The process was carried out. The mixed solution was prepared, the supernatant was removed, and it was dried to obtain the formula (IA-201-c 22.91 parts of the salt represented by ) were obtained. TIFF0007879325000161.tif73149 2.50 parts of salt represented by formula (IA-201-c), 50 parts of chloroform and ion exchange After adding 12.50 parts of water, the mixture was stirred at 23°C for 30 minutes. The resulting mixture was then mixed with formula (IA). After adding 1.29 parts of the salt represented by -201-d), stir at 23°C for 3 hours and then separate the liquids. The organic layer was removed. 20 parts of deionized water were added to the recovered organic layer, and it was incubated at 23°C for 30 minutes. After stirring for several minutes, the organic layer was separated and removed. This washing procedure was repeated five times. After the organic layer was concentrated, 30 parts of tert-butyl methyl ether were added to the resulting concentrate. After mixing and stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is dried to obtain formula (IA-20 3.08 parts of the salt represented by 1-e) were obtained. TIFF0007879325000162.tif66158 2.50 parts of salt represented by formula (IA-201-c), 50 parts of chloroform and ion exchange After adding 12.50 parts of water, the mixture was stirred at 23°C for 30 minutes. The resulting mixture was then mixed with formula (IA). After adding 1.44 parts of the salt represented by -201-f), stir at 23°C for 3 hours and then separate the liquids. The organic layer was removed. 20 parts of deionized water were added to the recovered organic layer, and it was incubated at 23°C for 30 minutes. After stirring for several minutes, the organic layer was separated and removed. This washing procedure was repeated five times. After the organic layer was concentrated, 30 parts of tert-butyl methyl ether were added to the resulting concentrate. After mixing and stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is dried to obtain formula (IA-20 3.12 parts of salt represented by 1 g were obtained. TIFF0007879325000163.tif81162 1.01 parts of salt represented by formula (IA-201-e), and represented by formula (IA-201-g) Mix 1.06 parts salt, 30 parts dimethylformamide, and 0.09 parts potassium carbonate, and 12 The mixture was stirred at 0°C for 4 hours, then cooled to 23°C. Chloroform was added to the resulting reaction mixture. Add 60 parts and 30 parts of deionized water, stir at 23°C for 30 minutes, then separate to form the organic layer. It was removed. 30 parts of deionized water were added to the recovered organic layer, and it was stirred at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated eight times. The resulting organic layer The concentrate is collected, and the concentrated residue is processed on a column (silica gel 60N (spherical, neutral) 100-210 μm; related Manufactured by Tokagaku Co., Ltd., developing solvent: chloroform / methanol (1 / 1) by fractionation, 1.18 parts of the salt represented by formula (IA-201) were obtained. MASS(ESI(+)Spectrum):M 2+ 288.0 (M / 2) MASS(ESI(-)Spectrum):M - 531.1

[0237] Example 6: Synthesis of the salt represented by formula (IB-128) TIFF0007879325000164.tif72168 1.01 parts of salt represented by formula (IA-201-e), and represented by formula (IA-201-g) Mix 0.53 parts salt, 30 parts dimethylformamide, and 0.17 parts potassium carbonate, and 12 The mixture was stirred at 0°C for 4 hours, then cooled to 23°C. Chloroform was added to the resulting reaction mixture. Add 60 parts and 30 parts of deionized water, stir at 23°C for 30 minutes, then separate to form the organic layer. It was removed. 30 parts of deionized water were added to the recovered organic layer, and it was stirred at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated eight times. The resulting organic layer The concentrate is collected, and the concentrated residue is processed on a column (silica gel 60N (spherical, neutral) 100-210 μm; related Manufactured by Tokagaku Co., Ltd., developing solvent: chloroform / methanol (1 / 1) by fractionation, 1.04 parts of the salt represented by formula (IB-128) were obtained. MASS(ESI(+)Spectrum):M 3+ 278.4 (M / 3) MASS(ESI(-)Spectrum):M - 531.1

[0238] Example 7: Synthesis of the salt represented by formula (IA-256) TIFF0007879325000165.tif76123 7.54 parts of salt represented by formula (IA-256-a), and represented by formula (IA-256-b) Mix 6.50 parts salt, 30 parts dimethylformamide, and 0.69 parts potassium carbonate, and 12 The mixture was stirred at 0°C for 4 hours, then cooled to 23°C. Chloroform was added to the resulting reaction mixture. Add 60 parts and 30 parts of deionized water, stir at 23°C for 30 minutes, then separate to form the organic layer. It was removed. 30 parts of deionized water were added to the recovered organic layer, and it was stirred at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated eight times. The resulting organic layer The concentrate is collected, and the concentrated residue is processed on a column (silica gel 60N (spherical, neutral) 100-210 μm; related Manufactured by Tokagaku Co., Ltd., developing solvent: chloroform / methanol (1 / 1) by fractionation, 1.48 parts of the salt represented by formula (IA-256) were obtained. MASS(ESI(+)Spectrum):M 2+ 355.0 (M / 2) MASS(ESI(-)Spectrum):M - 337.1

[0239] Example 8: Synthesis of the salt represented by formula (IB-172) TIFF0007879325000166.tif92163 7.54 parts of salt represented by formula (IA-256-a), and represented by formula (IA-256-b) Mix 3.25 parts salt, 30 parts dimethylformamide, and 1.38 parts potassium carbonate, and 12 The mixture was stirred at 0°C for 4 hours, then cooled to 23°C. Chloroform was added to the resulting reaction mixture. Add 60 parts and 30 parts of deionized water, stir at 23°C for 30 minutes, then separate to form the organic layer. It was removed. 30 parts of deionized water were added to the recovered organic layer, and it was stirred at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated eight times. The resulting organic layer The concentrate is collected, and the concentrated residue is processed on a column (silica gel 60N (spherical, neutral) 100-210 μm; related Manufactured by Tokagaku Co., Ltd., developing solvent: chloroform / methanol (1 / 1) by fractionation, 1.59 parts of the salt represented by formula (IB-172) were obtained. MASS(ESI(+)Spectrum):M 3+ 369.0 (M / 3) MASS(ESI(-)Spectrum):M - 337.1

[0240] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. These are referred to as "monomers (a1-1-3)" etc., according to their formula numbers. TIFF0007879325000167.tif3896

[0241] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) is used, and its molar ratio [monomer (a1-4-2):monomer (a1-1 -3): Mix the monomers (a1-2-6) in a ratio of 38:24:38. Furthermore, this monomer mixture contains methyl methyl in an amount equal to 1.5 times the total mass of all monomers. Isobutyl ketone was mixed. To the resulting mixture, azobisisobutyronite was added as an initiator. Add lyl to a concentration of 7 mol% relative to the total number of moles of all monomers, and then heat at 85°C. Polymerization was carried out by heating for approximately 5 hours. Afterwards, p-toluenesulfone was added to the polymerization reaction solution. An acidic aqueous solution was added, and the mixture was stirred for 6 hours before being separated. The resulting organic layer contained a large amount of n-heptane. By pouring it into the solution and allowing the resin to precipitate, then filtering and recovering it, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 Resin A1 (polymer) was obtained in a yield of 78%. This resin A1 has the following structural units It is what it is. TIFF0007879325000168.tif28125

[0242] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) are used, The molar ratio [monomer(a1-4-2):monomer(a1-2-6)] is 38:62. Mix them together, and then add to this monomer mixture, relative to the total mass of all monomers. Then, 1.5 times the mass of methyl isobutyl ketone was mixed in. To the resulting mixture, as an initiator, Azobisisobutyronitrile is added in a quantity of 7 mol% relative to the total number of moles of all monomers. Polymerization was carried out by adding it to and heating it at 85°C for about 5 hours. After that, the polymerization reaction solution was added to Then, an aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 6 hours before being separated. The resulting organic layer This is poured into a large amount of n-heptane to precipitate the resin, which is then filtered and recovered, thereby obtaining the weight-averaged fraction. The amount of eggs is approximately 5.4 x 10 3 Resin A2 (polymer) was obtained in a yield of 89%. It has the following structural units: TIFF0007879325000169.tif2887

[0243] <Preparation of the resist composition> As shown in Table 3, the following components were mixed, and the resulting mixture contained fluorine with a pore size of 0.2 μm. The resist composition was prepared by filtering through a resin filter.

[0244] [Table 3]

[0245] <Resin> A1, A2: Resin A1, Resin A2 <Acid Generator (B)> B1-25: Salt represented by formula (B1-25); described in Japanese Patent Publication No. 2011-126869. synthesized by the method TIFF0007879325000171.tif2667<Carboxylate (I)> IA-31: Salt represented by formula (IA-31) IB-2: Salt represented by formula (IB-2) IA-33: Salt represented by formula (IA-33) IB-4: Salt represented by formula (IB-4) IA-201: Salt represented by formula (IA-201) IB-128: Salt represented by formula (IB-128) IA-256: Salt represented by formula (IA-256) IB-172: Salt represented by formula (IB-172) <Quencher (C)> IX-1 IX-2 IX-3 TIFF0007879325000172.tif72108<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0246] (Electron beam exposure evaluation of resist compositions) A 6-inch silicon wafer is subjected to hexamethyldisilaza on a direct hot plate. The silicon wafer was treated at 90°C for 60 seconds using a solvent. The resist composition was then applied to this silicon wafer. The layer was spin-coated to a thickness of 0.04 μm. Then, direct hot plated... On the grid, the composition layer was formed by pre-baking for 60 seconds at the temperature shown in the "PB" column of Table 3. On the composition layer formed on the surface, an electron beam lithography machine [Hitachi Ltd.'s "HL-800D"] was used. Using 50 keV, the exposure level is changed in steps to create a line and space pattern. I drew it directly. After exposure, post-exposure is performed on a hot plate at the temperature shown in the "PEB" column of Table 3 for 60 seconds. Jar baking was performed, and then 2.38% by mass of tetramethylammonium hydroxide aqueous solution was added. A resist pattern was obtained by paddle development with a solution for 60 seconds. The obtained resist pattern (line and space pattern) is observed using a scanning electron microscope. I guess the line width and space width of the 60nm line and space pattern are in a 1:1 ratio. The exposure level was defined as the effective sensitivity.

[0247] Line Edge Roughness Evaluation (LER): Sidewall of a resist pattern manufactured with effective sensitivity. The amplitude of surface irregularities was measured using a scanning electron microscope to determine the line edge roughness. The results are shown in Table 4. [Table 4] Compared to comparative compositions 1 to 3, compositions 1 to 16 have line edge roughness (LER) It was good. [Industrial applicability]

[0248] The carboxylate salt of the present invention and the resist composition containing the carboxylate salt are line edge rough. It has good ness and is useful for semiconductor microfabrication.

Claims

1. A carboxylic acid generator comprising a carboxylic acid salt represented by formula (IA) or formula (IB), Acid generators other than the carboxylic acid generator, A resist composition containing a resin comprising a structural unit having an acid-unstable group and a structural unit represented by formula (a2-A). [In formulas (IA) and (IB), R １ , R ２ , R ３ and R ４ Each of these independently represents a hydrocarbon group having 1 to 24 carbon atoms and having substituents, and the hydrocarbon group is selected from the group consisting of chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining these, and at least one of the substituents is a halogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms. １ and R ２ , and also, R ３ and R ４ These atoms may bond to each other and, together with the sulfur atoms to which they are bonded, form a ring with 3 to 24 carbon atoms. R ５ , R ６ , R ７ , R ８ and R ９ each independently represents a halogen atom, a hydroxy group, a C1-C6 perfluoroalkyl group or a C1-C12 alkyl group, and the -CH ２ - contained in the alkyl group may be replaced by -O- or -CO-. m5 represents an integer from 0 to 2, and when m5 is 2, multiple R ５ They may be identical or different from one another. m6 represents an integer from 0 to 2, and when m6 is 2, multiple R ６ They may be identical or different from one another. m7 represents an integer from 0 to 2, and when m7 is 2, multiple R ７ They may be identical or different from one another. m8 represents an integer from 0 to 2, and when m8 is 2, multiple R ８ They may be identical or different from one another. X １ and X ２ Each of these independently represents a single bond, an oxygen atom, a sulfur atom, or an alkanediyl group having 1 to 6 carbon atoms, and the alkanediyl group contains -CH ２ The dash may be replaced by -O- or -CO-. X ０１ , X ０２ and X ０３ Each of these independently comprises a cyclic hydrocarbon group having 3 to 24 carbon atoms, which may have substituents (the cyclic hydrocarbon group contains -CH ２ - may be replaced by -O-, -S-, or -CO-.), a group formed by combining an alicyclic hydrocarbon group having 3 to 24 carbon atoms and a chain hydrocarbon group having 1 to 12 carbon atoms (the alicyclic hydrocarbon group and the chain hydrocarbon group contain -CH ２ - may be replaced by -O-, -S-, or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have substituents.), a C6 to C24 aromatic hydrocarbon group which may have substituents, or a group which is a combination of a C6 to C24 aromatic hydrocarbon group and a C1 to C12 chain hydrocarbon group (the chain hydrocarbon group contains -CH ２ The - may be replaced by -O-, -S-, or -CO-, and the aromatic hydrocarbon group and the chain hydrocarbon group may have substituents. [In formula (a2-A), R a50 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a51 This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 - (A a52 -X a52 ) nｂ - represents -R a50 This indicates the bonding position with the carbon atom to which it is bonded. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent, independently, -O-, -CO-O-, or -O-CO-. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, then multiple R a51 They may be identical or different from one another.

2. R １ , R ２ , R ３ and R ４ The resist composition according to claim 1, wherein each is independently a phenyl group having a substituent.

3. X ０１ , X ０２ and X ０３ However, each may independently have a fluorine atom or a hydroxyl group (the alicyclic hydrocarbon group contains -CH 2 - may be replaced by -O- or -CO-.), a group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (the alicyclic hydrocarbon group and the chain hydrocarbon group contain -CH 2 The resist composition according to claim 1 or 2, wherein the - may be replaced with -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom or a hydroxyl group.

4. The resist composition according to any one of claims 1 to 3, wherein the resin comprises at least one selected from the group consisting of structural units represented by formula (a1-1) and structural units represented by formula (a1-2). [In formulas (a1-1) and (a1-2), L a1 and L a2 These are, independently, -O- or *-O- (CH ２ ) k1 -CO-O- represents -CO-O-, k1 is an integer from 1 to 7, and * represents the association with -CO-. R a4 and R a5 Each of these independently represents either a hydrogen atom or a methyl group. R a6 and R a7 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

5. (1) A step of applying the resist composition according to any one of claims 1 to 4 onto a substrate, (2) A step of drying the coated composition to form a composition layer, (3) Exposure step of the composition layer, (4) A step of heating the composition layer after exposure, (5) A step of developing the composition layer after heating, A method for manufacturing a resist pattern that includes [the specified element].

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