Carboxylic acid salt, carboxylic acid generator, resist composition and method for producing resist pattern

Abstract

To provide a carboxylate, a carboxylic acid generator, and a resist composition capable of producing a resist pattern having good line edge roughness (LER).SOLUTION: The carboxylate represented by formula (I), the carboxylic acid generator, and the resist composition are provided. [In the formula, R1 and R2 each represent -O-L1-CO-O-R10; L1 represents an alkanediyl group; R4, R5, R7 and R8 each represent a halogen atom, a fluorinated alkyl group or a hydrocarbon group, provided that the hydrocarbon group may have a substituent and -CH2- contained in the hydrocarbon group may be substituted with -O-, -CO- or the like; R10 represents a group having a cyclic carbonate ester structure; X1 and X2 each represent S or O; m1 represents an integer of 1-5, m2 and m8 each represent an integer of 0-5, and m4, m5 and m7 each represent an integer of 0-4, where 1≤m1+m7≤5 and 0≤m2+m8≤5; and X0 represents a hydrocarbon group.]SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a carboxylate, a carboxylic acid generator, a resist composition and a resist pattern. It relates to a manufacturing method. [Background technology]

[0002] Patent Document 1 describes a resin containing a carboxylate represented by the following formula as a carboxylate generator. Dist compositions are described. TIFF0007682029000001.tif1455 Patent Document 2 describes a resist composition containing a salt represented by the following formula as an acid generator: It has been done. TIFF0007682029000002.tif3490 Patent Document 3 describes a resist composition containing a salt represented by the following formula as an acid generator: It has been done. TIFF0007682029000003.tif2687 Non-Patent Document 1 describes a salt represented by the following formula: TIFF0007682029000004.tif1185 Patent Document 4 describes a salt represented by the following formula: TIFF0007682029000005.tif2389 Patent Document 5 describes a salt represented by the following formula: TIFF0007682029000006.tif1156 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2011-039502 A [Patent Document 2] JP 2012-236816 A [Patent Document 3] JP 2011-085878 A [Patent Document 4] JP 2017-155036 A [Patent Document 5] Japanese Patent Application Publication No. 06-118651 [Non-patent literature]

[0004] [Non-Patent Document 1] Org.Lett.2018,20,4458-4461 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention relates to a resist pattern formed by a resist composition containing the above salt. , and carboxylates that form resist patterns with good line edge roughness (LER) provide. [Means for solving the problem]

[0006] The present invention includes the following inventions. [1] A carboxylate represented by formula (I). TIFF0007682029000007.tif35138 [In formula (I), R 1 and R 2 are each independently, -OR 10 , -O-CO-R 10 , -O-CO- OR 10 , -OL 1 -CO-OR 10 Represents. L 1 represents an alkanediyl group having 1 to 6 carbon atoms. R 4 , R 5 , R 7 and R 8 each independently represents a halogen atom, a fluorine atom having 1 to 6 carbon atoms, It represents an alkyl group or a hydrocarbon group having 1 to 18 carbon atoms, and the hydrocarbon group may have a substituent. The hydrocarbon group often contains -CH 2- is -O-, -CO-, -S- or -SO 2 - may be substituted. R 10 represents a group having a cyclic carbonate structure. X 1 and X 2 each independently represents an oxygen atom or a sulfur atom. m1 represents an integer of 1 to 5, and when m1 is 2 or more, the groups in the parentheses are mutually mutually exclusive. They may be the same or different. m2 represents an integer of 0 to 5, and when m2 is 2 or more, the groups in the parentheses are mutually mutually exclusive. They may be the same or different. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R 4 are the same They may be the same or different. m5 represents an integer of 0 to 4, and when m5 is 2 or more, a plurality of R 5 are the same They may be the same or different. m7 represents an integer of 0 to 4, and when m7 is 2 or more, a plurality of R 7 are the same They may be the same or different. m8 represents an integer of 0 to 5, and when m8 is 2 or more, a plurality of R 8 are the same They may be the same or different. However, 1≦m1+m7≦5, and 0≦m2+m8≦5. X 0 represents a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, -CH 2 - is -O-, -S-, -CO- or -SO 2 - It's okay if it's replaced by stomach.] [2]X 1 and X 2 [1] The carboxylate according to claim 1, wherein [3] R 10The group having a cyclic carbonate structure is a group represented by formula (Ix): A carboxylate according to the above item [1] or [2]. TIFF0007682029000008.tif3344[In formula (Ix), Ring W x represents a ring of a cyclic carbonate structure which may have a substituent. L 2 represents a single bond or a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, -CH contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -Replaced with It's okay to know. * denotes a binding site.] [4] m2 is 0, m8 is 1, and R 8 is a branched alkyl group having 3 or 4 carbon atoms The carboxylate according to any one of [1] to [3], [5]R 4 or R 5 is an iodine atom, a fluorine atom, or a trifluoromethyl group, [1 The carboxylate according to any one of the items [1] to [4]. [6] R in the benzene ring 4 The bond position of X 1 is in o- or m-position with respect to is R in the benzene ring 5 The bond position of X 2 It is o-th or m-th place with respect to Carboxylic acid salts of the above. [7]X 0 an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent (provided that the aliphatic -CH contained in aliphatic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Placed or an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent. The carboxylate according to any one of [1] to [6], [8]X0 is an alicyclic hydrocarbon group which may have a fluorine atom or a hydroxyl group (the -CH contained in alicyclic hydrocarbon group 2 - may be replaced by -O- or -CO-. ) or a halogen atom, a hydroxyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. The carboxylate according to any one of [1] to [7], wherein the aromatic hydrocarbon group may have . [9]X 0 The carboxylate according to [7], wherein TIFF0007682029000009.tif2737[In formula (aa), X a and X b each independently represents -O- or -S-. X 1a represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, Included -CH 2 - is -O-, -S-, -CO- or -SO 2 Even if it is replaced with - good. X 2a represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, Included -CH 2 - is -O-, -S-, -CO- or -SO 2 Even if it is replaced with - good. * -COO - represents the bond position with the carbon atom of

[10] A carboxylic acid generator comprising the carboxylate according to any one of [1] to [9]. .

[11]

[10] The carboxylic acid generator according to the present invention, an acid generator other than the carboxylic acid generator, and an acid A resist composition containing a resin having a labile group.

[12] The resin having an acid labile group is a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1 The resist composition according to

[11] , containing at least one selected from the group consisting of structural units represented by -2). TIFF0007682029000010.tif46102[In formula (a1-1) and formula (a1-2), L a1 and L a2 each independently represents -O- or *-O-(CH 2 ) k1 -CO-O- to represent, k1 represents an integer from 1 to 7, and * represents the bonding position to -CO-. R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. m1 represents an integer from 0 to 14. n1 represents an integer from 0 to 10. n1’ represents an integer from 0 to 3.]

[13] Further, the resist composition according to

[11] or

[0012] , containing a resin containing a structural unit having a fluorine atom.

[14] (1) A step of applying the resist composition according to any one of

[11] to

[13] on a substrate . (2) A step of drying the applied composition to form a composition layer. (3) A step of exposing the composition layer. (4) A step of heating the exposed composition layer, and (5) A step of developing the heated composition layer, a method for manufacturing a resist pattern including these steps.

Advantages of the Invention

[0007] ​​​By using a resist composition using the carboxylate of the present invention, it is possible to obtain a good line area. It is possible to produce resist patterns with low edge roughness (LER). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In this specification, the term "(meth)acrylic monomer" refers to an acrylic monomer and "(Meth)acrylate" and "at least one methacrylic monomer" are used. The terms "(meth)acrylic acid" and "(meth)acrylic acid" have the same meaning. In the case where the structure can be either a straight chain structure or a branched structure, either one may be used. -CH contained in the group 2 - is -O-, -S-, -CO- or -SO 2 When replaced with - The same examples apply to each group. A "combined group" refers to a group that is exemplified by It means a group in which two or more types of groups are bonded together, and the valence of these groups may be appropriately changed depending on the bonding form. "Derived from" or "derived from" means that the polymerizable C=C bond contained in the molecule is polymerized. When stereoisomers exist, all stereoisomers are included. Includes. In this specification, the term "solid content of a resist composition" refers to the fraction of the total amount of the resist composition that is 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 sometimes referred to as "salt (I)"). Regarding. 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 salt (I). It is sometimes called "On(I)". TIFF0007682029000011.tif35138 [wherein all symbols have the same meanings as defined above.]

[0010] In formula (I), R 1 and R 2 L included in 1 As the alkanediyl group in Methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, linear alkanediyl groups such as hexane-1,5-diyl group and hexane-1,6-diyl group; and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and branched alkanediyl groups such as 2-methylbutane-1,4-diyl group. L 1 is preferably an alkanediyl group having 1 to 3 carbon atoms, and more preferably a methylene group. is more preferable.

[0011] R 1 and R 2 R included in 10 The cyclic carbonate structure has the following atoms constituting the ring: The cyclic carbonate structure can be monocyclic or polycyclic. In addition to the oxygen atom forming the carbonate structure, a heteroatom such as an oxygen atom or a nitrogen atom may be used. The suffix may have a child. The number of carbon atoms in the cyclic carbonate structure is preferably 2 to 18, and more preferably 3 to 12. The ring of the cyclic carbonate structure is preferably a 4-membered ring to a 12-membered ring, more preferably a 5-membered ring. It is preferably an 8-membered ring, and more preferably a 5-membered ring.

[0012] Examples of the cyclic carbonate structure include structures represented by formulas (x1) to (x15). The structure represented by any one of the formulas (x1) to (x3) and (x9) is preferred, and the structure represented by the formula (x A structure represented by any one of formulas (x1) to (x2) is more preferred, and a structure represented by formula (x1) is more preferred. The bond may be at any position. TIFF0007682029000012.tif88153

[0013] The cyclic carbonate structure may have a substituent. The substituent may be a group having 1 to 1 carbon atoms. 2 alkyl group, alicyclic hydrocarbon group having 3 to 12 carbon atoms, hydroxy group, aryl group having 1 to 6 carbon atoms alkoxy groups and combinations of two or more of these groups. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Examples of the alkyl group include an isobutyl group, a tert-butyl group, a pentyl group, and a hexyl group. The group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. The alicyclic hydrocarbon group may be any one of a monocyclic, polycyclic, and spirocyclic group. Examples of the group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. monocyclic cycloalkyl groups such as cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl groups; Examples of the cycloalkyl group include polycyclic cycloalkyl groups such as a cycloalkyl group, a norbornyl group, and an adamantyl group. can be. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, Examples of the alkyl group include an aryloxy group and a hexyloxy group.

[0014] The group having a cyclic carbonate structure is preferably a group represented by formula (Ix). It is. TIFF0007682029000013.tif3344[In formula (Ix), Ring W x represents a ring of a cyclic carbonate structure which may have a substituent. L 2 represents a single bond or a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, -CH contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -Replaced with It's okay to know. * denotes a binding site.]

[0015] Examples of the group having a cyclic carbonate structure include the following structures. is a bond. TIFF0007682029000014.tif101159

[0016] L 2 The hydrocarbon group having 1 to 36 carbon atoms is preferably an aliphatic hydrocarbon group (an alkanediyl group, Chain hydrocarbon groups such as alkenediyl groups and alkynediyl groups, and monocyclic or polycyclic alicyclic groups Hydrocarbon groups, aromatic hydrocarbon groups, etc., and combinations of two or more of these groups are L may be a hydrocarbon group. 2 -CH contained in the hydrocarbon group 2 - is -O- , -S-, -CO- or -SO 2 - may be replaced.

[0017] Examples of the alkanediyl group include a methylene group, an ethylene group, and a propane-1,3-diyl group. Butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group , heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,1 Linear alkanediyl groups such as 2-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; The number of carbon atoms in the alkanediyl group is preferably 1 to 12, and more preferably is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenediyl group include an ethenediyl group, a propenediyl group, and an isopropenediyl group. group, butenediyl group, isobutenediyl group, tert-butenediyl group, pentenediyl group group, hexenediyl group, heptenediyl group, octynediyl group, isooctenediyl group, An example of such a group is a nonenediyl group. The alkynediyl group includes an ethynediyl group, a propynediyl group, and an isopropynediyl group. group, butynediyl group, isobutynediyl group, tert-butynediyl group, pentynediyl group group, a hexynediyl group, an octynediyl group, a nonynediyl group, and the like.

[0018] The alkanediyl group contains -CH 2 - is -O-, -S-, -CO- or -SO 2 - The groups that have been replaced by are hydroxy groups (-CH 2 -But-O- substituted), carboxy group (-CH contained in ethyl group) 2 -CH 2 -But-O- CO-), thiol group (-CH contained in methyl group) 2 - to -S- substituted group), alkanediyloxy group (any position contained in the alkanediyl group) -CH 2 - is replaced by -O-), alkanediyloxycarbonyl group (alkanediyloxycarbonyl group -CH at any position in the candiyl group 2 -CH 2 - is replaced by -O-CO- alkanediylcarbonyl group (a group in which -C is at any position in the alkanediyl group) H 2 - is replaced by -CO-), alkanediylcarbonyloxy group (alkane -CH at any position in the diyl group 2 -CH 2 - is replaced by -CO-O- ), an alkanediylthio group (an alkanediyl group having -CH 2 -but, -S- substituted), alkanediylsulfonyl group (a group contained in an alkanediyl group) -CH at any position 2 -But-SO 2 - substituted groups). The alkanediyloxy group includes an alkanediyloxy group having 1 to 17 carbon atoms. Examples of such groups include methyleneoxy groups, ethyleneoxy groups, propanediyloxy groups, butanediyloxy groups, and the like. yloxy group, pentanediyloxy group, hexanediyloxy group, octanediyloxy group Si group, 2-ethylhexanediyloxy group, nonanediyloxy group, decanediyloxy group group, undecanediyloxy group, and the like. The alkanediyloxycarbonyl group is an alkanediyloxy group having 2 to 17 carbon atoms. Carbonyl groups include, for example, methyleneoxycarbonyl groups, ethyleneoxycarbonyl groups, propanediyloxycarbonyl group, butanediyloxycarbonyl group, penta Hexanediyloxycarbonyl group, hexanediyloxycarbonyl group, octanediyloxycarbonyl group dicarbonyl group, 2-ethylhexanediyloxycarbonyl group, nonanediyloxycarbonyl group carbonyl group, decanediyloxycarbonyl group, undecanediyloxycarbonyl group, etc. Examples include: The alkanediylcarbonyl group is an alkanediylcarbonyl group having 2 to 18 carbon atoms. Examples of such groups include a methylene carbonyl group, an ethylene carbonyl group, and a propanediol group. carbonyl group, butanediylcarbonyl group, pentanediylcarbonyl group, hexanediyl Carbonyl group, octanediylcarbonyl group, 2-ethylhexanediylcarbonyl group, Nonanediylcarbonyl group, decanediylcarbonyl group, undecanediylcarbonyl group etc. The alkanediylcarbonyloxy group is an alkanediylcarbonyloxy group having 2 to 17 carbon atoms. Examples of the aryloxy group include a methylenecarbonyloxy group and an ethylenecarbonyloxy group. oxy group, propanediylcarbonyloxy group, butanediylcarbonyloxy group, penta Hexanediylcarbonyloxy group, hexanediylcarbonyloxy group, octanediylcarbonyloxy group nonanediylcarbonyloxy group, 2-ethylhexanediylcarbonyloxy group, oxy group, decanediylcarbonyloxy group, undecanediylcarbonyloxy group, etc. Examples include: Examples of the alkanediylthio group include alkanediylthio groups having 1 to 17 carbon atoms. Methylenethio group, ethylenethio group, propanediylthio group, butanediylthio group, penta Hexanediylthio group, Heptanediylthio group, Octanediylthio group , nonanediylthio group, decanediylthio group, undecanediylthio group, dodecanediyl Examples thereof include a thio group and a 2-methylpropanediylthio group. The alkanediylsulfonyl group includes a sulfonyl group having 1 to 17 carbon atoms, for example Examples include a methylenesulfonyl group, an ethylenesulfonyl group, and a propylenesulfonyl group. can be done. The substitution in the alkenediyl group and the alkynediyl group is the same as that of the above-mentioned alkane In the examples of substitutions in the diyl group, a carbon-carbon double bond or a carbon It may contain a -carbon triple bond.

[0019] Examples of monocyclic alicyclic hydrocarbon groups include cyclobutane-1,3-diyl group, cyclopenta cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclohexene-3,6- cycloalkanediyl groups such as cyclohexyl, ... Examples of cyclic alicyclic hydrocarbon groups include norbornane-1,4-diyl group, norbornane-2 ,5-diyl group, 5-norbornene-2,3-diyl group, adamantane-1,5-diyl and polycyclic cycloalkanediyl groups such as adamantane-2,6-diyl group. For example, the following groups may be mentioned: The binding site may be at any position. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, and more preferably 3 to 16. and more preferably 3 to 12. In addition, -CH contained in alicyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -S O 2 Examples of the group substituted with - include the groups shown below. The bonding site is any The positions of -O- and -CO- in the groups shown below can be -S -OR-SO 2 - may be replaced. TIFF0007682029000016.tif47155 Aromatic hydrocarbon groups include phenylene, naphthylene, anthrylene, biphenyl, and phenylene. The number of carbon atoms in the aromatic hydrocarbon group is preferably It is 6 to 18, more preferably 6 to 14, and further preferably 6 to 10. -CH contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 - Place When the carbon atom is replaced, the number of carbon atoms before the replacement is regarded as the total number of carbon atoms of the hydrocarbon group. The number may be one or may be two or more.

[0020] Examples of the hydrocarbon group that combines two or more types include an alkanediyl group and an alicyclic hydrocarbon group, and and / or an aromatic hydrocarbon group, and the like. The formula hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group are each a combination of two or more types. For example, -alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-alicyclic Formula: Hydrocarbon group -, -alkanediyl group -alicyclic hydrocarbon group -alkanediyl group -, -alkanediyl group candiyl group-aromatic hydrocarbon group-, -aromatic hydrocarbon group-alkanediyl group-, etc. Either group may be bonded to the oxygen atom.

[0021] L 2 The substituents of the hydrocarbon group include halogen atoms, cyano groups, hydroxy groups, Carboxy group, alkoxy group having 1 to 12 carbon atoms, alkoxycarbonyl group having 2 to 13 carbon atoms group, alkylcarbonyl group having 2 to 13 carbon atoms, alkylcarbonyloxy group having 2 to 13 carbon atoms A silyl group, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms groups, and alkylcarbonyloxy groups having 2 to 13 carbon atoms. Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. 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 butyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl oxy 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 the alkylcarbonyloxy group having 2 to 13 carbon atoms is the above-mentioned alkyl or alkoxy group. The aryl group represents a group having a carbonyl group or a carbonyloxy group bonded to the aryl group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy carbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 13 carbon atoms. Examples of the aryl group include an acetyl group, a propionyl group, and a butyryl group, and the like. The alkylcarbonyloxy group of 3 is an acetyloxy group, a propionyloxy group, butyryloxy group and the like. L 2 The hydrocarbon group in may have one or more substituents.

[0022] L 2 represents a single bond, an alkanediyl group having 1 to 6 carbon atoms (including - contained in the alkanediyl group). CH 2 - may be replaced by -O- or -CO-.) Formula hydrocarbon group (-CH contained in the alicyclic hydrocarbon group) 2 - is replaced with -O- or -CO- or an alkanediyl group having 1 to 6 carbon atoms and an alicyclic group having 3 to 18 carbon atoms. A group combining a hydrocarbon group (including the alkanediyl group and the alicyclic hydrocarbon group) CH 2 - may be replaced by -O- or -CO-; An alkanediyl group having 1 to 6 carbon atoms is more preferable, and an alkanediyl group having 1 to 3 carbon atoms is more preferable. It is more preferably an yl group, and even more preferably a methylene group. R 1 and R 2 is -O-CO-R 10 , -O-CO-OR 10 , -OL 1 -CO- OR 10 is preferably -O-CO-OR 10 , -OL 1 -CO-OR 10 It is more preferable that: R 1 and R 2 The bond positions of X 1 and X 2 The bond position is о, m, and p Any of the X 1 and X 2 The bond is p-positioned to the bond position of is preferred.

[0023] R 4 , R 5 , R 7 and R 8 The halogen atom is a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 4 , R 5 , R 7 and R 8 The fluorinated alkyl group having 1 to 12 carbon atoms is a group having a fluorine atom. represents an alkyl group having 1 to 12 carbon atoms, and a perfluoroalkyl group having 1 to 12 carbon atoms (e.g., Trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluoro 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, propyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group. The number of carbon atoms of the fluorinated alkyl group is preferably 1 to 6, More preferably, it is 1 to 4, and further preferably, it is 1 to 3. R 4 , R 5 , R 7 and R 8 Examples of the hydrocarbon group having 1 to 18 carbon atoms include alkyl groups and the like. Formulaic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof Examples of the group formed include The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. 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 and dodecyl group The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably It is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. 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. The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms. It is preferably 3 to 16, and more preferably 3 to 12. Specifically, the alicyclic hydrocarbon group is 2 Examples of the groups include the same groups as those exemplified in the above. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, The number of carbon atoms of the aromatic hydrocarbon group is preferably The number is preferably 6 to 18, more preferably 6 to 14, and further preferably 6 to 10. . The group formed by the combination is an aromatic hydrocarbon group and a chain hydrocarbon group. A group that combines (for example, aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic aromatic hydrocarbon group-*), groups combining alicyclic and chain hydrocarbon groups (e.g. , alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), aromatic A group that combines an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., an aromatic hydrocarbon group-alicyclic Cyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). Represents the binding site. Aromatic hydrocarbon groups - alkanediyl groups -* include aryl groups such as benzyl and phenethyl groups. Examples include ralkyl groups. Examples of alkyl groups - aromatic hydrocarbon groups -* include tolyl groups, xylyl groups, and cumenyl groups. Some examples include: Alicyclic hydrocarbon groups - alkanediyl groups - * include cyclohexylmethyl groups, cyclohexylmethyl groups, Hexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 -1-methylethyl, and the like. Examples of alkyl groups - alicyclic hydrocarbon groups -* include methylcyclohexyl, dimethylcyclohexyl, cyclohexyl group, 2-alkyladamantan-2-yl group, etc. Examples of the alkyl groups include alkyl groups. Examples of aromatic hydrocarbon groups - alicyclic hydrocarbon groups -* include phenylcyclohexyl groups. Can be obtained. Examples of alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include cyclohexylphenyl groups. Can be obtained. In addition, in the combination, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups are In addition, alicyclic hydrocarbon groups, chain hydrocarbon groups ( -CH contained in alkanediyl group, alkyl group) 2 - is -O-, -S-, -CO- or -SO 2 The combined groups may be replaced by -. It is okay to do so. -CH contained in the hydrocarbon group 2 - is -O-, -CO-, -S- or -SO 2 -Place The replaced groups are hydroxy groups (-CH 2 - is placed in -O- substituted group), carboxy group (-CH contained in ethyl group 2 -CH 2 -But -O-CO- thiol (-CH in a methyl group) 2 - is replaced by -S- alkoxy group (a group in which -CH 2 - to -O- substituted group), alkoxycarbonyl group (-C at any position in the alkyl group) H 2 -CH 2 - is replaced by -O-CO-), alkylcarbonyl group (alkyl Any position of -CH 2- is replaced by -CO-), alkylcarbo Nyloxy group (-CH at any position in the alkyl group) 2 -CH 2 -But -CO-O- substituted), alkylthio group (groups in which -CH 2 -but , -S- substituted), alkylsulfonyl group (any position in the alkyl -CH 2 -But-SO 2 - substituted groups), cycloalkoxy groups, cycloalkyl Alkoxy group, alkoxycarbonyloxy group, aromatic hydrocarbon group-carbonyloxy group and groups in which two or more of these groups are combined. The alkoxy group includes an alkoxy group having 1 to 17 carbon atoms, for example, methoxy. group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, oxy group, Ctyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, un The alkoxy group preferably has 1 to 11 carbon atoms. More preferably, it is 1 to 6, and further preferably, it is 1 to 4. The alkoxycarbonyl group, the alkylcarbonyl group and the alkylcarbonyloxy group are The above-mentioned alkyl or alkoxy group is bonded to a carbonyl or carbonyloxy group. Represents a group. The alkoxycarbonyl group includes an alkoxycarbonyl group having 2 to 17 carbon atoms. Examples of such groups include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms. Examples of the alkyl group include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms. Examples of such groups include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, and more preferably 2. The number of carbon atoms in the alkylcarbonyl group is preferably from 1 to 6, and more preferably from 2 to 4. The number is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 11, and more preferably 2 to 11. It is preferably 6, and more preferably 2 to 4. The alkylthio group includes an alkylthio group having 1 to 12 carbon atoms, for example, methyl. Examples of the alkylthio group include an alkylthio group, an ethylthio group, a propylthio group, and a butylthio group. The group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 4 carbon atoms. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 12 carbon atoms. Examples include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The alkylsulfonyl group preferably has 1 to 11 carbon atoms, and more preferably has 1 to 11 carbon atoms. It is preferably 6, and more preferably 1 to 4. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms. Examples of the cycloalkylalkoxy group include a cyclohexyloxy group. and cycloalkylalkoxy groups having a carbon number of 4 to 17, such as cyclohexylmethoxy. The alkoxycarbonyloxy group includes an alkoxy group having 2 to 16 carbon atoms. Examples of the aryloxy group include butoxycarbonyloxy groups. The aromatic hydrocarbon group-carbonyloxy group is an aromatic hydrocarbon group having 7 to 17 carbon atoms. Examples of the group include a carbonyloxy group, such as a benzoyloxy group. In addition, -CH contained in alicyclic hydrocarbon groups 2 - is replaced by -O- or -CO- The group is L 2 Examples of the groups include the same groups as those exemplified in the above. -CH contained in the hydrocarbon group 2 When - is replaced by -O- or -CO-, The number of carbon atoms before the substitution is the total number of carbon atoms in the hydrocarbon group. , 2 or more may be used, R 4 , R 5 , R 7 and R 8 The substituents which the hydrocarbon group may have include halogen. Atoms, cyano groups, alkyl groups having 1 to 12 carbon atoms (including —CH 2 -teeth, -O- or -CO- may be substituted. Examples of the halogen atom include the same groups as those mentioned above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those mentioned above. As a substituent, -CH contained in an alkyl group 2 - is replaced by -O- or -CO- When a group is substituted with a substituted aryl group, the number of carbon atoms before the substitution is the total number of carbon atoms in the alkyl group. Examples of the alkyl groups include hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbonyl groups, and alkyl groups. Examples of the alkyl group include an alkylcarbonyl group and an alkylcarbonyloxy group. Alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups and alkylcarbonyl groups Examples of the oxy group include the same groups as those mentioned above. The hydrocarbon group may have one substituent or multiple substituents.

[0024] X 1is preferably an oxygen atom. X 2 is preferably an oxygen atom. X 1 and X 2 The bond position of I + The bond position may be either о-position, m-position, or p-position. Among them, I + It is preferable that the bond is m- or p-position relative to the bonding position of p It is more preferred that the aryl group is bonded to the -position. m1 is preferably 1 or 2, and more preferably 1. It is preferred that m2 is 0, 1 or 2. m4 is preferably 0, 1, 2 or 4, more preferably 0, 1 or 2. It is. m5 is preferably 0, 1, 2 or 4, more preferably 0, 1 or 2. It is. m7 is preferably 0, 1 or 2, and more preferably 0 or 1. It is preferable that m8 is 0 or 1. R 4 and R 5 each independently represents a halogen atom, a fluoroalkyl group having 1 to 4 carbon atoms, or is an alkyl group having 1 to 6 carbon atoms (-CH 2 - is -O- or -CO -) is preferably a halogen atom, a Fluorinated alkyl group or alkyl group having 1 to 4 carbon atoms (-CH contained in the alkyl group) 2 -teeth , -O- or -CO- may be substituted. It is further preferred that the alkyl group is an iodine atom, a trifluoromethyl group, or an alkyl group having 1 to 4 carbon atoms. Preferred. R 7 and R 8each independently represents a halogen atom, a fluoroalkyl group having 1 to 4 carbon atoms, or is an alkyl group having 1 to 6 carbon atoms (-CH 2 - is -O- or -CO -) is preferably a halogen atom, a Fluorinated alkyl group or alkyl group having 1 to 4 carbon atoms (-CH contained in the alkyl group) 2 -teeth , -O- or -CO- may be substituted. Atom, iodine atom, perfluoroalkyl group having 1 to 4 carbon atoms or alkyl group having 1 to 4 carbon atoms Group (-CH contained in the alkyl group 2 - may be replaced by -O- or -CO-. It is more preferable that the alkyl group is a fluorine atom, an iodine atom, a trifluoromethyl group, Even more preferably, it is a methyl group, a t-butyl group, a hydroxy group or a methoxy group. If m2 is 0, m8 is 1, and R 8 is a branched alkyl group having 3 or 4 carbon atoms. It is preferable that When m4 is 2, R 1 The bond position of is X 1 It is preferably in the p-position relative to the bonding position of Two R's 4 One of them is X 1 m position relative to the bonding position (1st position) of It is preferred that one is bonded at the 3-position and the other at the 6-position. When m5 is 2, R 2 The bond position of is X 2 It is preferably in the p-position relative to the bonding position of Two R's 5 One of them is X 2 m position relative to the bonding position (1st position) of It is preferred that one is bonded at the 3-position and the other at the 6-position.

[0025] The cation of the salt (I) is represented by the following formulas (Ic-1) to (Ic-40). Examples of cations include: TIFF0007682029000017.tif209153

[0026] TIFF0007682029000018.tif231163

[0027] TIFF0007682029000019.tif98152

[0028] TIFF0007682029000020.tif115162

[0029] TIFF0007682029000021.tif208167

[0030] In formula (I), X 0 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 carbons, Examples of the -C contained in the aliphatic hydrocarbon group include a hydroxyl group and a group combining these groups. H 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced. 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 18 carbon atoms, and more preferably has 1 to 18 carbon atoms. It is preferably 1 to 12, more preferably 1 to 9, and even more preferably 1 to 6. and more preferably 1 to 4. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, and a butenyl group. isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples of such groups 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. -CH contained in chain hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -To The replaced groups are hydroxy groups (-CH in methyl groups) 2 - to -O- substituted group), carboxy group (-CH contained in ethyl group) 2 -CH 2 -But-OC O-), thiol group (-CH 2 - is placed in -S- substituted groups), alkoxy groups (-CH at any position in the alkyl group) 2 -but,- O- substituted group), alkoxycarbonyl group (any position in the alkyl group) -CH 2 -CH 2 - is replaced by -O-CO-), alkylcarbonyl group (alkoxy group -CH at any position in the alkyl group 2 - is replaced by -CO-), alkyl Carbonyloxy group (-CH at any position in the alkyl group) 2 -CH 2 -But-CO -O- substituted), alkylthio group (-C at any position in the alkyl group) H 2 - is replaced by -S-), alkylsulfonyl group (a group contained in an alkyl group -CH at any position 2 -But-SO2 - substituted groups). Thiol group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkyl Examples of the arylcarbonyloxy group include a thiol group having 1 to 17 carbon atoms and an aryl group having 1 to 17 carbon atoms. alkoxy group, alkoxycarbonyl group having 2 to 17 carbon atoms, alkylcarbonyl group having 2 to 18 carbon atoms As the alkyl group, the alkylcarbonyloxy group having 2 to 17 carbon atoms, and the alkylsulfonyl group, Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, and examples of the alkylsulfonyl groups include the same groups as those mentioned above. The alkylthio group includes an alkylthio group having 1 to 17 carbon atoms, for example, methylthio. Examples of the thio group include an ethylthio group and a propylthio group. The substitution in the alkenyl group and the alkynyl group is the same as that in the alkyl group described above. In the examples of substitutions, a carbon-carbon double bond or a carbon-carbon triple bond at any position is It is sufficient if it includes the above. 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, a cyclobutyl group, or a cyclopropyl 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 the polycyclic cycloalkyl group include the polycyclic cycloalkyl groups represented by the formula: Alicyclic hydrocarbon groups and -CH contained in alicyclic hydrocarbon groups 2 -, -O-, -S-, - CO- or -SO 2 Specific examples of the group substituted with - include the following groups. In the following groups, the attachment site can be at any position. TIFF0007682029000022.tif79161

[0031] TIFF0007682029000023.tif59160X 0 or -CH contained in the alicyclic hydrocarbon group 2 -But -O -, -S-, -CO- or -SO 2 The groups substituted with - include those of the formulae (Y1) to (Y71 ) is preferable, and the groups represented by the formulas (Y1) to (Y20), (Y26), (Y27), A group represented by any one of formulas (Y30), (Y31), (Y39) to (Y71) is preferable. More preferably, the formula (Y3), (Y4), (Y9), (Y11), (Y14), (Y 15), Formula (Y16), Formula (Y20), Formula (Y26), Formula (Y27), Formula (Y30), Formula (Y31), formula (Y39), formula (Y40), formula (y42), formula (y43), formula (Y49) Groups represented by the formulae (Y58) to (Y62) to (Y71) are more preferred. The number of carbon atoms in the hydride group is preferably 3 to 36, more preferably 3 to 24, and further It is preferably 3-18, and more preferably 3-16.

[0032] 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 preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. be. In the case of a combination of groups, the above groups each having a different valence (such as an alkanediyl group, ... cycloalkanetriyl group, alkanetetrayl group, cycloalkanediyl group, cycloalkanetriyl group A cycloalkyl group, a cycloalkanetetrayl group, etc. may be included.

[0033] The combined groups are: A group combining an alicyclic hydrocarbon group and a chain hydrocarbon group (the chain hydrocarbon group and the alicyclic Hydrocarbon groups in the formula -CH 2 - is -O-, -S-, -CO- or -SO 2 -Place may be replaced), A group that combines a chain hydrocarbon group and an aromatic hydrocarbon group (the chain hydrocarbon group -CH 2 - is -O-, -S-, -CO- or -SO 2 -), and A group that combines an alicyclic hydrocarbon group with an aromatic hydrocarbon group (including the alicyclic hydrocarbon group) -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by ) In addition, in the combination, alicyclic hydrocarbon groups, chain hydrocarbon groups and aromatic hydrocarbon groups may be used in combination of two or more of each. Specifically, the combined groups are Alicyclic hydrocarbon groups such as adamantylmethylene groups and cyclohexylmethylene groups - Chain carbonization Hydrogen group-*, (alicyclic hydrocarbon group) 2 -Acyclic hydrocarbon group-* (the acyclic hydrocarbon group and the fatty acid -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Placed (It may be replaced), Chain hydrocarbon groups such as methyladamantyl group, dimethyladamantyl group, etc. - Alicyclic hydrocarbons Group -*, (chain hydrocarbon group) 2 -alicyclic hydrocarbon group-* (the chain hydrocarbon group and the alicyclic -CH contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2-Replaced with (You may know), Aromatic hydrocarbon groups such as tolyl and xylyl groups - Aromatic hydrocarbon groups - * (Aromatic hydrocarbon groups Included in -CH 2 - is -O-, -S-, -CO- or -SO 2 - has been replaced by (also acceptable) Methylcyclohexylmethylene group and other chain hydrocarbon groups - alicyclic hydrocarbon groups - chain hydrocarbon groups Basic group -*, (chain hydrocarbon group) 2 -Alicyclic hydrocarbon group-Acyclic hydrocarbon group-*, (Acyclic carbon Hydrogen group-alicyclic hydrocarbon group) 2 - Acyclic hydrocarbon groups -* (The acyclic hydrocarbon groups and the alicyclic -CH contained in hydrogen radical 2 - is -O-, -S-, -CO- or -SO 2 -Replaced by (It may be possible to Aromatic hydrocarbon groups such as benzyl groups - Chain hydrocarbon groups -* (The chain hydrocarbon groups include -CH 2 - is -O-, -S-, -CO- or -SO 2 -), Aromatic hydrocarbon groups such as tolylmethyl groups - Aromatic hydrocarbon groups - Aromatic hydrocarbon groups - Aromatic hydrocarbon groups -* (The above -CH contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -Replaced with (You may know), Methyladamantane methylene adamantyl group, di(methyladamantane methylene)adamantyl group Manthyl group or 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 -Acyclic hydrocarbon groups-Alicyclic hydrocarbon groups-* , (chain hydrocarbon group)2 -Alicyclic hydrocarbon group-Acyclic hydrocarbon group-Alicyclic hydrocarbon group-*( -CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group 2 - is -O-, -S-, - CO- or -SO 2 -), Alicyclic hydrocarbon group-Acyclic hydrocarbon group-Acyclic hydrocarbon group-Acyclic hydrocarbon group-*, (alicyclic Formula: Hydrocarbon group 2 -Open chain hydrocarbon group-Alicyclic hydrocarbon group-Open chain hydrocarbon group-*, (Alicyclic Hydrocarbon group - Acyclic hydrocarbon group 2 -Alicyclic hydrocarbon group-Acyclic hydrocarbon group-*, (alicyclic carbon Hydrocarbon group-Linear hydrocarbon group-Alicyclic hydrocarbon group) 2 - Acyclic hydrocarbon group -* (The acyclic hydrocarbon group The -CH group contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or - SO 2 -), Acyclic hydrocarbon group - alicyclic hydrocarbon group - acyclic hydrocarbon group - alicyclic hydrocarbon group - acyclic hydrocarbon group Basic group -*, (chain hydrocarbon group) 2 -Alicyclic hydrocarbon group -Open chain hydrocarbon group -Alicyclic hydrocarbon Group-chain hydrocarbon group-*, (chain hydrocarbon group-alicyclic hydrocarbon group) 2 -Acyclic hydrocarbon group- Alicyclic hydrocarbon group-open chain hydrocarbon group-*, (open chain hydrocarbon group-alicyclic hydrocarbon group-open chain Hydrogen radical) 2 -Alicyclic hydrocarbon group-Acyclic hydrocarbon group-*, (Acyclic hydrocarbon group-Alicyclic Hydrogen group - linear hydrocarbon group - alicyclic hydrocarbon group) 2 -A chain hydrocarbon group-* (the chain hydrocarbon group group and the -CH 2 - is -O-, -S-, -CO- or -S O 2 -), Here, * indicates the bond position to the carbon atom of the carbonyl group.

[0034] X 0 The -CH 2 - is -O-, -S-, -CO- or - SO 2 When the substituent is replaced with -, the number of carbon atoms before the replacement is regarded as 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 following formula, the number of carbon atoms before the substitution is The total number of carbon atoms in the hydrocarbon group. X 0 The hydrocarbon group represented by the following formula 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. group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group 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 the group include a group obtained by combining the Examples of halogen atoms include fluorine, chlorine, bromine 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 of the alkyl group include an aryl 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 butyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl oxy 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 the alkylcarbonyloxy group having 2 to 13 carbon atoms is the above-mentioned alkyl or alkoxy group. The aryl group represents a group having a carbonyl group or a carbonyloxy group bonded to the aryl group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy carbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 13 carbon atoms. Examples of the aryl group include an acetyl group, a propionyl group, and a butyryl group, and the like. The alkylcarbonyloxy group of 3 is an acetyloxy group, a propionyloxy group, butyryloxy group and the like. Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the groups shown below. ** represents X 0 represents the bonding position with TIFF0007682029000024.tif17162The aromatic hydrocarbon group having 6 to 10 carbon atoms is an aryl group such as a phenyl group or a naphthyl group. Examples include: The combined group is a combination of a hydroxyl 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 consisting of an alicyclic hydrocarbon group having 3 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms; and groups in which a halogen atom and an alkyl group having 1 to 12 carbon atoms are combined. can be. Examples of the group combining a hydroxyl group and an alkyl group having 1 to 12 carbon atoms include hydroxyl Examples of the hydroxyalkyl group include a methyl group and a hydroxyethyl group, each of which has 1 to 12 carbon atoms. 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, tolyl groups, and xylyl groups. Examples of the alkylaryl groups 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. Examples of the group combining a halogen atom and an alkyl group having 1 to 12 carbon atoms include trifluoro. fluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group Examples of the perfluoroalkyl group include perfluoroalkyl groups having 1 to 12 carbon atoms.

[0035] 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 (-CH contained in the aliphatic hydrocarbon group) 2 - is -O-, -S-, -CO- or -SO 2 ) or a number of carbon atoms which may have a substituent. An aromatic hydrocarbon group having a carbon number of 6 to 36; More preferably, it is a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxyl group. An alicyclic hydrocarbon group which may have a group (the -CH 2 - is -O -, -S-, -CO- or -SO 2 -), an alicyclic hydrocarbon group and a chain hydrocarbon group (the -CH 2 -teeth,- O-, -S-, -CO- or -SO 2 - may be substituted, and the chain hydrocarbon group may Included -CH 2 - may be replaced by -O- or -CO-, and the alicyclic hydrocarbon The alkyl group and the chain hydrocarbon group are each a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or may have a hydroxy group), a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group which may have a hydroxy group, a group represented by formula (aa) or (bb) is a group represented by More preferably, *-alicyclic hydrocarbon group (-CH contained in the alicyclic hydrocarbon group) 2 - is -O-, -S-, -CO- or -SO 2 -, and the alicyclic carbon The hydrogen group has a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group. * is -COO - ), *-alicyclic hydrocarbon group - Acyclic hydrocarbon groups (-CH contained in the alicyclic hydrocarbon groups) 2 - is -O-, -S-, -C O- or -SO 2 - may be replaced by -, and -CH 2 - may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group and the chain carbon The hydrogen group has a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group. * is -COO - ), *-Acyclic hydrocarbon group-Alicyclic Formula hydrocarbon group (-CH contained in the chain hydrocarbon group) 2 - is replaced by -O- or -CO- The -CH contained in the alicyclic hydrocarbon group may be 2 - is -O-, -S-, -C O- or -SO 2 - may be substituted, and the chain hydrocarbon group and the alicyclic hydrocarbon group The group may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group. Good. *-COO -), fluorine atom, phenylene having 1 to 4 carbon atoms. an aromatic hydrocarbon group which may have a fluoroalkyl group or a hydroxyl group, or a group represented by formula (bb): More preferably, the polycyclic alicyclic hydrocarbon group is Included -CH 2 - is -O-, -S-, -CO- or -SO 2 Even if it is replaced with - The polycyclic alicyclic hydrocarbon group is preferably a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, * may have a -COO group or a hydroxyl group. - represents the bond position with the carbon atom of ), *-polycyclic alicyclic hydrocarbon group-chain hydrocarbon group (the polycyclic alicyclic hydrocarbon group Included -CH 2 - is -O-, -S-, -CO- or -SO 2 Even if it is replaced with - The chain hydrocarbon group often contains -CH 2 - is replaced by -O- or -CO- The polycyclic alicyclic hydrocarbon group and the chain hydrocarbon group may each be a fluorine atom, a carbon atom may have up to 4 perfluoroalkyl or hydroxy groups. * is -COO - Carbon ), *-chain hydrocarbon group-polycyclic alicyclic hydrocarbon group (represents the bond position with the chain hydrocarbon group) -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-, -CH contained in cyclic alicyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -, and the chain hydrocarbon group and the polycyclic alicyclic hydrocarbon group are It may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a hydroxy group. *-COO- ), fluorine atom, perfluor having 1 to 4 carbon atoms. an aromatic hydrocarbon group which may have an arylalkyl group or a hydroxyl group, represented by the formula (aa): or a group represented by formula (bb): Particularly preferred are an adamantanone group, a hydroxyadamantyl group, and a combination of an adamantyl group and an adamantanyl group. A group combining an alkyl group (the —CH 2 - is -O- or -CO -), a group represented by the formula (Y30F) or a fluorine atom, It is a phenyl group having 1 to 4 perfluoroalkyl groups or hydroxy groups. In the above groups, the alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably It is preferably 3 to 24, more preferably 3 to 18, and even more preferably 3 to 1 The number of carbon atoms in the chain hydrocarbon group is preferably 6, and more preferably 3 to 12. is 1 to 18, more preferably 1 to 12, even more preferably 1 to 9, More preferably, it is 1 to 6, and even more preferably, it is 1 to 4. The number of carbon atoms is preferably 6 to 36, more preferably 6 to 24, and further preferably Preferably, it is 6 to 18, more preferably 6 to 14, and even more preferably 6 to 1 The value is 0. TIFF0007682029000025.tif26127[In formula (aa), X a and X b each independently represents -O- or -S-. X 1 represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, -CH 2 - is -O-, -S-, -CO- or -SO 2 - It's okay if it's replaced by stomach. X 2 represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, -CH 2 - is -O-, -S-, -CO- or -SO 2 - It's okay if it's replaced by stomach. * -COO - represents the bond position with the carbon atom of [In formula (bb), L A represents an alkanediyl group having 1 to 6 carbon atoms which may have a fluorine atom or a halogen atom A compound having 6 to 14 carbon atoms, which may have a perfluoroalkyl group having 1 to 4 carbon atoms. represents an aromatic hydrocarbon group. L B represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, -CH 2 - is -O-, -S-, -CO- or -SO 2 - It's okay if it's replaced by stomach. R A represents a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, -CH 2 - is -O-, -S-, -CO- or -SO 2 - It's okay if it's replaced by stomach. * -COO - represents the bond position with the carbon atom of

[0036] X a and X b are preferably the same atom, and more preferably are both oxygen atoms. It is.

[0037] X 1a and X 2a Examples of the hydrocarbon group represented by the formula (I) include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and These hydrocarbon groups include substituted or unsubstituted groups, and groups each consisting of two or more of these. In addition, the -CH group contained in these hydrocarbon groups may be 2 -, -O-, -S -, -CO- or -SO 2 - may be substituted. Here, the number of carbon atoms in the hydrocarbon group is The term "substituted" refers to the number of carbon atoms in a hydrocarbon group that has no substituents or is not substituted.

[0038] X 1a Examples of the aliphatic hydrocarbon group include chain hydrocarbon groups such as alkanetriyl groups, alicyclic Examples of the alkyl group include a hydrocarbon group and a combination thereof. Specific examples of the alkanetriyl group include a methine group, an ethanetriyl group, a propanetriyl group, and a cyclohexyl group. Triyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl yl group, octanetriyl group, nonanetriyl group, decanetriyl group, undecanetriyl group Examples of the alkyl group include a cycloalkyl group and a dodecanetriyl group.

[0039] The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclobutanetriyl group, a cyclopentanetriyl group, and a cyclopentanetriyl group. Examples of the alkyl group include a cyclohexyl group, a cyclohexanetriyl group, and a cyclooctanetriyl group. Examples of the polycyclic alicyclic hydrocarbon group include a norbornane triyl group, a norbornane triyl 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 of the aryl group include phenyltriyl group. In the case of a combination of groups, the above groups each having a different valence (alkyl group, alkanediyl group, etc.) aryl group, alkanetetrayl group, cycloalkyl group, cycloalkanediyl group, cycloalkanediyl group, cantetrayl group, etc.) may be included.

[0040] X 1a 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 carbon atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxy group having 2 to 13 carbon atoms Carbonyl group, alkylcarbonyl group having 2 to 13 carbon atoms, alkyl Bonyloxy group, alicyclic hydrocarbon group having 3 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 10 carbon atoms groups or combinations thereof. 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 above.

[0041] X 1a The hydrocarbon group represented by the formula (I) is an alkane having 1 to 6 carbon atoms which may have a substituent. It is preferably a triyl group or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. Preferably, an alkanetriyl group having 1 to 6 carbon atoms, represented by the formulas (w1-1) to (w1-11): More preferably, it is an alkanetriyl group having 1 to 6 carbon atoms, a group represented by the formula (w1-1) or a polycyclic hydrocarbon group such as a group represented by formula (w1-3): or a monocyclic hydrocarbon group such as a group represented by formula (w1-6): I wish. TIFF0007682029000026.tif53143 [Formula (w1-1) to formula (w1-11), The ring may be a hydroxyl group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or a 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 having 6 to 10 carbon atoms, or a combination thereof It may have. * indicates the bond position.]

[0042] X 2a 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 it is further preferable that the ratio is 8 to 40. It is even more preferable, and 10 to 38 is even more preferable.

[0043] X 2a The substituents that the hydrocarbon group may have include a hydroxyl group, a halogen atom, and the like. a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group 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, alicyclic hydrocarbon groups having 3 to 12 carbon atoms, and to 10 aromatic hydrocarbon groups or combinations thereof. Halogen atoms, alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkyl group, alkylcarbonyloxy group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and Examples of the group combining the above include the same groups as above. X 2a The hydrocarbon group having 1 to 48 carbon atoms represented by the formula (I) has one or more substituents. It is okay to do so.

[0044] X 2a The hydrocarbon group in the formula (I) is a straight-chain or branched chain hydrocarbon group (e.g., alkanediyl group, etc.), monocyclic or polycyclic alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. In addition, 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 group and octane-1,8-diyl group; 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 group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Monocyclic cycloalkanediyl group, such as cyclohexene-1,4-diyl group, cyclooctane-1,5-diyl group, etc. a monocyclic alicyclic hydrocarbon group which is an yl group; Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic cycloalkanediyl groups such as 1,5-diyl group and adamantane-2,6-diyl group 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 combination of groups, the above groups each having a different valence (alkyl group, alkanetri group, etc.) yl group, alkanetetrayl group, cycloalkyl group, cycloalkanetriyl group, cyclo An alkanetetrayl group may be included. Examples of the combined group include a group that combines a chain hydrocarbon group and an alicyclic hydrocarbon group; Groups that combine a hydrocarbon group and an aromatic hydrocarbon group, 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, -chain hydrocarbon group-alicyclic hydrocarbon group, -chain hydrocarbon group-(alicyclic Cyclic hydrocarbon group) 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.), groups 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.)

[0045] X 2a As the hydrocarbon group in A chain hydrocarbon group having 2 to 18 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-, and the chain hydrocarbon group may have a substituent. stomach.), Alicyclic hydrocarbon groups having 3 to 18 carbon atoms (-CH contained in the alicyclic hydrocarbon groups) 2 -teeth,- O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a substituent.) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2-Placed (which may have a substituent) It is preferable that A chain hydrocarbon group having 4 to 18 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-, and the chain hydrocarbon group may have a substituent. ) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms (the alicyclic -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Placed (which may have a substituent) It is more preferable that A chain hydrocarbon group having 6 to 14 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-, and the chain hydrocarbon group may have a substituent. ) or A chain hydrocarbon group having 1 to 12 carbon atoms (-CH contained in the chain hydrocarbon group) 2 - is -O- or -CO-) and an alicyclic hydrocarbon group having 5 to 14 carbon atoms (the alicyclic -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Placed (which may have a substituent) It is even more preferable that there is.

[0046] Specifically, X 2a Examples of the hydrocarbon group in An alkanediyl group having 2 to 18 carbon atoms (the —CH 2 -teeth,- The alkanediyl group may be substituted with -O- or -CO-. ) Alicyclic hydrocarbon groups having 3 to 18 carbon atoms (-CH contained in the alicyclic hydrocarbon groups) 2 -teeth,- O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a substituent. An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- ) and an alicyclic hydrocarbon group having 3 to 18 carbon atoms ( The -CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 - (which may have a substituent), or An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- 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 (including —CH 2 - is -O- or -CO - may be replaced by -.) (the group may have a substituent). It is preferred that An alkanediyl group having 4 to 18 carbon atoms (the —CH 2 -teeth,- The alkanediyl group may be substituted with -O- or -CO-. ) An alkanediyl group having 1 to 12 carbon atoms (the —CH 2-teeth,- ) and an alicyclic hydrocarbon group having 3 to 16 carbon atoms ( The -CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 - (which may have a substituent), or An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- 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 (including —CH 2 - is -O- or -CO - may be replaced by -.) (the group may have a substituent). It is more preferable that An alkanediyl group having 6 to 14 carbon atoms (the —CH 2 -teeth,- The alkanediyl group may be substituted with -O- or -CO-. ) An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- may be replaced by -O- or -CO-.) and an adamantanediyl group (the adamantane -CH contained in the phenyl group 2 - may be replaced by -O- or -CO-. (The group may have a substituent.) Or An alkanediyl group having 1 to 12 carbon atoms (the —CH 2 -teeth,- may be replaced by -O- or -CO-.) and an adamantanediyl group and a C1-C1 2 alkyl group (-CH 2- is replaced by -O- or -CO- and (the group may have a substituent). Even more preferred.

[0047] 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. TIFF0007682029000027.tif34158[In the formula, R 1x , R 2x , R 3x , R 4x , R 5x and R 6x each independently represents an alkyl group having 1 to 6 carbon atoms; an alkyl group, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination of two or more of these groups group, and the alkyl group and the alicyclic hydrocarbon group each represent a -CH 2 -, -O-, -S -, -CO- or -SO 2 -, and the alkyl group and the alicyclic carbon atom may be replaced by -. 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 the above-mentioned alkyl group and alicyclic hydrocarbon group are combined one by one. The group may be a combination of two or more of either one or two or more of both. The combined carbon number of the groups is 39 or less, preferably 37 or less.

[0048] Among them, R 1x , R 2x , R 3x , R 4x , R 5x and R 6xAs for the carbon number 1-6, alkyl group (the alkyl group contains -CH 2 - is replaced by -O- or -CO- The alkyl group may have a substituent. Hydrocarbon groups (-CH contained in the alicyclic hydrocarbon group) 2 - is -O-, -S-, -CO- or -SO 2 -, and the alicyclic hydrocarbon group may have a substituent. ) or an alkyl group having 1 to 6 carbon atoms (the —CH 2 - is -O- or may be replaced by -CO-) and an alicyclic hydrocarbon group having 5 to 12 carbon atoms (the alicyclic Hydrocarbon groups in the formula -CH 2 - is -O-, -S-, -CO- or -SO 2 -Place and a group which may have a substituent. It is preferable that the methoxy group, the 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 —CH 2 - 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).

[0049] In formula (bb), L A and L B As the alkanediyl group having 1 to 6 carbon atoms, For example, a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, linear alkanes such as 1,5-pentanediyl, 1,6-hexanediyl, etc. Diyl group; propane-1,2-diyl group, 1-methylpropane-1,3-diyl group, 2- Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methyl Branched alkanes such as butan-1,4-diyl and 2-methylbutan-1,4-diyl The number of carbon atoms in the alkanediyl group is preferably 1 to 4, and more preferably 1 to 4. Preferably, it is 1 to 3. Examples of the alkanediyl group which may have a fluorine atom include a difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group, and and perfluoroalkanediyl groups such as perfluoropentanediyl group. L B -CH contained in the alkanediyl group 2 - is -O-, -S-, -CO- or -S O 2 When the alkanediyl group is substituted with -, the number of carbon atoms before the substitution is the total number of carbon atoms of the alkanediyl group. The alkanediyl group is a hydroxy group (-CH contained in a methyl group). 2 -But -O - substituted), carboxy group (-CH contained in ethyl group) 2 -CH 2 -But -O -CO- replaced group), thiol group (-CH 2 -But-S- ), alkoxy group (groups replaced by -CH at any position in the alkyl group) 2 -but , -O- substituted), alkoxycarbonyl group (any group contained in an alkyl group Position -CH 2 -CH 2 - is replaced by -O-CO-), alkylcarbonyl group ( -CH at any position in the alkyl group 2- is replaced by -CO-), alkylcarbonyloxy group (-CH at any position in the alkyl group) 2 -CH 2 -but,- CO-O- substituted), alkanediyloxy group (a group contained in an alkanediyl group) -CH at any position 2 - is replaced by -O-), alkanediyloxycarbo -nyl group (-CH at any position in the alkanediyl group) 2 -CH 2 -But -O-CO- ) an alkanediylcarbonyl group (any group contained in an alkanediyl group) -CH position 2 - is replaced by -CO-), alkylthio group (alkyl group -CH at any position 2 - is replaced by -S-), alkylsulfonyl group (-CH at any position in the alkyl group) 2 -But-SO 2 - substituted groups), Alkanediylcarbonyloxy group (-CH at any position contained in the alkanediyl group) 2 -CH 2 - is replaced by -CO-O-) alkanediylthio group (alkanediyl -CH at any position in the group 2 - is replaced by -S-), alkanediyl Sulfonyl group (-CH at any position in the alkanediyl group) 2 -But-SO 2 -To The aryl group may have a substituted group. Thiol group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkyl The alkylcarbonyloxy group, alkylthio group and alkylsulfonyl group are the same as those mentioned above. Can be obtained. Examples of the alkanediyloxy group include a methyleneoxy group, an ethyleneoxy group, a propanediyloxy group, and a propyleneoxy group. propanediyloxy group, butanediyloxy group, pentanediyloxy group, etc. . Examples of the alkanediylthio group include a methylenethio group, an ethylenethio group, and a propanediylthio group. Examples thereof include a diylthio group, a butanediylthio group, and a pentanediylthio group. Examples of the alkanediylsulfonyl group include a methylenesulfonyl group and an ethylenesulfonyl group. propanediylsulfonyl group, butanediylsulfonyl group, pentanediylsulfonyl group Examples thereof include a sulfonyl group. Examples of the alkanediyloxycarbonyl group include a methyleneoxycarbonyl group, Ethyleneoxycarbonyl group, propanediyloxycarbonyl group, butanediyloxy Examples thereof include a carbonyl group. Examples of the alkanediylcarbonyl group include a methylenecarbonyl group and an ethylenecarbonyl group. bonyl group, propanediylcarbonyl group, butanediylcarbonyl group, pentanediylcarbonyl group Examples include a carbonyl group. Examples of the alkanediylcarbonyloxy group include a methylenecarbonyloxy group, Ethylenecarbonyloxy group, propanediylcarbonyloxy group, butanediylcarbonyloxy group Examples of the aryl group include an aryloxy group. L A Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenylene group, Arylene groups such as phenylene groups, anthrylene groups, biphenylene groups, and phenanthrylene groups The aromatic hydrocarbon group preferably has 6 to 10 carbon atoms. and more preferably 6. L A Examples of the halogen atom that may be contained in the ring include a fluorine atom, a chlorine atom, a bromine atom, and Examples include an iodine atom. L A The perfluoroalkyl group having 1 to 4 carbon atoms that may be contained in fluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group groups, etc. L A represents an alkanediyl group having 1 to 4 carbon atoms which may have a fluorine atom or a halogen atom A compound having 6 to 10 carbon atoms, which may have a perfluoroalkyl group having 1 to 4 carbon atoms. The aromatic hydrocarbon group is preferably an alkane having 1 to 3 carbon atoms and a fluorine atom. A diyl group, a fluorine atom, an iodine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms It is more preferably a phenylene group which may be present. L B is a single bond or an alkanediyl group having 1 to 3 carbon atoms (the alkanediyl group -CH 2 - may be replaced by -O- or -CO-, A single bond, a methylene group or an ethylene group is more preferred.

[0050] R A The hydrocarbon group in the above is an aliphatic hydrocarbon group (alkyl group, alkenyl group, Aromatic hydrocarbon groups and the like, Examples of the groups include groups formed by combining The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, Examples of the alkyl group include an n-undecyl group and an n-dodecyl group. The number of carbon atoms in the alkyl group is preferably It is 1 to 18, more preferably 1 to 12, even more preferably 1 to 9, and even more preferably It is more preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, and a butenyl group. isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples of such groups 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. -CH contained in chain hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -To The substituted groups include hydroxyl groups, carboxyl groups, alkoxy groups, alkoxycarbyl groups, and carboxyl groups. aryl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkylthio groups, and a Examples thereof include an alkylsulfonyl group. Alkoxy group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyl Examples of the oxy group and alkylthio group include an alkoxy group having 1 to 17 carbon atoms, Alkoxycarbonyl groups having 2 to 17 carbon atoms, alkylcarbonyl groups having 2 to 18 carbon atoms, an alkylcarbonyloxy group having 1 to 17 carbon atoms, an alkylthio group having 1 to 17 carbon atoms, and Examples of alkylsulfonyl groups include the 17 alkylsulfonyl groups, and include the same groups as those described above. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spiro rings, and may be saturated or The monocyclic alicyclic hydrocarbon group may be, for example, cyclopropyl. group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo Monocyclic cycloalkyl groups such as octyl, cyclononyl, cyclodecyl, and cyclododecyl groups Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl. Examples of polycyclic cycloalkyl groups include polycyclic cycloalkyl groups such as adamantyl group and norbornyl group. Alicyclic hydrocarbon groups and -CH contained in alicyclic hydrocarbon groups 2 -, -O-, -S-, - CO- or -SO 2 Specific examples of the group substituted with - include the groups represented by the above formulae (y1) to (y7 The alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms. It is more preferably 3 to 24, even more preferably 3 to 18, and even more preferably It is preferably 3 to 16, and even more preferably 3 to 12. 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 preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. be. In the case of a combination of groups, the above groups each having a different valence (such as an alkanediyl group, ... cycloalkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) Good too. The group formed by the combination is an aromatic hydrocarbon group and a chain hydrocarbon group. A group that combines (for example, aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic aromatic hydrocarbon group-*), groups combining alicyclic and chain hydrocarbon groups (e.g. , alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), aromatic A group that combines an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., an aromatic hydrocarbon group-alicyclic Cyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). Represents the binding site. Aromatic hydrocarbon groups - alkanediyl groups -* include aryl groups such as benzyl and phenethyl groups. Examples include ralkyl groups. Examples of alkyl groups - aromatic hydrocarbon groups -* include tolyl groups, xylyl groups, and cumenyl groups. Some examples include: Alicyclic hydrocarbon groups - alkanediyl groups - * include cyclohexylmethyl groups, cyclohexylmethyl groups, Hexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 -1-methylethyl, and the like. Examples of alkyl groups - alicyclic hydrocarbon groups -* include methylcyclohexyl, dimethylcyclohexyl, cyclohexyl group, 2-alkyladamantan-2-yl group, etc. Examples of the alkyl groups include alkyl groups. Examples of aromatic hydrocarbon groups - alicyclic hydrocarbon groups -* include phenyladamantyl groups. can be done. Alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include adamantylphenyl groups, etc. can be done. In addition, in the combination, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups are In addition, any of the groups L may be a combination of two or more. B It may be bound to stomach. -CH contained in the hydrocarbon group 2 - is -O-, -S-, -CO- or -SO 2 -Place In addition to the above-mentioned groups, the substituted groups include cycloalkoxy groups, cycloalkylalkoxy groups, and the like. Aromatic hydrocarbon group-carbonyloxy group, alkoxycarbonyloxy group, Also included are groups formed by combining two or more of the groups listed above. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms. Examples of the cycloalkylalkoxy group include a cyclohexyloxy group. and cycloalkylalkoxy groups having a carbon number of 4 to 17, such as cyclohexylmethoxy. The alkoxycarbonyloxy group includes an alkoxy group having 2 to 16 carbon atoms. Examples of the aryloxy group include butoxycarbonyloxy groups. The aromatic hydrocarbon group-carbonyloxy group is an aromatic hydrocarbon group having 7 to 17 carbon atoms. Examples of the group include a carbonyloxy group, such as a benzoyloxy group. -CH contained in the hydrocarbon group 2 -, -O-, -S-, -SO 2 - or -CO- When the carbon atom is replaced, the number of carbon atoms before the replacement is regarded as the total number of carbon atoms of the hydrocarbon group. The number may be one or may be two or more.

[0051] R A The substituents which the hydrocarbon group may have include halogen atoms, cyano groups, carbon atoms, An alkyl group having a number of 1 to 12 (the —CH 2 - is -O-, -S-, -C O- or -SO 2 - may be substituted). Examples of the halogen atom include the same groups as those mentioned above. Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as those mentioned above. -CH in the alkyl group 2 Examples of the group in which - is replaced by -O- or -CO- include: Hydroxy group, carboxy group, alkoxy group, alkoxycarbonyl group, alkylcarbonyl group Examples of the alkyl group include an aryl group and an alkylcarbonyloxy group. Alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups and alkylcarbonyl groups The alkoxy group may be an alkoxy group having 1 to 11 carbon atoms, an alkoxy group having 2 to 11 carbon atoms, carboxyl group, alkylcarbonyl group having 2 to 12 carbon atoms, alkylcarbonyl group having 2 to 11 carbon atoms Examples of the alkyl group include an aryloxy group, and examples of the alkyl group include the same groups as those mentioned above. R A The hydrocarbon group in may have one or more substituents.

[0052] R A The hydrocarbon group in the formula (I) is an alkyl group having 1 to 12 carbon atoms which may have a substituent. (However, the —CH 2 - is -O-, -S-, -CO- or -SO 2 -) or a cyclic hydrocarbon having 3 to 18 carbon atoms which may have a substituent. A cyclic hydrocarbon group (wherein the -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be substituted.) is preferred, and a fluorine atom, a hydroxyl atom, A cyclic hydrocarbon group having 3 to 18 carbon atoms, which may have a silyl group or an alkyl group having 1 to 6 carbon atoms (but The cyclic hydrocarbon group is preferably -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by.) is preferred.

[0053] Examples of the cyclic hydrocarbon group include monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 18 carbon atoms and A cyclic hydrocarbon group such as an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination of these groups etc. The alicyclic hydrocarbon group, aromatic hydrocarbon group, and combined group are the same as those described above. Some examples include: In the combination, two or more types of alicyclic hydrocarbon groups and two or more types of aromatic hydrocarbon groups may be used. The above may be combined. B may be bound to

[0054] A cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group is a fluorine atom, a hydroxyl group or may have an alkyl group having 1 to 6 carbon atoms, and the -CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by . A fluorine atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Alicyclic hydrocarbon groups of 8 (-CH contained in the alicyclic hydrocarbon groups) 2 - is -O-, -S-, -CO- or -SO 2 -), or A compound having 6 to 1 carbon atoms, which may have a fluorine atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms. 8 is preferably an aromatic hydrocarbon group, A fluorine atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. Alicyclic hydrocarbon groups of 8 (-CH contained in the alicyclic hydrocarbon groups) 2 - is -O- or -CO - (which may be replaced by -) is more preferred. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, Cyclohexyl group, norbornyl group, adamantyl group, the following groups (binding site is arbitrary position) The aromatic hydrocarbon group is preferably a phenyl group or a naphthyl group. TIFF0007682029000028.tif1687

[0055] The carboxylate anion in the carboxylate salt represented by formula (I) may be any of the following: carboxylate anion and the like. TIFF0007682029000029.tif140162

[0056] TIFF0007682029000030.tif78134

[0057] TIFF0007682029000031.tif167141

[0058] TIFF0007682029000032.tif89154

[0059] TIFF0007682029000033.tif155143

[0060] TIFF0007682029000034.tif218160

[0061] TIFF0007682029000035.tif174160

[0062] Specific examples of the carboxylate (I) include the above-mentioned cations and carboxylate anions. Specific examples of the carboxylate (I) are shown in the table below. In the table below, each symbol is attached to the structure representing the above-mentioned carboxylate anion or cation. The symbol "~" indicates that the carboxylate (I) and the anion (I) correspond to each other. For example, the carboxylate (I-1) is an anion represented by the formula (Ia-1): and a cation represented by the formula (Ic-1), and the carboxylate (I-2) is a salt represented by the formula ( A salt consisting of an anion represented by formula (Ia-2) and a cation represented by formula (Ic-1), Carboxylate (I-96) is a compound represented by the formula (Ia-1) and an anion represented by the formula (Ic-2) and a cation represented by the formula: TIFF0007682029000036.tif25125 [Table 1]

[0063] Among them, the carboxylate (I) is preferably a carboxylate represented by the formula (Ia-1) to the formula (Ia-5), Formulae (Ia-10) to (Ia-21) and Formulae (Ia-57) to (Ia-66) and an anion represented by any one of formulas (Ic-1) to (Ic-40): The salts of the cations are preferably carboxylates (I-1) to carboxylates (I-2). Carboxylic acid salt (I-5), Carboxylic acid salt (I-10) ~ Carboxylic acid salt (I-21), Carboxylic acid salt (I- 57)~Carboxylic acid salt (I-66), Carboxylic acid salt (I-96)~Carboxylic acid salt (I-100) , Carboxylic acid salt (I-105) ~ Carboxylic acid salt (I-116), Carboxylic acid salt (I-152) ~ Carboxylic acid salt (I-161), Carboxylic acid salt (I-191) ~ Carboxylic acid salt (I-195), Carboxylic Acid Salt (I-200) ~ Carboxylic Acid Salt (I-211) Carboxylic Acid Salt (I-247) ~ Carboxylic Acid Salt (I-211) Carboxylic acid salt (I-256), carboxylate (I-286) ~ carboxylate (I-290), carboxylate Salt (I-295) ~ Carboxylic Acid Salt (I-306), Carboxylic Acid Salt (I-342) ~ Carboxylic Acid Salt (I-351), Carboxylic Acid Salt (I-381) ~ Carboxylic Acid Salt (I-385), Carboxylic Acid Salt ( I-390)~Carboxylic acid salt (I-401), Carboxylic acid salt (I-437)~Carboxylic acid salt (I -446), Carboxylic acid salt (I-476) ~ Carboxylic acid salt (I-480) Carboxylic acid salt (I-4 85)~Carboxylic acid salt (I-496), Carboxylic acid salt (I-532)~Carboxylic acid salt (I-54 1), Carboxylic acid salt (I-571) ~ Carboxylic acid salt (I-575), Carboxylic acid salt (I-580) )~Carboxylic acid salt (I-591), Carboxylic acid salt (I-627)~Carboxylic acid salt (I-636) , Carboxylic Acid Salt (I-666) ~ Carboxylic Acid Salt (I-670), Carboxylic Acid Salt (I-675) ~ Carboxylic acid salt (I-686), Carboxylic acid salt (I-722) ~ Carboxylic acid salt (I-731), Carboxylic acid salt (I-761) ~ Carboxylic acid salt (I-765), Carboxylic acid salt (I-770) ~ Carboxylic acid salt (I-770) Carboxylic acid salt (I-781), carboxylic acid salt (I-817) ~ carboxylic acid salt (I-826), carbo Carboxylic Acid Salt (I-856) ~ Carboxylic Acid Salt (I-860), Carboxylic Acid Salt (I-865) ~ Carboxylic Acid Salt (I-865) Salt (I-876), Carboxylic Acid Salt (I-912) ~ Carboxylic Acid Salt (I-921), Carboxylic Acid Salt (I-951)~Carboxylic acid salt (I-955), Carboxylic acid salt (I-960)~Carboxylic acid salt ( I-971), Carboxylic Acid Salt (I-1007) ~ Carboxylic Acid Salt (I-1016), Carboxylic Acid Salt (I-1046)~Carboxylic acid salt (I-1050), Carboxylic acid salt (I-1055)~Carboxylic acid salt Carboxylic acid salt (I-1102) ~ Carboxylic acid salt (I-1111), Lubricant salt (I-1141) ~ Carboxylic acid salt (I-1145), Carboxylic acid salt (I-1150) ~Carboxylic acid salt (I-1161), Carboxylic acid salt (I-1197) ~ Carboxylic acid salt (I-120 6), Carboxylic acid salt (I-1236) ~ Carboxylic acid salt (I-1240), Carboxylic acid salt (I-1 245)~Carboxylic acid salt (I-1256), Carboxylic acid salt (I-1292)~Carboxylic acid salt (I -1301), Carboxylic Acid Salt (I-1331) ~ Carboxylic Acid Salt (I-1335), Carboxylic Acid Salt (I-1340)~Carboxylic acid salt (I-1351), Carboxylic acid salt (I-1387)~Carboxylic acid salt Carboxylic acid salt (I-1426)~Carboxylic acid salt (I-1430), Lubricant (I-1435) ~ Carboxylic acid salt (I-1446), Carboxylic acid salt (I-1482) ~Carboxylic acid salt (I-1491), Carboxylic acid salt (I-1521) ~ Carboxylic acid salt (I-152 5), Carboxylic acid salt (I-1530) ~ Carboxylic acid salt (I-1541), Carboxylic acid salt (I-1 577)~Carboxylic acid salt (I-1586), Carboxylic acid salt (I-1616)~Carboxylic acid salt (I -1620), Carboxylic Acid Salt (I-1625) ~ Carboxylic Acid Salt (I-1636), Carboxylic Acid Salt (I-1672)~Carboxylic acid salt (I-1681), Carboxylic acid salt (I-1711)~Carboxylic acid salt Carboxylic acid salt (I-1715), carboxylate (I-1720) ~ carboxylate (I-1731), Lubricant salt (I-1767) ~ Carboxylic acid salt (I-1776), Carboxylic acid salt (I-1806) ~Carboxylic acid salt (I-1810), Carboxylic acid salt (I-1815) ~ Carboxylic acid salt (I-182 6), Carboxylic acid salt (I-1862) ~ Carboxylic acid salt (I-1871), Carboxylic acid salt (I-1 901)~Carboxylic acid salt (I-1905), Carboxylic acid salt (I-1910)~Carboxylic acid salt (I -1921), Carboxylic acid salt (I-1957)~Carboxylic acid salt (I-1966), Carboxylic acid salt (I-1996)~Carboxylic acid salt (I-2000), Carboxylic acid salt (I-2005)~Carboxylic acid salt Carboxylic acid salt (I-2016), carboxylate salt (I-2052) ~ carboxylate salt (I-2061), Lubricant salt (I-2091) ~ Carboxylic acid salt (I-2095), Carboxylic acid salt (I-2100) ~Carboxylic acid salt (I-2111), Carboxylic acid salt (I-2147) ~ Carboxylic acid salt (I-215 6), Carboxylic acid salt (I-2186) ~ Carboxylic acid salt (I-2190), Carboxylic acid salt (I-2 195)~Carboxylic acid salt (I-2206), Carboxylic acid salt (I-2242)~Carboxylic acid salt (I -2251), Carboxylic Acid Salt (I-2281) ~ Carboxylic Acid Salt (I-2285), Carboxylic Acid Salt (I-2290)~Carboxylic acid salt (I-2301), Carboxylic acid salt (I-2337)~Carboxylic acid salt Carboxylic acid salt (I-2346), carboxylate (I-2376) ~ carboxylate (I-2380), Lubricant salt (I-2385) ~ Carboxylic acid salt (I-2396), Carboxylic acid salt (I-2432) ~Carboxylic acid salt (I-2441), Carboxylic acid salt (I-2471) ~ Carboxylic acid salt (I-247 5), Carboxylic acid salt (I-2480) ~ Carboxylic acid salt (I-2491), Carboxylic acid salt (I-2 527)~Carboxylic acid salt (I-2536), Carboxylic acid salt (I-2566)~Carboxylic acid salt (I -2570), Carboxylic Acid Salt (I-2575) ~ Carboxylic Acid Salt (I-2586), Carboxylic Acid Salt (I-2622)~Carboxylic acid salt (I-2631), Carboxylic acid salt (I-2661)~Carboxylic acid salt Carboxylic acid salt (I-2665), carboxylate (I-2670) ~ carboxylate (I-2681), Lubricant salt (I-2717) ~ Carboxylic acid salt (I-2726), Carboxylic acid salt (I-2756) ~Carboxylic acid salt (I-2760), Carboxylic acid salt (I-2765) ~ Carboxylic acid salt (I-277 6), Carboxylic acid salt (I-2812) ~ Carboxylic acid salt (I-2821), Carboxylic acid salt (I-2 851)~Carboxylic acid salt (I-2855), Carboxylic acid salt (I-2860)~Carboxylic acid salt (I -2871), Carboxylic Acid Salt (I-2907) ~ Carboxylic Acid Salt (I-2916), Carboxylic Acid Salt (I-2946)~Carboxylic acid salt (I-2950), Carboxylic acid salt (I-2955)~Carboxylic acid salt Carboxylic acid salt (I-3002)~Carboxylic acid salt (I-3011), Lubricant salt (I-3041) ~ Carboxylic acid salt (I-3045), Carboxylic acid salt (I-3050) ~Carboxylic acid salt (I-3061), Carboxylic acid salt (I-3097) ~ Carboxylic acid salt (I-310 6), Carboxylic acid salt (I-3136) ~ Carboxylic acid salt (I-3140), Carboxylic acid salt (I-3 145)~Carboxylic acid salt (I-3156), Carboxylic acid salt (I-3192)~Carboxylic acid salt (I -3201), Carboxylic Acid Salt (I-3231) ~ Carboxylic Acid Salt (I-3235), Carboxylic Acid Salt (I-3240) ~ Carboxylic acid salt (I-3251), Carboxylic acid salt (I-3287) ~ Carboxylic acid salt Carboxylic acid salt (I-3296), carboxylate (I-3326) ~ carboxylate (I-3330), Lubricant salt (I-3335) ~ Carboxylic acid salt (I-3346), Carboxylic acid salt (I-3382) ~Carboxylic acid salt (I-3391), Carboxylic acid salt (I-3421) ~ Carboxylic acid salt (I-342 5), Carboxylic acid salt (I-3430) ~ Carboxylic acid salt (I-3441), Carboxylic acid salt (I-3 477)~Carboxylic acid salt (I-3486), Carboxylic acid salt (I-3516)~Carboxylic acid salt (I -3520), Carboxylic Acid Salt (I-3525) ~ Carboxylic Acid Salt (I-3536), Carboxylic Acid Salt (I-3572) ~ Carboxylic acid salt (I-3581), Carboxylic acid salt (I-3611) ~ Carboxylic acid salt Carboxylic acid salt (I-3615), carboxylate salt (I-3620) ~ carboxylate salt (I-3631), Lubricant salt (I-3667) ~ Carboxylic acid salt (I-3676), Carboxylic acid salt (I-3706) ~Carboxylic acid salt (I-3710), Carboxylic acid salt (I-3715) ~ Carboxylic acid salt (I-372 6), carboxylate (I-3762) to carboxylate (I-3771) are preferred.

[0064] <Method for producing salt (I)> The salt (I) can be prepared by dissolving a salt represented by formula (Ia) and a salt represented by formula (Ib) in a solvent. It can be produced by reacting TIFF0007682029000038.tif70163 [wherein all symbols have the same meanings as defined above. 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 together to form an aromatic ring. D is a hydrogen atom or a carbon atom represents a hydrocarbon group having a molecular weight of from 1 to 12. Solvents for this reaction include chloroform, acetonitrile, ion-exchanged water, etc. Can be obtained. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0065] 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 US Pat. No. 367, and include salts represented by the following formula: Examples include: TIFF0007682029000039.tif133164

[0066] In the salt (Ia), R 1 and R 2 But, -OL 1 -CO-OR 10 A salt (of formula The salt represented by formula (I-a1) is a compound represented by formula (Ic) and a compound represented by formula (Id). The compound can be produced by reacting the compound with the compound in a solvent in the presence of a base catalyst. TIFF0007682029000040.tif66163 [wherein all symbols have the same meanings as defined above.] Examples of bases include potassium carbonate, potassium iodide, pyridine, and triethylamine. Can be obtained. Solvents include chloroform, monochlorobenzene, dimethylformamide, and acetonitrile. tolyl, ethyl acetate, water, etc. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0067] The compound represented by formula (Id) may be, for example, the compound represented by the following formula: It can be easily obtained from the market and can also be easily produced by known methods. . TIFF0007682029000041.tif29107

[0068] The salt represented by formula (Ic) is a salt represented by formula (Ie) and a salt represented by formula (I-f1). The compound represented by formula (I-f2) is reacted with a compound represented by formula (I-f2) in a solvent in the presence of a catalyst. It can be produced by the following steps. TIFF0007682029000042.tif70161 [wherein all symbols have the same meanings as defined above.] The catalyst includes potassium carbonate, sodium hydride, and the like. Solvents include chloroform, monochlorobenzene, acetonitrile, water, etc. can be. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours. .

[0069] Examples of the salt represented by formula (Ie) include the salt represented by the following formula, which is readily available on the market. These compounds are readily available and can be easily produced by known methods. TIFF0007682029000043.tif41152

[0070] The compounds represented by formula (I-f1) and (I-f2) include the following: and the like, which are readily available on the market. TIFF0007682029000044.tif20104

[0071] The salt represented by formula (Ic) is a salt represented by formula (Ie) and a salt represented by formula (I-f4): The compound represented by formula (I-f5) is reacted in a solvent in the presence of potassium carbonate. It is also possible to produce the compound by reacting the compound and then treating it with an acid. TIFF0007682029000045.tif76155 [wherein all symbols have the same meanings as defined above. R ac represents an acid labile group. Solvents include chloroform, monochlorobenzene, acetonitrile, water, etc. can be. The reaction temperature is usually 15°C to 100°C, and the reaction time is usually 0.5 to 24 hours. . The acid includes p-toluenesulfonic acid, hydrochloric acid, and the like.

[0072] The compounds represented by formula (I-f4) and (I-f5) include the following: and the like, which are readily available on the market. TIFF0007682029000046.tif84154

[0073] In the salt (Ia), R 1 and R 2 But -OR 10 A salt represented by formula (I-a2) The salt represented by formula (Ic) and the compound represented by formula (I-d2) are reacted with a base It can be produced by reacting in a solvent in the presence of a catalyst. TIFF0007682029000047.tif66159 [wherein all symbols have the same meanings as defined above.] The base includes sodium hydroxide, potassium hydroxide, and the like. Solvents include chloroform, monochlorobenzene, dimethylformamide, and acetonitrile. tolyl, ethyl acetate, water, etc. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0074] Examples of the compound represented by formula (I-d2) include the compounds represented by the following formula: It is readily available on the market and can be easily produced by known methods. do. TIFF0007682029000048.tif2297

[0075] In the salt (Ia), R 1 and R 2 But -O-CO-OR 10 A salt of the formula (I- a3)) is a salt represented by formula (Ic) and a compound represented by formula (I-d2) and in the presence of carbonyldiimidazole in a solvent. can. TIFF0007682029000049.tif69163 [wherein all symbols have the same meanings as defined above.] Solvents include chloroform, monochlorobenzene, dimethylformamide, and acetonitrile. tolyl, ethyl acetate, water, etc. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0076] In the salt (Ia), R 1 and R 2 And, -O-CO-R 10 A salt of the formula (Ia The salt represented by formula (I-d4) is a salt represented by formula (Ic) and a compound represented by formula (I-d4): can be produced by reacting in a solvent in the presence of a base catalyst. TIFF0007682029000050.tif64167 [wherein all symbols have the same meanings as defined above.] Examples of bases include potassium carbonate, potassium iodide, pyridine, and triethylamine. Can be obtained. Solvents include chloroform, monochlorobenzene, dimethylformamide, and acetonitrile. tolyl, ethyl acetate, water, etc. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0077] Examples of the compound represented by formula (I-d4) include the compounds represented by the following formula: It is readily available on the market and can be easily produced by known methods. do. TIFF0007682029000051.tif2996

[0078] [Carboxylic Acid Generator] The carboxylic acid generator of the present invention is an acid generator containing a carboxylate (I). The carboxylate (I) can act as an acid generator in a resist composition. When the carboxylate (I) is used as an acid generator in the resist composition, may contain only one type or two or more types of carboxylates (I). In addition, the carboxylic acid generator of the present invention may be a residue other than the carboxylate (I), as described below. An acid generator known in the art (hereinafter sometimes referred to as "acid generator (B)") and / or a catalyst The resist composition may further contain a carboxylic acid generator other than the carboxylate (I) that is known in the resist field. The acid generator (B) may be used alone or in combination of two or more kinds. When the carboxylic acid generator of the present invention contains an acid generator (B) or the like, the carboxylic acid salt (I) and the content ratio of the acid generator (B) etc. (mass ratio; carboxylate (I):acid generator (B)), etc. is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2: The ratio is preferably 98 to 98:2, and more preferably 5:95 to 95:5.

[0079] [Resist Composition] The resist composition comprises a carboxylic acid generator containing the carboxylate (I) of the present invention and a carboxylate. An acid generator (B) other than the carboxylate (I) and a resin having an acid labile group (hereinafter referred to as "resin (A)") The term "acid labile group" as used 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 hydroxyl group or a carboxyl group). means a group which The resist composition further contains a quencher (hereinafter sometimes referred to as “quencher (C)”). It is preferable that the composition contains a solvent (hereinafter, sometimes referred to as "solvent (E)"). stomach.

[0080] <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. disulfone, ketone Examples of ionic acid generators include oni Onium salts containing ion cations (e.g. diazonium salts, phosphonium salts, sulfonium salts) The anion of the onium salt is typically a sulfonate anion. ion, sulfonylimide anion, sulfonylmethide anion, etc.

[0081] Examples of the acid generator (B) include those described in JP-A-63-26653 and JP-A-55-164824. JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate an acid when exposed to radiation, such as those described in US Pat. No. 5,312,712, can be used. In addition, a compound produced by a known method may be used. The acid generator (B) may be a compound containing two or more kinds of compounds. They may also be used in combination.

[0082] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)"). TIFF0007682029000052.tif2962[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms; It represents a aryl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CH 2 - may be replaced by -O- or -CO-, and the divalent saturated carbon atom A hydrogen atom contained in the hydrogen group may be substituted with a fluorine atom or a hydroxy group. Y is a methyl group which may have a substituent or a methyl group having 3 to 2 carbon atoms which may have a substituent. 4, and the -CH 2 -, -O-, - SO 2 It may be replaced by - or -CO-. Z + represents an organic cation.

[0083] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) is a trifluoromethyl group, a perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a perfluorohexyl group and a perfluorohexyl group. Q b1 and Q b2 are each independently a fluorine atom or a trifluoromethyl group. It is preferable that both are fluorine atoms.

[0084] L b1 The divalent saturated hydrocarbon group in the formula (I) is a straight-chain alkanediyl group, a branched alkanediyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A group formed by combining two or more of these may also be used. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- Linear alkanediyl groups such as diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group branched alkanediyl groups such as 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-1,4-diyl group and cyclooctane-1,5-diyl group a monocyclic divalent alicyclic saturated hydrocarbon group, Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like.

[0085] L b1 -CH contained in a divalent saturated hydrocarbon group represented by 2 - is replaced by -O- or -CO-. The replaced group is, for example, a group represented by any one of formulas (b1-1) to (b1-3). The groups represented by formulae (b1-1) to (b1-3) and their specific examples are In the examples of the groups represented by formulae (b1-4) to (b1-11), * and ** indicate the bond positions. and * represents the bonding position with -Y.

[0086] TIFF0007682029000053.tif26117 [In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atom contained in 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 saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-. However, L b6 and L b7The total number of carbon atoms is 23 or less.

[0087] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group -CH 2 When - 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 of the above. do.

[0088] 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, The hydrogen atoms contained in the radicals 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 hydride 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, A hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The divalent saturated hydrocarbon group contains -CH 2 - is replaced by -O- or -CO- Good too.

[0089] L b1 -CH contained in a divalent saturated hydrocarbon group represented by 2 - is replaced by -O- or -CO-. The replaced group is preferably a group represented by formula (b1-1) or formula (b1-3).

[0090] The group represented by formula (b1-1) is preferably any of the groups represented by formulas (b1-4) to (b1-8). Examples of such groups include those mentioned above. TIFF0007682029000054.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atom contained in 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, -CH 2 - 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 atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. 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 atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. 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 b14represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. 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, Included -CH 2 - may be replaced by -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 atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b16 ~L b18 The total number of carbon atoms is 19 or less.

[0091] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms is preferred. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12is 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, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms is preferred. 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, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms is preferred.

[0092] The group represented by formula (b1-3) is represented by formulas (b1-9) to (b1-11), Examples of the groups include those represented by the following formula: TIFF0007682029000055.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 alkylcarbonyloxy group may be substituted. 2 - is -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by 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 alkylcarbonyloxy group may be substituted. 2 - is -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by 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 alkylcarbonyloxy group may be substituted. 2 - is -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by 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.

[0093] In addition, in the groups represented by formulae (b1-9) to (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group.

[0094] The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0095] Examples of the group represented by formula (b1-4) include the following. TIFF0007682029000056.tif16154

[0096] Examples of the group represented by formula (b1-5) include the following. TIFF0007682029000057.tif68152

[0097] Examples of the group represented by formula (b1-6) include the following. TIFF0007682029000058.tif32164

[0098] Examples of the group represented by formula (b1-7) include the following. TIFF0007682029000059.tif57146

[0099] Examples of the group represented by formula (b1-8) include the following. TIFF0007682029000060.tif23150

[0100] Examples of the group represented by formula (b1-2) include the following. TIFF0007682029000061.tif31161

[0101] Examples of the group represented by formula (b1-9) include the following. TIFF0007682029000062.tif44137

[0102] Examples of the group represented by formula (b1-10) include the following. TIFF0007682029000063.tif92165

[0103] Examples of the group represented by formula (b1-11) include the following. TIFF0007682029000064.tif84164

[0104] The alicyclic hydrocarbon group represented by Y includes those represented by the formulae (Y1) to (Y11) and (Y36) to (Y38). Examples of the group include a group represented by the formula (Y38). -CH contained in the alicyclic hydrocarbon group represented by Y 2 -O-, -SO 2 -or-CO When substituted with -, the number may be one or more. Such groups include , groups represented by formulae (Y12) to (Y35) and (Y39) to (Y43). . TIFF0007682029000065.tif84170

[0105] 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 (Y43) and more preferably a group represented by formula (Y11), formula (Y15), or formula (Y16) ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39), a group represented by the formula (Y40), the formula (Y42) or the formula (Y43), and more preferably Or formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula ( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) It is a group represented by the following formula: The alicyclic hydrocarbon group represented by Y is represented by the formula (Y28) to the formula (Y35), the formula (Y39) to the formula (Y 40), when it is a spiro ring such as formula (Y42) or formula (Y43), between two oxygen atoms The alkanediyl group preferably has one or more fluorine atoms. In the alkanediyl group contained in the structure, the methylene group adjacent to the oxygen atom contains a fluorine atom. is preferably unsubstituted.

[0106] 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, 6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -( CH 2 ) ja -CO-OR b1 Group or -(CH 2 ) ja -O-CO-R b1 group (in the formula, R b1 teeth, Alkyl groups having 1 to 16 carbon atoms, alicyclic hydrocarbon groups having 3 to 16 carbon atoms, aromatic groups having 6 to 18 carbon atoms represents an aromatic hydrocarbon group or a group combining these; ja represents an integer of 0 to 4; The alkyl group and the alicyclic hydrocarbon group each represent a -CH 2 -, -O-, -SO 2 - or -CO-, and the alkyl group, the alicyclic hydrocarbon group and the aromatic The hydrogen atoms in the aromatic hydrocarbon group are replaced by hydroxyl groups or fluorine atoms. (etc.) The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxyl group, an alkyl group having 1 to 16 carbon atoms which may be substituted with an alkoxy group (the alkyl group -CH 2 - may be replaced by -O- or -CO-.) A cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, Glycidyloxy group, -(CH 2 ) ja -CO-OR b1 Group or -(CH 2 ) ja -O-CO -R b1 group (in the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon having 3 to 16 carbon atoms. ja represents a cyclic group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. represents an integer of 0 to 4. The —CH 2 -, -O-, -SO 2 The alkyl group may be replaced by - or -CO-. The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are substituted with hydroxyl groups or fluorines. may be replaced by an atomic atom.

[0107] Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexane group, and a cyclohexane group. Cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, Examples of the alicyclic hydrocarbon group include a chain hydrocarbon group. Examples of the alkyl group include a methylcyclohexyl group and a dimethylcyclohexyl group. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms. be. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and the like. Examples of the aromatic hydrocarbon group include aryl groups such as an alkyl group and an aryl group such as a phenyl group and a phenanthryl group. It may have a fluorine atom or an alicyclic hydrocarbon group, and may have a chain hydrocarbon group having 1 to 18 carbon atoms. Aromatic hydrocarbon groups (tolyl, xylyl, cumenyl, mesityl, p-methyl Phenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethyl phenyl group, 2-methyl-6-ethylphenyl group, etc.), and alicyclic carbons having 3 to 18 carbon atoms. Aromatic hydrocarbon groups having a hydride group (p-cyclohexylphenyl group, p-adamantyl The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. and more preferably 6 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromoalkyl group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 It is preferably from 1 to 6, and more preferably from 1 to 4. Examples of alkyl groups substituted with hydroxy groups include hydroxymethyl groups, hydroxy Examples of such groups include hydroxyalkyl groups such as an ethyl group. The aralkyl group includes a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and the like. Examples of the alkyl group include ethyl and naphthylethyl groups. -CH in the alkyl group 2 -O-, -SO 2 - or -CO- etc. The group includes an alkoxy group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkyl Examples of the carbonyl group include an alkylcarbonyloxy group and a combination thereof. do. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy group. The number of carbon atoms of the alkoxy group is preferably 1 to 12. It is preferably 1 to 6, and more preferably 1 to 4. Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propyl The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 12. It is preferably 1 to 6, and more preferably 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group is preferably Preferably, it is 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably It is preferably 2-6, and more preferably 2-4. Examples of the alkylcarbonyloxy group include an acetyloxy group and a propionyloxy group. Examples include a Si group, a butyryloxy group, etc. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the combined group include a group combining an alkoxy group and an alkyl group, an alkoxy group and an alkoxy group, an alkoxy group and an alkylcarbonyl group, a group combining an alkoxy group and an alkylcarbonyloxy group, etc. are included. Examples of the group combining an alkoxy group and an alkyl group include alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an ethoxymethyl group, etc. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkoxy group include alkoxyalkoxy groups such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, etc. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, an ethoxypropionyl group, etc. The number of carbon atoms in the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, an ethoxy Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, an ethoxy is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, an ethoxy acetyloxy group, an ethoxypropionyloxy group, etc. Examples of such groups include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the koxyalkylcarbonyloxy group is preferably 3 to 13, and more preferably The number is preferably 3 to 7, and more preferably 3 to 5. -CH contained in alicyclic hydrocarbon group 2 -O-, -SO 2 Replaced with - or -CO- etc. The groups represented by the formulae (Y12) to (Y35) and (Y39) to (Y43) are Examples of the group include a group

[0108] Y includes the following: TIFF0007682029000066.tif160165

[0109] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent. and more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. More preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. Even more preferably, it is an adamantyl group which may have a substituent. -CH constituting a silyl group or an adamantyl group 2 - is -CO-, -SO 2 - or -CO- Y is preferably an adamantyl group, a hydroxyadamantyl group, a methyl group, an oxoadamantyl group, or a group represented by the formula (Y42), the formula (Y100) to the formula (Y114), It is a group that is

[0110] The anion in the salt represented by formula (B1) is represented by the formulas (B1-A-1) to (B1- A-59) (hereinafter, "anion (B1-A-1), etc." according to the formula number) Formula (B1-A-1) to Formula (B1-A-4), Formula (B1 -A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 9) is more preferable. TIFF0007682029000067.tif154161

[0111] TIFF0007682029000068.tif65159

[0112] TIFF0007682029000069.tif101155

[0113] TIFF0007682029000070.tif64162

[0114] TIFF0007682029000071.tif111141

[0115] TIFF0007682029000072.tif123166

[0116] JPEG0007682029000073.jpg71166 Here R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably is a methyl group or an ethyl group. i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably Preferably, the alkyl group has 1 to 4 carbon atoms, the alicyclic hydrocarbon group has 5 to 12 carbon atoms, or a combination thereof. A group formed by combining these groups, more preferably a methyl group, an ethyl group, or a cyclohexyl group. or an adamantyl group. A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q 1 and Q 2 has the same meaning as above. Specific examples of the anion represented by formula (IA) include those described in JP 2010-204646 A. Examples of the anions include those described in Gazette No.

[0117] Preferred anions in the salt represented by formula (B1) include those represented by formulae (B1a-1) to (B1a-2) B1a-38) are examples of anions represented by the formula: TIFF0007682029000074.tif89152

[0118] TIFF0007682029000075.tif93139

[0119] TIFF0007682029000076.tif142156

[0120] TIFF0007682029000077.tif63150

[0121] Among them, the formulae (B1a-1) to (B1a-3) and the formulae (B1a-7) to (B1a-1 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a-3 8) is preferred.

[0122] 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 In some cases, they are referred to as "cation (b2-1)" depending on the formula number. TIFF0007682029000078.tif47169In equations (b2-1) to (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 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 having 1 to 12 carbon atoms, and fatty acids having 3 to 12 carbon atoms. The alicyclic group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms, 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 atom contained in the aromatic hydrocarbon group is replaced by a halogen atom, a hydroxyl group, or a group having 1 to 10 carbon atoms. 18 aliphatic hydrocarbon groups, fluorinated alkyl groups having 1 to 12 carbon atoms or alkoxy groups having 1 to 12 carbon atoms It may be substituted with a koxy group. R b4 and R b5 are bonded together to form a ring with the sulfur atom to which they are attached The ring may contain -CH 2 - may be replaced by -O-, -S- or -CO- good. R b7 and R b8 each independently represents a halogen atom, a hydroxyl group, or a fatty acid having 1 to 12 carbon atoms. It represents an aliphatic hydrocarbon group 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 b10each independently represents 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 together to form a ring with the sulfur atom to which they are attached The ring may contain -CH 2 - is 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 a prime number of 6 to 18, 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 means that they are bonded together to form a ring including the -CH-CO- to which they are attached. The ring may have -CH 2 - is replaced by -O-, -S- or -CO-. This is also possible. R b13 ~R b18 each independently represents a halogen atom, a hydroxyl group, or a fatty acid having 1 to 12 carbon atoms. Aliphatic hydrocarbon group, fluorinated alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms Represents. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14 are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, r2 When is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 teeth Identical or different, when t2 is 2 or more, multiple R b18 are the same or different. The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and An example of the alkyl group is 2-ethylhexyl. 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. 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. TIFF0007682029000079.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 replaced by aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl, dimethylcyclohexyl, 2-methyladamantan-2-yl, 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 Preferably, it is 20 or less. The term "fluorinated alkyl group" refers to an alkyl group having 1 to 12 carbon atoms and a fluorine atom. Examples of the fluoromethyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, and a perfluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 9, and more preferably 1 to 9. It is preferably 6, and more preferably 1 to 4. 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 an open-chain hydrocarbon group or an alicyclic hydrocarbon group. and an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms ( tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert -Butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group etc.), and aromatic hydrocarbon groups having alicyclic hydrocarbon groups with 3 to 18 carbon atoms (p-cyclo p-Aminophenyl group, p-phenylphenyl group, etc. In addition, when the aromatic hydrocarbon group contains a chain hydrocarbon group or an alicyclic hydrocarbon group, A chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples of the alkyl group include aryl groups. Examples of the chain hydrocarbon group in which a hydrogen atom is replaced by an aromatic hydrocarbon group include a benzyl group, a phenoxy group, and the like. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples of such groups include aralkyl groups. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy 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, chlorine, bromine and iodine atoms. do. The alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, and an ethyl Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group Si group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples thereof include an oxy group and a 2-ethylhexylcarbonyloxy group. R b4 and R b5 and form a ring together with the sulfur atom to which they are attached: The ring may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated. The ring may be one having 3 to 18 carbon atoms, and preferably one having 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 of the ring include the following rings, where * represents the bond position. TIFF0007682029000080.tif23144R b9 and Rb10 The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. The ring may be either a saturated or unsaturated ring. 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 thiolane-1-ium ring (tetrahydrothio ophenium ring), thian-1-ium ring, 1,4-oxathiane-4-ium ring, etc. Can be obtained. R b11 and R b12 The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. The ring may be either a saturated or unsaturated ring. 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.

[0123] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF0007682029000081.tif73149

[0124] TIFF0007682029000082.tif109166

[0125] Examples of the cation (b2-2) include the following cations. TIFF0007682029000083.tif18150

[0126] Examples of the cation (b2-3) include the following cations. TIFF0007682029000084.tif25122

[0127] Examples of the cation (b2-4) include the following cations. TIFF0007682029000085.tif62164

[0128] TIFF0007682029000086.tif70158

[0129] 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) ~ Formula (B1a-16), Formula (B1a-18), Formula ( B1a-19), an anion represented by any one of formulas (B1a-22) to (B1a-38) A combination of an amine and a cation (b2-1), a cation (b2-3) or a cation (b2-4). Examples include:

[0130] The acid generator (B) is preferably a compound represented by formula (B1-1) to formula (B1-56), 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 (B1-31) to (B1-56) are particularly preferred. TIFF0007682029000087.tif98161

[0131] TIFF0007682029000088.tif152165

[0132] TIFF0007682029000089.tif92158

[0133] TIFF0007682029000090.tif144161

[0134] TIFF0007682029000091.tif63168

[0135] TIFF0007682029000092.tif92158

[0136] In the resist composition of the present invention, the content of the carboxylate (I) in the resist composition 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 the resist composition of the present invention, the content of the acid generator (B) is based on 100% by weight of the resin (A). With respect to the amount of the glycerol, the amount is preferably 1 part by mass or more and 45 parts by mass or less, and more preferably 1 part by mass or more and 45 parts by mass or less. The content is preferably 0 parts by mass or less, and more preferably 3 parts by mass or more and 35 parts by mass or less. The composition may contain one type of acid generator (B) alone or a combination of two or more types.

[0137] <Resin (A)> 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). As the structural unit other than the structural unit (a1), a structural unit not having an acid labile group ( (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 described below (hereinafter referred to as a "structural unit ( a5) and other structural units derived from monomers known in the art etc.

[0138] <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. TIFF0007682029000093.tif2397 [In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms , an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, R represents an aromatic hydrocarbon group or a combination thereof; a1 and R a2 are combined with each other Together with the carbon atom to which they are bonded, they form an alicyclic hydrocarbon group having 3 to 20 carbon atoms. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * indicates the bond position.] TIFF0007682029000094.tif2379[In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a C1-12 represents a hydrocarbon group, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’ are bonded to each other to form, together with the carbon atom to which they are bonded and X, a heterocyclic group having 3 to 20 carbon atoms. and the —CH 2 - is replaced with -O- or -S- It may be replaced. X represents an oxygen atom or a sulfur atom. na′ represents 0 or 1. * represents a bond.]

[0139] Ra1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, Examples of the alkyl group include a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alkenyl group in the formula (I) is an ethenyl group, a propenyl group, an isopropyl group, Propenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, xenyl, heptenyl, octynyl, isooctynyl, and nonenyl groups. . R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, cycloalkyl groups such as butyl and cyclooctyl groups. Examples of the alkyl group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group ( * represents a bond.) etc. a1 , R a2 and R a3 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16. TIFF0007682029000095.tif10159R a1 , R a2 and R a3 The aromatic hydrocarbon group in the formula (I) is preferably a phenyl group, a naphthyl group, or Examples of aryl groups include aryl groups such as an anthryl group, a biphenyl group, and a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., alkylcycloalkyl groups or cycloalkylalkyl groups), benzyl groups, etc. Aromatic hydrocarbon groups having raryl groups and alkyl groups (p-methylphenyl group, p-tert-butylphenyl group, etc.) t-Butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diphenyl group phenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic groups having alicyclic hydrocarbon groups Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as phenylcyclohexyl groups. , ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form an alicyclic hydrocarbon group, -C(R a1 )(R a2 )(R a3 The alicyclic hydrocarbon group preferably has 3 carbon atoms. ~12. * indicates the bond position with -O-. TIFF0007682029000096.tif31135

[0140] R a1’ , R a2’ and R a3’ The hydrocarbon group in the formula (I) is an alkyl group, an alicyclic hydrocarbon group, groups, aromatic hydrocarbon groups, and groups formed by combining these groups. . The alkyl group and the alicyclic hydrocarbon group are R a1 , R a2 and R a3 The same groups as those listed in Can be obtained. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group and the like. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., alkylcycloalkyl groups or cycloalkylalkyl groups), aralkyl groups (e.g., aryl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl groups, p-tert-butylphenyl groups, etc.); rt-Butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-di ethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic hydrocarbon group Aromatic hydrocarbon groups (e.g., p-cyclohexylphenyl group, p-adamantylphenyl group), Aromatic hydrocarbon groups Alicyclic hydrocarbon groups having a hydrocarbon group (e.g., phenylcyclohexyl group) etc. R a2’ and R a3’ are bonded to each other to form a heterocyclic group together with the carbon atom to which they are bonded and X. When forming -C(R a1’ )(R a2’ )-XR a3’ Examples of the group include the following: * indicates the bond position. TIFF0007682029000097.tif21142R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0141] 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 na=1 The group is preferably a tert-butoxycarbonyl group. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamantane. Forming a ethyl 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; Ra3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following groups. * represents a bond. TIFF0007682029000098.tif170163

[0142] Specific examples of the group (2) include the following groups. * represents the bonding position. TIFF0007682029000099.tif68162

[0143] 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.

[0144] Of the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of such a bulky structure include those having an alicyclic hydrocarbon group. 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.

[0145] 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 a1-2) (hereinafter, may be 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) At least one or two structural units selected from the above may be used alone or in combination. More than one species may be used in combination. TIFF0007682029000100.tif42141 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 each independently represents -O- or * -O-(CH 2 ) k1 -CO represents --O--; k1 represents an integer of 1 to 7; and * represents a bond to --CO--. R a01 , R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or a halogen atom It represents an alkyl group having 1 to 6 carbon atoms which may have the following group: R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, alicyclic hydrocarbon group having 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof Represents a group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkene group having 2 to 8 carbon atoms, a cycloalkyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or represents a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0146] R a01 , R a4 and R a5 is preferably a hydrogen atom or a methyl group, and more preferably It is a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or -O-(CH 2 )k01 -CO- O- (wherein k01 is preferably an integer of 1 to 4, more preferably 1). ), and more preferably an oxygen atom. R a02 , R a03 and R a04 Alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic groups As the aromatic hydrocarbon group and a group formed by combining these, R a1 ~R a3 The same as the groups listed in The following groups are included: R a6 and R a7 Alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic As the hydrogen group and a group formed by combining these, R a1 , R a2 and R a3 The groups listed in Similar groups are mentioned. 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 methyl group or an ethyl group is more preferable, and a methyl group is even more preferable. 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 More preferably, it is a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, and even more preferably Alternatively, it is an ethyl group, an isopropyl group, or a t-butyl group. R a6 and R a7 The alkenyl group in the formula (I) is preferably an alkenyl group having 2 to 6 carbon atoms. and more preferably an ethenyl group, a propenyl group, an isopropenyl group, or a butenyl group. do. R a02 , R a03 and R a04The alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms. More preferably, it is 5 to 10. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms of the aromatic hydrocarbon group is preferably It is 6 to 12, and more preferably 6 to 10. The group consisting of a combination of an alkyl group and an alicyclic hydrocarbon group is It is preferred that the total number of carbon atoms in combination with the group is 18 or less. The group consisting of a combination of an alkyl group and an aromatic hydrocarbon group is It is preferred that the total number of carbon atoms in combination with the group is 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms. It is a hydrocarbon group, and more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group. do. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms. is 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 or an alkenyl group having 2 to 6 carbon atoms. or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group. is preferably a propyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, Preferred are an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, or a phenyl group. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0147] Examples of the structural unit (a1-0) include those represented by the formulae (a1-0-1) to (a1-0-18): and R in the structural unit (a1-0) a01 The equivalent The ethyl group is a hydrogen atom, a halogen atom, or a haloalkyl group (an alkyl group having a halogen atom). or other alkyl group. -0-10), (a1-0-13), or (a1-0-14) Units are preferred. TIFF0007682029000101.tif100167

[0148] 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 (a1-1-2) are included. -1-7) and R in the structural unit (a1-1) a4 Equivalent to The structural units represented by the formulas (a1-1-1) to (a1-1-2) are preferably those in which the methyl group is replaced by a hydrogen atom. A structural unit represented by any one of a1-1-4) is more preferable. TIFF0007682029000102.tif39167

[0149] The structural unit (a1-2) is any one of the structural units represented by formulas (a1-2-1) to (a1-2-14). R in the structural unit (a1-2) a5 The methyl group corresponding to water Examples of structural units include those in which a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group is substituted. As a result, the formula (a1-2-2), the formula (a1-2-5), the formula (a1-2-6) and the formula (a1- A structural unit represented by any one of formulas (a1-2-10) to (a1-2-14) is preferred. TIFF0007682029000103.tif67163

[0150] When the resin (A) contains the structural unit (a1-0), the content of the structural unit (a1-0) is determined based on the total amount of the structural units of the resin (A). The amount 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 units is usually 10 to 95 mol % based on the total structural units of the resin (A). The content is preferably 15 to 85 mol %, more preferably 15 to 80 mol %, and further preferably Preferably, it is 20 to 80 mol %, and even more preferably, it is 20 to 75 mol %.

[0151] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of the structural unit include a structural unit (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF0007682029000104.tif3854[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1-6 alkyl group which may have a halogen atom represents an alkyl group represented by the formula: R a33 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxya Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms It represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. Aa30 is a single bond or * -X a31 -(A a32 -X a32 ) nc - stands for -R. a32 Combined represents the bonding site with the carbon atom. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O-, or -O-CO-. nc represents 0 or 1. la represents an integer of 0 to 4. When la is an integer of 2 or more, R in Numbers a33 may be the same or different from each other. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH group contained in the divalent hydrocarbon group 2 - is replaced by -O- or -S- That's fine.]

[0152] R a32 and R a33 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: R a32 As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom, Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, phenyl 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples of the alkyl group include pentyl, pentyl, hexyl and perfluorohexyl groups. R a32 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or is more preferably an ethyl group, and further preferably a hydrogen atom or a methyl group. R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. can be done. R a33 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an iso Propoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy The alkoxy group is an alkoxy group having 1 to 4 carbon atoms. A methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. R a33 The alkoxyalkyl group in the formula (I) is preferably a methoxymethyl group or an ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples of the alkoxyalkyl group include the methyl group and the tert-butoxymethyl group. An alkoxyalkyl group having an alkyl group of 2 to 8 is preferred, and a methoxymethyl group or an ethoxyethyl group is more preferred. A methoxymethyl group is more preferred. R a33 The alkoxyalkoxy group in the formula (I) is preferably a methoxymethoxy group, a methoxyethoxy group, oxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxy group butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy The alkoxyalkoxy group is an alkoxyalkoxy group having 2 to 8 carbon atoms. A koxy group is preferred, and a methoxyethyl group or an ethoxyethyl group is more preferred. R a33 The alkylcarbonyl group in the formula (I) is an acetyl group, a propionyl group, or a butyl group. The alkylcarbonyl group is an alkylcarbonyl group having 2 to 3 carbon atoms. is preferred, and an acetyl group is more preferred. R a33 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, The alkylcarbonyloxy group includes a aryloxy group and a butyryloxy group. An alkylcarbonyloxy group having 2 to 3 carbon atoms is preferred, and an acetyloxy group is more preferred. R a33 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, An alkoxy group or an alkoxyalkoxy group having 2 to 8 carbon atoms is preferred, and a fluorine atom, an iodine atom, A nitrogen atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxy group. A methoxy group is more preferred, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, More preferred are methoxy and ethoxyethoxy groups.

[0153] *-X a31 -(A a32 -X a32 ) nc - includes *-O-, *-CO-O-, *-OC O-, *-CO-OA a32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO-, Among them, *-CO-O- and *-CO-OA are the most common. a32 -CO-O- or *- Office Automation a32 -CO-O- is preferred.

[0154] Examples of the alkanediyl group include a methylene group, an ethylene group, and a propane-1,3-diyl group. Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and and 2-methylbutane-1,4-diyl group. A a32 is preferably a methylene group or an ethylene group.

[0155] A a30 is a single bond, *-CO-O- or *-CO-OA a32 -CO-O- Preferred are single bonds, *-CO-O- or *-CO-O-CH 2 -CO-O- A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable.

[0156] la is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. R a34 , R a35 and R a36 The hydrocarbon group in the formula (I) is an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups combining these. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples include a silyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aryl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, The following groups (* indicates a bonding site): Some examples include: TIFF0007682029000105.tif10151 Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples of the aryl group include 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, and 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 having alicyclic hydrocarbon groups (p-cyclohexyl p-adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36 As for the carbon number 1-18, an 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 the groups include groups formed by combining these.

[0157] R a34 is preferably a hydrogen atom. R a35 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a It is an alicyclic hydrocarbon group, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is an alkyl group having 1 to 18 carbon atoms, a group having 3 to 1 R is an alicyclic hydrocarbon group having 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. a36 Archi 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.

[0158] -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid) and is eliminated to form a hydroxyl group. -OC(R a34 )(R a35 )-OR a36 is bonded to the o- or p-position of the benzene ring It is preferred that the linker be bonded at the p-position, and more preferred that the linker be bonded at the p-position.

[0159] Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers represented by the formula (a1-4-1) to (a1-4-2) are preferably included. -4-18) and R in the structural unit (a1-4) a32 In accordance with A structural unit in which the corresponding hydrogen atom is replaced by a halogen atom, a haloalkyl group, or an alkyl group. More preferably, the formula (a1-4-1) to the formula (a1-4-5) and the formula (a1- 4-10), (a1-4-13), and (a1-4-14) Examples include: TIFF0007682029000106.tif100166When the resin (A) has the structural unit (a1-4), the content of the structural unit (a1-4) 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 %.

[0160] The structural unit derived from a (meth)acrylic monomer having the group (2) is represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can also be mentioned. can be. TIFF0007682029000107.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 acetylene atom. Z a1 is a single bond or *-(CH 2 ) 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.

[0161] Examples of the halogen atom include a fluorine atom and a chlorine atom, with a fluorine atom 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 of the alkyl group include the ethyl 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 Of these, it is preferred that one is -O- and the other is -S-. It is preferable that s1 is 1. s1' is preferably an integer of 0 to 2. Z a1 is a single bond or -CH 2 -CO-O- is preferred.

[0162] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers represented by the formula (a1-5-1) to the formula (a1-5- 4), and the structural units represented by the formula (a1-5-1) or the formula (a1-5-2) are preferred. ) is more preferred. TIFF0007682029000108.tif34138When resin (A) has structural units (a1-5), the content of the structural units is determined based on the total structure of resin (A). The content of the copolymer is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0163] Further, examples of the structural unit (a1) include the following structural units. TIFF0007682029000109.tif27160When resin (A) contains the above structural unit, its content is based on the total structural units of resin (A). The content is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %. More preferred.

[0164] 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 that do not have 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 no 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, For example, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0165] <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 carboxylic hydroxy group. When a resist pattern is produced from the resist composition of the present invention, the exposure light source is KrF Using high energy rays such as excimer laser (248 nm), electron beam or EUV (extreme ultraviolet light) In this case, the structural unit (a2) is 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 using an ArF excimer laser (193 nm) or the like, 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.

[0166] In the structural unit (a2), the structural unit having a phenolic hydroxy group is represented by the formula (a 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") is can be done. TIFF0007682029000110.tif4450[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 hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxya Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms It represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - stands for -R. a50 Combined represents the bond position to 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, R in Numbers a51 may be the same or different.]

[0167] R a50 and R a51 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: R a50The 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 of the alkyl group 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 more preferably a hydrogen atom, a methyl group or is more preferably an ethyl group, and further 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, Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group or an ethyl group. A methyl group is more preferred. R a51 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an iso Examples of the group include a propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group. More preferred is a methoxy group. R a51 The alkoxyalkyl group in the formula (I) is preferably a methoxymethyl group or an ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples of the alkoxyalkyl group include the methyl group and the tert-butoxymethyl group. An alkoxyalkyl group having an alkyl group of 2 to 8 is preferred, and a methoxymethyl group or an ethoxyethyl group is more preferred. A methoxymethyl group is more preferred. R a51 The alkoxyalkoxy group in the formula (I) is preferably a methoxymethoxy group, a methoxyethoxy group, oxy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isopropoxy group butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy The alkoxyalkoxy group is an alkoxyalkoxy group having 2 to 8 carbon atoms. A koxy group is preferred, and a methoxyethoxy group or an ethoxyethoxy group is more preferred. R a51 The alkylcarbonyl group in the formula (I) is an acetyl group, a propionyl group, or a butyl group. The alkylcarbonyl group is an alkylcarbonyl group having 2 to 3 carbon atoms. is preferred, and an acetyl group is more preferred. R a51 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, The alkylcarbonyloxy group includes a aryloxy group and a butyryloxy group. An alkylcarbonyloxy group having 2 to 3 carbon atoms is preferred, and an acetyloxy group is more preferred. R a51 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, An alkoxy group or an alkoxyalkoxy group having 2 to 8 carbon atoms is preferred, and a fluorine atom, an iodine atom, A nitrogen atom, a hydroxy group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group or an ethoxy group. A methoxy group is more preferred, and a fluorine atom, an iodine atom, a hydroxy group, a methyl group, More preferred are methoxy and ethoxyethoxy groups.

[0168] *-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 the most common. 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- Preferred are single bonds, *-CO-O- or *-CO-O-CH 2 -CO-O- A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable. 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 that the carboxyl group is bonded to the

[0169] 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 US Pat. No. 5,12577. The structural unit (a2-A) is represented by formulas (a2-2-1) to (a2-2-16). In the structural units represented by formulas (a2-2-1) to (a2-2-16), R in structural unit (a2-A) a50 The methyl group corresponding to The structural unit (a2-) is substituted with a haloalkyl group or an alkyl group. A) is a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), Position, a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), Structural units represented by formulae (a2-2-12) to (a2-2-14) and (a2-2-1 ), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6) A structural unit represented by formula (a2-2-8), a structural unit represented by formula (a2-2-12) to formula (a2-2-13) In the structural unit represented by (a2-2-14), R in the structural unit (a2-A) a50 It is preferable that the structural unit is a structural unit in which a methyl group corresponding to the formula (a2 -2-3), structural units represented by formula (a2-2-8), structural units represented by formula (a2-2 -12) to the structural unit represented by formula (a2-2-14) and the structural unit represented by formula (a2-2-3) A structural unit represented by the formula (a2-2-8), a structural unit represented by the formula (a2-2-12) to the formula (a2 -2-14), R in the structural unit (a2-A) a50 In accordance with It is more preferable that the structural unit is a structural unit in which the corresponding methyl group is replaced with a hydrogen atom, and In the structural unit represented by formula (a2-2-8) and the structural unit represented by formula (a2-2-8), R in structural unit (a2-A) a50 The structure in which the methyl group corresponding to is replaced by a hydrogen atom More preferably, it is a unit. TIFF0007682029000111.tif63170Content 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, for example, by polymerization of the structural unit (a1-4) followed by p-toluenesulfonyl chloride. It can be incorporated into the resin (A) by treating it with an acid such as benzenesulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating the resin with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0170] In the structural unit (a2), the structural unit having an alcoholic hydroxy group is represented by the formula ( a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") Some examples include: TIFF0007682029000112.tif3957 formula (a2-1), L a3 is -O- or * -O-(CH 2 ) k2 represents -CO-O-, k2 represents an integer of any one 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 of 0 to 10.

[0171] In formula (a2-1), L a3 is preferably -O-, -O-(CH 2 ) 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.

[0172] 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 included. ), and the structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) is preferred. A structural unit represented by any one of the formulas (a2-1-1) or (a2-1- The structural unit represented by 3) is more preferred. TIFF0007682029000113.tif49138When resin (A) contains the structural unit (a2-1), its content is the total of all structural units of resin (A). The amount is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably It is preferably 1 to 35 mol %, more preferably 2 to 20 mol %, and even more preferably The content is usually 2 to 10 mol %.

[0173] <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 condensation ring of a monocyclic lactone ring with another ring. It may be 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 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. TIFF0007682029000114.tif51161 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH 2 ) k3 - It represents a group represented by CO-O- (k3 represents an integer of any 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 a24is 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 is -CH 2 - or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 each independently represents a carboxy group, a cyano group, or a carbon atom; Represents an aliphatic hydrocarbon group having 1 to 4 prime numbers. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 may be the same or different.]

[0174] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in The following radicals are available: ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl. Examples of the alkyl group include a t-butyl group. R a24 The halogen atom in the formula (I) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of atoms include: 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. Of these, preferred is an alkyl group having 1 to 4 carbon atoms, and more preferred is a 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 of the alkyl group include an alkyl group, a triiodomethyl group, and a triiodomethyl group.

[0175] L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a proline 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, pentamethylpropane Examples include 2-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

[0176] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferred or -O- or *-O-(CH 2 ) k3 In -CO-O-, k3 is 1 to 4 A group having any one of the integers, more preferably -O- and *-O-CH 2 -CO-O-, and An oxygen atom is preferred. R a18 ~R a21 is preferably a methyl group. R a22 and R a23are each independently preferably a carboxy group, a cyano group or a methyl group. It is a ethyl group. p1, q1 and r1 each independently represent an integer of preferably 0 to 2; More preferably, it is 0 or 1.

[0177] 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 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-CH 2 -CO-O- or -OC 2 H 4 -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)'. TIFF0007682029000115.tif4051 (in the formula, R a24 , L a7 has the same meaning as above.)

[0178] As the structural unit (a3), a monomer described in JP-A-2010-204646 can be used. , Monomers described in JP 2000-122294 A, and JP 2012-41274 A 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 any one of the formulas (a3-1) to (a3-2) R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to water Structural units which replace atomic atoms are preferred. TIFF0007682029000116.tif117165

[0179] 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). The amount 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 The content of the units (a3-4) is 1 to 60 moieties relative to the total structural units of the resin (A). % by mole is preferable, 1 to 50 mol % is more preferable, and 1 to 50 mol % is even more preferable.

[0180] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF0007682029000117.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, -CH 2 - may be replaced by -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, as well as groups formed by combining these groups.

[0181] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexa Examples include decyl, heptadecyl and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, Cycloalkyl groups such as cycloheptyl and cyclooctyl; decahydronaphthyl, adipyl, Polycyclic alicyclic carbons such as manthyl group, norbornyl group, and the following groups (* indicates the bond position): Examples of the aryl group include aryl groups. TIFF0007682029000118.tif11160 The 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. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0182] The structural unit (a4) may be any of the following: a4-3) and at least one structure selected from the group consisting of formula (a4-4) Units include: TIFF0007682029000119.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.

[0183] L 4a The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane-1, linear alkanediyl groups such as butane-1,4-diyl group, ethane-1,1 -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.

[0184] L 3a The perfluoroalkanediyl group in the formula (I) is a difluoromethylene group, 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 xanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group yl group, perfluoroadamantanediyl group, and the like.

[0185] L 4a is preferably a single bond, a methylene group or an ethylene group, and more preferably a single 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.

[0186] The structural unit (a4-0) may be any of the structural units shown below and the structural units ( a4-0) in R 5a The structural unit in which the methyl group corresponding to the can be done. TIFF0007682029000120.tif98165

[0187] TIFF0007682029000121.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, -CH contained in the hydrocarbon group 2 - may be replaced by -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, or a group represented by the formula (ag 1), where A a41 and R a42 At least one of the The group has a halogen atom (preferably a fluorine atom). TIFF0007682029000122.tif1383 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represents a divalent alkyl group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 is a divalent aliphatic hydrocarbon having 1 to 5 carbon atoms which may have a single bond or a substituent. Represents a group. X a41 and X a42 each independently represents -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 ]

[0188] R a42 The saturated hydrocarbon group in the formula (I) is preferably a chain saturated hydrocarbon group or a monocyclic or polycyclic alicyclic and groups formed by combining these. do.

[0189] 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 xadecyl, heptadecyl and octadecyl groups. 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 rings such as adamantyl group, norbornyl group, and the following groups (* indicates the bond position): Saturated hydrocarbon groups of the formula: TIFF0007682029000123.tif11160 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an aryl group with one or more alicyclic saturated hydrocarbon groups. Examples of the saturated alicyclic hydrocarbon group include -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl Examples of the alkyl group include an aryl group, an alkanediyl group, an alicyclic saturated hydrocarbon group, and an alkyl group.

[0190] R a42 The substituents of the formula (a-g3) are 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 of the atom include a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred. TIFF0007682029000124.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. . * stands for R a42 represents the bond position with However, R a42 -X a43 -A a45 In R a42 When 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 .

[0191] A a45 The aliphatic hydrocarbon group in the formula (I) is a methyl group, an ethyl group, a propyl group, a butyl group, group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, penta Alkyl groups such as decyl, hexadecyl, heptadecyl, and octadecyl groups; Monocyclic groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups alicyclic hydrocarbon radicals; and Decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* indicates the bond position): Examples of the polycyclic alicyclic hydrocarbon group include the polycyclic alicyclic hydrocarbon groups. TIFF0007682029000125.tif11160

[0192] 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) is preferably This is 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. More preferably, it is a saturated hydrocarbon group having a fluoroalkyl 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 alkyl group include a perfluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro perfluorooctyl and perfluoroheptyl groups. Examples of the aryl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3), including 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.

[0193] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 Yes, More preferably, it is a group represented by formula (a-g2). TIFF0007682029000126.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.

[0194] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably has 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.

[0195] A preferred structure of the group represented by formula (a-g2) is the following structure (* represents a carbonyl group). (This is the bond site with ). TIFF0007682029000127.tif13161

[0196] A a41 The alkanediyl group in the formula (I) is 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 the like. do. A a41 The substituents in the alkanediyl group represented by the formula (I) are a hydroxy group and an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkoxy group include alkoxy groups represented by the 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.

[0197] A in the group represented by formula (a-g1) a42 , A a43 and A a44 The divalent saturated hydrocarbon The substituents include linear or branched alkanediyl groups and monocyclic or polycyclic divalent alicyclic hydrocarbons. A divalent alicyclic hydrocarbon group is formed by combining an alkyl group and an alkanediyl group. Specifically, methylene group, ethylene group, propane-1,3-diamine group, etc. propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane -1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1 , 2-diyl group, etc. A a42 , A a43 and Aa44 The substituent of the divalent saturated hydrocarbon group represented by is a hydroxy group. and alkoxy groups having 1 to 6 carbon atoms. It is preferred that s is 0.

[0198] 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. In the following examples, * and ** indicates the bond position, and ** is -O-CO-R. a42 This is the bonding position with. TIFF0007682029000128.tif48153

[0199] The structural unit represented by formula (a4-1) includes the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to Examples of structural units that have been replaced include: TIFF0007682029000129.tif100142

[0200] TIFF0007682029000130.tif123141

[0201] As the structural unit represented by formula (a4-1), a structural unit represented by formula (a4-2) is preferred. I wish. TIFF0007682029000131.tif3150[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, H 2 - 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 total number of carbon atoms in the molecule is limited to 21.

[0202] L 44 The alkanediyl group of A a41 Examples of the groups include the same groups as those exemplified in the above. R f6 The saturated hydrocarbon group of R a42 Examples of the groups include the same groups as those exemplified in the above. L 44 The alkanediyl group in is preferably an alkanediyl group having 2 to 4 carbon atoms. Of these, an ethylene group is more preferred.

[0203] Examples of the structural unit represented by formula (a4-2) include the structural units represented by formulae (a4-1-1) to (a4 -1-11) are structural units represented by the following formulas. R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It can be mentioned as a structural unit.

[0204] TIFF0007682029000132.tif4658[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. vinegar. X f12 is *-O-CO- or *-CO-O-(* is A f13 represents the bond 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 f14At least one of L has a fluorine atom. 5 , A f13 and A f14 The total number of carbon atoms in the molecule is limited to 20.

[0205] 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 which may have a fluorine atom in or a divalent chain saturated hydrocarbon group which may have a fluorine atom and a It is preferably a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkane dialkyl 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 alkanediyl groups such as propanediyl, butanediyl and pentanediyl groups; Fluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoro perfluoroalkanediyl groups such as perfluorobutanediyl and perfluoropentanediyl groups Examples of the alkyl group include aryl groups. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either a monocyclic or a polycyclic group. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexa Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and the like. diyl group, perfluoroadamantanediyl group, and the like.

[0206] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are represented by 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 group, cyclopropylmethyl group, cyclopropyl group , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl group A methyl group and the like are preferred.

[0207] 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 A group containing a divalent alicyclic hydrocarbon group having from 1 to 12 carbon atoms is preferred, and a divalent chain hydrocarbon group having from 2 to 3 carbon atoms is preferred. A base 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 containing 3 to 1 More preferred is a group containing an alicyclic hydrocarbon group of A 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.

[0208] Examples of the structural unit represented by formula (a4-3) include the structural units represented by formula (a4-1'-1) to formula (a 4-1´-11) are structural units represented by the following formulas. R 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.

[0209] The structural unit (a4) also includes a structural unit represented by the formula (a4-4). TIFF0007682029000133.tif3858[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH 2 ) j1 -, -(CH 2 ) j2 -O-(CH 2 ) j3 -or-(CH 2 ) j4 - CO-O-(CH 2 ) 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.]

[0210] R f22 The saturated hydrocarbon group of R a42 The saturated hydrocarbon group may be the same as that represented by the following formula: R f22 represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or a carbon 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 an example, -(CH 2 ) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0211] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by the formula (a4-4), R f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced by aryl groups. TIFF0007682029000134.tif87160When the resin (A) has the structural unit (a4), the content thereof is the total of all 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.

[0212] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) is a straight-chain, branched or cyclic hydrocarbon group. Among them, 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): . TIFF0007682029000135.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, Included in -CH 2 - may be replaced by -O- or -CO-.

[0213] 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 cyclopentene group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include, for example, , adamantyl group and norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl Examples of the alkyl group 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.

[0214] L 55 The divalent saturated hydrocarbon group in the formula (I) is a divalent chain saturated hydrocarbon group or a divalent fatty acid group. Examples of the hydrocarbon group 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 propanediyl group. Examples of the alkyl groups include alkanediyl groups such as dialkyl groups, butanediyl groups, and pentanediyl groups. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the saturated hydrocarbon group include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adatomyl groups. Examples thereof include a manthanediyl group and a norbornanediyl group.

[0215] L 55 -CH contained in the divalent saturated hydrocarbon group represented by 2 - 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 bond positions, and * represents the bond position with an oxygen atom. TIFF0007682029000136.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 It 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 x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7each independently represents 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.

[0216] 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 A methylene group or an ethylene group is preferred. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8is 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.

[0217] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF0007682029000137.tif54134

[0218] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF0007682029000138.tif24131

[0219] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF0007682029000139.tif15145

[0220] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF0007682029000140.tif26114L 55 is preferably a single bond or a group represented by formula (L1-1).

[0221] The structural unit (a5-1) may be any of the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to the can be. TIFF0007682029000141.tif110150When resin (A) has structural unit (a5), its content is the total of all structural units of 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.

[0222] <Structural unit (a6)> The structural unit (a6) is -SO 2 - group, -SO 2 - group on the side chain It is preferable to do so. -SO 2 The structural unit having a - group is -SO 2 It may have a linear structure having a - group. Ishi, -SO 2 - groups, or may have a branched structure having -SO 2 -group-containing ring The ring structure may be a ring structure (monocyclic or polycyclic structure). 2 -group-containing ring More preferably, it is a structural unit having a -SO 2 A ring structure containing -O- (sul It is a structural unit that has a tetracyclic ring.

[0223] The sultone ring may be represented by the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and the formula ( T 1 The binding site can be any position. The sultone ring may be monocyclic, but is preferably polycyclic. The ring is made up of -SO 2 It means a bridged ring containing -O-, and has the formula (T 1 -1 ) and the formula (T 1 The sultone ring is represented by the formula (T 1 -2) The ring is made up of -SO 2 In addition to -O-, further heteroatoms Examples of the heteroatom include an oxygen atom, a sulfur atom, or a nitrogen atom. , preferably an oxygen atom. TIFF0007682029000142.tif3290

[0224] The sultone ring may have a substituent, and the substituent may be a halogen atom or a hydroxy group. an alkyl group having 1 to 12 carbon atoms, which may have a halogen atom, a hydroxyl group, a cyano groups, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aryl groups having 7 to 12 carbon atoms. Ralalkyl groups, glycidyloxy groups, alkoxycarbonyl groups having 2 to 12 carbon atoms, and Examples thereof include 2-4 alkylcarbonyl groups.

[0225] Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. . The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples of the alkyl group include a silyl group, an octyl group, and a decyl group, and preferably an alkyl group having 1 to 6 carbon atoms. More preferably, it is a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, Perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl The alkyl group, the perfluorohexyl group, the trichloromethyl group, the tribromomethyl group, and the triiodomethyl group. A trifluoromethyl group is preferable. Examples of alkyl groups having a hydroxy group include hydroxymethyl and 2-hydroxyethyl groups. Examples of the hydroxyalkyl groups include hydroxyalkyl groups having a methyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. The aryl group includes a phenyl group, a naphthyl group, an anthryl group, and a p-methylphenyl group. , p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group Examples of such groups include the phenyl group and the 2-methyl-6-ethylphenyl group. The aralkyl group includes a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and the like. Examples of the alkyl groups include ethyl and naphthylethyl groups. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Examples of the alkoxy group include a group in which an alkoxy group and a carbonyl group are bonded, and preferably, an alkoxy group having 6 or less carbon atoms. An example of the alkyl group is an oxycarbonyl group, and a more preferred example is a methoxycarbonyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be.

[0226] From the viewpoint of ease of production of the monomer from which the structural unit (a6) is derived, A sultone ring having a long chain length is preferred. The sultone ring is preferably a ring represented by the following formula (T1'). TIFF0007682029000143.tif3064[In formula (T1'), X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxyl group. a halogen atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, Aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, glycidyloxy groups, It represents an alkoxycarbonyl group having from 1 to 12 carbon atoms or an alkylcarbonyl group having from 2 to 4 carbon atoms. ma represents an integer of 0 to 9. When ma is 2 or more, multiple R 41 are the same It may be the same or different. The binding site is at any position.] X 11 is preferably an oxygen atom or a methylene group, more preferably a methylene group. do. R 41 Examples of the substituents include those similar to those of the sultone ring, and include a halogen atom or a hydroxyl group. An alkyl group having 1 to 12 carbon atoms which may have an alkoxy group is preferred.

[0227] The sultone ring is more preferably a ring represented by formula (T1). TIFF0007682029000144.tif2743[In formula (T1), R 8 is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxyl group. groups, halogen atoms, hydroxyl groups, cyano groups, alkoxy groups having 1 to 12 carbon atoms, Aryl groups having 7 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, glycidyloxy groups, 12 alkoxycarbonyl group or an alkylcarbonyl group having 2 to 4 carbon atoms. m represents an integer of 0 to 9. When m is 2 or more, a plurality of R 8 are the same may also be different. The binding site is at any position.]

[0228] R 8 is R 41 The same can be mentioned. ma in formula (T1') and m in formula (T1) are preferably 0 or 1, More preferably, it is 0.

[0229] Examples of the ring represented by formula (T1') and the ring represented by formula (T1) include the following rings. The binding site is at an arbitrary position. TIFF0007682029000145.tif54164

[0230] The structural unit having a sultone ring preferably has the following group: represents the binding site. TIFF0007682029000146.tif50162

[0231] -SO 2 It is preferable that the structural unit having a - group further has a group derived from a polymerizable group. The polymerizable group is preferably a vinyl group, an acryloyl group, a methacryloyl group, an acryloyl group, or a methacryloyl group. Oxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, Examples thereof include an acryloylthio group and a methacryloylthio group. Among them, the monomer from which the structural unit (a6) is derived is preferably an ethylenically unsaturated bond. It is preferably a monomer having a (meth)acrylic base monomer.

[0232] The structural unit (a6) is preferably a structural unit represented by the formula (Ix). TIFF0007682029000147.tif4956 [In formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, water represents a hydrogen atom or a halogen atom. A xx is an oxygen atom, -N(R c )- or a sulfur atom. A xrepresents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, -CH 2 - is -O-, -CO- or -N(R d )- may also be replaced. X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 is an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxyl group. a halogen atom, a hydroxyl group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, Aryl groups having 6 to 12 carbon atoms, aralkyl groups having 7 to 12 carbon atoms, glycidyloxy groups, It represents an alkoxycarbonyl group having from 1 to 12 carbon atoms or an alkylcarbonyl group having from 2 to 4 carbon atoms. ma represents an integer of 0 to 9. When ma is 2 or more, multiple R 41 are the same It may be the same or different. R c and R d each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0233] R x Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. can be done. R x Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and the like. butyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n -hexyl group, etc., preferably an alkyl group having 1 to 4 carbon atoms, more preferably is a methyl group or an ethyl group. R x Examples of the alkyl group having a halogen atom include a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Fluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group group and triiodomethyl group. R x is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably It is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

[0234] A x The divalent saturated hydrocarbon group may be a linear alkanediyl group, a branched alkanediyl group, or a and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A combination of two or more species may also be used. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Decane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,1 4-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group , heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1- linear alkanediyl groups such as diyl and propane-2,2-diyl groups; Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane Pan-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group branched alkanediyl groups such as alkanediyl groups; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-1,4-diyl group and cyclooctane-1,5-diyl group a monocyclic divalent alicyclic saturated hydrocarbon group, Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like.

[0235] R 41 , X 11 and ma may be the same as those in formula (T1'). Examples of the sultone ring include those mentioned above, and among them, those having a specific bond position are preferred. It is preferable.

[0236] Examples of the structural unit (a6) include the following structural units. TIFF0007682029000148.tif104168

[0237] Among them, formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula ( The structural units represented by the formula (a6-8) and the formula (a6-12) are preferred, and the structural units represented by the formula (a6-1), the formula ( a6-2), and the structural units represented by the formulae (a6-7) and (a6-8) are more preferred. When the resin (A) has the structural unit (a6), the content of the structural unit (a6) is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 50 mol %, more preferably 2 to 40 mol %, and more preferably 3 to 30 mol %. % is more preferred.

[0238] <Structural unit (II)> The resin (A) further includes 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 2016-79235 A, 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 the side chain and an organic anion.

[0239] The structural unit having a sulfonate group or a carboxylate group in the side chain is represented by the formula (II-2 -A') is preferably a structural unit represented by the formula: TIFF0007682029000149.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, Ru-CH 2 - may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon may be The hydrogen atom contained in the alkyl group is replaced by a halogen atom or a alkyl group having 1 to 10 carbon atoms which may have a halogen atom. 6 may be substituted with an alkyl or hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. . RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: Z.A. + represents an organic cation.

[0240] R III3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms and the like can be mentioned. R III3The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the following formula: , R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by the following formula: Examples include: 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, Propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group yl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. . A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include trifluoroalkyl groups. perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group Examples of the alkyl group include a perfluoropentyl group and a perfluorohexyl group. X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched alkyl group. and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A combination of the above is also acceptable. 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 group; butane-1,3-diyl group; 2-Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentamethylpropane Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohetane-1,3-diyl group, Cycloalkanediyl groups such as cyclohexanone-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 cyclohexyl-1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like. -CH contained in saturated hydrocarbon groups 2 - is replaced by -O-, -S- or -CO- Examples of the divalent group include those represented by the formulae (X1) to (X53). and -CH contained in saturated hydrocarbon groups 2 - is replaced by -O-, -S- or -CO- The number of carbon atoms in front of each is 17 or less. In the following formula, * represents A x1 Represents a bond with . TIFF0007682029000150.tif145161

[0241] 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 7represents 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.

[0242] ZA in formula (II-2-A') + represents the cation Z1 in the acid generator (B1). + Similar to Examples include:

[0243] The structural unit represented by the formula (II-2-A') is a structural unit represented by the formula (II-2-A) It is preferable that: TIFF0007682029000151.tif38109 [In formula (II-2-A), R III3 , X III3 and Z.A. + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom, or a phenyl group having 1 to 6 carbon atoms; When z2A is 2 or more, multiple R III2 and R III4 are mutually They may be the same or different. Q a and Q b each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents the alkyl group. R III2 , R III4 , Q a and Q b The perfluoroalkyl group having 1 to 6 carbon atoms is represented by the formula: For details, see the Q b1 The perfluoroalkyl group may be the same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by the following formula: can be.

[0244] 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 1. TIFF0007682029000152.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and Z.A. + has the same meaning 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, -CH 2 - may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon The hydrogen atoms contained in the 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 (I) include a methyl group, an ethyl group, a propyl group, and a propyl group. propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl aryl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups. Examples of the alkyl group include linear or branched alkyl groups such as a decyl group. X I2 As the divalent saturated hydrocarbon group represented by the formula: III3 Divalent saturated hydrocarbon represented by The same as those in the group can be mentioned.

[0245] 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 TIFF0007682029000153.tif5288 [In formula (II-2-A-2), R III3 , R III5 and Z.A. + has the same meaning as above. mA and nA each independently represent 1 or 2.

[0246] 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 International Publication No. 2012 / 050015. It can be done. + represents an organic cation. TIFF0007682029000154.tif86163

[0247] The structural unit having a sulfonio group and an organic anion in the side chain is represented by the formula (II-1-1): It is preferable that the structural unit is a structural unit that is TIFF0007682029000155.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 Reach BiR II3 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. 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 and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, an alicyclic hydrocarbon group, an aromatic 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 iodine atom. Atoms and the like can be mentioned. R II4 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the following formula: , R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by the following formula: Examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated hydrocarbon having 1 to 18 carbon atoms. The divalent saturated hydrocarbon group includes a -CH 2 - is -O-, -S- or Specifically, X may be replaced with -CO-. III3 2 with 1 to 18 carbon atoms The examples of the alkyl group include the same ones as those of the 4-valent saturated hydrocarbon group.

[0248] The structural unit containing a cation in formula (II-1-1) includes the structural units represented by the following formula: BiR II4 The group corresponding to the methyl group in the formula (I) is replaced with a hydrogen atom, a fluorine atom, trifluoromethyl, etc. Examples include replaced structural units. TIFF0007682029000156.tif84130

[0249] A - As the organic anion represented by the formula (I), a sulfonate anion, a sulfonylimide anion, Examples of the anion include sulfonylmethide anion and carboxylate anion. - Represented by The organic anion is preferably a sulfonate anion. More preferably, it is an anion contained in the salt represented by formula (B1).

[0250] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF0007682029000157.tif32137

[0251] Examples of sulfonylmethide anions include the following: TIFF0007682029000158.tif29123

[0252] Examples of carboxylate anions include the following: TIFF0007682029000159.tif42154

[0253] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF0007682029000160.tif90153 When the resin (A) contains the structural unit (II), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 4 mol %, based on the total structural units of the oil (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0254] The resin (A) may have structural units other than the above-mentioned structural units. The positions include structural units known in the art.

[0255] The resin (A) is preferably a resin composed of 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 or a structural unit having a cyclopentyl group) At least one selected from the group consisting of structural units, more preferably at least two and more preferably, the structural unit (a1-1) and / or the structural unit (a1-2). do. 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 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 following formula:

[0256] Each structural unit constituting the resin (A) may be used alone or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (e.g., radical polymerization methods). The content of each structural unit in the resin (A) can be determined by the following procedure. This 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 the present specification, the weight average molecular weight is preferably 1,000 or less, and more preferably 15,000 or less. The molecular weight is a value determined by gel permeation chromatography under the conditions described in the Examples. It is.

[0257] <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 the resin other than the resin (A) include a resin containing the structural unit (a4) or the structural unit (a5). (hereinafter, may be 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 the structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, and more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. Examples of the structural unit 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 preferable that the resin is composed only of the structural unit (a4). Each structural unit constituting the resin (X) may be used alone or in combination of two or more kinds. Using monomers that derive these structural units, a known polymerization method (e.g., radical polymerization method) is performed. The content of each structural unit in the resin (X) can be determined by the following procedure. This 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 method for measuring the weight average molecular weight is the same as in the case of resin (A). Furthermore, when the resist composition contains resin (X), the content of resin (X) is parts, preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, More preferably, the content is 1 to 40 parts by mass, and even more preferably, the content is 1 to 30 parts by mass. Particularly preferably, the amount is 1 to 8 parts by mass.

[0258] The content of the resin (A) in the resist composition is 8 to 100% 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 based on the solid content of the resist composition. The content of the resist is preferably 90% by mass or less and more preferably 99% by mass or less. The solid content of the product and the resin content relative to the solid content are measured by liquid chromatography or gas chromatography. It can be measured by known analytical means such as fluorography.

[0259] <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, for example, by liquid chromatography or gas chromatography. This 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 ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0260] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound or an acid generated from the acid generator (B). A salt that generates an acid having a weaker acidity than the above (excluding the carboxylate salt represented by formula (I)). In the case where the resist composition contains a quencher (C), The content of the compound is about 0.01 to 15 mass % based on the solid content of the resist composition. It is preferably about 0.01 to 10% by mass, more preferably about 0.1 to 5% by mass. It is more preferable that the content is about 0.1 to 3 mass %. stomach. 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 include secondary amines and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, 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, Ethyldibutyrate diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylamine 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, pyridinium 4-Methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-Di(4-pyridyl)propane, 1,2-Di(4-pyridyloxy)ethane, Di( 2-Pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide amine, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Among them, preferred are aromatic amines such as diisopropylaniline, and more preferred are aromatic amines such as diisopropylaniline. Examples include 2,6-diisopropylaniline. Ammonium salts include tetramethylammonium hydroxide, tetraisopropyl ammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl Ammonium hydroxide, tetraoctylammonium hydroxide, phenyl trime ethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium Examples include nickel hydroxide, tetra-n-butylammonium salicylate, and choline. and the like.

[0261] 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 having an acid dissociation constant of the acid generated from the salt usually of -3 < pKa, preferably a salt of -1 < pKa < 7, and more preferably a salt of 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as " intramolecular salt of weak acid (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. 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 an intramolecular salt of weak acid (D). (B), and more preferably an intramolecular salt of weak acid (D). ) and having a carboxylic acid anion ), and more preferably an intramolecular salt of weak acid (D). TIFF0007682029000161.tif94163

[0262] Examples of the intramolecular salt of weak acid (D) include the following salts. TIFF0007682029000162.tif72165

[0263] <Other Components> The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter referred to as "other components") (F)) may be contained. There are no particular limitations on other components (F). However, additives known in the resist art, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc., may be used. Agents, dyes, etc. can be used.

[0264] 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. It can be from 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) such as the above. The mixing time is Depending on the mixing temperature, the appropriate time can be selected from 0.5 to 24 hours. The mixing means is not particularly limited, and stirring and mixing, etc. can be used. After mixing the components, filter the mixture using a filter with a pore size of about 0.003 to 0.2 μm. It is preferable that

[0265] <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) A step of 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. To apply the resist composition onto a 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. It is preferable that the heating time is 10 to 180 seconds. The pressure during the process is 1 to 1.0×10 5 It is preferable that the pressure is about Pa. The obtained 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), F 2 Ultraviolet lasers such as excimer lasers (wavelength 157 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert the 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". 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 (so-called heat treatment) in order to promote the deprotection reaction of the acid labile group. The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150 degrees Celsius. The composition layer after heating is usually developed using a developing device and a developing solution. Examples include the dip method, paddle method, spray method, dynamic dispensing method, etc. The development temperature is preferably, for example, 5 to 60°C, and the development time is preferably, for example, 5 to 300 seconds. By selecting the type of developer as follows, a positive resist pattern or a negative resist pattern can be produced. When producing a positive resist pattern from the resist composition of the present invention, an alkali developer is used. The alkali developer may be any of various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide, (2-hydroxy ethyl)trimethylammonium hydroxide (commonly known as choline), etc. can be mentioned. The alkali developer may contain a surfactant. After development, it is preferable to wash the resist pattern with ultrapure water and then remove the water remaining on the substrate and the pattern. When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as an "organic-based developer") is used. Examples of the organic solvent contained in the organic-based developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether acetate solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole, etc. In the organic-based developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially only the organic solvent. ​ Among them, organic developers include those 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 even more preferable that the components are qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 10%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. It is preferable to wash the resist pattern after development with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and any solvent containing a general organic solvent may be used. Any suitable solvent may be used, preferably an alcohol or ester solvent. After cleaning, it is preferable to remove any rinsing liquid remaining on the substrate and the pattern.

[0266] <Application> The resist composition of the present invention is a resist composition for exposure to a KrF excimer laser, Resist composition for exposure to ximer laser, resist composition for exposure to electron beam (EB) or EU The resist composition is preferably used for V exposure, particularly for ArF excimer laser exposure. This is suitable for use in microfabrication of semiconductors. EXAMPLES

[0267] The present invention will be described 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 Entec). In the examples, the value of this molecular ion peak is indicated as "MASS."

[0268] Example 1: Synthesis of a salt represented by formula (I-1617) TIFF0007682029000163.tif37139 20 parts of the compound represented by formula (I-1617-a), 20 parts of the compound represented by formula (I-1617-c) 2.28 parts of the compound, 100 parts of ethyl acetate, and 15 parts of tetrahydrofuran were mixed and heated at 23° C. The mixture was stirred at RT for 30 minutes. Compound 6 represented by formula (I-1617-b) was added to the resulting mixture. 0.55 parts of n-heptane was added to the reaction mass and stirred at 23° C. for 18 hours. Add 70 parts of ethyl acetate and 70 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the organic layer. The organic layer was added with 60 parts of ion-exchanged water and stirred at 23°C for 30 minutes. The organic layer was separated and washed with water four times. The organic layer was concentrated. The concentrated mass was then passed through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical ( The compound of formula (I- 7.48 parts of the compound represented by 1617-d) were obtained. TIFF0007682029000164.tif43154 0.95 parts of the compound represented by formula (I-1617-d) and 10 parts of tetrahydrofuran After mixing and stirring at 23°C for 30 minutes, the mixture was cooled to 5°C and 0.14 parts of sodium hydride was added. To the resulting mixture, 1.01 parts of a salt represented by formula (I-1617-e) was added. The mixture was stirred at 5° C. for 3 hours. 6.30 parts of 1N hydrochloric acid was added to the resulting mixture, and the mixture was then cooled to 23° C. The mixture was heated to 23° C. and stirred for 6 hours at 23° C. To the resulting mixture, 30 parts of chloroform and ion 15 parts of exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, after which the organic layer was separated and taken out. The organic layer was concentrated, and the concentrated residue was mixed with 1 part of acetonitrile and 1 part of tert-butyl methyl ether. Add 30 parts of ethyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 1.24 parts of a salt represented by the formula (I-1617-f) was obtained. TIFF0007682029000165.tif52156 Mix 0.62 parts of the salt represented by the formula (I-1617-f) and 30 parts of dimethylformamide. The mixture was mixed and stirred at 23°C for 30 minutes, after which 0.16 parts of potassium carbonate and 0.0 parts of potassium iodide were added. The mixture was heated to 75° C. and 5 parts of the amine compound represented by the formula (I-1617-g) was added to the mixture. 0.45 parts of the compound was added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added to the mixture and incubated at 23°C for 30 minutes. After stirring for 10 minutes, the organic layer was separated and separated. After stirring at 23°C for 30 minutes, the organic layer was separated and the water washing procedure was repeated. The organic layer was concentrated to give the compound represented by the formula (I-1617-h). 0.71 parts of the salt were obtained. TIFF0007682029000166.tif63160 0.77 parts of a salt represented by the formula (I-1617-h), 0.27 parts of salt and 20 parts of chloroform were added, and the mixture was stirred at 23° C. for 3 hours. 15 parts of ion-exchanged water was added to the mixture, stirred at 23°C for 30 minutes, and then the organic layer was separated. To the resulting organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was then separated and washed with water five times. By condensing, 0.75 parts of a salt represented by the formula (I-1617) was obtained. MASS(ESI(+)Spectrum):M + 813.1 MASS(ESI(-)Spectrum):M - 193.1

[0269] Example 2: Synthesis of a salt represented by formula (I-1619) TIFF0007682029000167.tif60165 0.77 parts of a salt represented by the formula (I-1617-h), 0.40 parts of salt and 20 parts of chloroform were added, and the mixture was stirred at 23° C. for 3 hours. 15 parts of ion-exchanged water was added to the mixture, stirred at 23°C for 30 minutes, and then the organic layer was separated. To the resulting organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was then separated and washed with water five times. By condensing, 0.95 parts of a salt represented by the formula (I-1619) was obtained. MASS(ESI(+)Spectrum):M + 813.1 MASS(ESI(-)Spectrum):M - 337.1

[0270] Example 3: Synthesis of salt represented by formula (I-667) TIFF0007682029000168.tif36142 3.80 parts of the compound represented by formula (I-667-a) and 6.40 parts of Oxone (registered trademark) The mixture was 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 3.68 parts of the compound represented by b) and 18.40 parts of chloroform was added, and the mixture was stirred for 5 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 ethyl acetate, stirred at 23°C for 30 minutes, and then filtered. The filtrate was concentrated. To the concentrated residue, 125 parts of chloroform and 25 parts of acetonitrile were added, and the mixture was stirred at 23° C. for 30 After stirring for 30 minutes, 60 parts of 5% hydrochloric acid was added and stirred at 23°C for 30 minutes. The mixture was then separated to obtain an organic layer. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was separated and washed with water three times. The organic layer was concentrated. To the concentrated mixture, 45 parts of tert-butyl methyl ether was added, and the mixture was stirred at 23° C. for 30 minutes. Then, filtration was carried out to obtain 2.37 parts of the salt represented by the formula (I-667-c). TIFF0007682029000169.tif42138 0.95 parts of the compound represented by the formula (I-1617-d) and 10 parts of tetrahydrofuran After mixing and stirring at 23°C for 30 minutes, the mixture was cooled to 5°C and 0.14 parts of sodium hydride was added. To the resulting mixture, 2.32 parts of a salt represented by formula (I-667-c) was added, The mixture was stirred at 5° C. for 3 hours. 6.30 parts of 1N hydrochloric acid was added to the resulting mixture, and the temperature was then raised to 23° C. The temperature was raised and the mixture was stirred at 23° C. for 6 hours. The resulting mixture was added with 30 parts of chloroform and ion exchange 15 parts of exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, after which the organic layer was separated and taken out. The organic layer was concentrated, and the concentrated residue was mixed with 1 part of acetonitrile and 1 part of tert-butyl methyl ether. 30 parts of ether was added, and the mixture was stirred at 23°C for 30 minutes. The supernatant was removed and the mixture was concentrated. As a result, 2.19 parts of a salt represented by the formula (I-667-f) was obtained. TIFF0007682029000170.tif34159 1.37 parts of the salt represented by the formula (I-667-f) and 30 parts of dimethylformamide were mixed. After stirring at 23°C for 30 minutes, 0.16 parts of potassium carbonate and 0.05 parts of potassium iodide were added. The mixture was heated to 75° C. and the mixture was diluted with 1,000 ml of ... 0.45 parts of the compound was added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. To the mixture, 50 parts of chloroform and 20 parts of a 5% aqueous oxalic acid solution were added and the mixture was incubated at 23°C for 30 minutes. After stirring for 1 hour, the mixture was separated to separate the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and separated. The organic layer was concentrated to obtain a compound represented by the formula (I-667-g). 1.14 parts of salt were obtained. TIFF0007682029000171.tif51129 0.60 parts of a salt represented by the formula (I-667-g), a salt represented by the formula (I-1617-i) 0.27 parts of toluene and 20 parts of chloroform were added, and the mixture was stirred at 23° C. for 3 hours. Add 15 parts of ion-exchanged water to the mixture, stir at 23°C for 30 minutes, and then separate the mixture to separate the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. Thereby, 0.63 parts of a salt represented by the formula (I-667) was obtained. MASS(ESI(+)Spectrum):M + 617.1 MASS(ESI(-)Spectrum):M - 193.1

[0271] Example 4: Synthesis of salt represented by formula (I-669) TIFF0007682029000172.tif51140 0.60 parts of a salt represented by the formula (I-667-g), a salt represented by the formula (I-1619-i) 0.40 parts of toluene and 20 parts of chloroform were added, and the mixture was stirred at 23° C. for 3 hours. Add 15 parts of ion-exchanged water to the mixture, stir at 23°C for 30 minutes, and then separate the mixture to separate the organic layer. To the obtained organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. Thereby, 0.75 parts of a salt represented by the formula (I-669) was obtained. MASS(ESI(+)Spectrum):M + 617.1 MASS(ESI(-)Spectrum):M - 337.1

[0272] Example 5: Synthesis of a salt represented by formula (I-2664) TIFF0007682029000173.tif37139 6.57 parts of the compound represented by formula (I-2664-a), 6.57 parts of the compound represented by formula (I-1617-c) 0.23 parts of the compound to be treated, 30 parts of ethyl acetate, and 15 parts of tetrahydrofuran were mixed, and the mixture was cooled to room temperature for 23 The mixture was stirred at ℃ for 30 minutes. The compound represented by formula (I-1617-b) was added to the resulting mixture. 0.66 parts of n-heptane was added and the mixture was stirred at 23° C. for 18 hours. 00 parts of ethyl acetate and 20 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and the organic layer was separated. 20 parts of ion-exchanged water was added to the recovered organic layer and stirred at 23° C. for 30 minutes. The organic layer was then separated and washed with water four times. The concentrated mass was then loaded onto a column (Silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical The compound was extracted using a solvent mixture (manufactured by Epson Corporation, developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain the compound of the formula ( 6.28 parts of the compound represented by I-2664-d) were obtained. TIFF0007682029000174.tif42153 2.26 parts of the compound represented by the formula (I-2664-d) and 10 parts of tetrahydrofuran After mixing and stirring at 23°C for 30 minutes, the mixture was cooled to 5°C and 0.14 parts of sodium hydride was added. To the resulting mixture, 2.32 parts of a salt represented by formula (I-667-c) was added, The mixture was stirred at 5° C. for 3 hours. 6.30 parts of 1N hydrochloric acid was added to the resulting mixture, and the temperature was then raised to 23° C. The temperature was raised and the mixture was stirred at 23° C. for 6 hours. The resulting mixture was added with 30 parts of chloroform and ion exchange 15 parts of exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, after which the organic layer was separated and taken out. The organic layer was concentrated, and the concentrated residue was mixed with 1 part of acetonitrile and 1 part of tert-butyl methyl ether. 30 parts of ether was added, and the mixture was stirred at 23°C for 30 minutes. The supernatant was removed and the mixture was concentrated. As a result, 1.01 parts of a salt represented by the formula (I-2664-f) was obtained. TIFF0007682029000175.tif36163 Mix 1.00 parts of the salt represented by the formula (I-2664-f) and 30 parts of dimethylformamide. The mixture was mixed and stirred at 23°C for 30 minutes, after which 0.08 parts of potassium carbonate and 0.0 parts of potassium iodide were added. The mixture was heated to 75° C. and 3 parts of the amine compound represented by the formula (I-1617-g) was added to the mixture. 0.44 parts of the compound was added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added to the mixture and incubated at 23°C for 30 minutes. After stirring for 10 minutes, the organic layer was separated and separated. After stirring at 23°C for 30 minutes, the organic layer was separated and the water washing procedure was repeated. The organic layer was concentrated to obtain the compound represented by the formula (I-2664-b). 1.08 parts of the salt were obtained. TIFF0007682029000176.tif59164 0.82 parts of a salt represented by the formula (I-2664-b), 0.40 parts of salt and 20 parts of chloroform were added, and the mixture was stirred at 23° C. for 3 hours. 15 parts of ion-exchanged water was added to the mixture, stirred at 23°C for 30 minutes, and then the organic layer was separated. To the resulting organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was then separated and washed with water five times. By condensing, 0.95 parts of a salt represented by the formula (I-2664) was obtained. MASS(ESI(+)Spectrum):M + 868.9 MASS(ESI(-)Spectrum):M - 337.1

[0273] Example 6: Synthesis of salt represented by formula (I-3614) TIFF0007682029000177.tif42161 2.26 parts of the compound represented by formula (I-2664-d), 2.26 parts of the compound represented by formula (I-1617-e) 0.78 parts of the salt and 30 parts of dimethylformamide were mixed and stirred at 23° C. for 30 minutes. After that, the temperature was raised to 90° C. To the resulting mixture, 1.44 parts of potassium carbonate was added, and the mixture was heated to 90° C. The mixture was stirred at 40° C. for 3 hours. 6.30 parts of 1N hydrochloric acid was added to the mixture, and the temperature was raised to 23° C. The mixture was stirred at 23° C. for 6 hours. 50 parts of chloroform and ion-exchanged water were added to the resulting mixture. After stirring at 23° C. for 30 minutes, the organic layer was separated and taken out. To the organic layer, 30 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. This water washing procedure was repeated three times. The resulting organic layer was concentrated, and the concentrated residue was 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the mixture, and the mixture was stirred at 23°C. After stirring for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound represented by formula (I-3614-f). 1.63 parts of a salt represented by the formula: TIFF0007682029000178.tif59145 Mix 1.21 parts of the salt represented by the formula (I-3614-f) and 30 parts of dimethylformamide. The mixture was mixed and stirred at 23°C for 30 minutes, after which 0.16 parts of potassium carbonate and 0.0 parts of potassium iodide were added. The mixture was heated to 75° C. and 5 parts of the amine compound represented by the formula (I-1617-g) was added to the mixture. 0.90 parts of the compound was added, and the mixture was stirred at 75°C for 5 hours and then cooled to 23°C. 50 parts of chloroform and 20 parts of 5% aqueous oxalic acid solution were added to the mixture and incubated at 23°C for 30 minutes. After stirring for 10 minutes, the organic layer was separated and separated. After stirring at 23°C for 30 minutes, the organic layer was separated and the water washing procedure was repeated. The organic layer was concentrated to give the compound represented by the formula (I-3614-h). 1.39 parts of the salt were obtained. TIFF0007682029000179.tif62163 1.24 parts of a salt represented by the formula (I-3614-h), 0.40 parts of salt and 20 parts of chloroform were added, and the mixture was stirred at 23° C. for 3 hours. 15 parts of ion-exchanged water was added to the mixture, stirred at 23°C for 30 minutes, and then the organic layer was separated. To the resulting organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was then separated and washed with water five times. By condensing, 1.36 parts of a salt represented by the formula (I-3614) was obtained. MASS(ESI(+)Spectrum):M + 1316.7 MASS(ESI(-)Spectrum):M - 337.1

[0274] Example 7: Synthesis of a salt represented by formula (I-2569) TIFF0007682029000180.tif36165 0.58 parts of the salt represented by formula (I-667-f) and 30 parts of chloroform were mixed, and the mixture was cooled to 23°C. The mixture was stirred at ℃ for 30 minutes. The compound represented by formula (I-2569-a) was added to the resulting mixture. 0.19 parts of toluene was added, and the mixture was stirred at 50° C. for 2 hours. 0.13 parts of the compound represented by 2569-b) was added, and the mixture was stirred at 50° C. for 3 hours. After that, the mixture was cooled to 23° C. 15 parts of a 5% aqueous oxalic acid solution was added to the mixture, and the mixture was cooled to 23° C. After stirring for 30 minutes at 40°C, the mixture was separated to separate the organic layer. After adding 5 parts of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. The above procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. Add 30 parts of tert-butyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 0.63 parts of a salt represented by the formula (I-2569-h) was obtained. TIFF0007682029000181.tif58133 0.58 parts of a salt represented by the formula (I-2569-h), 0.40 parts of salt and 20 parts of chloroform were added, and the mixture was stirred at 23° C. for 3 hours. 15 parts of ion-exchanged water was added to the mixture, stirred at 23°C for 30 minutes, and then the organic layer was separated. To the resulting organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was then separated and washed with water five times. By condensing, 0.77 parts of a salt represented by the formula (I-2569) was obtained. MASS(ESI(+)Spectrum):M + 603.1 MASS(ESI(-)Spectrum):M - 337.1

[0275] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-3)" etc. depending on their formula numbers. TIFF0007682029000182.tif43144

[0276] Synthesis Example 1: Synthesis of Resin A1 As the monomer, monomer (a1-1-3), monomer (a1-2-6), monomer ( a2-1-1 and monomer (a3-4-2) were used in the molar ratio [monomer (a1-1 -3): Monomer (a1-2-6): Monomer (a2-1-1): Monomer (a3-4- 2)) was mixed in a ratio of 45:14:2.5:38.5, and 1.5 mass of the total monomers were mixed. A solution was prepared by adding 2 times the amount of propylene glycol monomethyl ether acetate. In addition, azobisisobutyronitrile and azobis(2,4-dimethylvaleronyl) were used as initiators. Tolyl) was added at 1 mol% and 3 mol% based on the total monomer amount, respectively, and these were mixed at 73 The mixture was heated at 5° C. for about 5 hours. The 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 with 0.05% NaOH and filtered, 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. TIFF0007682029000183.tif36126

[0277] Synthesis Example 2: Synthesis of Resin X1 As the monomers, monomer (a5-1-1) and monomer (a4-0-12) were used, The molar ratio [monomer (a5-1-1):monomer (a4-0-12)] was 50:50. Mix so that the total amount of monomers becomes 1.2 times by mass of methyl isobutyl ketone is added to the mixture. Azobis(2,4-dimethylvaleronitrile) was added to the solution as an initiator. The mixture was heated at 70° C. for about 5 hours. The resin was precipitated by pouring it into a large amount of a mixed solvent of methanol and water, and the resin was filtered and the weight average Molecular weight 1.0×10 4 Resin X1 was obtained in a yield of 91%. Resin X1 has the following structural unit: It has the following. TIFF0007682029000184.tif3082

[0278] <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. [Table 2]

[0279] <Resin> A1, X1: Resin A1, Resin X1 <Acid Generator (B)> B1-21: A salt represented by the formula (B1-21) B1-22: a salt represented by the formula (B1-22) TIFF0007682029000186.tif2896<Carboxylate(I)> I-667: A salt represented by the formula (I-667) I-669: A salt represented by the formula (I-669) I-1617: A salt represented by the formula (I-1617) I-1619: A salt represented by the formula (I-1619) I-2569: A salt represented by the formula (I-2569) I-2664: A salt represented by the formula (I-2664) I-3614: A salt represented by the formula (I-3614) <Quencher (C)> IX-1 IX-2 IX-3 IX-4 IX-5 IX-6 TIFF0007682029000187.tif89157<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0280] <Production and Evaluation of Resist Patterns> On a 12-inch silicon wafer, an organic anti-reflective coating composition [ARC-29; Nissan Chemical The coating was then baked at 205°C for 60 seconds to produce a 78 mm thick film. Then, the organic anti-reflective film was formed on the organic anti-reflective film. The composition is spin-coated so that the film thickness of the composition layer after drying (pre-baking) is 100 nm. After coating, the silicon wafer was placed on a direct hot plate and heated to 300°C. The composition layer was formed on the silicon wafer by pre-baking for 60 seconds at the temperature indicated in the column. . The composition layer formed on the silicon wafer is then exposed to an ArF excimer laser stepper for immersion exposure. - [XT:1900Gi; Manufactured by ASML, NA=1.35, Annular σ out = 0.85 σ in =0.65 XY-pol. Lighting], trench pattern (pitch 12 0 nm / trench width 40 nm) was formed by changing the exposure amount stepwise using a mask. The exposure was performed by immersing the sample in ultrapure water. After exposure, post-heat the film on a hot plate for 60 seconds at the temperature specified in the "PEB" column of Table 2. The composition layer on the silicon wafer was then exposed to a developer. Dynamic dye was applied for 20 seconds at 23°C using butyl acetate (Tokyo Chemical Industry Co., Ltd.) as a dye. Development was carried out by the dispense method to produce a negative resist pattern.

[0281] In the obtained resist pattern, the exposure dose at which the trench pattern width becomes 40 nm is The effective sensitivity was

[0282] <Line Edge Roughness Evaluation (LER)> The amplitude of the unevenness of the wall surface of the obtained resist pattern was observed and measured using a scanning electron microscope. The results are shown in Table 3. The values ​​in the table indicate the amplitude (nm). [Table 3] [Industrial Applicability]

[0283] The carboxylate of the present invention and the resist composition containing the carboxylate provide excellent line edge roughness. Since it is possible to obtain resist patterns with good LER, it is suitable for semiconductor microfabrication. This is extremely useful industrially.

Claims

1. A carboxylate represented by formula (I): [In formula (I), R １ and R ２ each independently represents -O-R １０ , -O-CO-R １０ , -O-CO-OR １０ , -O-L １ -C-O-R １０ Represents. L １ represents an alkanediyl group having 1 to 6 carbon atoms. R ４ , R ５ , R ７ and R ８ each independently represents a halogen atom, a fluorinated alkyl group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 18 carbon atoms, the hydrocarbon group optionally having a substituent, and -CH 2 - is -O-, -CO-, -S- or -SO ２ It may be replaced by -. R １０ represents a group having a cyclic carbonate structure represented by formula (x1) to formula (x15). X １ and X ２ each independently represents an oxygen atom or a sulfur atom. m1 represents an integer of 1 to 5, and when m1 is 2 or more, the groups in multiple parentheses may be the same or different. m2 represents an integer of 0 to 5, and when m2 is 2 or more, the groups in the parentheses may be the same or different. 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 4, and when m5 is 2 or more, a plurality of R ５ may be the same or different from each other. m7 represents an integer of 0 to 4, and when m7 is 2 or more, a plurality of R ７ may be the same or different from each other. m8 represents an integer of 0 to 5, and when m8 is 2 or more, a plurality of R ８ may be the same or different from each other. However, 1≦m1+m7≦5, and 0≦m2+m8≦5. X ０ represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (-CH contained in the alicyclic hydrocarbon group). ２ may be replaced by -O- or -CO-), an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a group combining an alicyclic hydrocarbon group having 3 to 18 carbon atoms with a chain hydrocarbon group having 1 to 12 carbon atoms (the -CH contained in the alicyclic hydrocarbon group and the chain hydrocarbon group). ２ - is -O-, -S-, -CO- or -SO ２ - which may be replaced by -.

2. X １ and X ２ The carboxylate according to claim 1, wherein is an oxygen atom.

3. R １０ The carboxylate according to claim 1 or 2, wherein the group having a cyclic carbonate structure is a group represented by any one of formulas (x1) to (x8).

4. m2 is 0, m8 is 1, R ８ The carboxylate according to any one of claims 1 to 3, wherein is a branched alkyl group having 3 or 4 carbon atoms.

5. R ４ Or R ５ The carboxylate according to any one of claims 1 to 4, wherein is an iodine atom, a fluorine atom, or a trifluoromethyl group.

6. R in the benzene ring ４ The bonding position of X １ or m-position to R ５ The bonding position of X ２ The carboxylate according to claim 5, wherein the carboxylate is in the o-position or m-position relative to the

7. X ０ is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (-CH contained in the alicyclic hydrocarbon group). ２ 7. The carboxylate according to claim 1, wherein - may be replaced by -O- or -CO-, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.

8. X ０ is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom or a hydroxyl group (the —CH 2 8. The carboxylate according to claim 1, wherein - may be replaced by -O- or -CO-, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a halogen atom, a hydroxyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms.

9. A carboxylic acid generator comprising the carboxylate according to any one of claims 1 to 8.

10. 10. A resist composition comprising the carboxylic acid generator according to claim 9, an acid generator other than the carboxylic acid generator, and a resin having an acid labile group.

11. 11. The resist composition according to claim 10, wherein the resin having an acid labile group comprises at least one member 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 It 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, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

12. The resist composition according to claim 10 or 11, further comprising a resin that includes a structural unit having a fluorine atom.

13. (1) A step of applying the resist composition according to any one of claims 10 to 12 onto a substrate; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) developing the composition layer after heating; A method for producing a resist pattern comprising the steps of:

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