Resist composition

Abstract

To provide a resist composition capable of producing a resist pattern with a good mask error factor (MEF).SOLUTION: A resist composition comprises a carboxylic acid generator containing a carboxylate represented by Formula (I), an acid generator other than the carboxylic acid generator, and a resin containing structural units with acid-labile groups and structural units represented by formula (a3-4).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist composition. [Background technology]

[0002] Patent Document 1 discloses a resin containing a carboxylic acid salt represented by the following formula as a carboxylic acid generator. A synthetic composition is described. TIFF0007813327000001.tif3050 Patent Document 2 discloses a photosensitive resin containing a carboxylic acid salt represented by the following formula as a carboxylic acid generator. A synthetic composition is described. TIFF0007813327000002.tif3052 Patent Document 3 describes a salt represented by the following formula: TIFF0007813327000003.tif1750

[0003] Patent Document 4 describes a salt represented by the following formula: TIFF0007813327000004.tif21112 [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-39502 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-88367 [Patent Document 3] Japanese Patent Application Laid-Open No. 1973-123860 [Patent Document 4] Japanese Patent Application Publication No. 2018-030830 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention relates to a resist pattern formed using a resist composition containing the above-mentioned carboxylate. Cumulative resist patterns with better mask error factor (MEF) than quartz. The present invention provides a hydroxybenzoate. [Means for solving the problem]

[0006] The present invention includes the following inventions. [1] A carboxylate represented by formula (I). TIFF0007813327000005.tif48113 [In formula (I), R 1a and R 2a each independently represents a carbon number which may have a hydrogen atom or a fluorine atom, 1 to 18 hydrocarbon groups (-CH2- contained in the hydrocarbon groups is not limited to -O-, -S-, -CO - or -SO2- may be replaced.) or R 1a and R 2a and are connected to each other a ring (or rings) having 3 to 36 carbon atoms which may be bonded to one another and which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms; -CH2- contained in the alkyl group may be replaced with -O- or -CO-, -CH2- contained in the ring is replaced by -O-, -S-, -CO- or -SO2- It may be formed. R 3a represents a hydrogen atom or R 1a and R 2a and R 3a and bond to each other, and the fluorine atom or a ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms (the alkyl group -CH2- contained in the ring may be replaced by -O- or -CO-, and - contained in the ring CH2- may be replaced by -O-, -S-, -CO- or -SO2-. Form. R 4 is a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. The fluorinated alkyl group and the —CH2— contained in the alkyl group are each independently —O— or It may be replaced by -CO-. R 5 represents a halogen atom, a fluoroalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, group or -O-CO-CR 1b R 2b R 3b and the fluorinated alkyl group and the alkyl group The -CH2- contained in the formula may be replaced by -O- or -CO-. R 1b and R 2b each independently represents a carbon number which may have a hydrogen atom or a fluorine atom, 1 to 18 hydrocarbon groups (-CH2- contained in the hydrocarbon groups is not limited to -O-, -S-, -CO - or -SO2- may be replaced.) or R 1b and R 2b and are connected to each other a ring (or rings) having 3 to 36 carbon atoms which may be bonded to one another and which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms; -CH2- contained in the alkyl group may be replaced with -O- or -CO-, -CH2- contained in the ring is replaced by -O-, -S-, -CO- or -SO2- It may be formed. R 3b represents a hydrogen atom or R 1b and R 2b and R 3b and bond to each other, and the fluorine atom or a ring having 3 to 36 carbon atoms which may have an alkyl group having 1 to 12 carbon atoms (the alkyl group -CH2- contained in the ring may be replaced by -O- or -CO-, and - contained in the ring CH2- may be replaced by -O-, -S-, -CO- or -SO2-. Form. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R 4 are the same as each other They may be the same or different. m5 represents an integer of 0 to 5, and when m5 is 2 or more, a plurality of R 5 are the same as each other They may be the same or different. X 0 represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and The -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. stomach.] [2]X 0 an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that the aliphatic -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-. The carboxylic acid salt according to [1], wherein [3]X 0 is an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxy group (the alicyclic The —CH 2 — contained in the hydrocarbon group may be replaced by —O— or —CO—. ) or a group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are combined (the alicyclic hydrocarbon group and The —CH2— contained in the chain hydrocarbon group may be replaced by —O— or —CO—. The alicyclic hydrocarbon group and the chain hydrocarbon group each have a fluorine atom or a hydroxy group. The carboxylate according to [1] or [2], wherein [4] A carboxylic acid generator containing the carboxylic acid salt according to any one of [1] to [3]. [5] The carboxylic acid generator according to [4], an acid generator other than the carboxylic acid generator, and an acid-inhibiting agent A resist composition containing a resin having a stable group. [6] The resin having an acid labile group is a resin having a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1- 2) is a resin containing at least one selected from the group consisting of structural units represented by the formula [5] The resist composition described above. TIFF0007813327000006.tif46102 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or -O-(CH2) k1 -CO-O represents -, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 are each independently an alkyl group having 1 to 8 carbon atoms, a It represents an alicyclic hydrocarbon group or a group formed by combining these groups. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. [7] The method according to [5] or [6], further comprising the step of: The resist composition described above. [8] (1) A process for applying the resist composition according to any one of [5] to [7] onto a substrate. The course, (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A method for producing a resist pattern, comprising the step of developing the composition layer after heating. [Effects of the Invention]

[0007] By using a resist composition using the carboxylic acid salt of the present invention, it is possible to obtain a good masking effect. Resist patterns can be produced using a multi-factor (MEF). DETAILED DESCRIPTION OF THE INVENTION

[0008] In this specification, the term "(meth)acrylic monomer" refers to a monomer having a structure such as "CH2=CH-CO-" Monomers having the structure "CH2=C(CH3)-CO-" and monomers having the structure "CH2=C(CH3)-CO-" Similarly, "(meth)acrylate" and "(Meth)acrylic acid" refers to "a group consisting of acrylate and methacrylate" "At least one selected from the group consisting of acrylic acid and methacrylic acid" and "at least one selected from the group consisting of acrylic acid and methacrylic acid "at least one of" "CH2=C(CH3)-CO-" or "CH2=CH-C When a structural unit having "O-" is exemplified, structural units having both groups are also exemplified. In addition, in the groups described in this specification, a linear structure and a branched structure are For those which can have both structures, either one is acceptable. It means a group in which two or more of the indicated groups are bonded, and the valence of these groups changes appropriately depending on the bonding form. "Derived from" or "derived from" refers to a polymerizable C=C This means that the bond becomes a -CC- group by polymerization. When stereoisomers exist, all Includes stereoisomers. In this specification, the term "solid content of the resist composition" refers to the amount of the solid content of the resist composition that is the remaining amount of the resist composition. This refers to the total of all components excluding the solvent (E) described below.

[0009] [Salt represented by formula (I)] The present invention relates to a carboxylate represented by formula (I) (hereinafter referred to as "carboxylate (I)"). (There is.) In salt (I), the side with a negative charge is called an anion (I), and the side with a positive charge is called a cationic It is sometimes called "On(I)". TIFF0007813327000007.tif48113 [wherein all symbols have the same meanings as defined above.]

[0010] R 1a , R 1b , R 2a and R 2b The hydrocarbon group may be a chain hydrocarbon such as an alkyl group. Aromatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof Examples of such groups include: Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 12 carbon atoms. Preferably, it is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. It is even more preferably 1 to 2. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spirocyclic groups, and may be saturated or unsaturated. The alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, ... Cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group group, monocyclic cycloalkyl groups such as cyclododecyl group, norbornyl group, adamantyl group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 100. It is preferably 18, more preferably 3 to 16, and even more preferably 3 to 12. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. The number of carbon atoms in the group is preferably 6 to 18, more preferably 6 to 14, and even more preferably Usually it is 6 to 10. Examples of groups formed by combining these include cyclopentylmethyl. adamantylmethyl group, etc., which are a combination of an alicyclic hydrocarbon group and a chain hydrocarbon group Aromatic hydrocarbon groups and chain hydrocarbon groups such as aryl groups, benzyl groups, and phenethyl groups are combined. Examples include groups such as In the case of a group formed by combining the above groups, groups with different valences (2 containing valent or trivalent groups (chain hydrocarbon groups, alicyclic saturated hydrocarbon groups, aromatic hydrocarbon groups, etc.) It may be included. R 1a , R 2a , R 1b and R 2b a hydrocarbon group represented by R 1a and R 2a , R 1b and R 2b , R 1a and R 2a and R 3a or R 1b and R 2b and R 3b and are bonded together to form -CH2- in the ring is replaced by -O-, -S-, -CO- or -SO2- In the case where R is substituted, the number of carbon atoms before substitution is the total number of carbon atoms in the hydrocarbon group or ring. 1 a and R 2a , R 1a and R 2a and R 3a , R 1b and R 2b or R 1b and R 2b and R 3b Toga When the ring formed by bonding each other has an alkyl group, the number of carbon atoms in the alkyl group is The number of carbon atoms is the total number of carbon atoms in the ring. R 1a , R 2a , R 1b or R 2b When is a hydrocarbon group, the number of carbon atoms in the hydrocarbon group is and each independently is preferably 1 to 18, more preferably 1 to 14. More preferably, R is 1 to 12. 1a and R 2a , R 1b and R 2b , R 1a and R 2a and R 3a or R 1b and R 2b and R 3b When they are bonded to each other to form a ring, the carbon atoms of the ring The prime numbers are each independently preferably 3 to 24, and more preferably 3 to 18. It is preferable that the number of carbon atoms is 3 to 16, and more preferable that the number of carbon atoms is 3 to 16. R 1a and R 2a , R 1a and R 2a and R 3a , R 1b and R 2b or R 1b and R 2b and R 3 b and may be bonded to each other to form a ring, the alkyl group that may be included therein is, for example, the above-mentioned Similar groups are mentioned.

[0011] Examples of alkyl groups in which -CH2- is replaced with -O- or -CO- include: Hydroxy group (a group in which -CH2- in a methyl group is replaced with -O-), carbo an oxy group (an ethyl group in which -CH2-CH2- is replaced with -O-CO-); Alkoxy group having 1 to 11 carbon atoms (-CH2- contained in alkyl group having 2 to 12 carbon atoms) , -O- substituted), alkoxycarbonyl group having 2 to 11 carbon atoms (groups having 3 to 1 (a group in which -CH2-CH2- in the alkyl group of 2 is replaced with -O-CO-), Alkylcarbonyl groups with 2 to 12 carbon atoms (-CH contained in alkyl groups with 2 to 12 carbon atoms) 2- is replaced by -CO-), alkylcarbonyloxy group having 2 to 11 carbon atoms ( -CH2-CH2- in the alkyl group having 3 to 12 carbon atoms is replaced with -CO-O- Examples include groups such as The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy Examples thereof include a siloxy group, a nonyloxy group, a decyloxy group, and an undecyloxy group. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group are A carbonyl group or a carbonyloxy group is bonded to the alkyl group or the alkoxy group. Represents a group. The alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group, a bromine group, a methyl ... Examples of the alkylcarbonyl group include an acetyl group, a propyl group, and the like. The alkylcarbonyloxy group includes acetyl, ... Examples thereof include an oxy group, a propionyloxy group, and a butyryloxy group.

[0012] R 1a and R 2a , R 1a and R 2a and R 3a , R 1b and R 2b or R 1b and R 2b and R 3 b and bond to each other to form a ring, -C(R 1a )(R 2a )(R 3a ) or -C (R 1b )(R 2b )(R 3b ) includes the following groups. * indicates a carbonyl group. Represents the bonding site with the carbon atom. TIFF0007813327000008.tif86163R 1a , R 2a , R 1b and R 2b are each independently a hydrogen atom or a fluorine atom. A hydrocarbon group having 1 to 14 carbon atoms which may have a substituent (-CH2- contained in the hydrocarbon group is -O-, -S-, -CO- or -SO2- may be substituted, or R 1 a and R 2a , R 1b and R 2b and are bonded to each other, and are each a fluorine atom or an alkyl group having 1 to 12 carbon atoms. a ring having 3 to 24 carbon atoms which may have a methyl group (the —CH2— contained in the alkyl group is —O— or -CO-, and -CH2- contained in the ring may be replaced by -O-, -S- , -CO- or -SO2- may be replaced by each independently being a hydrogen atom or a carbon atom having 1 to 12 carbon atoms which may have a fluorine atom; A hydrogen group (the -CH2- contained in the hydrocarbon group is -O-, -S-, -CO- or -SO2 - may be replaced by ) or R 1a and R 2a , R 1b and R 2b and each other a ring ( -CH2- contained in the alkyl group may be replaced with -O- or -CO-, -CH2- contained in the ring is replaced by -O-, -S-, -CO- or -SO2- It is more preferable to form Each independently represents a hydrogen atom, a chain hydrocarbon group having 1 to 12 carbon atoms, or a fluorine atom. an adamantyl group optionally having a nitrogen atom (the —CH— contained in the adamantyl group is —O -, -S-, -CO- or -SO2-) or a fluorine atom A spiro ring containing an adamantyl group (the adamantyl group and the spiro ring -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. or R 1a and R 2a , R 1b and R 2b and bonded to each other, and an adamantyl group optionally having up to 6 alkyl groups (wherein the —CH2— contained in the alkyl group is , -O- or -CO-, and -CH2 contained in the adamantyl group - may be replaced by -O-, -S-, -CO- or -SO2-), fluorine A spiro ring containing an adamantyl group which may have an atom or an alkyl group having 1 to 6 carbon atoms (the adamantyl group The —CH2— contained in the alkyl group may be replaced by —O— or —CO—, The damantyl group and the —CH2— contained in the spiro ring are each independently selected from —O—, —S—, —CO—, and — It is more preferable to form a cyclohexane-2-sulfonyl group, in which the cyclohexane-2-sulfonyl group may be replaced by SO2-. Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a fluorine atom an adamantyl group optionally having -CH2- in the adamantyl group; may be replaced by -S-, -CO- or -SO2-, or R 1a and R 2a , R 1b and R 2b and bonded to each other, and have a fluorine atom or an alkyl group having 1 to 6 carbon atoms. an adamantyl group (wherein the —CH2— contained in the alkyl group is substituted with —O— or —CO—) The —CH2— contained in the adamantyl group may be replaced by —O—, —S—, — It is even more preferable to form a methyl group. .

[0013] R 3a and R 3b are each independently a hydrogen atom or R 1a and R 2a and R 3a also is R 1b and R 2b and R 3b and are bonded to each other, and A ring having 3 to 24 carbon atoms which may have a group (-CH2- contained in the alkyl group is -O- or may be replaced by -CO-, and -CH2- contained in the ring may be replaced by -O-, -S-, It is preferable to form a cycloalkyl group, in which the cycloalkyl group may be replaced by —CO— or —SO—, hydrogen atom or R 1a and R 2a and R 3a or R 1b and R 2b and R 3b and are connected to each other a ring having 3 to 16 carbon atoms which may be bonded to a ring having 3 to 16 carbon atoms and which may have a fluorine atom or an alkyl group having 1 to 6 carbon atoms (the The —CH2— contained in the alkyl group may be replaced by —O— or —CO—. -CH2- in the ring is replaced by -O-, -S-, -CO- or -SO2-. It is more preferable to form hydrogen atom or R 1a and R 2a and R 3a or R 1b and R 2b and R 3b and are connected to each other an adamantyl group optionally having a fluorine atom or an alkyl group having 1 to 6 carbon atoms (the alkyl group The -CH2- contained in the alkyl group may be replaced by -O- or -CO-, and the -CH2- in the manthyl group is replaced by -O-, -S-, -CO- or -SO2-. adamantane which may have a fluorine atom or an alkyl group having 1 to 6 carbon atoms; Spiro ring containing a butyl group (-CH2- contained in the alkyl group is -O- or -CO-) The —CH2— contained in the adamantyl group and the spiro ring may be replaced by — may be replaced by -O-, -S-, -CO- or -SO2-. More preferably, hydrogen atom or R 1a and R 2a and R 3a or R 1b and R 2b and R 3b and are connected to each other an adamantyl group optionally having a fluorine atom or an alkyl group having 1 to 6 carbon atoms (the alkyl group The -CH2- contained in the alkyl group may be replaced by -O- or -CO-, and the -CH2- in the manthyl group is replaced by -O-, -S-, -CO- or -SO2-. It is even more preferable to form a

[0014] R 4 and R 5 The halogen atoms include fluorine atoms, chlorine atoms, iodine atoms, and bromine atoms. Examples include children. R 4 and R 5 Examples of the fluorinated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a difluoromethyl group, Fluoromethyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group Perfluoropropyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octyl Perfluorobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5 fluorinated alkyl groups such as -nonafluoropentyl and perfluorohexyl groups; The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 4, more preferably 1 to 3. . R 4 and R 5 Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group Examples of alkyl groups include a silyl group, an octyl group, and a nonyl group. The number of carbon atoms in the alkyl group is preferably Preferably, it is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. R 4 and R 5 The -CH2- contained in the fluorinated alkyl group and the alkyl group represented by the formula When the fluorinated alkyl group is substituted with O- or -CO-, the number of carbon atoms before the substitution is and the total number of carbon atoms in the alkyl group. R 4 and R 5 The -CH2- contained in the alkyl group represented by the formula (I) is substituted with -O- or -CO-. The substituted group is a hydroxy group (-CH2- contained in a methyl group is replaced with -O-). carboxyl group (the -CH2-CH2- in the ethyl group is replaced by -O-CO -substituted), alkoxy groups having 1 to 11 carbon atoms (among alkyl groups having 2 to 12 carbon atoms (groups in which -CH2- in the above is replaced with -O-), alkoxycarbonyl groups having 2 to 11 carbon atoms A hydroxyl group (-CH2-CH2- contained in an alkyl group having 3 to 12 carbon atoms) is replaced with -O-CO- alkylcarbonyl groups having 2 to 12 carbon atoms (groups substituted with alkylcarbonyl groups having 2 to 12 carbon atoms) alkyl groups having 2 to 11 carbon atoms, a carbonyloxy group (-CH2-CH2- contained in an alkyl group having 3 to 12 carbon atoms) -CO-O- is substituted). R 4 and R 5 -CH2- contained in the fluorinated alkyl group represented by the formula: The group substituted with - includes a fluorinated alkoxy group having 1 to 5 carbon atoms (a fluorinated alkoxy group having 2 to 6 carbon atoms). a group in which -CH2- in a substituted alkyl group is replaced with -O-, a fluoroalkyl group having 2 to 5 carbon atoms Fluorinated alkoxycarbonyl group (-CH2- contained in fluorinated alkyl group having 3 to 6 carbon atoms) (a group in which -CH2- is replaced by -O-CO-), a fluorinated alkylcarbonyl group having 2 to 6 carbon atoms A fluoroalkyl group (a fluoroalkyl group having 2 to 6 carbon atoms in which -CH2- is replaced with -CO-) fluorinated alkylcarbonyloxy groups having 2 to 5 carbon atoms (fluorinated alkyl groups having 3 to 6 carbon atoms), (a group in which -CH2-CH2- in an alkyl group is replaced with -CO-O-) can be. Alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups and alkylcarbonyl groups Examples of the oxy group include the same groups as those mentioned above. Fluorinated alkoxy groups, fluorinated alkoxycarbonyl groups, fluorinated alkylcarbonyl groups, and The fluorinated alkylcarbonyloxy group is a group in which one or more hydrogen atoms of the groups exemplified above are substituted. It can be replaced with a fluorine atom. R 4 and R 5 is -O-CO-C(R 1a )(R 2a )(R 3a ) even if it is the same group They may be different groups. m4 and m5 each independently represent preferably 0, 1, 2 or 3, and more preferably 0, 1 or 2. is preferred, and 0 or 1 is more preferred. R 4 represents a fluorine atom, a fluorinated alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. (The -CH2- contained in the fluorinated alkyl group and the alkyl group is -O- or -CO-. It is preferable that the aryl group is substituted with aryl. R 5 is a fluorine atom, a fluorinated alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 6 carbon atoms ( The -CH2- contained in the fluorinated alkyl group and the alkyl group is replaced with -O- or -CO-. may be replaced) or -O-CO-C(R 1b )(R 2b )(R 3b ) is more preferred.

[0015] -O-CO-C(R 1a )(R 2a )(R 3a ) is the bond position of the iodine atom. The amino acid may be in any of the m-, p-, and p-positions, but the p-position is preferred. R 4 and R 5 The bonding position of the iodine atom can be either the o-position, m-position, or p-position. In particular, R 5 is -O-CO-C(R 1a )( R 2a )(R 3a ) is preferably bonded at the same position as

[0016] Examples of the cation (I) include the following cations: TIFF0007813327000009.tif164144

[0017] In formula (I), X0 The hydrocarbon group represented by the formula (I) is an aliphatic hydrocarbon group (alkyl chain hydrocarbon groups such as alkyl, alkenyl, and alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbons Examples of the -C contained in the aliphatic hydrocarbon group include a hydroxyl group and a group combining these groups. H2- may be replaced by -O-, -S-, -CO- or -SO2-. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 12 carbon atoms. Preferably, it is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. do. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples include an octynyl group, an isooctynyl group, and a nonenyl group. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, Examples thereof include a nonynyl group. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spirocyclic groups, and may be saturated or unsaturated. The alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, ... Cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group group, monocyclic cycloalkyl groups such as cyclododecyl group, norbornyl group, adamantyl group, etc. Examples of polycyclic cycloalkyl groups include the following. The alicyclic hydrocarbon group and the -CH2- contained in the alicyclic hydrocarbon group are -O-, -S-, - Specific examples of the group substituted with CO- or -SO2- include the following groups. X 0 The alicyclic hydrocarbon group represented by the formula (Y1) to (Y41) (* represents a bonding position.) are preferred, and the formulas (Y1) to (Y20), (Y26), and (Y27) are preferred. ), a group represented by any one of formula (Y30), formula (Y31), formula (Y39) to formula (Y41) It is more preferable that the formula (Y3), (Y4), (Y9), (Y11), and (Y 14), Formula (Y15), Formula (Y16), Formula (Y20), Formula (Y26), Formula (Y27), Formula It is further preferred that the group is a group represented by formula (Y30), formula (Y31), formula (Y39) or formula (Y40). The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, and more preferably is 3 to 16, and more preferably 3 to 12. TIFF0007813327000010.tif80155

[0018] Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, Examples of aromatic hydrocarbon groups include aryl groups such as phenanthryl and binaphthyl groups. The prime number is preferably 6 to 36, more preferably 6 to 24, and even more preferably It is 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. be. In the case of a combined group, the above groups may be groups with different valences (alkanediyl group, alkanediyl group, etc.). cycloalkanetriyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group It may contain a cycloalkanetetrayl group, etc.

[0019] The combined groups are: A group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are combined (the chain hydrocarbon group and the alicyclic hydrocarbon group) -CH2- contained in the hydrocarbon group of the formula may be replaced with -O-, -S-, -CO- or -SO2-. may be replaced), A group in which a chain hydrocarbon group and an aromatic hydrocarbon group are combined (a group in which the chain hydrocarbon group is included) -CH2- may be replaced by -O-, -S-, -CO- or -SO2-), and A group in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined (the alicyclic hydrocarbon group -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. ) In addition, in the combination, an alicyclic hydrocarbon group, a chain hydrocarbon group, and an aromatic hydrocarbon group may be used in combination of two or more of each. Specifically, the combined groups include: Alicyclic hydrocarbon groups such as adamantylmethylene groups and cyclohexylmethylene groups - chain carbonization Hydrogen group-*, (alicyclic hydrocarbon group) 2-chain hydrocarbon group-* (the chain hydrocarbon group and the alicyclic hydrocarbon group) -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-. (may be replaced), Chain 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 -CH2- in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-. (You may also know), Aromatic hydrocarbon groups such as tolyl and xylyl groups (aromatic hydrocarbon groups) -CH2- contained in is replaced by -O-, -S-, -CO- or -SO2- (also acceptable), Acyclic hydrocarbon groups such as methylcyclohexylmethylene groups - alicyclic hydrocarbon groups - Acyclic hydrocarbons Aromatic group-*, (acyclic hydrocarbon group) 2-alicyclic hydrocarbon group-aromatic hydrocarbon group-*, (aromatic hydrocarbon group) Hydrogen group-alicyclic hydrocarbon group) 2-chain hydrocarbon group-* (the chain hydrocarbon group and the alicyclic hydrocarbon group) -CH2- contained in the hydrogen hydride group is replaced by -O-, -S-, -CO- or -SO2-. (It may be possible to Aromatic hydrocarbon groups such as benzyl groups - Chain hydrocarbon groups - * (The chain hydrocarbon groups -CH2- may be replaced by -O-, -S-, -CO- or -SO2-), Aromatic hydrocarbon group - Aromatic hydrocarbon group - Aromatic hydrocarbon group - *(The aromatic hydrocarbon group -CH2- in the hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2-. (You may also know Methyladamantane methylene adamantyl group, di(methyladamantane methylene)adamantyl group Mantyl and other open-chain hydrocarbon groups - alicyclic hydrocarbon groups - open-chain hydrocarbon groups - alicyclic hydrocarbon groups -*, (open-chain hydrocarbon group-alicyclic hydrocarbon group-open-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 hydrocarbon group and the alicyclic hydrocarbon group is not limited to —O—, —S—, — may be replaced by CO- or -SO2-), Alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic 2-chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group-*, (alicyclic Hydrocarbon group - Acyclic hydrocarbon group) 2-alicyclic hydrocarbon group - Acyclic hydrocarbon group -*, (alicyclic hydrocarbon Hydrocarbon group-acyclic hydrocarbon group-alicyclic hydrocarbon group) 2-acyclic hydrocarbon group-*(the acyclic hydrocarbon The —CH2— contained in the alkyl group and the alicyclic hydrocarbon group is not —O—, —S—, —CO— or — SO2- may be substituted), Acyclic hydrocarbon group - Alicyclic hydrocarbon group - Acyclic hydrocarbon group - Alicyclic hydrocarbon group - Acyclic hydrocarbon group Group-*, (chain hydrocarbon group) 2-alicyclic hydrocarbon group-chain hydrocarbon group-alicyclic hydrocarbon Group-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 Hydrogen hydride group) 2-alicyclic hydrocarbon group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon Hydrogen group - chain hydrocarbon group - alicyclic hydrocarbon group) 2-chain hydrocarbon group - * (the chain hydrocarbon The —CH2— contained in the group and the alicyclic hydrocarbon group is —O—, —S—, —CO— or —S O2- may be substituted), Here, * indicates the bonding position with the carbon atom of the carbonyl group.

[0020] X 0 -CH2- contained in the hydrocarbon group represented by the formula: When it is replaced by SO2-, the number of carbon atoms before the replacement is the total number of carbon atoms in the hydrocarbon group. Also, X 0 When a substituent is bonded to a hydrocarbon group represented by the formula: The total number of carbon atoms in the hydrocarbon group.

[0021] X 0 The hydrocarbon group represented by the formula (I) may have one or more substituents. The substituents include a hydroxy group, a halogen atom, a cyano group, and an alkyl group having 1 to 12 carbon atoms. groups, alkoxy groups having 1 to 12 carbon atoms, alkoxycarbonyl groups having 2 to 13 carbon atoms, Alkylcarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyloxy groups having 2 to 13 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a combination thereof; Examples of such groups include groups obtained by combining two or more groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl Examples thereof include a methyl group and a nonyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a bromine group, and a methyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl hydroxyl group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group etc. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and and the alkylcarbonyloxy group having 2 to 13 carbon atoms is the alkyl or alkoxy group described above. represents a group in which a carbonyl group or a carbonyloxy group is bonded to a group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a methyl group. alkylcarbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 13 carbon atoms. Examples of the group include an acetyl group, a propionyl group, and a butyryl group, and the group has 2 to 13 carbon atoms. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a bromide group, and a hydroxyl group. Examples thereof include a thyryloxy group. Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** indicates X 0 represents the bonding position with TIFF0007813327000011.tif17162The aromatic hydrocarbon group having 6 to 10 carbon atoms includes aryl groups such as phenyl and naphthyl groups. Examples include: The combined group is a combination of a hydroxy group and an alkyl group having 1 to 12 carbon atoms. a group in which an alkyl group having 1 to 12 carbon atoms is combined with an aromatic hydrocarbon group having 6 to 10 carbon atoms; a group comprising an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms; Examples of such groups include a group containing a substituted or unsubstituted aryl group. Examples of the group combining a hydroxy group with an alkyl group having 1 to 12 carbon atoms include hydroxy Examples include hydroxyalkyl groups having 1 to 12 carbon atoms, such as a methyl group and a hydroxyethyl group. do. A group formed by combining an alkyl group having 1 to 12 carbon atoms with an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the alkyl group include aralkyl groups having 7 to 22 carbon atoms, such as benzyl groups, and carbon atoms such as tolyl and xylyl groups. Examples include alkylaryl groups having 7 to 22 prime numbers. A combination of an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the group include a cyclohexylphenyl group.

[0022] X 0 The hydrocarbon group represented by the formula (I) is preferably a hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. 2 aliphatic hydrocarbon group (-CH2- contained in the aliphatic hydrocarbon group is -O-, -S-, may be replaced by -CO- or -SO2-), and an aromatic hydrocarbon group of any one of the formulas (aa) to (36) or a group represented by formula (aa), More preferably, it is an alicyclic hydrocarbon group which may have a hydroxy group or a fluorine atom ( However, -CH2- contained in the alicyclic hydrocarbon group is not -O-, -S-, -CO- or -S O2- may be substituted), and an alicyclic hydrocarbon group and a chain hydrocarbon group may be combined. The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or - The —CH2— contained in the chain hydrocarbon group may be replaced by —O— or —CO—, and the alicyclic hydrocarbon group and the chain hydrocarbon group are It may have a fluorine atom or a hydroxy group. an optionally substituted aromatic hydrocarbon group or a group represented by formula (aa), More preferably, the *-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 hydroxy group or a fluorine atom. * represents -COO - carbon atoms of represents the bonding position with the alicyclic hydrocarbon group.) *-alicyclic hydrocarbon group-alkyl group (the alicyclic hydrocarbon group The -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. The —CH2— contained in the alkyl group may be replaced with —O— or —CO—. The alicyclic hydrocarbon group and the alkyl group may have a fluorine atom or a hydroxy group. *-COO - ), a fluorine atom or a hydroxy group. an aromatic hydrocarbon group which may be present or a group represented by formula (aa), More preferably, *-polycyclic alicyclic hydrocarbon group (wherein the polycyclic alicyclic hydrocarbon group The -CH2- contained may be replaced by -O-, -S-, -CO- or -SO2-. Preferably, the polycyclic alicyclic hydrocarbon group may have a hydroxy group or a fluorine atom. -COO -), *-Polycyclic alicyclic hydrocarbon group-Alkyl -CH2- contained in the polycyclic alicyclic hydrocarbon group is not -O-, -S-, -CO- or -SO2-, and the -CH2- contained in the alkyl group may be replaced by -O - or -CO-, and the polycyclic alicyclic hydrocarbon group and the alkyl The group may have a fluorine atom or a hydroxy group. * represents -COO - bond with the carbon atom ) an aromatic hydrocarbon group which may have a fluorine atom or a hydroxy group, or A group represented by (aa), Particularly preferred are an adamantanone group, a hydroxyadamantyl group, and a combination of an adamantyl group and an adamantanone group. A group in which the —CH2— contained in the alkyl group is —O— or —CO— -), a group represented by formula (Y30F), a group having a hydroxy group It is a phenyl group or a group represented by formula (aa). In the above groups, the number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, and more preferably The number of carbon atoms in the chain hydrocarbon group is preferably 3 to 16, and more preferably 3 to 12. Preferably, it is 1 to 12, more preferably 1 to 9, and even more preferably 1 to 6. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6, and even more preferably 1 to 4. The number of carbon atoms is preferably 1 to 36, more preferably 6 to 24, and even more preferably 6 to 18. More preferably, it is 6-14, and even more preferably, it is 6-10. TIFF0007813327000012.tif2666[In formula (aa), X a and X b each independently represents -O- or -S-. X 1represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and The -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. stomach. X 2 represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and The -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. stomach. * indicates the bonding position of the carbonyl group to the carbon atom.

[0023] X a and X b are preferably the same atom, and more preferably both are oxygen atoms. It's nice.

[0024] X 1 and X 2 The hydrocarbon group represented by the formula (I) is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or The hydrocarbon groups include groups in which two or more of these groups are combined. -CH2- may be replaced by -O-, -S-, -CO- or -SO2-.

[0025] X 1 The aliphatic hydrocarbon group includes a chain hydrocarbon group such as an alkanetriyl group, an alicyclic hydrocarbon group, and the like. Examples of the alkyl group include a hydroxyl group and a combination thereof. Specific examples of the alkanetriyl group include a methine group, an ethanetriyl group, a propanetriyl group, and a methyltriyl group. Triyl group, butanetriyl group, pentanetriyl group, hexanetriyl group, heptanetriyl group yl group, octanetriyl group, nonanetriyl group, decantriyl group, undecanetriyl group Examples thereof include a methyl group, a dodecanetriyl group, and the like.

[0026] The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutanetriyl group and a cyclopentanetriyl group. Examples thereof include a cyclohexyl group, a cyclohexanetriyl group, and a cyclooctanetriyl group. Examples of polycyclic alicyclic hydrocarbon groups include norbornanetriyl group, norbornanetriyl group, group, adamantanetriyl group, and the like. Examples of the aromatic hydrocarbon group include a benzenetriyl group, a naphthalenetriyl group, an anthracene group, and Examples thereof include a benzotriyl group. In the case of a combined group, the above groups each having a different valence (such as an alkyl group, an alkanediyl group, etc.) alkanetetrayl group, cycloalkyl group, cycloalkanediyl group, cycloalkenyl group, cantetrayl group, etc.) may be included.

[0027] X 1 The hydrocarbon group represented by the formula (I) has 1 to 24 carbon atoms and further has one or more substituents. The substituent may be a hydroxy group, a halogen atom, a cyano group, a group having a carbon number Alkyl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, alkoxy groups with 2 to 13 carbon atoms alkylcarbonyl group, alkylcarbonyl group having 2 to 13 carbon atoms, alkylcarbonyl group having 2 to 13 carbon atoms Nyloxy group, alicyclic hydrocarbon group having 3 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 10 carbon atoms Or a group combining these groups. Halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups alkylcarbonyloxy groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and the like Examples of the group combining these include the same groups as those mentioned above.

[0028] X 1 The hydrocarbon group represented by the formula (I) is an alkane group having 1 to 6 carbon atoms which may have a substituent. It is preferably an aryl group or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. Alkanetriyl groups having 1 to 6 carbon atoms, represented by formula (w1-1) to formula (w1-11), More preferably, it is an alkanetriyl group having 1 to 6 carbon atoms, a group represented by the formula (w1-1), a polycyclic hydrocarbon group such as a group represented by formula (w1-3) or a group represented by formula (w1-2) or a monocyclic hydrocarbon group such as a group represented by formula (w1-6). It's nice. TIFF0007813327000013.tif62148 [Formula (w1-1) to formula (w1-11), The ring may contain a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms. an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, Alkylcarbonyl group, alkylcarbonyloxy group having 2 to 13 carbon atoms, alkylcarbonyloxy group having 3 to 12 carbon atoms an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a combination thereof It may have. * represents a bond position. In formulas (w1-9) to (w1-11), the three bond positions are arbitrary. The position can be any position.]

[0029] X 2 The number of carbon atoms in the hydrocarbon group represented by the formula (I) is preferably 2 to 48, and more preferably 4 to 48. It is more preferable that the ratio is 6 to 44, and even more preferable that the ratio is 8 to 40. It is more preferable that the number of carbon atoms is 10 to 38, and even more preferable that the number of carbon atoms is 10 to 38. The hydrocarbon group may have a substituent. It may be replaced by -S-, -CO- or -SO2-. Here, the number of carbon atoms in the hydrocarbon group is the number of carbon atoms in the hydrocarbon group that does not have a substituent and is not replaced. It means prime number.

[0030] X 2 The substituents that the hydrocarbon group may have include a hydroxy group, a halogen atom, and the like. Atom, cyano group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, carbon number Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyloxy groups having 3 to 13 carbon atoms, alicyclic hydrocarbon groups having 3 to 12 carbon atoms, and alkylcarbonyloxy groups having 6 to 13 carbon atoms. 10 aromatic hydrocarbon groups or groups combining these groups. Halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups alkyl groups, alkylcarbonyloxy groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and Examples of the group combining the above include the same groups as those mentioned above. X 2 The hydrocarbon group having 1 to 48 carbon atoms represented by the formula (I) has one or more substituents. It may be possible.

[0031] X 2 The hydrocarbon group in the formula (I) is a straight-chain or branched chain hydrocarbon group (e.g., arylene). candiyl group, etc.), monocyclic or polycyclic alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Two or more of these groups may be combined. 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 octane-1,7-diyl and octane-1,8-diyl; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group branched alkanediyl groups such as 2-methylbutane-1,4-diyl groups; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa monocyclic cycloalkanediyl group, such as cyclohexan-1,4-diyl group, cyclooctane-1,5-diyl group, 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 and adamantane-2,6-diyl groups a polycyclic alicyclic hydrocarbon group, Phenylene group, naphthylene group, biphenylene group, anthrylene group, phenanthrylene group and aromatic hydrocarbon groups such as a binaphthylene group. In the case of a combined group, the above groups may be groups with different valences (alkyl groups, alkanetri groups, etc.). yl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cyclo An alkanetetrayl group may be included. The combined group includes a group in which a chain hydrocarbon group and an alicyclic hydrocarbon group are combined, a chain hydrocarbon group Groups that combine hydrocarbon groups and aromatic hydrocarbon groups, and alicyclic hydrocarbon groups and aromatic hydrocarbon groups Specifically, a group in which one or more alicyclic hydrocarbon groups are combined with a chain hydrocarbon group can be mentioned. A group in which - is bonded (for example, - a chain hydrocarbon group - an alicyclic hydrocarbon group, - a chain hydrocarbon group - (alicyclic Cyclic hydrocarbon groups)2, etc.), groups in which one or more chain hydrocarbon groups are bonded to an alicyclic hydrocarbon group (e.g. For example, -alicyclic hydrocarbon group-chain hydrocarbon group, -alicyclic hydrocarbon group-(chain hydrocarbon group) 2, etc.), 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 Cyclic hydrocarbon group-chain hydrocarbon group)2, etc.

[0032] X 2 The hydrocarbon group in A chain hydrocarbon group having 2 to 18 carbon atoms (-CH2- contained in the chain hydrocarbon group is -O- or -CO-, and the chain hydrocarbon group may have a substituent. ) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH2- contained in the chain hydrocarbon group is -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon group -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-. and the group (which may have a substituent) is a combination of Preferably, A chain hydrocarbon group having 4 to 18 carbon atoms (-CH2- contained in the chain hydrocarbon group is -O- or -CO-, and the chain hydrocarbon group may have a substituent. ) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH2- contained in the chain hydrocarbon group is -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (the alicyclic hydrocarbon group -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-. and the group (which may have a substituent) is a combination of It is more preferable that A chain hydrocarbon group having 6 to 14 carbon atoms (-CH2- contained in the chain hydrocarbon group is -O- or -CO-, and the chain hydrocarbon group may have a substituent. ) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH2- contained in the chain hydrocarbon group is -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 14 carbon atoms (the alicyclic hydrocarbon group -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-. and the group (which may have a substituent) is a combination of It is even more preferable that there is.

[0033] Specifically, X 2 Examples of the hydrocarbon group in an alkanediyl group having 2 to 18 carbon atoms (wherein —CH2— contained in the alkanediyl group is — The alkanediyl group may be substituted with -O- or -CO-. ) an alkanediyl group having 1 to 12 carbon atoms (wherein —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 ( The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO2-. and (which may have a substituent), or an alkanediyl group having 1 to 12 carbon atoms (wherein —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. an alkyl group having 1 to 12 carbon atoms (wherein -CH2- in the alkyl group is -O- or -CO -) (which may have a substituent). It is preferred that an alkanediyl group having 4 to 18 carbon atoms (wherein —CH2— contained in the alkanediyl group is — The alkanediyl group may be substituted with -O- or -CO-. ) an alkanediyl group having 1 to 12 carbon atoms (wherein —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 ( The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO2-. and (which may have a substituent), or an alkanediyl group having 1 to 12 carbon atoms (wherein —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. an alkyl group having 1 to 12 carbon atoms (wherein -CH2- in the alkyl group is -O- or -CO -) (which may have a substituent). It is more preferable that an alkanediyl group having 6 to 14 carbon atoms (wherein —CH— contained in the alkanediyl group is — The alkanediyl group may be substituted with -O- or -CO-. ) an alkanediyl group having 1 to 12 carbon atoms (wherein —CH2— contained in the alkanediyl group is — may be replaced by -O- or -CO-) and an adamantanediyl group (the adamantane The -CH2- contained in the benzyl group may be replaced by -O- or -CO-. a group consisting of (which may have a substituent), or an alkanediyl group having 1 to 12 carbon atoms (wherein —CH2— contained in the alkanediyl group is — may be replaced by -O- or -CO-.) and an adamantanediyl group and a C1-C1 2 alkyl group (-CH2- contained in the alkyl group is replaced by -O- or -CO-) and (the group may have a substituent). Even more preferable.

[0034] Specifically, X 2 is the formula (X 2 -1), a group represented by the formula (X 2 -2), a group represented by the formula (X 2 -3) or a group represented by the formula (X 2 -4) is preferred. TIFF0007813327000014.tif34158[In the formula, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x are each independently an alkyl group having 1 to 6 carbon atoms. alkyl group, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination of two or more of these groups The —CH2— contained in the alkyl group and the alicyclic hydrocarbon group represents —O—, —S -, -CO- or -SO2-, and the alkyl group and the alicyclic carbon The hydrogen group may have a substituent. * is X a and X b represents the bond position with The combined group is a group in which one of the above alkyl groups and one of the above alicyclic hydrocarbon groups are combined. The group may be a combination of two or more of either one or two or more of both. The total number of carbon atoms in the groups is 39 or less, preferably 37 or less.

[0035] Among them, R 1x , R 2x , R 3x , R 4x , R 5x and R 6xAs for the carbon number 1 to 6, alkyl group (wherein -CH2- in the alkyl group is replaced with -O- or -CO-) The alkyl group may have a substituent.) A hydrocarbon group (the -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO- or The alicyclic hydrocarbon group may be substituted with -SO2-, and the alicyclic hydrocarbon group may have a substituent. ) or an alkyl group having 1 to 6 carbon atoms (the -CH2- contained in the alkyl group is -O- or may be replaced by -CO-) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (the alicyclic -CH2- contained in the hydrocarbon group of the formula may be replaced with -O-, -S-, -CO- or -SO2-. and a group (which may have a substituent) in which It is preferable that the alkoxy group is a methoxy group, an adamantyl group (the —CH 2- may be replaced by -O- or -CO-, and the adamantyl group has a substituent ) or an alkyl group having 1 to 6 carbon atoms (the —CH2 - may be replaced by -O- or -CO-. It is more preferable that the group is a group having a substituent (which may have a substituent).

[0036] The carboxylate anion in the carboxylate salt represented by formula (I) may be any of the following: Examples include carboxylate anions. TIFF0007813327000015.tif98162

[0037] TIFF0007813327000016.tif119144

[0038] TIFF0007813327000017.tif125139

[0039] TIFF0007813327000018.tif122154

[0040] TIFF0007813327000019.tif115153

[0041] TIFF0007813327000020.tif41148

[0042] Specific examples of the carboxylate (I) include carboxylates obtained by arbitrarily combining the above-mentioned cations and anions. Specific examples of the carboxylate (I) are shown in the table below. In the table below, each symbol represents the symbol attached to the structure representing the anion or cation described above. For example, the carboxylate (I-1) is a compound obtained by combining an anion represented by formula (Ia-1) and a compound represented by formula (I -c-1) and a cation represented by the formula shown below. TIFF0007813327000021.tif1796

[0043] [Table 1] TIFF0007813327000023.tif223160 TIFF0007813327000024.tif223160 TIFF0007813327000025.tif223160 TIFF0007813327000026.tif223160 TIFF0007813327000027.tif223160 TIFF0007813327000028.tif223160 TIFF0007813327000029.tif223160 TIFF0007813327000030.tif223160 TIFF0007813327000031.tif223160 TIFF0007813327000032.tif223160 TIFF0007813327000033.tif223160 TIFF0007813327000034.tif223160 TIFF0007813327000035.tif223160 TIFF0007813327000036.tif223160 TIFF0007813327000037.tif223160 TIFF0007813327000038.tif223160 TIFF0007813327000039.tif223160 TIFF0007813327000040.tif223160 TIFF0007813327000041.tif223160 TIFF0007813327000042.tif171162

[0044] Among them, the carboxylate (I) includes carboxylate (I-1) to carboxylate (I -5), Carboxylate (I-55) ~ Carboxylate (I-59), Carboxylate (I-1 09) ~ Carboxylate (I-113), Carboxylate (I-163) ~ Carboxylate (I -167), Carboxylate (I-217) ~ Carboxylate (I-221), Carboxylate (I-271) ~ Carboxylate (I-275), Carboxylate (I-325) ~ Carvone Acid salt (I-329), Carboxylate (I-379) ~ Carboxylate (I-383), Calcium Carboxylate (I-433) ~ Carboxylate (I-437), Carboxylate (I-487) ~ Carboxylate (I-491), Carboxylate (I-541) ~ Carboxylate (I-545) ), Carboxylate (I-595) ~ Carboxylate (I-599), Carboxylate (I-6 49) ~ Carboxylate (I-653), Carboxylate (I-703) ~ Carboxylate (I -707), carboxylates (I-757) to (I-761) are preferred.

[0045] <Method for producing carboxylate (I)> The carboxylic acid salt (I) is a compound represented by the formula (Ia) and the formula (Ib) and the like in a solvent. TIFF0007813327000043.tif50161 [wherein all symbols have the same meanings as defined above.] X represents a chlorine atom, a bromine atom, or an iodine atom. R A , R B and R C each independently represents a hydrocarbon group having 1 to 12 carbon atoms, or R A , R B and R C may combine to form an aromatic ring. D is a hydrogen atom or a carbon atom represents a hydrocarbon group of 1 to 12.] Examples of solvents used in this reaction include chloroform, acetonitrile, and ion-exchanged water. It can be obtained. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0046] The salt represented by formula (Ib) is disclosed in JP 2011-39502 A and JP 2014-888 A. The salts can be synthesized by referring to the method described in the publication of No. 367, and include salts represented by the following formula: Examples include: TIFF0007813327000044.tif145156

[0047] The salt represented by formula (Ia) is a compound represented by formula (Ic) and a compound represented by formula (Id). The compound can be produced by reacting the compound with a salt thereof in a solvent in the presence of a catalyst. TIFF0007813327000045.tif46135 [wherein all symbols have the same meanings as defined above.] Catalysts include potassium peroxymonosulfate (Oxone®), sulfuric acid, p-toluenesulfonyl ether, and the like. enesulfonic acid and the like. Examples of the solvent include chloroform, monochlorobenzene, and acetonitrile. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0048] The compound represented by formula (Ic) includes compounds represented by the following formula, and is commercially available. It is more readily available and can be easily produced by known methods. . TIFF0007813327000046.tif48139

[0049] The compound represented by formula (Id) includes compounds represented by the following formula, and is commercially available. It can be more easily obtained. TIFF0007813327000047.tif1417

[0050] The salt represented by the following formula (I-a1) is prepared by reacting a compound represented by formula (Ie) with potassium iodate: The reaction of ammonium with sulfuric acid in a solvent and then mixing with sodium bromide It can be manufactured. TIFF0007813327000048.tif47140 [wherein all symbols have the same meanings as defined above.] Solvents include acetic acid, acetic anhydride, chloroform, monochlorobenzene, and acetonitrile. etc. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0051] The compound represented by formula (Ie) includes compounds represented by the following formula, and is commercially available. It is more readily available and can be easily produced by known methods. . TIFF0007813327000049.tif46135

[0052] [Acid Generator] The acid generator of the present invention is an acid generator containing a carboxylic acid salt (I). The phosphate (I) can act as an acid generator in the resist composition. When the carboxylic acid salt (I) is used as an acid generator in the resist composition, the acid generator is one kind of It may contain only one or two or more kinds of carboxylates (I). Furthermore, the acid generator of the present invention can be used in the resist field other than the carboxylic acid salt (I), as will be described later. a known acid generator (hereinafter sometimes referred to as "acid generator (B)") and / or a carboxylic acid The composition may further contain a carboxylic acid generator other than the salt (I) that is known in the resist field. The agent (B) and the like may be used alone or in combination of two or more kinds. When the acid generator of the present invention contains an acid generator (B) or the like, the carboxylic acid salt (I) and the acid generator The ratio of the content of the carboxylate (I) to the content of the acid generator (B) (mass ratio; carboxylate (I): acid generator (B), etc.) is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98 :2, and more preferably 5:95 to 95:5.

[0053] [Resist Composition] The resist composition comprises a carboxylic acid generator containing the carboxylic acid salt (I) of the present invention and a carboxylic acid generator containing the carboxylic acid salt (I). An acid generator (B) other than the carboxylic acid salt (I) and a resin having an acid labile group (hereinafter referred to as "resin (A)") The "acid labile group" herein refers to a group that has a leaving group and is labile to contact with an acid. The leaving group is eliminated by contact to form a hydrophilic group (e.g., a hydroxy group or a carboxy group). means a group The resist composition may further contain a quencher (hereinafter referred to as "quencher (C)"). It is preferable that the liquid contains a solvent (hereinafter sometimes referred to as "solvent (E)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). stomach.

[0054] <Acid generator (B)> The acid generator (B) may be either a nonionic or ionic acid generator. Biocides include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, etc.). sulfonates, oximesulfonates, N-sulfonyloxyimides, sulfonyloxyketones ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfones, ketones Examples of ionic acid generators include ionic acid generators such as ionic acid generators (sulfones, sulfonyldiazomethanes, etc.). Onium salts containing ammonium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples of onium salts include sulfonate anions. anion, sulfonylimide anion, sulfonylmethide anion, etc.

[0055] Examples of the acid generator (B) include those disclosed in JP-A-63-26653 and JP-A-55-164824; JP 62-69263, JP 63-146038, JP 63-163452 , JP 62-153853 A, JP 63-146029 A, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate acids when exposed to radiation, such as those described in US Pat. No. 126,712, can be used. In addition, compounds produced by known methods may be used. The acid generator (B) may be a mixture of two or more compounds. They may also be used in combination.

[0056] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a compound represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)"). TIFF0007813327000050.tif2962[In formula (B1), Q b1 and Q b2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents an alkyl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the divalent saturated hydrocarbon group The contained —CH2— may be replaced by —O— or —CO—, and the divalent saturated carbon The hydrogen atoms contained in the hydrogen hydride group may be substituted with fluorine atoms or hydroxy groups. Y is a methyl group which may have a substituent or a C3-C1 8, and -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z + represents an organic cation.

[0057] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) includes a trifluoromethyl group, a pentafluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a fluoropentyl group and a perfluorohexyl group. Q b1 and Q b2 are each independently a fluorine atom or a trifluoromethyl group. and more preferably, both are fluorine atoms.

[0058] L b1The divalent saturated hydrocarbon group in candiyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these groups It may also be a group formed by combining two or more of the following. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- linear alkanediyl groups such as diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group branched alkanediyl groups such as 2-methylbutane-1,4-diyl groups; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa cycloalkanediyl groups such as cyclohexene-1,4-diyl and cyclooctane-1,5-diyl a monocyclic divalent alicyclic saturated hydrocarbon group; Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Examples include a hydrogen group.

[0059] L b1-CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group may be, for example, a group represented by any one of formulas (b1-1) to (b1-3). In addition, groups represented by formula (b1-1) to formula (b1-3) and their components are exemplified. In the exemplary groups represented by formulae (b1-4) to (b1-11), * and ** represent bonds. * represents the bonding position with -Y.

[0060] TIFF0007813327000051.tif26117 [In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0061] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group When -CH2- is replaced by -O- or -CO-, the number of carbon atoms before the replacement is The number of carbon atoms in the hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 The divalent saturated hydrocarbon groups are the same as those mentioned above. can be.

[0062] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the divalent saturated hydrocarbon The hydrogen atoms contained in the hydrogen group may be substituted with fluorine atoms. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. The —CH2— contained in the divalent saturated hydrocarbon group is replaced with —O— or —CO—. That's fine.

[0063] L b1 -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group is preferably a group represented by formula (b1-1) or formula (b1-3).

[0064] The group represented by formula (b1-1) includes those represented by formulas (b1-4) to (b1-8), respectively. Examples of such groups include: TIFF0007813327000052.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the divalent saturated hydrocarbon group The contained -CH2- may be replaced by -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the formula may be replaced with -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b16 ~L b18 The total number of carbon atoms is 19 or less.

[0065] L b8is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0066] The group represented by formula (b1-3) is represented by formulas (b1-9) to (b1-11), respectively. Examples include groups represented by the following formula: TIFF0007813327000053.tif23140[In formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atom may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atom may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —CH2— contained in the alkylcarbonyloxy group may be replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atom may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0067] In addition, in the groups represented by formula (b1-9) to formula (b1-11), saturated When a hydrogen atom contained in a mono- or di-hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is the number of carbon atoms of the saturated hydrocarbon group.

[0068] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a bromide group, and a bromine group. Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0069] Examples of the group represented by formula (b1-4) include the following. TIFF0007813327000054.tif16154

[0070] Examples of the group represented by formula (b1-5) include the following. TIFF0007813327000055.tif68152

[0071] Examples of the group represented by formula (b1-6) include the following. TIFF0007813327000056.tif32164

[0072] Examples of the group represented by formula (b1-7) include the following. TIFF0007813327000057.tif57146

[0073] Examples of the group represented by formula (b1-8) include the following. TIFF0007813327000058.tif23150

[0074] Examples of the group represented by formula (b1-2) include the following. TIFF0007813327000059.tif31161

[0075] Examples of the group represented by formula (b1-9) include the following. TIFF0007813327000060.tif44137

[0076] Examples of the group represented by formula (b1-10) include the following. TIFF0007813327000061.tif92165

[0077] Examples of the group represented by formula (b1-11) include the following. TIFF0007813327000062.tif84164

[0078] The alicyclic hydrocarbon group represented by Y is, for example, X in formula (I). 0 As an example of Examples thereof include groups represented by formulae (Y1) to (Y11) and (Y36) to (Y38). The —CH2— contained in the alicyclic hydrocarbon group represented by Y is —O—, —S(O)2— or — When the group is replaced with CO-, the number of CO- may be one or more. Examples thereof include groups represented by formulae (Y12) to (Y35) and (Y39) to (Y41). can be.

[0079] The alicyclic hydrocarbon group represented by Y is preferably a group represented by the formula (Y1) to the formula (Y20), Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y41) and more preferably a group represented by formula (Y11), formula (Y15), or formula (Y16 ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39) or a group represented by formula (Y40), and more preferably a group represented by formula (Y11), formula (Y1 5), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula ( Y39) or a group represented by formula (Y40). The alicyclic hydrocarbon group represented by Y is selected from the group consisting of the formulae (Y28) to (Y35), the formulae (Y39) to (Y In the case of a spiro ring containing an oxygen atom such as 40), an alkanediyl group between the two oxygen atoms is used. The group preferably has one or more fluorine atoms. In the candiyl group, the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom. It is preferable to have

[0080] The substituent of the methyl group represented by Y is a halogen atom, a hydroxyl group, a methyl group having 3 to 1 carbon atoms, or 6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -( CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, a The alkyl group and the alicyclic group are each an aromatic hydrocarbon group having 1 to 18 carbon atoms or a combination thereof. -CH2- contained in the hydrocarbon group is replaced by -O-, -SO2- or -CO-. The hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be The atom may be substituted with a hydroxy group or a fluorine atom. It represents any integer. The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxy group, a hydroxyl group ... an alkyl group having 1 to 12 carbon atoms which may be substituted with an alkyl group having 3 to 16 carbon atoms; Hydrocarbon groups, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, carbon Aralkyl groups having 7 to 21 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms, and glycidyloxy groups. , -(CH2) ja -CO-OR b1 group or -(CH2) ja -O-CO-R b1 base( In the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, a carbon atom, The alkyl group and the aromatic hydrocarbon group each having 6 to 18 carbon atoms or a combination thereof are -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2- or -CO-. The alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may contain a group selected from the group consisting of methyl, ... The hydrogen atom may be replaced by a hydroxy group or a fluorine atom. It represents any integer of the above.)

[0081] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclohexyl group. cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, Examples include a carboxyl group and an adamantyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and the like. Examples of aromatic hydrocarbon groups include aryl groups such as an alkyl group and a phenanthryl group. It may have a hydrocarbon group or an alicyclic hydrocarbon group, and may have a chain hydrocarbon group having 1 to 18 carbon atoms. The aromatic hydrocarbon groups include tolyl, xylyl, cumenyl, mesityl, p- Ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2 phenyl group, etc., and the alicyclic hydrocarbon group having 3 to 18 carbon atoms. The aromatic hydrocarbon group is p-cyclohexylphenyl, p-adamantylphenyl. Examples thereof include a methyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromine group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group etc. Examples of alkyl groups substituted with hydroxy groups include hydroxymethyl groups, hydroxy Examples include hydroxyalkyl groups such as an ethyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hydroxyl group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy groups. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and the like. Examples include an ethyl group and a naphthylethyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. etc.

[0082] Examples of Y include the following: TIFF0007813327000063.tif151153

[0083] Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. More preferably, it is an adamantyl group which may have a substituent, and the alicyclic hydrocarbon group or -CH2- constituting the adamantyl group is replaced with -CO-, -S(O)2- or -CO-. Y is more preferably an adamantyl group or a hydroxyadamantyl group. group, an oxoadamantyl group, or a group represented by the following formula: TIFF0007813327000064.tif60162

[0084] The anion in the salt represented by formula (B1) includes the anions represented by formula (B1-A-1) to formula (B1- A-55) (hereinafter, "anion (B1-A-1)" and so on according to the formula number) Formula (B1-A-1) to Formula (B1-A-4), Formula (B1 -A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 5) is more preferred.

[0085] TIFF0007813327000065.tif111143

[0086] TIFF0007813327000066.tif128166

[0087] TIFF0007813327000067.tif93145

[0088] TIFF0007813327000068.tif126140

[0089] TIFF0007813327000069.tif114154 Here R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 is, for example, an aliphatic hydrocarbon having 1 to 12 carbon atoms. a group, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or A group formed by combining these is more preferred, and a methyl group, an ethyl group, a cyclohexyl group, It is a silyl group or an adamantyl group. A4 is a single bond or an alkanediyl having 1 to 4 carbon atoms. It is the base. Q b1 and Q b2 has the same meaning as above. Specific examples of the anion in the salt represented by formula (B1) include those described in JP-A-2010-20 Examples of anions include those described in JP-A-4646.

[0090] Preferable anions in the salt represented by formula (B1) include those represented by formula (B1a-1) to formula (B1a-2). B1a-34) are examples of anions. TIFF0007813327000070.tif193158

[0091] TIFF0007813327000071.tif185163

[0092] Among them, the compounds represented by formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a- 16), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a- 30) is preferred.

[0093] Z1 + Examples of the organic cation include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations, and Among these, organic sulfonium cations are Preferred are iodonium and organic iodonium cations, and more preferred are arylsulfonium cations. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter Below, depending on the formula number, it may be called "cation (b2-1)" etc.). TIFF0007813327000072.tif77115In equations (b2-1) to (b2-4), R b4 ~R b6 are each independently a chain hydrocarbon group having 1 to 30 carbon atoms, a chain hydrocarbon group having 3 to 36 carbon atoms, It represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the chain hydrocarbon group The hydrogen atoms contained in the alkyl group are hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, and alkyl groups with 3 to 12 carbon atoms. It may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group are halogen atoms, aliphatic hydrocarbon groups having 1 to 18 carbon atoms, may be substituted with an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atoms contained in the aromatic hydrocarbon group are replaced by halogen atoms, hydroxy groups, or groups having 1 carbon atom. It may be substituted with up to 12 alkoxy groups. R b4 and R b5 are bonded to each other and form a ring with the sulfur atom to which they are attached. -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. good. R b7 and R b8 are each independently a hydroxy group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms. Or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5; When m2 is 2 or more, multiple R b7 may be the same or different, and when n2 is 2 or more, R in Numbers b8 may be the same or different. R b9 and R b10 are each independently a chain hydrocarbon group having 1 to 36 carbon atoms or a chain hydrocarbon group having 3 to 4 carbon atoms, Represents 36 alicyclic hydrocarbon groups. R b9 and R b10 are bonded to each other and form a ring with the sulfur atom to which they are attached -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. Good too. R b11 is a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, It represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the chain hydrocarbon group are It may be substituted with an aromatic hydrocarbon group having 6 to 18 prime numbers, and the aromatic hydrocarbon group The hydrogen atom is preferably an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group. R b11 and R b12 are bonded to each other to form a ring including the -CH-CO- to which they are attached. -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. It is also possible. R b13 ~R b18 are each independently a hydroxy group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms. Or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4; u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14 are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, r2 When is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 teeth Identical or different, when t2 is 2 or more, multiple R b18 are the same or different. The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and An example of an alkyl group is a 2-ethylhexyl group. In particular, R b9 ~R b12 The chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and a monocyclic alicyclic hydrocarbon group may be Examples of the hydrogen group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. cycloalkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl and adamantyl groups. , norbornyl group, and the following groups. TIFF0007813327000073.tif10159 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms. Examples of alicyclic hydrocarbon groups in which hydrogen atoms are substituted with aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyl 2-Isopropyladamantan-2-yl group, methylnor Examples of the alkyl group include a bornyl group and an isobornyl group. In the alicyclic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 1. Preferably it is 20 or less. Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group. The aromatic hydrocarbon group having a chain hydrocarbon group may be a tolyl group, Xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group Examples of the phenyl group include a 2,6-diethylphenyl group and a 2-methyl-6-ethylphenyl group. The aromatic hydrocarbon group having an alicyclic hydrocarbon group is a p-cyclohexylphenyl group. , p-adamantylphenyl group, etc. In addition, when the aromatic hydrocarbon group is a chain hydrocarbon group, When the alkyl group has a chain hydrocarbon group or an alicyclic hydrocarbon group, the alkyl group is a chain hydrocarbon group having 1 to 18 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms. Alicyclic hydrocarbon groups of 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples thereof include a methyl group. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include a benzyl group, a phenyl group, and a phenyl group. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples include aralkyl groups. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hydroxyl group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy groups. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be done. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group and an ethylcarbonyloxy group. Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group silyl group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include an oxy group and a 2-ethylhexylcarbonyloxy group. R b4 and R b5 and bond together with the sulfur atom to which they are attached to form a ring The ring may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. The ring may have 3 to 18 carbon atoms, and preferably has 4 to 18 carbon atoms. The ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples include the following rings, where * indicates the bonding position. TIFF0007813327000074.tif23144Rb9 and R b10 The ring formed by combining and can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of the ring include a 3-membered ring to a 12-membered ring. Preferably, it is a 3- to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothio) thiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring, etc. It can be obtained. R b11 and R b12 The ring formed by combining and can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of the ring include a 3-membered ring to a 12-membered ring. and preferably a 3- to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring , oxonorbornane ring, oxoadamantane ring, etc.

[0094] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF0007813327000075.tif79158

[0095] TIFF0007813327000076.tif74143

[0096] Examples of the cation (b2-2) include the following cations. TIFF0007813327000077.tif18127

[0097] Examples of the cation (b2-3) include the following cations. TIFF0007813327000078.tif26140

[0098] Examples of the cation (b2-4) include the following cations. TIFF0007813327000079.tif134147

[0099] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, The acid generator (B) is preferably a compound represented by the formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), an aniline represented by any one of formulas (B1a-22) to (B1a-34) Examples include a combination of an on with a cation (b2-1) or a cation (b2-3).

[0100] The acid generator (B) is preferably a compound represented by formula (B1-1) to formula (B1-48), Among them, those containing an arylsulfonium cation are preferred, Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B Those represented by formulas (1-31) to (B1-48) are particularly preferred. TIFF0007813327000080.tif119149

[0101] JPEG0007813327000081.jpg77147

[0102] JPEG0007813327000082.jpg147147

[0103] JPEG0007813327000083.jpg61154

[0104] TIFF0007813327000084.tif107143

[0105] In the resist composition of the present invention, the content of the carboxylate (I) is The solid content is preferably 0.1% by mass or more and 35% by mass or less, and more preferably 0.5% by mass or more and 30% by mass or less. % by mass or less is more preferable, and 1% by mass or more and 25% by mass or less is even more preferable. In addition, when an acid generator (B) or the like is contained, the carboxylate (I) and the acid generator (B) or the like The total content is preferably 1 part by mass or more (more preferably 3 parts by mass or more), preferably 55 parts by mass or less (more preferably 50 parts by mass or less, and even more preferably Preferably, the amount is 45 parts by mass or less.

[0106] <Resin (A)> The resin (A) contains a structural unit having an acid labile group (hereinafter, sometimes referred to as "structural unit (a1)"). The resin (A) may further contain a structural unit other than the structural unit (a1). The structural unit other than the structural unit (a1) is preferably a structural unit ( (hereinafter sometimes referred to as "structural unit (s)"), structural unit (a1) and structural unit (s) other than (for example, a structural unit having a halogen atom described later (hereinafter referred to as "structural unit (a4) "), a structural unit having a non-leaving hydrocarbon group (hereinafter referred to as "structural unit ( a5)) and other structural units derived from monomers known in the art etc.

[0107] <Structural unit (a1)> The structural unit (a1) is a monomer having an acid labile group (hereinafter referred to as "monomer (a1)"). (in some cases). The acid labile group contained in the resin (A) is a group represented by formula (1) (hereinafter also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF0007813327000085.tif2397 [In formula (1), R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 8 carbon atoms. , an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group combining these, or R a1 and R a2 are bonded to each other and together with the carbon atoms to which they are bonded form alicyclic hydrocarbons having 3 to 20 carbon atoms. Form a group. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * indicates the bond position.] TIFF0007813327000086.tif2379 [In formula (2), R a1’ and R a2’ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms, represents a hydrocarbon group of 2, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ Reach BiR a3’ are bonded to each other and together with the carbon atoms to which they are bonded and X, form a group having 3 to 20 carbon atoms. A heterocyclic ring is formed, and -CH2- contained in the hydrocarbon group and the heterocyclic ring is -O- or -S- may be replaced by . X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * denotes a binding site.]

[0108] R a1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, or a propyl group. Examples of the alkyl group include an alkyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, ... Examples of cycloalkyl groups include cycloheptyl and cyclooctyl groups. Examples of the hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups: (* indicates a bonding site.) a1 , R a2 and R a3 Alicyclic carbonization of The hydrogen group preferably has 3 to 16 carbon atoms. TIFF0007813327000087.tif10150 Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexane. xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group , adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. do. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 ) (R a2 )(R a3 ) includes the following rings. The non-aromatic hydrocarbon ring is preferably It has 3 to 12 carbon atoms. * indicates the bonding site with -O-. TIFF0007813327000088.tif31135

[0109] R a1’ , R a2’ and R a3’ The hydrocarbon group in the Examples of the alkyl group include a hydroxyl group, an aromatic hydrocarbon group, and a group formed by combining these groups. can be done. The alkyl group and the alicyclic hydrocarbon group are represented by R a1 , R a2 and Ra3 The same groups as those listed in Examples include: Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples include aryl groups such as a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, alkyl groups Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups with alicyclic hydrocarbon groups (p-cyclohexane adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. An aryl-cycloalkyl group is exemplified. R a1’ and R a2’ are bonded to each other and together with the carbon atoms to which they are bonded and X, When forming a ring, -C(R a1’ )(R a2’ )-XR a3’ Examples of rings include the following: * indicates a binding site. TIFF0007813327000089.tif21142R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0110] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and n A group where a=1. As the group, a tert-butoxycarbonyl group is preferred. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamannes Forms a methyl group, R a3 is an alkyl group, ma=0, and na=1. In formula (1), R a1 and R a2 are each independently an alkyl group, and R a3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following: * represents a binding site. TIFF0007813327000090.tif78168

[0111] Specific examples of group (2) include the following groups: * represents the bonding position. TIFF0007813327000091.tif68162

[0112] The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond. More preferably, it is a (meth)acrylic monomer having an acid labile group.

[0113] Among the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of the compound having a bulky structure such as an alicyclic hydrocarbon group include: A resin (A) having a structural unit derived from a monomer (a1) having the above structure is used in a resist composition. This can improve the resolution of the resist pattern.

[0114] As a structural unit derived from a (meth)acrylic monomer having a group (1), 0) (hereinafter, may be referred to as structural unit (a1-0)), -1) (hereinafter, may be referred to as structural unit (a1-1)) or a structural unit represented by the formula ( a1-2) (hereinafter, sometimes referred to as structural unit (a1-2)) Preferably, the structural unit (a1-1) is selected from the group consisting of the structural unit (a1-2). These may be used alone or in combination of two or more. They may be used in combination. TIFF0007813327000092.tif41136 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or * -O-(CH2) k1 - represents CO-O-, k1 represents an integer of 1 to 7, and * represents the bonding position with -CO-. vinegar. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 are each independently an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups or groups combining these groups. R a6 and R a7 are each independently an alkyl group having 1 to 8 carbon atoms, a It represents an alicyclic hydrocarbon group or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0115] R a01 , R a4 and R a5 is preferably a methyl group. L a01 , L a1 and La2 is preferably an oxygen atom or —O—(CH2) k01 -C OO- (wherein k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a77 alkyl groups, alicyclic hydrocarbon groups and and groups combining these include R in formula (1). a1 , R a2 and R a3 Similar to the groups listed in Examples of the group include the following. R a02 , R a03 , and R a04 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. A group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. do. R a6 and R a7 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, it is a methyl group, an ethyl group, or an isopropyl group, and even more preferably, it is an ethyl group. The alkyl group is an isopropyl group or an isopropyl group. R a02 , R a03 and R a04 The alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms, More preferably, it is 5 to 10. The group in which an alkyl group and an alicyclic hydrocarbon group are combined is The total number of carbon atoms in combination with the group is preferably 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl The alkyl group is an alkyl group or an ethyl group. R a04is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. be. R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably The alkyl group is preferably an ethyl group, an ethyl group, or an isopropyl group, and more preferably an ethyl group or an isopropyl group. It is a aryl group. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0116] Examples of the structural unit (a1-0) include those represented by the formulae (a1-0-1) to (a1-0-12): and R in the structural unit (a1-0) a01 Methionine equivalent The structural units of the formula (a1-0-1) to the formula (a1-0) are exemplified by those in which a methyl group is replaced with a hydrogen atom. -10) is preferred. TIFF0007813327000093.tif66158

[0117] Examples of the structural unit (a1-1) include those described in JP-A-2010-204646. Among them, structural units derived from the monomers of formula (a1-1-1) to formula (a1 -1-4) and R in the structural unit (a1-1) a4 In accordance with Structural units in which the corresponding methyl group is replaced with a hydrogen atom are preferred, and those represented by the formulae (a1-1-1) to (a1-1-2) are A structural unit represented by any one of (a1-1-4) is more preferred. TIFF0007813327000094.tif44114

[0118] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to formula (a1-2-6). and R in the structural unit (a1-2) a5 The methyl group corresponding to Examples of structural units in which atoms are replaced include those represented by formula (a1-2-2), formula (a1-2-5), and A structural unit represented by any one of the formulas (a1-2-6) is preferred. TIFF0007813327000095.tif36161

[0119] When the resin (A) contains the structural unit (a1-0), its content is determined based on the total structural units of the resin (A). It is usually 5 to 60 mol %, preferably 5 to 50 mol %, more preferably The content is usually 10 to 40 mol %. When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), The total content of these is usually 10 to 95 mol % based on the total structural units of the resin (A), and preferably It is preferably 15 to 85 mol %, more preferably 15 to 80 mol %, and even more preferably Preferably, it is 20 to 80 mol %, and even more preferably, it is 20 to 75 mol %.

[0120] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of such structural units include those (hereinafter, may be referred to as "structural unit (a1-4)"). TIFF0007813327000096.tif3867[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1-6 alkyl group optionally having a halogen atom represents an alkyl group represented by the formula: R a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of R a33 are mutual may be the same or different. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH2- contained in the alkyl group and the divalent hydrocarbon group is replaced by -O- or -S-. That's fine.]

[0121] R a32 and R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an iso ... Examples of the alkyl group include a propyl group, a butyl group, a pentyl group, and a hexyl group. An alkyl group having 1 to 4 prime numbers is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even more preferable. R a32 and R a33 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl 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 group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoro 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, Examples of the alkyl group include an alkyl group, a hexyl group, and a perfluorohexyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. Among them, alkoxy groups having 1 to 4 carbon atoms are particularly preferred. A methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred. . Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a bromide group, and a bromine group. Examples thereof include a thyryloxy group. R a34 , R a35 and R a36 The hydrocarbon group in the formula (I) may be an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups combining these groups. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a methyl group. Examples include a sil group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the cyclopentyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, butyl group, adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include: TIFF0007813327000097.tif10151Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples include aryl groups such as a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, alkyl groups Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups with alicyclic hydrocarbon groups (p-cyclohexane adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36 As for carbon number 1 to 18, alkyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Examples of groups include groups formed by combining these.

[0122] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred, and a methoxy group and an ethoxy group are also preferred. is more preferred, and a methoxy group is even more preferred. la is preferably 0 or 1, and more preferably 0. R a34 is preferably a hydrogen atom. R a35 is preferably an alkyl group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms, more preferably More preferably, it is a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, a Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is a group formed by an alkyl group having 1 to 18 carbon atoms, a group formed by an alkyl group having 3 to 1 carbon atoms, R is an alicyclic hydrocarbon group having 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. a36 Archi in The R alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 Aromatic carbonization in The hydrogen group is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0123] -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid), it is eliminated to form a hydroxy group. Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a1-4-1) to formula (a1-4-2) are preferred. -4-12) and R a32 The hydrogen atom corresponding to The structural units of formula (a1-4-1) to formula (a1-4- 5), and structural units represented by formula (a1-4-10). TIFF0007813327000098.tif68157When the resin (A) has the structural unit (a1-4), the content thereof is determined based on the total structure of the resin (A). It is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, based on the total of the structural units. It is more preferable that the content is 10 to 40 mol %.

[0124] The structural unit derived from a (meth)acrylic monomer having the group (2) includes a structural unit represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can be. TIFF0007813327000099.tif4354 formula (a1-5), R a8 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Represents an atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 represents the bonding position with L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0125] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group Examples include the methyl group and the trifluoromethyl group. In formula (a1-5), R a8 is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 is preferably an oxygen atom. L 52 and L 53 Among these, it is preferred that one is —O— and the other is —S—. s1 is preferably 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or —CH2—CO—O—.

[0126] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers of formula (a1-5-1) to formula (a1-5- 4), and the structural units represented by formula (a1-5-1) or formula (a1-5-2) are preferred. ) is more preferred. TIFF0007813327000100.tif34138When the resin (A) has the structural unit (a1-5), the content thereof is determined based on the total structure of the resin (A). The content is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %, based on the structural units. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0127] Examples of the structural unit (a1) include a structural unit represented by the formula (a1-0X) (hereinafter referred to as structural unit). It is sometimes called the structural unit (a1-0X). TIFF0007813327000101.tif3961[In formula (a1-0X), R x1 represents a hydrogen atom or a methyl group. R x2 and R x3 each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms. Ar x1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms.]

[0128] R x2 and R x3 The saturated hydrocarbon group includes alkyl groups, alicyclic hydrocarbon groups, and the like. and groups formed by combining the above. The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl groups. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. do. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and a monocyclic alicyclic hydrocarbon group Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples include: Ar x1 Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, and the like. Examples include aryl groups having 6 to 36 prime numbers. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 1 8, and more preferably a phenyl group. Ar x1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably Preferably, the alkyl group is a phenyl group or a naphthyl group, and more preferably a phenyl group. R x1 , R x2 and R x3 are each independently preferably a methyl group or an ethyl group. A methyl group is preferable.

[0129] The structural unit (a1-0X) may be any of the structural units and structural units (a1-0X) shown below. R in x1 Examples of compounds include those in which the methyl group corresponding to the structure is replaced with a hydrogen atom. The unit (a1-0X) is the structural unit (a1-0X-1) to the structural unit (a1-0X-3). It is preferable that TIFF0007813327000102.tif34161 When the resin (A) has the structural unit (a1-0X), the content of the structural unit (a1-0X) in the resin (A) is It is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, based on the total monomers in the copolymer. It is more preferable that the content is 10 to 40 mol %, and even more preferable that the content is 10 to 40 mol %. The resin (A) may contain two or more types of structural units (a1-0X).

[0130] Further, examples of the structural unit (a1) include the following structural units. TIFF0007813327000103.tif27160When resin (A) contains the above structural unit, its content is The content is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %. More preferable.

[0131] <Structural unit(s)> The structural unit (s) is a monomer that does not have an acid labile group (hereinafter referred to as "monomer (s)"). The monomer from which the structural unit (s) is derived is an acid-inhibiting monomer known in the resist field. Monomers without stabilizing groups can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. A structural unit having an oxy group and not having an acid labile group (hereinafter referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid labile group (hereinafter referred to as "structural unit"). When a resin having the structural unit (a3) ​​is used in the resist composition of the present invention, This can improve the resolution of the resist pattern and the adhesion to the substrate.

[0132] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may also be a hydroxyl group. When a resist pattern is produced from the resist composition of the present invention, KrF is used as the exposure light source. High energy rays such as excimer laser (248 nm), electron beam, or EUV (extreme ultraviolet) are used. In this case, the structural unit (a2) may be a structural unit having a phenolic hydroxy group ( a2) is preferred, and it is more preferred to use the structural unit (a2-A) described below. When an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) is The structural unit (a2) having an alcoholic hydroxy group is preferred, and the structural unit (a2) described below is It is more preferable to use the structural unit (a2) alone. It may contain two or more kinds.

[0133] The structural unit (a2) having a phenolic hydroxy group is a structural unit of the formula (a 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") can be done. TIFF0007813327000104.tif4146[In formula (a2-A), R a50 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. represents an alkyl group. R a51 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - represents -R a50 is combined represents the bond position with the carbon atom. A a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, multiple R in Numbers a51 may be the same or different from each other.]

[0134] R a50 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. can be. R a50 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom is, for example, tri Fluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2 -trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoroethyl group 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluoropropyl group 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-nonafluoropentyl group Examples include ethyl, pentyl, hexyl and perfluorohexyl groups. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is more preferably an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a51 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, or the like. Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. can be done. R a51 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an isopropyl ... Examples include a propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methyl group is more preferred. A hydroxy group is more preferred. R a51 The alkylcarbonyl group in the formula (I) includes an acetyl group, a propionyl group, and a butyl group. Examples thereof include an aryl group. R a51The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, or Examples of such groups include an aryloxy group and a butyryloxy group. R a51 is preferably a methyl group.

[0135] *-X a51 -(A a52 -X a52 ) nb - includes *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, Among them, *-CO-O- and *-CO-OA are a52 -CO-O- or *- Office Automation a52 -CO-O- is preferred. Examples of the alkanediyl group include a methylene group, an ethylene group, and a propane-1,3-diyl group. Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and and 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group. A a50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- Preferably, it is a single bond, *-CO-O-, or *-CO-O-CH2-CO-O-. A single bond or *-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred. mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the ortho- or para-position of the benzene ring, and more preferably to the para-position. It is more preferred to bind to

[0136] Examples of the structural unit (a2-A) include those described in JP-A-2010-204634 and JP-A-2012- Examples of structural units include those derived from monomers described in Japanese Patent Publication No. 12577. The structural unit (a2-A) is represented by the formulas (a2-2-1) to (a2-2-6). The structural units and the structural units represented by formulas (a2-2-1) to (a2-2-6) R in the structural unit (a2-A) a50 The structure in which the methyl group corresponding to The structural unit (a2-A) is a structural unit represented by the formula (a2-2-1): A structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), and a structural unit represented by formula (a2-2-7) A structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), or a structural unit represented by formula ( In the structural unit represented by a2-2-6), R in the structural unit (a2-A) a50 to Preferably, the structural unit has a corresponding methyl group substituted for a hydrogen atom. TIFF0007813327000105.tif42166Content of structural unit (a2-A) when structural unit (a2-A) is contained in resin (A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, based on all structural units. % by mole, more preferably 15 to 65 mol %, and even more preferably 20 to 65 mol %. It is 65 mol%. The structural unit (a2-A) can be prepared by, for example, polymerizing the structural unit (a1-4) and then reacting the polymer with p-toluenesulfonyl ether. It can be incorporated into the resin (A) by treating it with an acid such as phenylsulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0137] The structural unit (a2) having an alcoholic hydroxy group includes a structural unit represented by the formula ( a2-1) (hereinafter referred to as "structural unit (a2-1)") Examples include: TIFF0007813327000106.tif4058 formula (a2-1), L a3 is -O- or * -O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents the bonding position with —CO—. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer between 0 and 10.

[0138] In equation (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0139] Examples of the structural unit (a2-1) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a2-1-1) to formula (a2-1-6) are examples. ) is preferred, and a structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) The structural unit represented by formula (a2-1-1) or formula (a2-1- The structural unit represented by 3) is more preferred. TIFF0007813327000107.tif49138When resin (A) contains the structural unit (a2-1), its content is the total of all structural units of resin (A). It is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably It is preferably 1 to 35 mol %, more preferably 1 to 20 mol %, and even more preferably The content is usually 1 to 10 mol %.

[0140] <Structural unit (a3)> The lactone ring contained in the structural unit (a3) ​​is a β-propiolactone ring, a γ-butyrolactone ring, or It may be a monocyclic ring such as a lactone ring or a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring with another ring. Preferably, the ring is a γ-butyrolactone ring, an adamantane lactone ring, or a γ -Bridged ring containing a butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) Examples include: The structural unit (a3) ​​is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or a structural unit represented by formula (a3-4). One of these may be contained alone, Two or more types may be contained. TIFF0007813327000108.tif50156 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6are each independently -O- or -O-(CH2) k3 - It represents a group represented by CO—O— (k3 represents an integer of 1 to 7). L a7 -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- vinegar. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or represents a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 are each independently a carboxy group, a cyano group or a carbon atom. It represents an aliphatic hydrocarbon group having 1 to 4 prime numbers. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or Ra25 may be the same or different.]

[0141] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in butyl, sec-butyl and tert-butyl groups. Examples include alkyl groups such as t-butyl groups. R a24 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine. Examples include atoms. R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Preferably, the alkyl group has 1 to 4 carbon atoms, and more preferably, the methyl group. or an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group Examples include a methyl group and a triiodomethyl group.

[0142] L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane group, or a methyl group. Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pe hexane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentaerythritol Examples include 2-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

[0143] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferred or -O- or *-O-(CH2) k3 In -CO-O-, k3 is any of 1 to 4 groups each of which is an integer, more preferably -O- and *-O-CH2-CO-O-, and An oxygen atom is preferred. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group or a methyl group. It is a methyl group. p1, q1, and r1 each independently represent an integer of preferably 0 to 2, More preferably, it is 0 or 1.

[0144] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a It is a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably -O- or *-OL a8 -CO-O-, more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF0007813327000109.tif4326 (in the formula, R a24 , L a7 has the same meaning as above.)

[0145] The structural unit (a3) ​​may be a monomer described in JP-A-2010-204646. , the monomers described in JP-A-2000-122294, and JP-A-2012-41274 Examples of the structural unit (a3) ​​include structural units derived from the monomers described in the above publication. , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , formula (a3-3-1), formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-1 2), and in the structural unit, the structural unit represented by formula (a3-1) to formula (a3-2) R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to water Structural units that replace elementary atoms are preferred. TIFF0007813327000110.tif115165 When the resin (A) contains the structural unit (a3), the total content of the structural unit (a3) ​​is the total content of all structural units of the resin (A). It is usually 1 to 70 mol %, preferably 1 to 65 mol %, more preferably The content is usually 1 to 60 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) The content of the units (a3-4) is 1 to 60 moles relative to the total structural units of the resin (A). % by mole, more preferably 1 to 50 mol %, and even more preferably 1 to 50 mol %.

[0146] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF0007813327000111.tif3165[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, The —CH2— contained in the group may be replaced with —O— or —CO—. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain hydrocarbon group and a monocyclic or polycyclic alicyclic hydrocarbon group. groups, and groups formed by combining these groups.

[0147] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include decyl, heptadecyl and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, ... Cycloalkyl groups such as cycloheptyl and cyclooctyl; decahydronaphthyl, adducts, etc. Polycyclic alicyclic carbons such as manthyl group, norbornyl group, and the following groups (* indicates the bonding position): Examples include a hydrogen hydride group. TIFF0007813327000112.tif11160The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0148] The structural unit (a4) includes the formula (a4-0), the formula (a4-1), the formula (a4-2), the formula (a4-3), the formula (a4-4), the formula (a4-5), the formula (a4-6), the formula (a4-7), the formula (a4-8), the formula (a4-9), the formula (a4-10), the formula (a4-11), the formula (a4-12), the formula (a4-13), the formula ( a4-3) and a structure represented by at least one selected from the group consisting of formula (a4-4) Units include: TIFF0007813327000113.tif3953[In formula (a4-0), R 5a represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. represents a fluorocycloalkanediyl group. R 6a represents a hydrogen atom or a fluorine atom.

[0149] L 4a The alkanediyl group in the formula (I) includes a methylene group, an ethylene group, a propane-1, linear alkanediyl groups such as butane-1,3-diyl and butane-1,4-diyl; -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane Branched alkanes such as pan-1,3-diyl and 2-methylpropane-1,2-diyl groups An example is a diyl group.

[0150] L 3a The perfluoroalkanediyl group in 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, 3-diyl group, perfluorooctane-4,4-diyl group, and the like. L 3a The perfluorocycloalkanediyl group in perfluorocyclopentanediyl group, perfluorocycloheptanediyl group yl group, perfluoroadamantanediyl group, and the like.

[0151] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond, bond, a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably or a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0152] The structural unit (a4-0) may be the following structural unit or a structural unit ( a4-0) in R 5a The structural unit in which the methyl group corresponding to can be done. TIFF0007813327000114.tif95165

[0153] TIFF0007813327000115.tif5170[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, The -CH2- contained in the hydrocarbon group may be replaced with -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, or a group represented by the formula (ag 1), where A a41 and R a42 At least one of the following is a substituent: It contains a halogen atom (preferably a fluorine atom). TIFF0007813327000116.tif1383 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 are each independently a divalent group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 is a single bond or a divalent aliphatic hydrocarbon having 1 to 5 carbon atoms which may have a substituent. Represents a group. X a41 and X a42 are each independently -O-, -CO-, -CO-O- or -O-CO - represents. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates the bond position, and the * on the right is -O-CO-R a42 ]

[0154] R a42 The saturated hydrocarbon group in the formula (I) is a chain saturated hydrocarbon group or a monocyclic or polycyclic alicyclic group. saturated hydrocarbon groups of the formula: do.

[0155] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, heptyl group, Examples include a decyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups; Polycyclic alicyclic groups such as adamantyl group, norbornyl group, and the following groups (* indicates the bonding position): saturated hydrocarbon groups of the formula: TIFF0007813327000117.tif11160The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic saturated hydrocarbon groups. -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkanediyl group Examples include an -alkanediyl group, -alicyclic saturated hydrocarbon group, and -alkyl group.

[0156] R a42 The substituents of the formula (a-g3) include halogen atoms and groups represented by the formula (a-g3). The halogen atom may be at least one selected from the group consisting of fluorine atom, Examples include a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom. TIFF0007813327000118.tif752[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . * denotes R a42 represents the bond position with However, Ra42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a4 5 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom .

[0157] A a45 The aliphatic hydrocarbon group in group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, penta Alkyl groups such as decyl, hexadecyl, heptadecyl and octadecyl groups; cyclo Monocyclic alicyclic groups such as pentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups hydrocarbon groups of the formula: and decahydronaphthyl, adamantyl, norbornyl, and the following groups: and polycyclic alicyclic hydrocarbon groups such as the group (where * indicates a bonding position). TIFF0007813327000119.tif11160

[0158] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and / or a saturated hydrocarbon group having a group represented by formula (a-g3) More preferable. R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom. It is preferably a saturated hydrocarbon group having a fluorocarbon group, more preferably a perfluoroalkyl group or a perfluorosilyl group. Preferably, the alkyl group is a chloroalkyl group, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the fluoro groups include perfluoromethyl, perfluoroethyl, and perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples of perfluorocycloalkyl groups include perfluoroheptyl and perfluorooctyl groups. Examples of the cyclohexyl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3) and the number of carbon atoms contained in the group represented by R a42 The total number of carbon atoms is preferably 15 or less. When the alkyl group has a group represented by formula (a-g3) as a substituent, The number is preferably one.

[0159] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 Yes, More preferred is a group represented by formula (a-g2). TIFF0007813327000120.tif874[In formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. represent. X a44 represents **-O-CO- or **-CO-O- (** represents A a46 The bond position with vinegar.). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 of At least one of them has at least one halogen atom. * indicates the bond position with the carbonyl group.]

[0160] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. A a47 The aliphatic hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0161] A preferred structure of the group represented by formula (a-g2) is the following structure (* indicates a carbonyl group): (This is the bonding position with ). TIFF0007813327000121.tif13161

[0162] A a41 The alkanediyl group in the formula (I) includes a methylene group, an ethylene group, a propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 linear alkanediyl groups such as propane-1,2-diyl, butane-1,6-diyl; ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- and branched alkanediyl groups such as 2-methylbutane-1,4-diyl and 2-methylbutane-1,4-diyl. do. A a41 The substituents in the alkanediyl group represented by the formula (I) include a hydroxy group and an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkoxy group include alkoxy groups of formula 6. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably It is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

[0163] A in the group represented by formula (a-g1) a42 , A a43 and A a44 The bivalent saturated The hydrocarbon group may be a straight-chain or branched alkanediyl group or a monocyclic or polycyclic divalent alicyclic group. By combining a cycloaliphatic hydrocarbon group with an alkanediyl group and a divalent alicyclic hydrocarbon group, Specifically, a methylene group, an ethylene group, a propane-1 ,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methyl Propane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane Examples include a pan-1,2-diyl group. A a42 , A a43 and A a44 The substituent of the divalent saturated hydrocarbon group represented by is hydroxyl. Examples of the alkoxy group include an alkoxy group and an alkoxy group having 1 to 6 carbon atoms. Preferably, s is 0.

[0164] In the group represented by formula (a-g1), X a42 is -O-, -CO-, -CO-O- or Examples of the -O-CO- group include the following groups: ** indicates the bond position, and ** is -O-CO-R a42 This is the bonding position with TIFF0007813327000122.tif48153

[0165] The structural unit represented by formula (a4-1) includes the following structural units and R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to Examples of structural units that have been replaced include: TIFF0007813327000123.tif100142

[0166] TIFF0007813327000124.tif122141

[0167] The structural unit represented by formula (a4-1) is preferably a structural unit represented by formula (a4-2). I wish. TIFF0007813327000125.tif3454[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and —C H2- may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The maximum total carbon number is 21.]

[0168] L 44 The alkanediyl group of A a41 Examples of the groups include the same groups as those exemplified in R f6 The saturated hydrocarbon group of R a42 Examples of the groups include the same groups as those exemplified in L 44 The alkanediyl group in the formula (I) is preferably an alkanediyl group having 2 to 4 carbon atoms. An ethylene group is more preferred.

[0169] Examples of the structural unit represented by formula (a4-2) include those represented by formula (a4-1-1) to formula (a4 -1-11) are structural units represented by the structural unit (a4-2). R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It is one of the structural units.

[0170] TIFF0007813327000126.tif5164[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. Af13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. vinegar. X f12 is *-O-CO- or *-CO-O-(* is A f13 represents the bonding position with . A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may contain a fluorine atom. However, A f13 and A f14 At least one of L has a fluorine atom, 5 , A f13 and A f14 The total number of carbon atoms in a molecule is limited to 20.

[0171] L 5 The alkanediyl group in a41 The same as those exemplified for the alkanediyl group The following groups are mentioned: A f13 The divalent saturated hydrocarbon group optionally having a fluorine atom in or a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent chain saturated hydrocarbon group which may have a fluorine atom It is a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanediyl group. It is a aryl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include a methylene group, an ethylene group, alkanediyl groups such as dialkyl groups, propanediyl groups, butanediyl groups and pentanediyl groups; Fluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoro perfluoroalkanediyl groups such as perfluorobutanediyl groups and perfluoropentanediyl groups Examples thereof include a methyl group. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexyl group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and the like. diyl group, perfluoroadamantanediyl group, and the like.

[0172] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 in The same groups as those exemplified above can be mentioned. Among them, trifluoromethyl group, difluoromethyl group, ethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorohexyl group. Fluorinated alkyl groups such as fluorooctyl groups, cyclopropylmethyl groups, cyclopropyl groups , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantine A methyl group is preferred.

[0173] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group is a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent chain hydrocarbon group having 3 carbon atoms. A group containing a divalent alicyclic hydrocarbon group having 2 to 12 carbon atoms is preferred, and a divalent chain hydrocarbon group having 2 to 3 carbon atoms is preferred. A basic group is more preferred. A f14 The saturated hydrocarbon group is a chain hydrocarbon group having 3 to 12 carbon atoms and an aliphatic hydrocarbon group having 3 to 12 carbon atoms. Groups containing cyclic hydrocarbon groups are preferred, and chain hydrocarbon groups having 3 to 10 carbon atoms and groups having 3 to 1 carbon atoms are also preferred. A group containing an alicyclic hydrocarbon group of A is more preferred. f14 is preferably carbon It is a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably, cyclopropylmethyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups.

[0174] Examples of the structural unit represented by formula (a4-3) include those represented by formula (a4-1'-1) to formula (a 4-1'-11) are structural units represented by the following formulas. KerR f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-3). It is one of the structural units that can be mentioned.

[0175] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF0007813327000127.tif4365[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -or-(CH2) j4 - CO-O-(CH2) j5 - represents. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0176] R f22 The saturated hydrocarbon group of R a42 The saturated hydrocarbon group may be the same as the saturated hydrocarbon group represented by the following formula: R f22 represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or a carbon atom having a fluorine atom An alicyclic hydrocarbon group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms and a fluorine atom is preferred. A fluorine atom-containing alkyl group having 1 to 6 carbon atoms is more preferred. In formula (a4-4), A f21 As -(CH2) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0177] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by R in the structural unit (a4-4) f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced. TIFF0007813327000128.tif87160When the resin (A) has the structural unit (a4), its content is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and more preferably 3 to 10 mol % is more preferred.

[0178] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) may be a straight-chain, branched or cyclic hydrocarbon group. Among these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The group is preferred. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1): . TIFF0007813327000129.tif3972[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in the alicyclic hydrocarbon group The atom may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The —CH2— contained in the formula may be replaced with —O— or —CO—.

[0179] R 52 The alicyclic hydrocarbon group in may be either a monocyclic or polycyclic group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclopentyl group. Examples of the polycyclic alicyclic hydrocarbon group include: , an adamantyl group, and a norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group Examples of alkyl groups include an octyl group and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. do. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably Examples thereof include an adamantyl group, a norbornyl group, and a cyclohexyl group.

[0180] L 55 The divalent saturated hydrocarbon group in the above is a divalent chain saturated hydrocarbon group and a divalent fatty acid group. Examples include cyclic saturated hydrocarbon groups, and preferably divalent chain saturated hydrocarbon groups. Examples of the divalent chain saturated hydrocarbon group include a methylene group, an ethylene group, and a propanediol group. alkanediyl groups such as butanediyl, pentanediyl, and the like. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adatom group. Examples include a mantanediyl group and a norbornanediyl group.

[0181] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * and ** represent bonding positions, and * represents the bonding position with an oxygen atom. TIFF0007813327000130.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 represents the bond position with . L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 are each independently a single bond or a divalent aliphatic saturated carbon atom having 1 to 14 carbon atoms. Represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0182] L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a methylene group or an ethylene group. L x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond. L x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a methylene group or an ethylene group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably , a cyclohexanediyl group, or an adamantanediyl group.

[0183] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF0007813327000131.tif54134

[0184] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF0007813327000132.tif24131

[0185] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF0007813327000133.tif15145

[0186] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF0007813327000134.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0187] The structural unit (a5-1) includes the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to can be. TIFF0007813327000135.tif110150When the resin (A) has the structural unit (a5), its content is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and more preferably 3 to 15 mol % is more preferred.

[0188] <Structural unit (II)> The resin (A) further contains a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit”). The structural unit (II) may specifically include is a structural unit described in JP-A-2016-79235, and has a sulfonate group in the side chain. or a structural unit having a carboxylate group and an organic cation or a sulfonio group on a side chain and an organic anion.

[0189] A structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007813327000136.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- contained in the saturated carbon may be replaced by -O-, -S- or -CO-. The hydrogen atom contained in the hydrogen hydride group is a halogen atom, a carbon number which may have a halogen atom It may be substituted with 1 to 6 alkyl groups or hydroxy groups. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the water contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. stomach. RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a group having 1 carbon atom which may have a halogen atom Represents an alkyl group of 1 to 6. ZA + represents an organic cation.

[0190] R III3 The halogen atom represented by the formula (I) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples include uran atoms. R III3 The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom is represented by the formula: R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by Examples include the same things. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, and the like. , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples thereof include a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. do. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include trifluoroalkyl groups. Fluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroiso Propyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group Examples of the alkyl group include a perfluoropentyl group, a perfluorohexyl group, and the like. X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched hydrocarbon group. and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. It may be a combination of the above. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group linear alkanediyl groups such as decane-1,12-diyl; butane-1,3-diyl; 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentaerythritol Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohetane-1,3-diyl group, Cycloalkanediyl groups such as cyclohexan-1,4-diyl group and cyclooctane-1,5-diyl group norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane Divalent polycyclic alicyclic saturated carbons such as benzophenone-1,5-diyl and adamantane-2,6-diyl groups Examples thereof include a hydrogen hydride group. -CH2- in saturated hydrocarbon groups is replaced with -O-, -S- or -CO- Examples of such groups include divalent groups represented by formulae (X1) to (X53). The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-. The number of carbon atoms in each of the preceding groups is 17 or less. In the following formulas, * and ** represent bonding positions, is A x1 represents the bonding position with TIFF0007813327000137.tif145161

[0191] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0192] ZA in formula (II-2-A') + is the cation Z1 in the acid generator (B1). + Similar to Examples include:

[0193] The structural unit represented by formula (II-2-A') is a structural unit represented by formula (II-2-A) It is preferable that: TIFF0007813327000138.tif38109 [In formula (II-2-A), R III3 , X III3 and ZA + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 are each independently a hydrogen atom, a fluorine atom, or a group having 1 carbon atom represents a perfluoroalkyl group having a number of 1 to 6, and when z2A is 2 or more, a plurality of R III2 and R III4 may be the same as or different from each other. Q a and Q b are each independently a fluorine atom or a perfluoroalkane having 1 to 6 carbon atoms. represents a alkyl group.] R III2 , R III4 , Q a and Q b Perfluoroalkyl groups having 1 to 6 carbon atoms, represented by The Q group mentioned above is b1 The same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by Examples include:

[0194] The structural unit represented by formula (II-2-A) is a structural unit represented by formula (II-2-A-1). It is preferable that the position is . TIFF0007813327000139.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and ZA + means the same as above . R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents an integer of 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and the saturated hydrocarbon group -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon The hydrogen atoms contained in the alkyl group may be substituted with halogen atoms or hydroxy groups. R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula include a methyl group, an ethyl group, and , propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and and dodecyl groups. X I2 As the divalent saturated hydrocarbon group represented by X III3 Divalent saturated carbon represented by The same as the hydrogen chloride group can be mentioned.

[0195] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). More preferred are structural units in which TIFF0007813327000140.tif5288 [In formula (II-2-A-2), R III3 , R III5 and ZA + has the same meaning as above. mA and nA each independently represent 1 or 2.]

[0196] Examples of the structural unit represented by formula (II-2-A') include the following structural units, R III3 The group corresponding to the methyl group is a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a halogen atom an alkyl group having 1 to 6 carbon atoms which may have one or more atoms (for example, a trifluoromethyl group, etc.); and structural units described in WO 2012 / 050015. ZA + represents an organic cation. TIFF0007813327000141.tif86163

[0197] The structural unit having a sulfonio group and an organic anion in the side chain is represented by formula (II-1-1): It is preferable that the structural unit is a structural unit that can be formed by the above-mentioned method. TIFF0007813327000142.tif3791 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 and R II3 are bonded to each other to form a ring with the sulfur atom to which they are attached. That's fine. R II4 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. represents an alkyl group. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I) include a phenylene group. and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group and an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups formed by combining these groups. R II4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodide atom. Examples include elementary atoms. R II4 As an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by is R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by Some examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated carbon atom having 1 to 18 carbon atoms. The -CH2- contained in the divalent saturated hydrocarbon group may be -O-, -S- or may be replaced by -CO-. Specifically, X III3 The number of carbon atoms is 1 to 1 Examples thereof include the same divalent saturated hydrocarbon groups as those of 8.

[0198] The structural unit containing a cation in formula (II-1-1) includes the structural units represented by the following formulas: BiR II4 The group corresponding to the methyl group in the formula (1) is a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. Examples include replaced structural units. TIFF0007813327000143.tif84130

[0199] A - Examples of the organic anion represented by the formula include a sulfonate anion, a sulfonylimide anion, and Examples include sulfonylmethide anions, carboxylic acid anions, and the like. - is expressed as The organic anion is preferably a sulfonate anion. More preferably, it is an anion contained in the salt represented by formula (B1).

[0200] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF0007813327000144.tif43135

[0201] Examples of sulfonylmethide anions include the following: TIFF0007813327000145.tif29123

[0202] Examples of carboxylate anions include the following: TIFF0007813327000146.tif51153

[0203] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF0007813327000147.tif161141When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 30 mol %, based on the total structural units of the fat (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0204] The resin (A) may have structural units other than the above-mentioned structural units. The moieties include structural units known in the art.

[0205] The resin (A) is preferably a resin comprising the structural unit (a1) and the structural unit (s). . The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably a cyclohexyl group and a structural unit having a cyclopentyl group) At least one selected from the group consisting of structural units, more preferably at least two selected from the group consisting of and more preferably the structural unit (a1-1) and the structural unit (a1-2). The structural unit (s) is preferably selected from the group consisting of the structural unit (a2) and the structural unit (a3): The structural unit (a2) is preferably represented by the formula (a2-A): The structural unit (a3) ​​is preferably a structural unit represented by the formula (a2-1) or a structural unit represented by the formula (a2-2). or a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-3). a3-4) is at least one selected from the group consisting of structural units represented by the formula:

[0206] The structural units constituting the resin (A) may be used singly or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (for example, radical polymerization methods). The content of each structural unit contained in the resin (A) can be determined by the following procedure. It can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more). 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 In this specification, the weight average molecular weight is 1,000 or less, and more preferably 15,000 or less. The molecular weight is determined by gel permeation chromatography under the conditions described in the examples. is.

[0207] <Resins other than Resin (A)> The resist composition of the present invention may contain a resin other than the resin (A) in combination. Examples of resins other than the resin (A) include those containing the structural unit (a4) or the structural unit (a5). Examples of the resin include a resin having the above structure (hereinafter, sometimes referred to as resin (X)). As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In resin (X), the content of structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. Examples of structural units that the resin (X) may further have include the structural unit (a2), the structural unit (a3) and structural units derived from other known monomers. X) is preferably a resin consisting of only the structural unit (a4) and / or the structural unit (a5). It is more preferable that the resin is composed only of the structural unit (a4). The structural units constituting the resin (X) may be used alone or in combination of two or more. Using monomers that derive these structural units, a known polymerization method (e.g., radical polymerization method) can be used. The content of each structural unit in the resin (X) can be determined by the following procedure. It can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more). 0 or more) and 80,000 or less (more preferably 60,000 or less). The weight average molecular weight can be measured by the same method as in the case of resin (A). Furthermore, when the resist composition contains resin (X), the content of resin (X) is 100 mass % of resin (A). parts, preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, More preferably, it is 1 to 40 parts by mass, and particularly preferably, it is 1 to 30 parts by mass. The amount is preferably 1 to 8 parts by mass.

[0208] The content of resin (A) in the resist composition is 8% by weight based on the solid content of the resist composition. It is preferably 0% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. In addition, when a resin other than the resin (A) is contained, the resin (A) and the resin other than the resin (A) are preferably mixed. The total content of the resin is 80% by mass or more and 99% by mass or less of the solid content of the resist composition. The content is preferably 90% by mass or more and more preferably 99% by mass or less. The solid content of the product and the resin content relative to it are measured by liquid chromatography or gas chromatography. It can be measured by known analytical means such as graphy.

[0209] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less. It is preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of the solvent (E) is 99% by mass or less. The content of the solvent (E) is measured by, for example, liquid chromatography or gas chromatography. It can be measured by known analytical means such as chromatography. The solvent (E) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate and ethyl pyruvate; acetone, methyl isobutyl esters; ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; γ-butyrolactone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0210] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound or an acid generated from the acid generator (B). Salts that generate an acid weaker in acidity than the above (excluding carboxylates represented by formula (I)). When the resist composition contains a quencher (C), the quencher (C The content of the compound (I) is about 0.01 to 15 mass % based on the solid content of the resist composition. The content is preferably about 0.1 to 10% by mass, and more preferably about 0.1 to 10% by mass. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary amines, Amines include secondary amines and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, and diisopropylamine. aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine , octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine amine, triethylamine, trimethylamine, tripropylamine, tributylamine, Tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine , methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine, Ethyldibutylamine diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexane xylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropylamine Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine amine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -Dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-Pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide amine, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Among them, preferred are aromatic amines such as diisopropylaniline, and more preferred are aromatic amines such as diisopropylaniline. Examples include 2,6-diisopropylaniline. 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.

[0211] 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 the salts represented by the following formula, the salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as " weak acid intramolecular salt (D)"), and the salts described in JP-A-2012-229206 , JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is preferably a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably a weak acid intramolecular salt (D). TIFF0007813327000148.tif113145

[0212] ​​​Examples of the weak acid inner salt (D) include the following salts. TIFF0007813327000149.tif95145

[0213] <Other ingredients> The resist composition of the present invention may contain components other than the above-mentioned components (hereinafter referred to as "other components") as needed. It may contain other ingredients (F). The resist composition may contain additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc. Agents, dyes, etc. can be used.

[0214] <Preparation of Resist Composition> The resist composition of the present invention comprises a carboxylate (I), a resin (A), an acid generator (B), and In addition, if necessary, resins other than resin (A), solvent (E), quencher (C) and the like The composition can be prepared by mixing the other component (F) in any order. The temperature during mixing is not limited to 10 to 40°C, depending on the type of resin, etc. An appropriate temperature can be selected depending on the solubility of the compound in the solvent (E), etc. The mixing time is Depending on the mixing temperature, an appropriate time can be selected from 0.5 to 24 hours. The mixing means is not particularly limited, and stirring and mixing or the like can be used. After mixing the components, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable that

[0215] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) applying the resist composition of the present invention onto a substrate; (2) drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating is included. To apply the resist composition to the substrate, a commonly used device such as a spin coater is used. The substrate can be an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be cleaned, and an anti-reflection film or the like may be formed on the substrate. It may be possible. The composition after coating is dried to remove the solvent and form a composition layer. For example, the solvent can be evaporated using a heating device such as a hot plate (prebaking). The heating temperature is 50 to 200°C. The heating time is preferably 10 to 180 seconds. The pressure during this process is 1 to 1.0 x 10 5 It is preferable that the pressure is about Pa. The resulting composition layer is usually exposed using an exposure machine. The exposure light source may be a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert wavelength and emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range, electron beams, Various types of light sources can be used, such as those that irradiate ultraviolet light (EUV). In this case, the irradiation of these radiations is sometimes collectively called "exposure". The exposure is usually carried out through a mask corresponding to the desired pattern. In the case of lines, exposure may be performed by direct writing without using a mask. The composition layer after exposure is subjected to a heat treatment (or The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150°C. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of methods include the dip method, paddle method, spray method, and dynamic dispense method. The development temperature is preferably, for example, 5 to 60°C, and the development time is, for example, 5 The time is preferably 300 seconds or less. By selecting the type of developer as follows: Either a positive resist pattern or a negative resist pattern can be produced. When a positive resist pattern is produced from the resist composition of the present invention, a developer An alkaline developer is used. The alkaline developer is a type of alkaline water used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include an aqueous solution of ethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is removed. It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, a developer A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers include ketones such as 2-hexanone and 2-heptanone. Glycol ether solvents such as propylene glycol monomethyl ether acetate Ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and aromatic hydrocarbon solvents such as the above. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, The content is more preferably 95% by mass or more and 100% by mass or less, and more preferably substantially only an organic solvent. More preferable. Among them, organic developers include developers containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass. Preferably, the content is 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. It is more preferable that the mixture is qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 100%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. After development, the resist pattern is preferably washed with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and solvents containing general organic solvents are also usable. A solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0216] <Application> The resist composition of the present invention is a resist composition for exposure to KrF excimer laser, ArF excimer laser, Resist composition for exposure to ultraviolet laser, resist composition for exposure to electron beam (EB) or EU resist compositions for V exposure, particularly resist compositions for electron beam (EB) exposure or EUV exposure The composition is suitable as a resist composition for semiconductors and is useful for microfabrication of semiconductors. [Example]

[0217] The present invention will be explained in more detail with reference to examples. "%" and "parts" are by weight unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analytical conditions for gel permeation chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (Tosoh Corporation) Eluent: tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation) The structure of the compound was determined by mass spectrometry (LC: Agilent 1100, MASS: Agilent The molecular ion peak was measured using a LC / MSD (manufactured by ent). In the examples, the value of this molecular ion peak is indicated by "MASS."

[0218] Example 1: Synthesis of salt represented by formula (I-164) TIFF0007813327000150.tif33148 4.76 parts of the compound represented by formula (I-164-a) and 6.40 parts of Oxone (registered trademark) The mixture was mixed and stirred at 23°C for 30 minutes, and then cooled to 5°C. After adding 0.56 parts, the mixture was stirred at 5°C for 30 minutes. A mixed solution of 4.15 parts of the compound represented by b) and 20.74 parts of chloroform was added, and the resulting mixture was stirred for 5 minutes. After stirring at 23°C for 30 minutes, the mixture was further stirred at 23°C for 2 hours. The mixture was added to 120 parts of ethanol, stirred at 23°C for 30 minutes, and then filtered. The filtrate obtained was concentrated. To the concentrated residue, 125 parts of chloroform and 25 parts of acetonitrile were added, and the mixture was stirred at 23°C for 30 minutes. After stirring for 30 minutes, 50 parts of 5% hydrochloric acid was added and the mixture was stirred at 23°C for 30 minutes. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and washed with water three times. To the concentrated mixture was added 45 parts of tert-butyl methyl ether, and the mixture was stirred at 23°C for 30 minutes. Thereafter, filtration was carried out to obtain 3.33 parts of the salt represented by the formula (I-164-c). TIFF0007813327000151.tif51148 0.69 parts of a salt represented by formula (I-164-d), 1 part of a salt represented by formula (I-164-c) 0.12 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Five parts of a 5% aqueous solution of oxalic acid was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.02 parts of the salt represented by the formula (I-164) was obtained. MASS(ESI(+)Spectrum):M + 395.1 MASS(ESI(-)Spectrum):M - 193.1

[0219] Example 2: Synthesis of salt represented by formula (I-326) TIFF0007813327000152.tif26143 9 parts of potassium iodate, 14.39 parts of the compound represented by formula (I-326-a), 2 parts of acetic acid 7 parts of acetic anhydride and 13.5 parts of acetic anhydride were mixed, stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, 9 parts of sulfuric acid was added over 10 minutes, and the mixture was stirred at 5°C for 3 hours. The mixture was stirred at 23° C. for 12 hours. To the resulting mixture, 27 parts of tert-butyl methyl ether was added. 27 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 2 hours, and then filtered. The organic layer was separated and extracted. The resulting organic layer was mixed with 4.5 parts of sodium bromide and ion-exchange Add 13.5 parts of the mixed solution, stir at 23°C for 2 hours, and then filter. 2.59 parts of the salt of formula (I-326-b) were obtained. TIFF0007813327000153.tif55148 0.69 parts of a salt represented by formula (I-164-d), 1 part of a salt represented by formula (I-326-b) 0.24 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Five parts of a 5% aqueous solution of oxalic acid was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.56 parts of the salt represented by the formula (I-326) was obtained. MASS(ESI(+)Spectrum):M + 397.0 MASS(ESI(-)Spectrum):M - 193.1

[0220] Example 3: Synthesis of salt represented by formula (I-596) TIFF0007813327000154.tif26161 9 parts of potassium iodate, 27 parts of the compound represented by formula (I-596-a), 27 parts of acetic acid, and The mixture was stirred at 23°C for 30 minutes and then cooled to 5°C. To the resulting mixture, 9 parts of sulfuric acid was added over 10 minutes, and the mixture was stirred at 5°C for 3 hours. The mixture was stirred at rt for 12 hours. To the resulting mixture was added 27 parts of tert-butyl methyl ether and 27 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 2 hours, and then filtered. The obtained filtrate was separated. The organic layer was extracted by adding 4.5 parts of sodium bromide and 1 part of ion-exchanged water. 3.5 parts of the mixed solution was added, and the mixture was stirred at 23°C for 2 hours, followed by filtration to obtain a compound of formula (I 4.68 parts of the salt represented by formula (I)-596-b) were obtained. TIFF0007813327000155.tif57145 0.69 parts of a salt represented by formula (I-164-d), 1 part of a salt represented by formula (I-596-b) 0.86 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Five parts of a 5% aqueous solution of oxalic acid was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.39 parts of the salt represented by the formula (I-596) was obtained. MASS(ESI(+)Spectrum):M + 637.2 MASS(ESI(-)Spectrum):M - 193.1

[0221] Example 4: Synthesis of salt represented by formula (I-166) TIFF0007813327000156.tif59154 1.03 parts of a salt represented by formula (I-166-d), 1 part of a salt represented by formula (I-164-c) 0.12 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Five parts of a 5% aqueous solution of oxalic acid was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.33 parts of the salt represented by the formula (I-166) was obtained. MASS(ESI(+)Spectrum):M + 395.1 MASS(ESI(-)Spectrum):M - 337.1

[0222] Example 5: Synthesis of salt represented by formula (I-328) TIFF0007813327000157.tif67148 1.03 parts of a salt represented by formula (I-166-d), 1 part of a salt represented by formula (I-326-b) 0.24 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Five parts of a 5% aqueous solution of oxalic acid was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.39 parts of the salt represented by the formula (I-328) was obtained. MASS(ESI(+)Spectrum):M + 397.0 MASS(ESI(-)Spectrum):M - 337.1

[0223] Example 6: Synthesis of salt represented by formula (I-220) TIFF0007813327000158.tif36146 5.01 parts of the compound represented by formula (I-220-a) and 6.40 parts of Oxone (registered trademark) The mixture was mixed and stirred at 23°C for 30 minutes, and then cooled to 5°C. After adding 0.56 parts, the mixture was stirred at 5°C for 30 minutes. A mixed solution of 4.15 parts of the compound represented by b) and 20.74 parts of chloroform was added, and the resulting mixture was stirred for 5 minutes. After stirring at 23°C for 30 minutes, the mixture was further stirred at 23°C for 2 hours. The mixture was added to 120 parts of ethanol, stirred at 23°C for 30 minutes, and then filtered. The collected filtrate was concentrated. After that, 125 parts of chloroform and 25 parts of acetonitrile were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. After stirring for 30 minutes, 50 parts of 5% hydrochloric acid was added and the mixture was stirred at 23°C for 30 minutes. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and washed with water three times. To the concentrated mixture was added 45 parts of tert-butyl methyl ether, and the mixture was stirred at 23°C for 30 minutes. Thereafter, filtration was carried out to obtain 3.48 parts of the salt represented by the formula (I-220-c). TIFF0007813327000159.tif59154 1.03 parts of a salt represented by formula (I-166-d), 1 part of a salt represented by formula (I-220-c) 0.16 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Five parts of a 5% aqueous solution of oxalic acid was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.46 parts of the salt represented by the formula (I-220) was obtained. MASS(ESI(+)Spectrum):M + 409.1 MASS(ESI(-)Spectrum):M - 337.1

[0224] Example 7: Synthesis of salt represented by formula (I-274) TIFF0007813327000160.tif41152 5.26 parts of the compound represented by formula (I-274-a) and 6.40 parts of Oxone (registered trademark) The mixture was mixed and stirred at 23°C for 30 minutes, and then cooled to 5°C. After adding 0.56 parts, the mixture was stirred at 5°C for 30 minutes. A mixed solution of 4.15 parts of the compound represented by b) and 20.74 parts of chloroform was added, and the resulting mixture was stirred for 5 minutes. After stirring at 23°C for 30 minutes, the mixture was further stirred at 23°C for 2 hours. The mixture was added to 120 parts of ethanol, stirred at 23°C for 30 minutes, and then filtered. The collected filtrate was concentrated. After that, 125 parts of chloroform and 25 parts of acetonitrile were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. After stirring for 30 minutes, 50 parts of 5% hydrochloric acid was added and the mixture was stirred at 23°C for 30 minutes. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated and washed with water three times. To the concentrated mixture was added 45 parts of tert-butyl methyl ether, and the mixture was stirred at 23°C for 30 minutes. Thereafter, filtration was carried out to obtain 3.13 parts of the salt represented by the formula (I-274-c). TIFF0007813327000161.tif59154 1.03 parts of a salt represented by formula (I-166-d), 1 part of a salt represented by formula (I-274-c) 0.19 parts of ethanol and 10 parts of chloroform were mixed and stirred at 23°C for 12 hours. Five parts of a 5% aqueous solution of oxalic acid was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated. Five parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 1.41 parts of the salt represented by the formula (I-274) was obtained. MASS(ESI(+)Spectrum):M + 423.1 MASS(ESI(-)Spectrum):M - 337.1

[0225] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-3)" etc. according to their formula numbers. TIFF0007813327000162.tif44145

[0226] Synthesis Example 1: Synthesis of Resin A1 As the monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( a2-1-1 and monomer (a3-4-2) were used, and the molar ratio [monomer (a1-1 -3): Monomer (a1-2-6): Monomer (a2-1-1): Monomer (a3-4- 2)) was mixed so that the ratio was 45:14:2.5:38.5, and 1.5 mass of the total monomer amount was added. A solution was prepared by adding 2 times the amount of propylene glycol monomethyl ether acetate. In addition, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were used as initiators. Tolyl) were added at 1 mol% and 3 mol% of the total monomer amount, respectively, and these were mixed at 73 The resulting reaction mixture was poured into a large amount of a mixed solvent of methanol and water. The resin was allowed to settle and filtered. The resulting resin was again diluted with propylene glycol monohydrate. The solution obtained by dissolving in methyl ether acetate was poured into a methanol / water mixed solvent. The resin was precipitated by filtration and the reprecipitation procedure was repeated twice to obtain a resin with a weight average molecular weight of 7. .8×10 3 Resin A1 was obtained in a yield of 69%. This resin A1 has the following structural units: It is something. TIFF0007813327000163.tif36125

[0227] Synthesis Example 2: Synthesis of Resin X1 Monomer (a5-1-1) and monomer (a4-0-12) were used as monomers, The molar ratio [monomer (a5-1-1):monomer (a4-0-12)] was 50:50. Mix well until the mixture becomes uniform, and then add methyl isobutyl ketone in an amount 1.2 times the mass of the total monomer amount to form a solution. To this solution, azobis(2,4-dimethylvaleronitrile) was added as an initiator. The resulting reaction mixture was heated at 70°C for about 5 hours. The resin was then poured into a large amount of methanol / water mixed solvent to precipitate, and the resin was filtered and the weight average Molecular weight 1.0×10 4 Resin X1 was obtained in a yield of 91%. This resin X1 has the following structural units: It is something that we possess. TIFF0007813327000164.tif3082

[0228] <Preparation of Resist Composition> As shown in Table 2, the following components were mixed, and the resulting mixture was passed through a fluorine-containing filter with a pore size of 0.2 μm. The mixture was filtered through a resin filter to prepare a resist composition.

[0229] [Table 2]

[0230] <Resin> A1, X1: Resin A1, Resin X1 <Acid generator (B)> B1-21: a salt represented by formula (B1-21) B1-22: a salt represented by formula (B1-22) TIFF0007813327000166.tif3196<Carboxylate(I)> I-164: A salt represented by formula (I-164) I-166: A salt represented by the formula (I-166) I-220: A salt represented by the formula (I-220) I-274: A salt represented by the formula (I-274) I-326: A salt represented by the formula (I-326) I-328: A salt represented by the formula (I-328) I-596: A salt represented by the formula (I-596) <Carboxylic Acid Generator (IX)> IX-1: TIFF0007813327000167.tif3151IX-2: TIFF0007813327000168.tif3153IX-3: TIFF0007813327000169.tif1750IX-4: TIFF0007813327000170.tif3572<solvent> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts

[0231] <Resist pattern production and evaluation> A silicon wafer was coated with an organic anti-reflective coating composition (ARC-29; Nissan Chemical Co., Ltd.). The wafer was then baked at 205°C for 60 seconds to form a 78 nm thick film. An organic anti-reflective film was formed. Then, the resist composition was applied onto the organic anti-reflective film. The solution was applied (spin coated) so that the film thickness after drying would be 85 nm. Place the wafer on a direct hot plate and heat it for 60 seconds at the temperature listed in the "PB" column of Table 2. The silicon wafer on which the composition layer was formed was subjected to immersion exposure. ArF excimer stepper (XT:1900Gi; ASML, NA=1.35, 3 / 4Annular XY polarization, contact hole pattern (hole pitch 90n The exposure dose was gradually changed using a mask to form a 55 nm hole diameter. Ultrapure water was used as the immersion medium. After exposure, post-process the film on a hot plate for 60 seconds at the temperature specified in the "PEB" column of Table 2. Then, the composition layer on the silicon wafer was exposed to a developer. Dynamic decontamination was performed using butyl acetate (Tokyo Chemical Industry Co., Ltd.) at 23°C for 20 seconds. Development was carried out by a dispense method to produce a negative resist pattern.

[0232] In the resist pattern obtained after development, the diameter of the hole formed using the mask is The exposure amount resulting in 45 nm was taken as the effective sensitivity.

[0233] <Mask Error Factor (MEF) evaluation> In terms of effective sensitivity, the mask hole diameter (the diameter of the hole in the transparent part of the mask) is 5 7nm, 56nm, 55nm, 54nm, 53nm (hole pitch is 90nm in all cases) A resist pattern was formed using the mask. The horizontal axis represents the mask hole diameter, and the The regression analysis was performed by plotting the hole diameter of the resist pattern formed (transferred) on the substrate on the vertical axis. The slope of the line was calculated as the MEF value. The results are shown in Table 3. The values ​​in the table indicate MEF values.

[0234] [Table 3] Compared with comparative compositions 1 to 4, compositions 1 to 7 have a smaller slope of the regression line, and the mask error The MEF (Meaning of Examination Factor) evaluation was favorable. [Industrial Applicability]

[0235] The carboxylic acid salt of the present invention and the resist composition containing the carboxylic acid salt provide excellent mask error prevention. Since it is possible to obtain a resist pattern with a micro-effect film (MEF), it is suitable for semiconductor microfabrication. This is extremely useful industrially.

Claims

1. a carboxylic acid generator containing a carboxylic acid salt represented by formula (I); an acid generator other than the carboxylic acid generator; A resist composition comprising: a resin including a structural unit having an acid labile group and a structural unit represented by formula (a3-4): [In formula (I), R １ａ and R ２ａ each independently represents a hydrocarbon group having 1 to 18 carbon atoms which may have a hydrogen atom or a fluorine atom (a —CH ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by .) or R １ａ and R ２ａ and are bonded to each other, and a ring having 3 to 36 carbon atoms which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms (the —CH contained in the alkyl group) is ２ - may be replaced by -O- or -CO-, and -CH contained in the ring ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by . ) R ３ａ represents a hydrogen atom, or R １ａ and R ２ａ and R ３ａ and are bonded to each other, and a ring having 3 to 36 carbon atoms which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms (the —CH contained in the alkyl group) is ２ - may be replaced by -O- or -CO-, and -CH contained in the ring ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by . ) R ４ represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and the —CH 2 - may be replaced by -O- or -CO-. R ５ represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or —O—CO—CR １ｂ R ２ｂ R ３ｂ and the fluorinated alkyl group and the —CH 2 - may be replaced by -O- or -CO-. R １ｂ and R ２ｂ each independently represents a hydrocarbon group having 1 to 18 carbon atoms which may have a hydrogen atom or a fluorine atom (a —CH ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by .) or R １ｂ and R ２ｂ and are bonded to each other, and a ring having 3 to 36 carbon atoms which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms (the —CH contained in the alkyl group) is ２ - may be replaced by -O- or -CO-, and -CH contained in the ring ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by . ) R ３ｂ represents a hydrogen atom, or R １ｂ and R ２ｂ and R ３ｂ and are bonded to each other, and a ring having 3 to 36 carbon atoms which may have a fluorine atom or an alkyl group having 1 to 12 carbon atoms (the —CH contained in the alkyl group) is ２ - may be replaced by -O- or -CO-, and -CH contained in the ring ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by . ) m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R ４ may be the same or different from each other. m5 represents an integer of 0 to 5, and when m5 is 2 or more, a plurality of R ５ may be the same or different from each other. X ０ represents an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent (the —CH ２ - is -O-, -S-, -CO- or -SO ２ -), a group in which an alicyclic hydrocarbon group having 3 to 24 carbon atoms is combined with a chain hydrocarbon group having 1 to 18 carbon atoms (the -CH contained in the alicyclic hydrocarbon group and the chain hydrocarbon group may be replaced with -), ２ - is -O-, -S-, -CO- or -SO ２ -, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a substituent.), an aromatic hydrocarbon group having 6 to 24 carbon atoms which may have a substituent, or a group in combination of an aromatic hydrocarbon group having 6 to 24 carbon atoms and a chain hydrocarbon group having 1 to 18 carbon atoms (the -CH contained in the chain hydrocarbon group ２ - is -O-, -S-, -CO- or -SO ２ -, and the aromatic hydrocarbon group and the chain hydrocarbon group may have a substituent. [In formula (a3-4), L ａ７ represents -O-, *-O-L ａ８ -O-, *-O-L ａ８ -CO-O-, *-O-L ａ８ -CO-O-L ａ９ -CO-O- or *-O-L ａ８ -O-CO-L ａ９ represents -O-. L ａ８ and L ａ９ each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R ａ２４ represents an alkyl group having 1 to 6 carbon atoms which may have one or more halogen atoms, a hydrogen atom, or a halogen atom. R ａ２５ represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. w1 represents an integer of 0 to 8. When w1 is 2 or more, a plurality of R ａ２５ may be the same or different.

2. X ０ is an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxy group (-CH contained in the alicyclic hydrocarbon group) 2 - may be replaced by -O- or -CO-) or a group in which an alicyclic hydrocarbon group and a chain hydrocarbon group are combined (the -CH 2 The resist composition according to claim 1, wherein - may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain hydrocarbon group may contain a fluorine atom or a hydroxy group.

3. 3. The resist composition according to claim 1, wherein the resin having an acid labile group is a resin containing at least one selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2): [In formula (a1-1) and formula (a1-2), L ａ１ and L ａ２ are each independently —O— or *—O—(CH ２ ) ｋ１ represents —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. R ａ４ and R ａ５ each independently represents a hydrogen atom or a methyl group. R ａ６ and R ａ７ each 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 of 0 to 14. n1 represents an integer of 0 to 10. n1′ represents an integer of 0 to 3.

4. 4. The resist composition according to claim 1, further comprising a resin containing a structural unit having a fluorine atom.

5. 5. The resist composition according to claim 1, wherein the acid generator other than the carboxylic acid generator comprises a salt represented by formula (B1). [In formula (B1), Q ｂ１ and Q ｂ２ each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L ｂ１ represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ２ The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and —CH ２ - is -O-, -S(O) ２ It may be replaced by - or -CO-. Z1 ＋ represents an organic cation.

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