Method for manufacturing resist compositions and resist patterns

Abstract

To provide a resist composition from which a resist pattern can be produced with a good pattern collapse margin (PCM).SOLUTION: The resist composition contains: an acid generator containing a salt represented by formula (I); and a resin containing a structural unit having an acid-labile group and a structural unit represented by formula (a2-A). [In the formula (I), L1 and R1 each represent a substituted / unsubstituted hydrocarbon group, and -CH2- in the group may be substituted with -O-, -S- or the like; X1 represents -CO-O-, -O-CO- or the like; R2 represents a halogen atom or an alkyl group; and m1 represents an integer of 1-3 and m2 represents an integer of 0-4].SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Patent Document 1 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The item is described. Patent Document 2 (TIFF0007848299000001.tif3357) describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Each item is described individually. Patent Document 3 (TIFF0007848299000002.tif33127) describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The item is described. Patent Document 4 (TIFF0007848299000003.tif2854) describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The item is described. TIFF0007848299000004.tif3362 [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2004-203858 [Patent Document 2] Japanese Patent Publication No. 2005-097254 [Patent Document 3] Japanese Patent Application Publication No. 09-244234 [Patent Document 4] Japanese Patent Publication No. 2017-088865 [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention provides a resist composition that forms a resist pattern having better pattern collapse resistance (PCM) than a resist pattern formed from the resist composition containing the above salt. That is, an object of the present invention is to provide a resist composition that forms a resist pattern having better pattern collapse resistance (PCM).

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF0007848299000005.tif3499[In formula (I), L 1 represents a hydrocarbon group having 1 to 28 carbon atoms, which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-. X 1 represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O-, where * represents the bonding site with L. 1 R 1 represents a hydrocarbon group having 1 to 24 carbon atoms, which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-. m1 represents an integer of any one of 1 to 3. When m1 is 2 or more, a plurality of L, 1 X, 1 and R 1 may be the same as or different from each other. R 2 represents a halogen atom or an alkyl group having 1 to 6 carbon atoms. m2 represents an integer of any one of 0 to 4. When m2 is 2 or more, a plurality of R 2 may be the same as or different from each other. Z + represents an organic cation.] [2]R 1 ​However, a cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group has substituents) It is also fine.) A hydrocarbon group containing (the -CH2- contained in the hydrocarbon group is -O-, -S-, The salt described in [1] may be replaced by -SO2- or -CO-. [3]L 1 The salt described in [1] or [2], wherein is an alkanediyl group having 1 to 4 carbon atoms. [4] A salt as described in any of [1] to [3], where m1 is 2. An acid generator containing a salt described in any of [5][1] to [4]. A resist composition containing the acid generator described in [6][5] and a resin having an acid-unstable group. [7] Resins having acid-unstable groups are structural units represented by formula (a1-1) and formula (a1- The register described in [6] includes at least one selected from the group consisting of structural units represented in (2). Stress composition. TIFF0007848299000006.tif4291[In formulas (a1-1) and (a1-2), L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents k1 represents an integer from 1 to 7, and * represents the bonding site with -CO-. R a4 and R a5 Each of these independently represents either a hydrogen atom or a methyl group. R a6 and R a7 These are, independently, an alkyl group with 1 to 8 carbon atoms and an alicyclic group with 3 to 18 carbon atoms. This represents a hydrocarbon group or a group formed by combining these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3. [8] Resins having acid-unstable groups include structural units represented by formula (a2-A) [6] or [7] is the resist composition described in [7]. TIFF0007848299000007.tif4654[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents the alkyl group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyl This represents a luoxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or * -X a51 -( A a52 -X a52 ) nb - represents -R a50 they combine This represents the bonding site with the carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, Number R a51 They may be identical or different from one another. [9] Further contains a salt that generates an acid that is less acidic than the acid generated by the acid generator. A resist composition according to any one of [6] to [8].

[10] (1)[6]~[9] is applied to the substrate. process, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) A step of developing the composition layer after heating, A method for manufacturing a resist pattern that includes [the specified element]. [Effects of the Invention]

[0006] By using a resist composition containing the salt of the present invention, good pattern deformation resistance ( Resist patterns can be manufactured using PCM. [Modes for carrying out the invention]

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

[0008] [Salt represented by formula (I)] This invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In salt (I), the side with a negative charge is called "anion (I)," and the side with a positive charge is called "antion (I)." It is sometimes referred to as "On (I)". TIFF0007848299000008.tif3499[In this formula, all symbols have the same meaning as described above.]

[0009] In equation (I), L 1 Examples of divalent hydrocarbon groups in this context include alkanediyl groups and other divalent groups. Vale chain hydrocarbon groups, monocyclic or polycyclic divalent alicyclic hydrocarbon groups, divalent aromatic hydrocarbon water Elementary groups are listed, and groups are formed by combining two or more of these groups (for example, alicyclic hydrocarbon groups) It may also be a divalent hydrocarbon group formed from an alkanediyl group. Examples of alkanediyl groups include 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 group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,1 2-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, Pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane Linear alkanediyl groups such as n-1,17-diyl groups; and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Examples include branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group. The number of carbon atoms in the lucandiyl group is preferably 1 to 12, more preferably 1 to 9. More preferably 1 to 6, and even more preferably 1 to 4. Examples of monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups include cyclobutane-1,3-di Iyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclo Monocyclic divalent alicyclic groups such as locutane-1,5-diyl groups and cycloalkanediyl groups Saturated hydrocarbon groups; and norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic saturated carbon such as 1,5-diyl group and adamantane-2,6-diyl group A hydrogen group is an example. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, and more preferably The range is 3 to 16, and more preferably 3 to 12. Examples of divalent aromatic hydrocarbon groups include phenylene, naphthylene, anthrylene, and bivalent groups. Examples include aromatic hydrocarbon groups such as phenylene groups, phenanthrylene groups, and arylene groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14. Yes, and more preferably 6 to 10. As a group combining two or more types, a combination of an alicyclic saturated hydrocarbon group and an alkanediyl group is used. Examples include combined groups and groups that combine aromatic hydrocarbon groups and alkanediyl groups. . Examples of groups combining an alicyclic saturated hydrocarbon group and an alkanediyl group include, for example, -2 Valence alicyclic saturated hydrocarbon group -alkanediyl group-,-alkanediyl group-divalent alicyclic saturated Japanese hydrocarbon group -alkanediyl group-,-alkanediyl group-divalent alicyclic saturated hydrocarbon group - are some examples. Examples of groups combining an aromatic hydrocarbon group and an alkanediyl group include, for example, a -2 valent group. Aromatic hydrocarbon group -alkanediyl group-,-alkanediyl group-divalent aromatic hydrocarbon group Examples include -alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-, etc. . L 1 The -CH2- contained in the divalent hydrocarbon group with 1 to 28 carbon atoms is -O-, -S-, It may be replaced with -SO2- or -CO-. L 1The -CH2- group in hydrocarbon groups with 1 to 28 carbon atoms is -O-, -S-, or -SO2 -If replaced by -CO-, the number of carbon atoms before replacement is equal to the number of carbon atoms in the hydrocarbon group. Let's assume that.

[0010] L 1 The substituents that may be present are a hydroxyl group, a carboxyl group, a halogen atom, and a hydroxyl group. A group, alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, group with 2 to 13 carbon atoms Alkoxycarbonyl groups, alkylcarbonyl groups with 2 to 13 carbon atoms, Examples include alkylcarbonyloxy groups or groups combining these. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkyl groups with 1 to 12 carbon atoms include methyl, ethyl, propyl, and isopropyl groups. butyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl Examples include C13 groups and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9. Preferably, it is 1 to 6, and more preferably 1 to 4. Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, and b Toxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group These are some examples. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and The alkylcarbonyloxy group having 2 to 13 carbon atoms is the alkyl or alkoxy group described above. This represents a group to which a carbonyl group or a carbonyloxy group is bonded. Examples of alkoxycarbonyl groups with 2 to 13 carbon atoms include the methoxycarbonyl group and the ethoxycarbonyl group. Examples include carbonyl groups and butoxycarbonyl groups, which are alkylcarbonyl groups with 2 to 13 carbon atoms. Examples of acetyl groups include acetyl groups, propionyl groups, and butyryl groups, with 2 to 1 carbon atoms. 3. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, Examples include butyryloxy groups. The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. More preferably, it is an alkyl group or halogen atom having 1 to 4 carbon atoms, and methyl It is even more preferable that the group be a fluorine atom or a fluorine atom.

[0011] L 1 This refers to an alkanediyl group having 1 to 4 carbon atoms (however, the -C contained in the alkanediyl group is...). H2- may be replaced by -O- or -CO-. ) Alkanes with 1 to 4 carbon atoms A group formed by combining a diyl group and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (however, the alkali The -CH2- contained in the nucleotide group may be replaced with -O- or -CO-, The -CH2- contained in the alicyclic hydrocarbon group can be converted to -O-, -S-, -SO2-, or -CO-. It may be replaced.) Or it may have an alkanediyl group having 1 to 4 carbon atoms and substituents. A group formed by combining an aromatic hydrocarbon group having 6 to 18 carbon atoms (however, the alkanediyl The -CH2- group contained in the group may be replaced by -O- or -CO-. Preferably, an alkanediyl group having 1 to 4 carbon atoms, and an alkanediyl group having 1 to 4 carbon atoms and carbon A group formed by combining an alicyclic hydrocarbon group with prime numbers 3 to 18 (however, the alkanediyl group The -CH2- contained may be replaced by -O- or -CO-. ) or carbon-1 A group formed by combining an alkanediyl group of ~4 and a phenylene group which may have substituents. However, the -CH2- contained in the alkanediyl group may be replaced by -O- or -CO- and it is more preferable that it is so, and it is further preferable that it is an alkanediyl group having 1 to 4 carbon atoms and it is even more preferable that it is a methylene group or an ethylene group.

[0012] R 1 Examples of the hydrocarbon group in R include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and groups formed by combining these. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-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, n-undecyl group, n-dodecyl group, etc. The number of carbon atoms of the alkyl group is preferably 1 to 9, more preferably 1 to 4. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 9, further preferably 1 to 6, and even more preferably 1 to 4. Examples of the alkenyl group include ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, octynyl group, isooctynyl group, nonenyl group, etc. Examples of the alkynyl group include ethynyl group, propynyl group, isopropynyl group, butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, nonynyl group, etc. ​​​​​​​​​​​​The alicyclic hydrocarbon group may be monocyclic, polycyclic or spirocyclic, and may be either saturated or unsaturated. Examples of the monocyclic alicyclic hydrocarbon group include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo octyl group, cyclononyl group, cyclodecyl group, cyclododecyl group and other monocyclic cycloal kyl groups. Examples of the polycyclic alicyclic hydrocarbon group include, for example, decahydronaphthyl group, adamantyl group, norbornyl group and other polycyclic cycloalkyl groups. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and still more preferably 5 to 16. Specifically, examples of the alicyclic hydrocarbon group include the groups represented below. TIFF0007848299000009.tif40151 Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, biphenyl group, anthryl group, phenanthryl group, binaphthyl group and the like. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10.

[0013] In the case of a combined group, groups with different valences (alkane diyl group, alkane triyl group, cycloalkane diyl group, cycloalkane triyl group, etc.) may be included in the above-mentioned groups and may also be included. Examples of the group formed by combination include a group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group (for example, aromatic hydrocarbon group-alkane diyl group-*, alkyl group-aromatic hydrocarbon group-*), a group formed by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (for example , alicyclic hydrocarbon group-alkane diyl group-*, alkyl group-alicyclic hydrocarbon group-*), and an aromatic group combined with an alicyclic hydrocarbon group (for example, aromatic hydrocarbon group-alicyclic hydrocarbon group-*), etc. A group that combines a fragrant hydrocarbon group and an alicyclic hydrocarbon group (for example, an aromatic hydrocarbon group - alicyclic hydrocarbon group) Examples include cyclic hydrocarbon groups (*) and alicyclic hydrocarbon groups (*) (aromatic hydrocarbon groups). This indicates the joining point. Aromatic hydrocarbon groups - alkanediyl groups - * include benzyl groups, phenethyl groups, etc. One example is the larchyl group. Examples of alkyl-aromatic hydrocarbon groups-* include tolyl groups and xylyl groups. Examples of alicyclic hydrocarbon groups - alkanediyl groups -* include cyclohexylmethyl group, cyclo Hexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 Examples include cycloalkylalkyl groups such as -yl-1-methylethyl. Examples of alkyl-alicyclic hydrocarbon groups include methylcyclohexyl group and dimethylcyclohexyl group. Cyclohexyl group, 2-alkyladamantan-2-yl group, and other alkyl groups Examples include the luquill group. Examples of aromatic hydrocarbon groups (alicyclic hydrocarbon groups) include the phenyladamantyl group. It is possible. Examples of alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include the adamantylphenyl group. It is possible.

[0014] Groups in which the -CH2- contained in a hydrocarbon group is replaced by -O- or -CO- include: Alkoxy groups such as hydroxyl, carboxyl, methoxy, ethoxy, and butoxy groups , cycloalkoxy groups such as cyclohexyloxy groups, cyclohexylmethoxy groups, etc. Alkylcarbonyl groups such as acetyl groups and methoxycarbonyl groups Alkoxycarbonyl groups such as alkoxy groups, alkylcarbonyloxy groups such as acetyloxy groups, and butyrate Alkoxycarbonyloxy groups such as xycarbonyloxy groups, aromatic groups such as benzoyloxy groups Examples include aromatic hydrocarbon groups and carbonyloxy groups. Furthermore, the -CH2- contained in the alicyclic hydrocarbon group is -O-, -CO-, or -SO2- The replaced groups include those listed below. TIFF0007848299000010.tif68154 The -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -SO2- or -CO- If a substitution has occurred, the number of carbon atoms before the substitution shall be considered the total number of carbon atoms in the hydrocarbon group. The number can be one, or two or more.

[0015] R 1 The substituents that the hydrocarbon group may have include a halogen atom, a cyano group, and a carbon atom. Alkyl groups number 1 to 12 (the -CH2- contained in the alkyl group is -O-, -S-, -C Examples include those that may be replaced by O- or -SO2-. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkyl groups with 1 to 12 carbon atoms include methyl, ethyl, propyl, and isopropyl groups. butyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl Examples include C13 groups and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9. Preferably, it is 1 to 6, and more preferably 1 to 4. As a substituent, the -CH2- group in the alkyl group is replaced with -O- or -CO-. If this is the case, the number of carbon atoms before replacement shall be the total number of carbon atoms of the alkyl group. The replaced group and For example, a hydroxyl group (a group in which the -CH2- contained in a methyl group is replaced by -O-) , the carboxyl group (the -CH2-CH2- contained in the ethyl group is replaced by -O-CO-) a group in which any -CH2- at an arbitrary position in the alkyl group is replaced by -O- (alkoxy group), a group in which -CH2-CH2- at an arbitrary position in the alkyl group is replaced by -O-CO- (alkoxycarbonyl group), a group in which -CH2- at an arbitrary position in the alkyl group is replaced by -CO- (alkylcarbonyl group), a group in which -CH2-CH2- at an arbitrary position in the alkyl group is replaced by -CO-O- (alkylcarbonyloxy group), etc. can be mentioned. As the alkoxy group, an alkoxy group having 1 to 11 carbon atoms can be mentioned. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. can be mentioned. The number of carbon atoms of the alkoxy group is preferably 1 to 6, and more preferably 1 to 4. The alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 11 carbon atoms can be mentioned. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. can be mentioned. As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 12 carbon atoms can be mentioned. For example, an acetyl group, a propionyl group, a butyryl group, etc. can be mentioned. As the alkylcarbonyloxy group, an alkylcarbonyloxy group having 2 to 11 carbon atoms can be mentioned. For example, an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. can be mentioned. a group in which any -CH2- at an arbitrary position in the alkyl group is replaced by -O- (alkoxy group), a group in which -CH2-CH2- at an arbitrary position in the alkyl group is replaced by -O-CO- (alkoxycarbonyl group), a group in which -CH2- at an arbitrary position in the alkyl group is replaced by -CO- (alkylcarbonyl group), a group in which -CH2-CH2- at an arbitrary position in the alkyl group is replaced by -CO-O- (alkylcarbonyloxy group), etc. can be mentioned. [[ID=ID=10]] a group in which any -CH2- at an arbitrary position in the alkyl group is replaced by -O- (alkoxy group), a group in which -CH2-CH2- at an arbitrary position in the alkyl group is replaced by -O-CO- (alkoxycarbonyl group), a group in which -CH2- at an arbitrary position in the alkyl group is replaced by -CO- (alkylcarbonyl group), a group in which -CH2-CH2- at an arbitrary position in the alkyl group is replaced by -CO-O- (alkylcarbonyloxy group), etc. can be mentioned. As the alkoxy group, an alkoxy group having 1 to 11 carbon atoms can be mentioned. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. can be mentioned. The number of carbon atoms of the alkoxy group is preferably 1 to 6, and more preferably 1 to 4. As the alkoxy group, an alkoxy group having 1 to 11 carbon atoms can be mentioned. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. can be mentioned. The number of carbon atoms of the alkoxy group is preferably 1 to 6, and more preferably 1 to 4. As the alkoxy group, an alkoxy group having 1 to 11 carbon atoms can be mentioned. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. can be mentioned. The number of carbon atoms of the alkoxy group is preferably 1 to 6, and more preferably 1 to 4. [[ID=ID=19]]As the alkoxy group, an alkoxy group having 1 to 11 carbon atoms can be mentioned. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. can be mentioned. The number of carbon atoms of the alkoxy group is preferably 1 to 6, and more preferably 1 to 4. As the alkoxy group, an alkoxy group having 1 to 11 carbon atoms can be mentioned. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, etc. can be mentioned. The number of carbon atoms of the alkoxy group is preferably 1 to 6, and more preferably 1 to 4. The alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. The alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. The alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-mentioned alkyl group or alkoxy group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 11 carbon atoms can be mentioned. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. can be mentioned. As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 12 carbon atoms can be mentioned. For example, an acetyl group, a propionyl group, a butyryl group, etc. can be mentioned. As the alkylcarbonyloxy group, an alkylcarbonyloxy group having 2 to 11 carbon atoms can be mentioned. For example, an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. can be mentioned. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 11 carbon atoms can be mentioned. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. can be mentioned. As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 12 carbon atoms can be mentioned. For example, an acetyl group, a propionyl group, a butyryl group, etc. can be mentioned. As the alkylcarbonyloxy group, an alkylcarbonyloxy group having 2 to 11 carbon atoms can be mentioned. For example, an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. can be mentioned. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 11 carbon atoms can be mentioned. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. can be mentioned. As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 12 carbon atoms can be mentioned. For example, an acetyl group, a propionyl group, a butyryl group, etc. can be mentioned. As the alkylcarbonyloxy group, an alkylcarbonyloxy group having 2 to 11 carbon atoms can be mentioned. For example, an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. can be mentioned. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 11 carbon atoms can be mentioned. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. can be mentioned. As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 12 carbon atoms can be mentioned. For example, an acetyl group, a propionyl group, a butyryl group, etc. can be mentioned. As the alkylcarbonyloxy group, an alkylcarbonyloxy group having 2 to 11 carbon atoms can be mentioned. For example, an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. can be mentioned. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 11 carbon atoms can be mentioned. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. can be mentioned. As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 12 carbon atoms can be mentioned. For example, an acetyl group, a propionyl group, a butyryl group, etc. can be mentioned. As the alkylcarbonyloxy group, an alkylcarbonyloxy group having 2 to 11 carbon atoms can be mentioned. For example, an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. can be mentioned. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 11 carbon atoms can be mentioned. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. can be mentioned. As the alkylcarbonyl group, an alkylcarbonyl group having 2 to 12 carbon atoms can be mentioned. For example, an acetyl group, a propionyl group, a butyryl group, etc. can be mentioned. As the alkylcarbonyloxy group, an alkylcarbonyloxy group having 2 to 11 carbon atoms can be mentioned. For example, an acetyloxy group, a propionyloxy group, a butyryloxy group, etc. can be mentioned. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 6, more preferably 2 to 4. Yes. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 6, more preferably 2 to The answer is 4. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 6, and more preferably Or it is 2 to 4. R 1 The hydrocarbon group in may have one substituent or multiple substituents.

[0016] R 1 The hydrocarbon group in this context is a cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon The group may have substituents.) A hydrocarbon group containing (the -CH2- contained in the hydrocarbon group is (It may be replaced by -O-, -S-, -SO2-, or -CO-.) preferable.

[0017] Hydrocarbon groups containing cyclic hydrocarbon groups include monocyclic or polycyclic alicyclic groups with 3 to 18 carbon atoms. Formula hydrocarbon groups and cyclic hydrocarbon groups such as aromatic hydrocarbon groups having 6 to 18 carbon atoms, or these A combination of these groups, monocyclic or polycyclic alicyclic hydrocarbon groups with 3 to 18 carbon atoms and carbon 6 ~18 aromatic hydrocarbon groups and other cyclic hydrocarbon groups and chain hydrocarbon groups (alkyl groups) with 1 to 6 carbon atoms. Examples include groups formed by arbitrarily combining an alkene group, an alkenyl group, or an alkynyl group. As for alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups, they are the same as the groups described above. Some examples can be listed.

[0018] The combined bases are, A group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (the combined group contains (The -CH2- may be replaced with -O-, -S-, -CO-, or -SO2-) , alicyclic hydrocarbon groups and chain hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups) The combined group (the -CH2- contained in the combined group is -O-, -S-, -CO- (or may be replaced with -SO2-) and aromatic hydrocarbon groups and chain hydrocarbon groups (A A group formed by combining an alkyl group, an alkenyl group, or an alkynyl group (the combined group contains The -CH2- group may be replaced with -O-, -S-, -CO-, or -SO2-. ) are some examples. In addition, in combinations, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups ( Alkyl groups, alkenyl groups, alkynyl groups, etc. may be combined in pairs of two or more types. Also, which of the bases is X 1 It may also be bonded to the above group with different valencies. group (alkanediyl group, alkanetriyl group, cycloalkanediyl group, cycloalkanediyl group) It may contain (such as a nitryl group). 1 hydrocarbon groups containing cyclic hydrocarbon groups The total number of carbon atoms can be, for example, 3 to 24, preferably 4 to 18, and more preferably 5 to 16. It seems so.

[0019] Specific examples of combined elements include: Adamantylmethyl group, adamantylethyl group, cyclohexylmethyl group, cyclohex Silethyl group, etc., alicyclic hydrocarbon group - chain hydrocarbon group - *(the chain hydrocarbon group and the alicyclic hydrocarbon group) The -CH2- contained in the cyclic hydrocarbon group is replaced by -O-, -S-, -CO-, or -SO2-. (It may be replaced), Chains such as methyladamantyl group, methylcyclohexyl group, and dimethylcyclohexyl group. Formula hydrocarbon group - Alicyclic hydrocarbon group - * (contained in the chain hydrocarbon group and the alicyclic hydrocarbon group) The -CH2- group may be replaced with -O-, -S-, -CO-, or -SO2-. ), Chain hydrocarbon group such as tolyl group, xylyl group - aromatic hydrocarbon group - *(the chain hydrocarbon The -CH2- contained in the group is replaced by -O-, -S-, -CO-, or -SO2-. (It's okay.) Chain-type hydrocarbon group - alicyclic hydrocarbon group - chain-type hydrocarbon group, such as methylcyclohexylmethyl group Elemental group -*(The -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group are -O-, (May be replaced by -S-, -CO-, or -SO2-), Aromatic hydrocarbon groups such as benzyl groups and phenethyl groups - chain hydrocarbon groups - *(the chain hydrocarbon The -CH2- contained in the hydrogen group is replaced by -O-, -S-, -CO-, or -SO2-. (Even if it's okay) Chain hydrocarbon group such as tolymethyl group - aromatic hydrocarbon group - chain hydrocarbon group - *(the chain The -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -CO-, or -SO2-. (It may be replaced), Aromatic hydrocarbon group - alicyclic hydrocarbon group - *(the alicyclic carbon The -CH2- contained in the hydrogenated group is replaced by -O-, -S-, -CO-, or -SO2-. (It's okay if it's not), Alicyclic hydrocarbon groups such as cyclohexylphenyl and adamantylphenyl groups - aromatic Hydrocarbon group -*(The -CH2- contained in this alicyclic hydrocarbon group is -O-, -S-, -CO Examples include - (which may be replaced with -SO2-), etc. Here, * is X 1 The conclusion This indicates the joining point.

[0020] The substituents that the cyclic hydrocarbon group may have include halogen atoms, cyano groups, and carbon number 1 to 12 alkyl groups (the -CH2- contained in the alkyl group is -O-, -S-, -CO Examples include - (which may be replaced by -SO2-). Halogen atoms, alkyl groups having 1 to 12 carbon atoms (the -CH2- contained in the alkyl group is As for -O-, -S-, -CO- or -SO2- (which may be replaced by these), as mentioned above Similar to the above, these can be cited.

[0021] A cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have substituents) is, A cycloaliphatic hydrocarbon group having 3 to 18 carbon atoms (the cycloaliphatic hydrocarbon group may have substituents, The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -SO2-, or -CO- (may be replaced by) or an aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic carbon The hydrogen group may preferably have substituents. Alicyclic hydrocarbon groups having 3 to 18 carbon atoms (these alicyclic hydrocarbon groups are alkyl groups having 1 to 4 carbon atoms) The alicyclic ring may have one or more selected from the group consisting of a group, a hydroxyl group, and a fluorine atom. The -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -SO2-, or -CO-. (may be replaced), or an aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic hydrocarbon group This is selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, hydroxyl groups, and fluorine atoms. It is more preferable that the above conditions are met. Alicyclic hydrocarbon groups having 5 to 16 carbon atoms (these alicyclic hydrocarbon groups are alkyl groups having 1 to 4 carbon atoms) The alicyclic ring may have one or more selected from the group consisting of a group, a hydroxyl group, and a fluorine atom. The -CH2- contained in the hydrocarbon group is replaced with -O-, -S-, -SO2-, or -CO-. It is even preferable that it may be replaced.

[0022] It contains a cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have substituents). As for hydrocarbon groups, Preferably, a hydrocarbon group containing an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon The group may have substituents, and the -CH2- contained in the hydrocarbon group may be -O-, -S-, (may be replaced by -SO2- or -CO-), or aromatic carbon with 6 to 18 carbon atoms. Hydrocarbon group containing a hydrogen group (the aromatic hydrocarbon group may have substituents, the hydrocarbon The -CH2- contained in the group is replaced by -O-, -S-, -SO2-, or -CO-. (It is also acceptable) More preferably, a hydrocarbon group containing an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic carbon The hydrogen group is selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, hydroxyl groups, and fluorine atoms. It may have one or more of the -CH2- contained in the hydrocarbon group, -O-, -S-, - (may be replaced by SO2- or -CO-), or aromatic carbon with 6 to 18 carbon atoms Hydrogen group containing a hydrogen group (the aromatic hydrocarbon group is an alkyl group having 1 to 4 carbon atoms, a hydroxyl group) It may have one or more selected from the group consisting of a fluorine group and a fluorine atom, and the hydrocarbon group may contain The -CH2- group may be replaced with -O-, -S-, -SO2-, or -CO-. ) and More preferably, an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon group is carbon It has one or more elements selected from the group consisting of alkyl groups (number 1 to 4), hydroxyl groups, and fluorine atoms. It is also possible that the -CH2- contained in the alicyclic hydrocarbon group be -O-, -S-, -SO2- (or may be replaced with -CO-), alicyclic hydrocarbon groups having 3 to 18 carbon atoms and carbon atoms A group that combines 1 to 6 chain-like hydrocarbon groups (the alicyclic hydrocarbon group has 1 to 4 carbon atoms) It may have one or more selected from the group consisting of a hydroxyl group, a hydroxyl group, and a fluorine atom. The -CH2- contained in the combined group is converted to -O-, -S-, -SO2-, or -CO-. (may be replaced), aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic hydrocarbon group is , one or more selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, hydroxyl groups, and fluorine atoms (May have the above), or an aromatic hydrocarbon group having 6 to 18 carbon atoms and a chain carbon having 1 to 6 carbon atoms. A group combined with a hydrogen group (the aromatic hydrocarbon group is an alkyl group having 1 to 4 carbon atoms, hydride) It may have one or more selected from the group consisting of a roxy group and a fluorine atom, and the combination The -CH2- contained in the group is replaced by -O-, -S-, -SO2-, or -CO-. (It is also acceptable) More preferably, an alicyclic hydrocarbon group having 5 to 16 carbon atoms (the alicyclic hydrocarbon group is One or more selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, hydroxyl groups, and fluorine atoms. It may have -CH2-, -O-, -S-, -SO (May be replaced by 2- or -CO-) or alicyclic hydrocarbons having 5 to 16 carbon atoms A group that combines a group with a chain-like hydrocarbon group having 1 to 4 carbon atoms (the alicyclic hydrocarbon group has a carbon number It has one or more elements selected from the group consisting of 1 to 4 alkyl groups, hydroxyl groups, and fluorine atoms. It is also possible that the -CH2- contained in the combined group is -O-, -S-, -SO2- or (It may be replaced with -CO-).

[0023] m1 is an integer from 1 to 3, preferably 1 or 2, and more preferably 2. If 1 is 1 or 2, then SO3- For this, the following structure, which is an m substitution, is preferred. It's nice. TIFF0007848299000011.tif38135

[0024] R 2 Examples of alkyl groups with 1 to 6 carbon atoms include methyl, ethyl, propyl, and isopodium groups. Ropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, etc. Examples include alkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 4, and more preferably The values ​​are 1 to 3. R 2 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. It can be done. m2 is an integer between 0 and 4, and preferably an integer between 0 and 2. In one embodiment, it is preferable that m2 is 0. In another embodiment, m2 is It is preferable that it be 1 or 2. If m2 is 1, R 2 The fact that it is a halogen atom Preferably, R 2 It is more preferable that it is a fluorine atom or an iodine atom. When m2 is 2 If, R 2 One of the atoms is a halogen atom, and the other is a halogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable that it be a group, R 2 One of them is a fluorine atom or an iodine atom, and the other is a fluorine atom It is more preferable that the atom is a carbon atom, an iodine atom, or an alkyl group having 1 to 3 carbon atoms.

[0025] Examples of anions (I) include the following anions. Among them, equation (Ia -1) ~ Formula (Ia-8), Formula (Ia-14), Formula (Ia-15) ~ Formula (Ia-23), Formula Anions represented by formulas (Ia-29) and (Ia-30) are preferred. TIFF0007848299000012.tif247159

[0026] TIFF0007848299000013.tif232161

[0027] Z + Examples of organic cations include organic onium cations, organic sulfonium cations, and Organic iodonium cation, organic ammonium cation, benzothiazolium cation and Examples include organic phosphonium cations. Among these, organic sulfonium cations are particularly noteworthy. Organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) (hereinafter) Depending on the formula number, it may be referred to as "cation (b2-1)," etc. ) is one example.

[0028] In formulas (b2-1) to (b2-4) of TIFF0007848299000014.tif48166, R b4 ~R b6 These are, independently, chain hydrocarbon groups with 1 to 30 carbon atoms and groups with 3 to 36 carbon atoms. This term represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and is contained in the chain-like hydrocarbon group. The hydrogen atoms present are found in hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, and lipid groups with 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms and aliphatic hydrocarbon groups with 1 to 18 carbon atoms. They may also be substituted with an alkylcarbonyl group or glycidyloxy group having 2 to 4 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group are halogen atoms, hydroxyl groups, or C1 groups. It may be substituted with ~12 alkoxy groups. R b4 and Rb5 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. Even if the -CH2- contained in the ring is replaced by -O-, -S-, or -CO- good. R b7 and R b8 These are, independently, a halogen atom, a hydroxyl group, and a lipid with 1 to 12 carbon atoms. This represents a fatty hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer between 0 and 5. When m2 is 2 or more, multiple R b7 They may be the same or different, and when n2 is 2 or more, multiple Number R b8 They may be the same or different. R b9 and R b10 Each of these is independently a chain-like hydrocarbon group having 1 to 36 carbon atoms or a group having 3 to 3 carbon atoms. It represents 36 alicyclic hydrocarbon groups. R b9 and R b10 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. It may be done, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. That's good too. R b11 This consists of a hydrogen atom, a chain hydrocarbon group with 1 to 36 carbon atoms, and an alicyclic carbon group with 3 to 36 carbon atoms. This represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 This refers to a chain-type hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or This represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in this chain-like hydrocarbon group are carbon It may be substituted with an aromatic hydrocarbon group having prime numbers 6 to 18, and the aromatic hydrocarbon group contains The hydrogen atom is a carbon-1 to carbon-12 alkoxy group or a carbon-1 to carbon-12 alkyl carbonyl group. It may be substituted with an oxy group. Rb11 and R b12 These molecules bond to each other, forming a ring including the -CH-CO- groups to which they are joined. It is also possible that the -CH2- contained in the ring is replaced by -O-, -S-, or -CO-. That's fine. R b13 ~R b18 These are, independently, a hydroxyl group and an aliphatic hydrocarbon group having 1 to 12 carbon atoms. Alternatively, it represents an alkoxy group having 1 to 12 carbon atoms. L b31 This represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer between 0 and 5. q2 and r2 each independently represent an integer between 0 and 4. u2 represents either 0 or 1. When o2 is 2 or more, multiple R b13 They are the same or different, and when p2 is 2 or more, multiple R b14 They are the same or different, and when q2 is 2 or more, multiple R b15 They are the same or different, r2 When there are 2 or more R b16 They are the same or different, and when s2 is 2 or more, multiple R b17 teeth If the same or different, and t2 is 2 or more, multiple R b18 They are either the same or different.

[0029] Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, and butyl groups. Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and Examples include alkyl groups with a 2-ethylhexyl group. In particular, R b9 ~R b12 The chain-like hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and monocyclic alicyclic carbon Examples of hydrogen groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of cycloalkyl groups include cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include the decahydronaphthyl group and the adamantyl group. Examples include norbornyl groups and the following groups. TIFF0007848299000015.tif10158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably These have 4 to 12 carbon atoms.

[0030] As an example of an alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, methylcyclohex xyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyl Ruadamantan-2-yl group, 2-isopropyladamantan-2-yl group, methyl nor Examples include bornyl groups and isobornyl groups. Hydrogen atoms are substituted with aliphatic hydrocarbon groups. In alicyclic hydrocarbon groups, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferable. The number is 20 or less.

[0031] Aromatic hydrocarbon groups include phenyl, biphenyl, naphthyl, and phenanthryl groups. Examples include aryl groups. Aromatic hydrocarbon groups include chain hydrocarbon groups or alicyclic hydrocarbon groups. It may have an elementary group, and an aromatic hydrocarbon group having a chain-like hydrocarbon group (tolyl group, xyl t-butylphenyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl (e.g., 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group) and alicyclic carbon Aromatic hydrocarbon groups having a hydrogenated group (p-cyclohexylphenyl group, p-adamantyl group) Examples include phenyl groups, etc. Furthermore, if the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, Chain-type hydrocarbon groups with 1 to 18 prime numbers and alicyclic hydrocarbon groups with 3 to 18 carbon atoms are preferred. As an aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group, p-methoxyphenyl Examples include the 'L' group. Examples of chain hydrocarbon groups in which hydrogen atoms are substituted with aromatic hydrocarbon groups include the benzyl group and the ferrous hydrocarbon group. Netyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. An example is the aralkyl group.

[0032] Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups, etc. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It is possible. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkylcarbonyloxy groups include methylcarbonyloxy group and ethylcarbonyl Oxy group, propyl carbonyloxy group, isopropyl carbonyloxy group, butylcarbon Bonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy C group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include oxy groups and 2-ethylhexylcarbonyloxy groups.

[0033] R b4 and R b5The ring formed when these atoms bond to each other and together with the sulfur atom they bond to is The rings may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may have 3 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Furthermore, the ring containing the sulfur atom can be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. For example, the following ring can be cited. * indicates a bonding site. TIFF0007848299000016.tif23143

[0034] R b9 and R b10 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothi Examples include the ophenium ring, thian-1-ium ring, and 1,4-oxatian-4-ium ring. It can be done. R b11 and R b12 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring Examples include oxonorbornane rings and oxoadamantane rings.

[0035] Among cations (b2-1) to (b2-4), preferably cation (b2 -1) The following cations can be considered as cations (b2-1): TIFF0007848299000017.tif80158

[0036] TIFF0007848299000018.tif99143

[0037] The following cations can be considered as cations (b2-2): TIFF0007848299000019.tif18150

[0038] The following cations can be considered as cations (b2-3): TIFF0007848299000020.tif26140

[0039] The following cations can be considered as cations (b2-4): TIFF0007848299000021.tif82166

[0040] Salt (I) is a combination of the above-mentioned anion and the above-mentioned organic cation, which can be any combination. They can be combined. Preferably, the salt (I) is from formulas (Ia-1) to (Ia-8) ), formula (Ia-14), formula (Ia-15) ~ formula (Ia-23), formula (Ia-29), formula ( Anions represented by any of Ia-30), and cations (b2-1), cations (b2 -2) or combinations with cations (b2-3) are also possible.

[0041] Examples of salt (I) include the salts listed in Table 1. In the table below, each symbol corresponds to the above A This represents the symbols attached to structures that represent nions or cations. For example, the salt (I-1) is represented by formula (Ia This refers to a salt consisting of the anion shown in (-1) and the cation represented by formula (b2-c-1). The following salts are represented. TIFF0007848299000022.tif3981 [Table 1] TIFF0007848299000024.tif223154 TIFF0007848299000025.tif223154 TIFF0007848299000026.tif223154 TIFF0007848299000027.tif223154 TIFF0007848299000028.tif177156 In particular, salt (I) is salt (I-1) to salt (I-8), salt (I-14), salt (I-15 )~Salt (I-23), Salt (I-29), Salt (I-30), Salt (I-34)~Salt (I-41 ), salt (I-47), salt (I-48) ~ salt (I-56), salt (I-62), salt (I-63 ), salt (I-67)~salt (I-74), salt (I-80), salt (I-81)~salt (I-89 ), salt (I-95), salt (I-96), salt (I-100) ~ salt (I-107), salt (I- 113), Salt (I-114) ~ Salt (I-122), Salt (I-128), Salt (I-129) , salt (I-133) ~ salt (I-140), salt (I-146), salt (I-147) ~ salt (I -155), salt (I-161), salt (I-162), salt (I-166) ~ salt (I-173 ), salt (I-179), salt (I-180) ~ salt (I-188), salt (I-194), salt ( I-195), Salt (I-199) ~ Salt (I-206), Salt (I-212), Salt (I-21 3) Salt (I-221), salt (I-227), and salt (I-228) are preferred.

[0042] <Method for producing salt (I)> Salt (I) is reacted in a solvent with the salt represented by formula (Ia) and the salt represented by formula (Ib). It can be manufactured by responding to the process. TIFF0007848299000029.tif44165[In the formula, all signs have the same meaning as above. X represents a chlorine atom, a bromine atom, [Represents an iodine atom or CH3SO4.] The solvents include chloroform, monochlorobenzene, dimethylformamide, and acetonamide. Examples include tolyl, ethyl acetate, and water. The reaction temperature is typically between 15°C and 80°C, and the reaction time is typically between 0.5 and 24 hours.

[0043] Examples of salts represented by formula (Ia) include those represented by the following formula, which are readily available on the market. It can be readily obtained and can also be easily manufactured by known methods. TIFF0007848299000030.tif116167

[0044] The salt represented by formula (Ib) is the same as the salt represented by formula (Ic) and the salt represented by formula (Id) It can be produced by reacting the compound with a solvent in the presence of a base catalyst. TIFF0007848299000031.tif41168[In this formula, all symbols have the same meaning as described above.] Examples of bases include potassium carbonate, potassium iodide, pyridine, and triethylamine. It can be done. The solvents include chloroform, monochlorobenzene, dimethylformamide, and acetonamide. Examples include tolyl, ethyl acetate, and water. The reaction temperature is typically between 15°C and 80°C, and the reaction time is typically between 0.5 and 24 hours.

[0045] Salts represented by formula (Ic) include, for example, the salts represented below, and are available in larger quantities on the market. It can be easily obtained. Compounds represented by formula (Id) TIFF0007848299000032.tif2184 include, for example, the compounds shown below, and It can be easily obtained from the market and can also be easily manufactured using known methods. . TIFF0007848299000033.tif32163

[0046] [Acid Generator] The acid generator of the present invention is an acid generator containing salt(I). It contains one type of salt(I). It may contain two or more types of salt (I). The acid generator of the present invention, in addition to salt (I), contains an acid generator known in the resist field (hereinafter referred to as "acid generator"). It may contain a herbal agent (B), which may be used alone. You may use one type, or you may use two or more types in combination.

[0047] The acid generator (B) may be either nonionic or ionic. As herbal preparations, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate ester) are used. Sulfonate, oximesulfonate, N-sulfonyloxiimide, sulfonyloxyke Ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, keto Examples include sulfones, sulfonyl diazomethanes, etc. Ionic acid generators include onions. Onium salts containing um cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples include salts (iodonium salts). An anion of anium salts is aniodonium sulfonate. Examples include onium, sulfonylimide anion, sulfonylmethide anion, etc.

[0048] As the acid generator (B), those described in JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, US Patent No. 3,779, 778, US Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., and compounds that generate an acid upon irradiation can be used. . Further, compounds produced by known methods may also be used. The acid generator (B) may be used in combination of two or more.

[0049] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as "acid generator (B1)". However, salt (I) is excluded.) is. TIFF0007848299000034.tif2861 [In the formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be replaced by a fluorine atom or a hydroxy group. Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 2 4 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + This represents an organic cation.

[0050] Q b1 and Q b2 The perfluoroalkyl group represented by is a trifluoromethyl group, perfluoro Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro Butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perflu Examples include the olopentyl group and the perfluorohexyl group. Q b1 and Q b2 Each of these independently consists of a fluorine atom or a trifluoromethyl group. Preferably, both are fluorine atoms, and more preferably, both are fluorine atoms.

[0051] L b1 Examples of divalent saturated hydrocarbon groups in this context include linear alkanediyl groups and branched alkanediyl groups. Examples include dipropyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these groups It may also be a group formed by combining two or more of these types. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- Linear alkanediyl groups such as diyl groups; An ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group and other branched alkanediyl groups; A cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohex A monocyclic divalent alicyclic saturated hydrocarbon group which is; A norbornane-1,4-diyl group, a norbornane-2,5-diyl group, an adamantane- 1,5-diyl group, an adamantane-2,6-diyl group and other polycyclic divalent alicyclic saturated hydrocarbon groups and the like can be mentioned.

[0052] L b1 In the divalent saturated hydrocarbon group represented by, -CH2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO- Examples of the resulting group include a group represented by any of formulas (b1-1) to (b1-3). In formulas (b1-1) to (b1-3) and the groups represented by formulas ( b1-4) to (b1-11) which are specific examples thereof, * represents the bonding site to -Y.

[0053] ) to (b1-11) which are specific examples thereof, * represents the bonding site to -Y.

[0053] TIFF0007848299000035.tif26117 [In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group ​The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms. L b5 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. L b7 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less. * and ** represent bonding sites, with * representing the bonding site with Y.

[0054] In the groups represented by formulas (b1-1) to (b1-3), the saturated hydrocarbon group is included. If -CH2- is replaced by -O- or -CO-, the number of carbon atoms before replacement is... This is the number of carbon atoms in the hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups. ru. L b2 The bond is preferably a single bond. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 Preferably, the divalent saturated hydrocarbon group has 1 to 8 carbon atoms, and the divalent saturated hydrocarbon water The hydrogen atoms in the elementary group may be substituted with fluorine atoms. L b5 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 The saturated hydrocarbon group is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms. L b7 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. The -CH2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO-. That's good too.

[0055] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The replaced group is preferably the group represented by formula (b1-1) or formula (b1-3). The base represented by equation (b1-1) is shown in equations (b1-4) to (b1-8), respectively. The basis for this is listed below. TIFF0007848299000036.tif49119[In formula (b1-4), Lb8 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. In formula (b1-5), L b9 This represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and contains The -CH2- group may be replaced by -O- or -CO-. L b10 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b12 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 This represents a divalent saturated hydrocarbon group with 1 to 19 carbon atoms. L b14 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. L b15 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b13 ~Lb15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and this divalent saturated hydrocarbon group The -CH2- group may be replaced by -O- or -CO-. L b17 This represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. L b18 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. * and ** represent bonding sites, with * representing the bonding site with Y. L b8 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 This is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. Lb16 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 This is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0056] The base represented by equation (b1-3) is given by equations (b1-9) to (b1-11), respectively. The bases that can be represented are listed below. TIFF0007848299000037.tif23140[In formula (b1-9), L b19 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b20 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b22 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b25 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b26 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less. * and ** represent bonding sites, with * representing the bonding site with Y.

[0057] Furthermore, between the group represented by formula (b1-9) and the group represented by formula (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before replacement is defined as the number of carbon atoms in the saturated hydrocarbon group. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, and b thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group These are some examples.

[0058] The following are examples of bases represented by formula (b1-4): TIFF0007848299000038.tif16150

[0059] The following are examples of bases represented by formula (b1-5): TIFF0007848299000039.tif72148

[0060] The following are examples of bases represented by formula (b1-6): TIFF0007848299000040.tif29150

[0061] The following are examples of bases represented by formula (b1-7): TIFF0007848299000041.tif64150

[0062] The following are examples of bases represented by formula (b1-8): TIFF0007848299000042.tif23150

[0063] The following are examples of bases represented by formula (b1-2): TIFF0007848299000043.tif31161

[0064] The following are examples of bases represented by formula (b1-9): TIFF0007848299000044.tif43138

[0065] The following are examples of bases represented by formula (b1-10): TIFF0007848299000045.tif89157

[0066] The following are examples of bases represented by formula (b1-11): TIFF0007848299000046.tif81158

[0067] Examples of alicyclic hydrocarbon groups represented by Y include formulas (Y1) to (Y11), formula (Y36) to (Y36). Examples of groups represented by formula (Y38) include those shown. The -CH2- contained in the alicyclic hydrocarbon group represented by Y is either -O-, -S(O)2-, or - When replaced by CO-, the number of replacements may be one or two or more. For example, the bases represented by equations (Y12) to (Y35) and (Y39) to (Y43) are listed. It can be done. The alicyclic hydrocarbon group represented by TIFF0007848299000047.tif83168Y is preferably formula (Y1) to formula (Y20), formula ( Y26), equation (Y27), equation (Y30), equation (Y31), equation (Y39) to equation (Y43) A group represented by any of the following, more preferably by formula (Y11), formula (Y15), or formula (Y16) ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39) A group represented by formula (Y40), formula (Y42), or formula (Y43), more preferably Alternatively, see equation (Y11), equation (Y15), equation (Y20), equation (Y26), equation (Y27), equation ( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43) It is a base represented by . The alicyclic hydrocarbon group represented by Y is given by formulas (Y28) to (Y35), (Y39), and (Y 40) If it is a spiro ring containing an oxygen atom, such as formula (Y42) or formula (Y43), 2 The alkanediyl group between the oxygen atoms preferably has one or more fluorine atoms. Furthermore, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom It is preferable that the fluorine atom is not substituted.

[0068] The substituents of the methyl group represented by Y include halogen atoms, hydroxyl groups, and groups with 3 to 1 carbon atoms. 6 alicyclic hydrocarbon groups, C6-C18 aromatic hydrocarbon groups, glycidyloxy groups, -( CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 teeth, Alkyl groups with 1 to 16 carbon atoms, alicyclic hydrocarbon groups with 3 to 16 carbon atoms, and aromatic groups with 6 to 18 carbon atoms. Represents a fragrant hydrocarbon group or a group formed by combining these. ja is an integer from 0 to 4. The alkyl group and the alicyclic hydrocarbon group contain -CH2-, -O-, -S(O ) may be replaced with 2- or -CO-, and the alkyl group, the alicyclic hydrocarbon group and The hydrogen atom contained in the aromatic hydrocarbon group is replaced by a hydroxyl group or a fluorine atom. (It is acceptable to have them.) These are some examples. The substituents of the alicyclic hydrocarbon group represented by Y include halogen atoms, hydroxyl groups, and hydroxyl groups. A C1-C16 alkyl group which may be substituted with a roxy group (the alkyl group contains -CH2- may be replaced by -O- or -CO-. ), lipids with 3 to 16 carbon atoms. Cyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, aralkyl groups with 7 to 21 carbon atoms, Glycidyloxy group, -(CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO -Rb1 group (in the formula, R b1 This refers to alkyl groups with 1 to 16 carbon atoms and alicyclic carbonized water with 3 to 16 carbon atoms. This represents an elementary group, an aromatic hydrocarbon group with 6 to 18 carbon atoms, or a group formed by combining these. ja is, Represents an integer between 0 and 4. -CH contained in the alkyl group and the alicyclic hydrocarbon group. The 2- may be replaced with -O-, -S(O)2-, or -CO-, and the alkyl group The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are hydroxyl or Examples include: (It may be replaced by a fluorine atom.)

[0069] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, and methyl cyclohexyl groups. Chlohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, no Examples include the rubornyl group and the adamantyl group. Alicyclic hydrocarbon groups are chain hydrocarbon groups. They may also contain, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. be. Examples of aromatic hydrocarbon groups include phenyl groups, biphenyl groups, naphthyl groups, and ant groups. Examples include aryl groups such as lyl groups and phenanthryl groups. Aromatic hydrocarbon groups are chain carbon groups. It may have a hydrogenated group or an alicyclic hydrocarbon group, and may have an aromatic carbon having a chain hydrocarbon group Hydrogen group (tolyl group, xylyl group, cumenyl group, mesityl group, p- ethylphenyl group, p- tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl Aromatic hydrocarbon groups having phenyl groups (such as phenol groups) and alicyclic hydrocarbon groups (p-cyclohexylphenyl Examples include nyl groups, p-adamantylphenyl groups, etc. The number of carbon atoms in aromatic hydrocarbon groups Preferably, it is 6 to 14, and more preferably 6 to 10. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, and b Tyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group Examples include the following. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 It is ~9, more preferably 1~6, and even more preferably 1~4. Alkyl groups substituted with hydroxyl groups include hydroxymethyl groups and hydroxy Examples include hydroxyalkyl groups such as ethyl groups. Examples of aralkyl groups include benzyl group, phenethyl group, phenylpropyl group, and naphthyl group. Examples include tyl groups and naphthylethyl groups. The -CH2- group in the alkyl group is replaced by -O-, -S(O)2-, or -CO-, etc. Examples of such groups include alkoxy groups, alkoxycarbonyl groups, alkylcarbonyl groups, and alkoxycarbonyl groups. Examples include chlorocarbonyloxy groups or groups combining these. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 12. Yes, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups. Examples include alkoxycarbonyl groups and butoxycarbonyl groups. The number of carbon atoms in the alkoxycarbonyl group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples include the following. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably The value is between 2 and 6, and more preferably between 2 and 4. Examples of alkylcarbonyloxy groups include acetyloxy groups and propionyloxy groups. Examples include the cy group and the butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of combined groups include groups that combine an alkoxy group and an alkyl group, and A group combining a lucoxy group and an alkoxy group, or a group combining an alkoxy group and an alkylcarbonyl group. Groups combining these, groups combining an alkoxy group and an alkylcarbonyloxy group, etc. It can be listed. Examples of groups combining an alkoxy group and an alkyl group include the methoxymethyl group. Alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, and ethoxymethyl group For example, the number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, and more preferably k is 2 to 6, and more preferably 2 to 4. Groups that combine alkoxy groups include methoxymethoxy groups and metoxy groups. Alkoxyalkoxy groups such as xyethoxy group, ethoxymethoxy group, and ethoxyethoxy group Examples include the following. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, and more Preferably, it is 2 to 6, and more preferably 2 to 4. Examples of groups combining an alkoxy group and an alkylcarbonyl group include methoxyacetyl. Alco groups such as methoxypropionyl group, ethoxyacetyl group, and ethoxypropionyl group Examples include xyalkylcarbonyl groups. The number of carbon atoms in an alkoxyalkylcarbonyl group is... Preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. be. Groups that combine an alkoxy group and an alkylcarbonyloxy group include methoxya Cetyloxy group, Methoxypropionyloxy group, Ethoxyacetyloxy group, Ethoxy Examples include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the coxyalkylcarbonyloxy group is preferably 3 to 13, and more preferably The value of k is between 3 and 7, and more preferably between 3 and 5. The -CH2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S(O)2-, or -CO-, etc. The substituted bases are expressed in equations (Y12) to (Y35) and (Y39) to (Y43). Examples of such bases include:

[0070] The following are examples of Y: TIFF0007848299000048.tif155167

[0071] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms, which may have substituents. More preferably, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, which may have substituents. More preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents. More preferably, an adamantyl group which may have substituents, and the alicyclic hydrocarbon group Alternatively, the -CH2- group constituting the adamantyl group can be replaced with -CO-, -S(O)2-, or -CO-. It may be replaced. Specifically, Y is preferably an adamantyl group, hydroxyadamantine. The group is represented by a tyl group, an oxoadamantyl group, or by formulas (Y42), (Y100) to (Y114). It is the basis for this.

[0072] The anions in the salt represented by formula (B1) are given by formula (B1-A-1) ~ formula (B1- Anions represented by A-59) (hereinafter referred to as "anion (B1-A-1)" etc. depending on the formula number) In some cases, this is preferable, and formulas (B1-A-1) to (B1-A-4), formula (B1 -A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 An anion represented by any of 9) is more preferred.

[0073] TIFF0007848299000049.tif143153

[0074] TIFF0007848299000050.tif64156

[0075] TIFF0007848299000051.tif87146

[0076] TIFF0007848299000052.tif160156

[0077] TIFF0007848299000053.tif165161 Here R i2 ~R i7 These are, independently of each other, for example, alkyl groups having 1 to 4 carbon atoms, preferably The group is either a methyl group or an ethyl group. i8 For example, a chain-like hydrocarbon group having 1 to 12 carbon atoms. Preferably, alkyl groups having 1 to 4 carbon atoms, alicyclic hydrocarbon groups having 5 to 12 carbon atoms, or these. A group formed by combining these, more preferably a methyl group, an ethyl group, or a cyclohex group. It is either an adamantyl group or an adamantyl group. A41 These are single bonds or alkanediyl compounds with 1 to 4 carbon atoms. It is the basis. Q b1 and Q b2 This expresses the same meaning as above. Specifically, the anion in the salt represented by formula (B1) is as shown in Japanese Patent Publication No. 2010-20. Anions listed in Public Gazette No. 4646 are examples.

[0078] Preferably, the anion in the salt represented by formula (B1) is formula (B1a-1) ~ formula ( The anions represented by B1a-38 are listed below. TIFF0007848299000054.tif125153

[0079] TIFF0007848299000055.tif92138

[0080] TIFF0007848299000056.tif167156

[0081] In particular, equations (B1a-1) to (B1a-3), and equations (B1a-7) to (B1a-1) 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a-3) An anion represented by any of 8) is preferred.

[0082] Z1 + Examples of organic cations include organic onium cations and organic sulfonium cations. Organic iodium cation, organic ammonium cation, benzothiazolium cation and Examples include organic phosphonium cations. Among these, organic sulfonium cationic cations are particularly noteworthy. N and organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. It is important. As an aryl sulfonium cation, the cation Z in formula (I) is important. + Similar Some examples can be listed.

[0083] The acid generator (B) is a combination of the anion and the organic cation described above, and these are They can be combined in any way. The acid generator (B) is preferably of formula (B1a-1)~ Equations (B1a-3) and (B1a-7) to (B1a-16), (B1a-18), and Animates expressed by (B1a-19), or any of the formulas (B1a-22) to (B1a-38) Examples include combinations of ON and cation (b2-1) or cation (b2-3).

[0084] The acid generator (B) is preferably represented by formulas (B1-1) to (B1-56), respectively. Examples include those containing arylsulfonium cations, among which those containing arylsulfonium cations are preferred. Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B 1-31) The form represented by formula (B1-56) is particularly preferred. TIFF0007848299000057.tif61150

[0085] TIFF0007848299000058.tif72163

[0086] TIFF0007848299000059.tif79150

[0087] TIFF0007848299000060.tif64150

[0088] TIFF0007848299000061.tif87145

[0089] JPEG0007848299000062.jpg63157

[0090] TIFF0007848299000063.tif152169

[0091] When the acid generator contains salt (I) and acid generator (B), salt (I) and acid generator (B) The ratio of the content of each (mass ratio; salt (I): acid generator (B)) is usually 1:99 to 99:1. Yes, preferably 2:98 to 98:2, and more preferably 5:95 to 95:5. More preferably 10:90~90:10, and especially preferably 15:85~85: It is 15. In the resist composition of the present invention, the total content of the acid generator is as follows: resin (A)1 Preferably 1 to 45 parts by mass, more preferably 1 part by mass, per 00 parts by mass The amount is 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less.

[0092] [Resist composition] The resist composition of the present invention comprises an acid generator containing salt (I) and a resin having an acid-unstable group ( It contains the following (sometimes referred to as "resin (A)"). Here, "acid-unstable group" refers to the elimination group. It has a group, and upon contact with an acid, the leaving group is removed, and the constituent unit becomes a hydrophilic group (for example, hydroxy This refers to a group that converts into a constituent unit having a carboxyl group or a carboxyl group. The resist composition of the present invention generates an acid that is less acidic than the acid generated by the acid generator. It may contain a quencher such as salt (hereinafter sometimes referred to as "quencher (C)"). Preferably, it contains a solvent (which may be referred to as "solvent (E)" below).

[0093] <Resin (A)> Resin (A) is a structural unit having an acid-unstable group (hereinafter referred to as "structural unit (a1)"). The resin (A) may further contain structural units other than structural unit (a1). Preferred. Structural units other than structural unit (a1) include structural units that do not have acid-unstable groups ( (Hereinafter referred to as "structural unit (s)"), structural unit (a1), and other structural units (s) Structural units (for example, structural units having halogen atoms as described later (hereinafter referred to as "structural unit (a4)") In some cases, this may be referred to as "structural unit ( a5) In some cases, this refers to structural units derived from monomers known in the art. These are some examples.

[0094] <Structural unit (a1)> Structural unit (a1) is a monomer having an acid-unstable group (hereinafter referred to as "monomer (a1)"). It is derived from (in some cases). The acid-unstable group contained in resin (A) is the group represented by formula (1) (hereinafter also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF0007848299000064.tif2197 [In formula (1), R a1 , R a2 and R a3 Each of these is an alkyl group having 1 to 8 carbon atoms, R represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms or a combination thereof. a1 and R a2 These are alicyclic hydrocarbon groups with 3 to 20 carbon atoms that bond to each other and together with the carbon atoms to which they are bonded. It forms. ma and na each independently represent 0 or 1, and at least one of ma and na This represents 1. * indicates a connection site. TIFF0007848299000065.tif2379 [In formula (2), R a1' and R a2' Each of these is independently a hydrogen atom or a carbon atom with 1 to 12 carbon atoms. Represents a hydrogenated group, R a3' R represents a hydrocarbon group with 1 to 20 carbon atoms. a2' and R a3' they They bond together, and together with the carbon atoms to which they bond and X, they form a heterocyclic group with 3 to 20 carbon atoms. Furthermore, the -CH2- contained in the hydrocarbon group and the heterocyclic group is replaced by -O- or -S- That's fine. X represents either an oxygen atom or a sulfur atom. 'na' represents either 0 or 1. * indicates a connection site.

[0095] R a1 , R a2 and R a3 The alkyl groups in this include methyl, ethyl, and propyl groups. Examples include butyl groups, pentyl groups, hexyl groups, heptyl groups, and octyl groups. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in this case may be either monocyclic or polycyclic. Monocyclic alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, and cyclohexyl group. Examples include cycloalkyl groups such as butyl groups and cyclooctyl groups. Polycyclic alicyclic carbonized water The elementary groups include decahydronaphthyl group, adamantyl group, norbornyl group and the following groups ( * indicates a binding site. Examples include: R a1 , R a2 and R a3 The carbon of the alicyclic hydrocarbon group The number is preferably between 3 and 16. TIFF0007848299000066.tif11161 Examples of groups combining alkyl groups and alicyclic hydrocarbon groups include methylcyclohexyl Xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group Examples include adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. ru. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 )(R a2 )(R a3 Examples of such groups include the following: Alicyclic hydrocarbon groups are preferably those having 3 carbon atoms. It is ~12. * represents the bond site with -O-. TIFF0007848299000067.tif34158

[0096] R a1' , R a2' and R a3' Examples of hydrocarbon groups in this context include alkyl groups and alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups and groups formed by combining them. Alkyl and alicyclic hydrocarbon groups are R a1 , R a2 and R a3 Similar to the basis mentioned above, It can be done. Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, and phenanthryl. Examples include aryl groups and the like. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (Cycloalkylalkyl groups, etc.), aralkyl groups (benzyl groups, etc.), alkyl groups Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group) xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6 -Ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexyl Silphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group (Fe Examples include ylcyclohexyl groups, etc. R a2' and R a3' These atoms bond with each other, forming a heterocycle together with the carbon atoms and X to which they are bonded. If it is done, -C(R a1' )(R a2' )-XR a3' The following rings are examples of this. * This represents a bonding site. TIFF0007848299000068.tif18125R a1' and R a2' Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0097] The following are examples of base (1): In equation (1), R a1 , R a2 and R a3 It is an alkyl group, ma=0, and na=1 A group that is a tert-butoxycarbonyl group. In equation (1), R a1 , R a2 However, together with the carbon atoms to which these bond, adamant Forms a chill group, R a3 A group that is an alkyl group, with ma=0 and na=1. In equation (1), R a1 and R a2 Each of them is an alkyl group independently, and R a3 Adama A methyl group with ma=0 and na=1. The following are specific examples of group (1). * indicates a bonding site. TIFF0007848299000069.tif74158

[0098] The following are specific examples of group (2). * indicates a bonding site. TIFF0007848299000070.tif67153

[0099] The monomer (a1) preferably has an acid-unstable group and an ethylenically unsaturated bond. Mer, more preferably a (meth)acrylic monomer having an acid-unstable group.

[0100] Among (meth)acrylic monomers having an acid-unstable group, preferably those having 5 to 20 carbon atoms. Examples include those having alicyclic hydrocarbon groups. A resin (A) having structural units derived from monomer (a1) is used in the resist composition. This allows for an improvement in the resolution of the resist pattern.

[0101] As a structural unit derived from a (meth)acrylic monomer having group (1), formula (a1- A structural unit represented by (0) (hereinafter sometimes referred to as structural unit (a1-0)), formula (a1 A structural unit represented by -1) (hereinafter sometimes referred to as structural unit (a1-1)) or formula ( The structural units represented by a1-2) (hereinafter sometimes referred to as structural units (a1-2)) are listed below. Preferably, from the group consisting of structural unit (a1-1) and structural unit (a1-2) These are at least one selected structural unit. These may be used individually or in combination of two or more. They can be used together. TIFF0007848299000071.tif46150[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO- O- represents O-, k1 represents an integer from 1 to 7, and * represents the bonding site with -CO-. R a01 , R a4 and R a5 Each of these independently represents either a hydrogen atom or a methyl group. R a02 , R a03 and R a04 These are, independently, alkyl groups with 1 to 8 carbon atoms and alkyl groups with 3 to 8 carbon atoms. This represents 18 alicyclic hydrocarbon groups or groups formed by combining these groups. R a6 and R a7 These are, independently, an alkyl group with 1 to 8 carbon atoms and an alicyclic group with 3 to 18 carbon atoms. This represents a hydrocarbon group or a group formed by combining these groups. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

[0102] R a01 , R a4 and R a5 The group is preferably a methyl group. L a01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 -CO-O- (wherein k01 is preferably an integer from 1 to 4, more preferably 1) . ), more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 Alkyl groups, alicyclic hydrocarbon groups and so As a base formed by combining these, R in equation (1) a1 , R a2 and R a3 Similar groups to those listed above can be listed. It can be done. R a02 , Ra03 , and R a04 The alkyl group in this case is preferably an alkyl group having 1 to 6 carbon atoms. It is a group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. ru. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. More preferably a methyl group, an ethyl group, or an isopropyl group, and even more preferably an ethyl group. Alternatively, it is an isopropyl group. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 5 to It is 12, and more preferably 5 to 10. Groups that combine alkyl groups and alicyclic hydrocarbon groups are formed by combining these alkyl groups and alicyclic hydrocarbon groups. It is preferable that the total number of carbon atoms in the combined group is 18 or less. R a02 and R a03 The alkyl group is preferably a C1-C6 alkyl group, and more preferably a methyl group. It is either an ethyl group or an ethyl group. R a04 Preferably, an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. The group is a methyl group, more preferably an ethyl group, a cyclohexyl group, or an adamantyl group. be. R a6 and R a7 The alkyl group is preferably a C1-C6 alkyl group, and more preferably a methyl group. The group is an ethyl group or an isopropyl group, and more preferably an ethyl group or an isopropyl group. That is the case. m1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0103] Examples of structural units (a1-0) are given by equations (a1-0-1) to (a1-0-12). A structural unit represented by one of the following and R in the structural unit (a1-0) a01 Methi equivalent to Examples of structural units in which the ∫ group is replaced by a hydrogen atom include equations (a1-0-1) to (a1-0 A structural unit represented by any of the following (-10) is preferred. TIFF0007848299000072.tif59150

[0104] As for the structural unit (a1-1), for example, as described in Japanese Patent Publication No. 2010-204646 Examples of structural units derived from monomers include those from formula (a1-1-1) to formula (a1 -1-4) A structural unit represented by any of the above and R in the structural unit (a1-1) a4 Equivalent to A structural unit in which the methyl group is replaced by a hydrogen atom is preferred, and formulas (a1-1-1) to ( A structural unit represented by any of a1-1-4) is more preferable. TIFF0007848299000073.tif49132

[0105] The structural unit (a1-2) is one of the following equations: (a1-2-1) to (a1-2-6). Structural units represented by and R in structural units (a1-2) a5 The methyl group corresponding to the hydrogen source Examples of structural units that have been replaced by children are given by equations (a1-2-2), (a1-2-5), and equation A structural unit represented by any of (a1-2-6) is preferred. TIFF0007848299000074.tif36161

[0106] Resin (A) is structural unit (a1-0) and / or structural unit (a1-1) and / or structural unit If positions (a1-2) are included, the total content of these is, relative to the total structural units of resin (A), Typically 10 to 95 mol%, preferably 15 to 90 mol%, and more preferably 20 ~85 mol%, more preferably 25~80 mol%, and even more preferably It is 30-75 mol%.

[0107] A structural unit having a base (2) in structural unit (a1) is represented by formula (a1-4). Examples of structural units (hereinafter sometimes referred to as "structural units (a1-4)") include the following. TIFF0007848299000075.tif3667[In formula (a1-4), R a32 This is a hydrogen atom, a halogen atom, or a C1-C6 atom which may have a halogen atom. It represents the alkyl group. R a33 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyl This represents a luoxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer between 0 and 4. If la is 2 or greater, multiple R a33 They are intertwined They may be the same or different. R a34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R a36 R represents a hydrocarbon group with 1 to 20 carbon atoms. a35 and R a36 they combine with each other and Together with the -CO- to which they bond, they form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the carbonized water The -CH2- contained in the elementary group and the divalent hydrocarbon group is replaced by -O- or -S- That's good too.

[0108] R a32 and R a33 The alkyl groups in this context are methyl, ethyl, propyl, and iso. Examples include propyl groups, butyl groups, pentyl groups, and hexyl groups. The alkyl group is carbon A alkyl group with prime numbers 1 to 4 is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even better. R a32 and R a33 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. These are some examples. Examples of C1-C6 alkyl groups that may have a halogen atom include trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoro Ethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl Group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl Group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluor Lopentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl Examples include the hexyl group, perfluorohexyl group, etc. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. Examples include oxy groups and hexyloxy groups. In particular, alkoxy groups having 1 to 4 carbon atoms. A group is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred. . Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It can be done. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, and b Examples include thyryloxy groups. R a34 , R a35 and R a36 Examples of hydrocarbon groups in this context include alkyl groups and alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups and groups formed by combining these. Alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples include syl groups, heptyl groups, and octyl groups. The alicyclic hydrocarbon group may be monocyclic or polycyclic. Monocyclic alicyclic hydrocarbon group Examples include cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups. Examples of cycloalkyl groups include decahydrona. Phthyl groups, adamantyl groups, norbornyl groups, and the following groups (* indicates a bonding site), etc. It can be listed. TIFF0007848299000076.tif10151 Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclophenyl group) Xylphenyl group, p-adamantylphenyl group, etc., phenylcyclohexyl group, etc. Examples include reel-cycloalkyl groups. In particular, R a36 As for, A Lukyl group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms or Examples of groups formed by combining these include

[0109] In equation (a1-4), R a32 A hydrogen atom is preferred as the element. R a33 Preferably, the group is an alkoxy group having 1 to 4 carbon atoms, and also includes methoxy and ethoxy groups. A methoxy group is more preferable, and a methoxy group is even more preferable. For la, 0 or 1 is preferred, and 0 is more preferred. R a34 Preferably, it is a hydrogen atom. R a35 Preferably, it is an alkyl group or alicyclic hydrocarbon group having 1 to 12 carbon atoms. Preferably, it is a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, or a C3 to 18 carbon atom Alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof The group formed is more preferably an alkyl group having 1 to 18 carbon atoms, or a group having 3 to 1 carbon atoms. It is an 8-cell alicyclic aliphatic hydrocarbon group or an aralkyl group having 7 to 18 carbon atoms. a36 in The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 in The aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms.

[0110] -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36 is an acid (for example) It is eliminated upon contact with p-toluenesulfonic acid, forming a hydroxyl group.

[0111] As for structural units (a1-4), for example, see Japanese Patent Publication No. 2010-204646. Examples include monomer-derived structural units. Preferably, formulas (a1-4-1) to (a1 -4-12) Structural units and R a32 The hydrogen atom corresponding to this is placed on the methyl group. Examples of replaced structural units include, more preferably, formulas (a1-4-1) to (a1-4- 5) Examples of structural units can be found in equations (a1-4-10). TIFF0007848299000077.tif69158

[0112] If resin (A) has structural units (a1-4), the content thereof is the total structural unit of resin (A). Preferably, the amount is 5 to 60 mol% of the total production units, and preferably 5 to 50 mol%. This is more preferable, and even more preferable is 10 to 40 mol%.

[0113] As structural units derived from (meth)acrylic monomers having group (2), formula (a1 Structural units represented by -5) (hereinafter sometimes referred to as "structural units (a1-5)") are also mentioned. It can be done. TIFF0007848299000078.tif4253 formula (a1-5), R a8 This may have a halogen atom, or it may have a C1-C6 alkyl group, a hydrogen atom, or a halogen It represents an atom. Z a1 This is a single bond or *-(CH2) h3 -CO-L 54 - represents one of 1-4. Represents an integer of L, where * is L 51 This represents the connection point. L 51 , L 52 , L 53 and L 54 These represent either -O- or -S- independently. s1 represents an integer between 1 and 3. s1' represents an integer between 0 and 3.

[0114] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. C1-C6 alkyl groups that may have a halogen atom include methyl group, ethyl group, Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group Examples include tyl groups and trifluoromethyl groups. In equation (a1-5), R a8 This is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 A single bond or *-CH2-CO-O- is preferred.

[0115] Examples of structural units (a1-5) are described in Japanese Patent Publication No. 2010-61117. Examples of monomer-derived structural units include those from formula (a1-5-1) to formula (a1-5- 4) The structural units represented by formula (a1-5-1) or formula (a1-5-2 A structural unit represented by ) is more preferable. TIFF0007848299000079.tif31130

[0116] If resin (A) has structural units (a1-5), the content thereof is the total structural unit of resin (A). The amount is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and 5 to 40 mol% relative to the production unit. A mol% is more preferable, and 5 to 30 mol% is even more preferable.

[0117] In addition, the following structural units (a1) can also be listed. TIFF0007848299000080.tif26160

[0118] When resin (A) contains structural units such as (a1-3-1) to (a1-3-7) above The content is preferably 5 to 60 mol% relative to the total structural units of resin (A), and 5 to 5 0 mol% is more preferable, and 10 to 40 mol% is even more preferable.

[0119] <Structural unit (s)> A structural unit (s) is a monomer that does not have an acid-unstable group (hereinafter referred to as "monomer (s)"). It is derived from (there is a combination). The monomer that derives the structural unit (s) is an acid-resistant monomer known in the field of resists. Monomers without a stable group can be used. The structural unit (s) preferably has a hydroxyl group or a lactone ring. A structural unit having a xyl group and not having an acid-unstable group (hereinafter referred to as "structural unit (a2)") A structural unit having a lactone ring and / or not having an acid-unstable group (hereinafter referred to as "structural unit") If a resin having a "production unit (a3)" is used in the resist composition of the present invention, This improves the resolution of the resist pattern and its adhesion to the substrate.

[0120] <Structural Unit (a2)> The hydroxyl group in structural unit (a2) can be an alcoholic hydroxyl group or a phenolic group. A hydroxyl group may also be used. When manufacturing a resist pattern from the resist composition of the present invention, KrF is used as the exposure light source. High-energy beams such as excimer lasers (248 nm), electron beams, or EUV (ultra-ultraviolet light) are used. If present, the structural unit (a2) is a structural unit having a phenolic hydroxyl group ( a2) is preferred, and it is even more preferable to use the structural unit (a2-A) described later. When using an ArF excimer laser (193 nm), the structural unit (a2) is A A structural unit (a2) having a hydroxyl group is preferred, and the structural unit (a2) described later is -1) is more preferable. The structural unit (a2) contains one type alone. It is acceptable to include two or more types.

[0121] Structural units having a phenolic hydroxyl group in structural unit (a2) include those of formula (a Examples of structural units represented by 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") include It is possible. TIFF0007848299000081.tif4348[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 atom which may have a halogen atom. This represents a luquill group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy groups, C2-C4 alkylcarbonyl groups, C2-C4 alkylcarbonyl This represents a luoxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 -( A a52 -X a52 ) nb - represents -R a50 they combine This represents the bonding site with the carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, Number R a51 They may be identical or different from one another.

[0122] R a50 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. It can be done. R a50 Examples of C1-C6 alkyl groups that may have a halogen atom include: Fluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2 -Trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pelf Luoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, pel Fluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropene Examples include tyl groups, pentyl groups, hexyl groups, and perfluorohexyl groups. R a50 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable. R a51 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Examples include the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. It is possible. R a51 The alkoxy groups in this context include methoxy, ethoxy, propoxy, and iso Examples include propoxy groups, butoxy groups, sec-butoxy groups, and tert-butoxy groups. A carbon-1 to carbon-4 alkoxy group is preferred, and a methoxy group or ethoxy group is more preferred. A toxic group is even more preferable. R a51 The alkylcarbonyl groups in this context include acetyl, propionyl, and butyric groups. Examples include the lyl group. R a51 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups and propionyl groups. Examples include the luoxy group and the butyryloxy group. R a51 A methyl group is preferred.

[0123] *-X a51 -( A a52 -X a52 ) nb - for example, *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, These include *-CO-O- and *-CO-OA. a52 -CO-O- or *- OA a52 -CO-O- is preferred.

[0124] Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and Examples include 2-methylbutane-1,4-diyl groups. A a52 It is preferable that this is a methylene group or an ethylene group.

[0125] Aa50 These are single bonds, *-CO-O- or *-CO-OA a52 Being a CO-O Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. More preferably, the bond is a single bond or even more preferably *-CO-O-.

[0126] mb is preferably 0, 1, or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxyl group is preferably bonded to the ortho or para position of the benzene ring, and the para position It is more preferable for them to bond.

[0127] As for the structural unit (a2-A), see Japanese Patent Publication No. 2010-204634, Japanese Patent Publication No. 2012- Examples include monomer-derived structural units described in Publication No. 12577. The structural unit (a2-A) is represented by equations (a2-2-1) to (a2-2-6). In structural units and structural units represented by formulas (a2-2-1) to (a2-2-6), the structure R in unit (a²-A) a50 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom. Examples include: Structural unit (a2-A) is a structural unit represented by formula (a2-2-1), formula ( Structural units represented by formula (a2-2-3), structural units represented by formula (a2-2-6), and formula (a Structural units represented by formula (a2-2-1), structural units represented by formula (a2-2-3), or formula (a2 In the structural unit represented by -2-6), R in the structural unit (a2-A) a50 This corresponds to It is preferable that the structural unit is one in which the methyl group is replaced by a hydrogen atom. TIFF0007848299000082.tif42166

[0128] Content of structural unit (a2-A) when structural unit (a2-A) is present in resin (A) This is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, relative to the total structural units. It is mol%, more preferably 15-65 mol%, and even more preferably 20- It is 65 mol%. Structural unit (a2-A) is polymerized using structural unit (a1-4), for example, and then p-Tol It can be incorporated into resin (A) by treating it with an acid such as ene sulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0129] Structural units having an alcoholic hydroxyl group in structural unit (a2) include those with the formula ( The structural unit represented by a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") It can be listed. TIFF0007848299000083.tif3958 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 -CO-O- represents, k2 represents an integer between 1 and 7. * represents a connection site with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 Each of these independently represents a hydrogen atom, a methyl group, or a hydroxyl group. o1 represents an integer between 0 and 10.

[0130] In equation (a2-1), L a3 Preferably, -O-, -O-(CH2) f1 -CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-. R a14The group is preferably a methyl group. R a15 Preferably, it is a hydrogen atom. R a16 This is preferably a hydrogen atom or a hydroxyl group. o1 is preferably an integer between 0 and 3, more preferably 0 or 1.

[0131] As for the structural unit (a2-1), for example, see Japanese Patent Publication No. 2010-204646. Examples of structural units derived from monomers are given by equations (a2-1-1) to (a2-1-6). A structural unit represented by any of the following formulas is preferred, from formula (a2-1-1) to formula (a2-1-4) A structural unit represented by either formula (a2-1-1) or formula (a2-1- The structural unit represented in 3) is even more preferable. TIFF0007848299000084.tif53151

[0132] If resin (A) contains structural units (a2-1), the content of these units is the total structural unit content of resin (A). For each position, it is usually 1 to 45 mol%, preferably 1 to 40 mol%, and more preferably The amount is 1 to 35 mol%, more preferably 1 to 20 mol%, and even more preferably The percentage is between 1 and 10 mol%.

[0133] <Structural unit (a3)> The lactone rings of structural unit (a3) ​​are a β-propiolactone ring and a γ-butyrolactone ring. It can be a monocyclic ring such as a δ-valerolactone ring, and the contraction of a monocyclic lactone ring with other rings. A ring compound is also acceptable. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or γ - A bridged ring containing a butyrolactone ring structure (e.g., a structural unit represented by the following formula (a3-2)) These are some examples.

[0134] The structural unit (a3) ​​is preferably formula (a3-1), formula (a3-2), formula (a3-3) Alternatively, it is a structural unit represented by formula (a3-4). These may be contained individually. It may contain two or more types. TIFF0007848299000085.tif52164[In formulas (a3-1), (a3-2), (a3-3), and (a3-4), L a4 , L a5 and L a6 These are, independently, -O- or *-O-(CH2) k3 -CO-O -(where k3 represents an integer from 1 to 7) represents a base. L a7 is -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -C OOL a9 -CO-O- or *-OL a8 -O-CO-L a9 Represents -O- L a8 and L a9 Each of these independently represents an alkanediyl group with 1 to 6 carbon atoms. * indicates a bonding site with a carbonyl group. R a18 , R a19 and R a20 Each of these independently represents either a hydrogen atom or a methyl group. R a24 This may have a halogen atom, an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halo It represents a gen atom. X a3 represents -CH2- or an oxygen atom. R a21 This represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. R a22 , R a23 and R a25 Each of these independently comprises a carboxyl group, a cyano group, or a carbon-1 to This represents four aliphatic hydrocarbon groups. p1 represents an integer between 0 and 5. q1 represents an integer between 0 and 3. r1 represents an integer between 0 and 3. w1 represents an integer between 0 and 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a23 and / or R a25 They may be the same as each other, or they may be different.

[0135] R a21 , R a22 , R a23 and R a25 Examples of aliphatic hydrocarbon groups in this context include methyl and ethyl groups. group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group Examples of alkyl groups include the following. R a24 The halogen atoms in this include fluorine, chlorine, bromine, and iodine atoms. A child is mentioned. R a24 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Groups such as butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group Examples include, preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups. An example is the ethyl group. R a24 Examples of alkyl groups having a halogen atom include trifluoromethyl group, pe Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroethyl group Olobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, per Fluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl Examples include the triiodomethyl group and others. L a8 and L a9 Examples of alkanediyl groups in this context include methylene group, ethylene group, and propane group. -1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, penta n-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 Examples include the -1,4-diyl group and the 2-methylbutane-1,4-diyl group.

[0136] In equations (a3-1) to (a3-3), L a4 ~L a6 Each is, independently and preferably is -O- or *-O-(CH2) k3 In -CO-O-, k3 is one of 1 to 4 The base is an integer, more preferably -O- and *-O-CH2-CO-O-, even more preferably 'k' is an oxygen atom. R a18 ~R a21 The group is preferably a methyl group. R a22 and R a23 Each of these is independently preferably a carboxyl group, a cyano group, or a methyl group That is the case. p1, q1, and r1 are each independently, preferably integers between 0 and 2. More preferably, it is 0 or 1.

[0137] In equation (a3-4), R a24 Preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is a group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably water It is an elementary atom or a methyl group. R a25 The group is preferably a carboxyl group, a cyano group, or a methyl group. La7 Preferably -O- or *-OL a8 -CO-O- and, far more -O -, -O-CH2-CO-O- or -O-C2H4-CO-O- w1 is preferably an integer between 0 and 2, and more preferably 0 or 1. In particular, formula (a3-4)' is preferred over formula (a3-4). TIFF0007848299000086.tif4151 (in the formula, R a24 , L a7 (This expresses the same meaning as above.)

[0138] The structural unit (a3) ​​is the monomer described in Japanese Patent Publication No. 2010-204646. , monomers described in Japanese Patent Publication No. 2000-122294, Japanese Patent Publication No. 2012-41274 Structural units derived from monomers described in the publication are listed. Structural unit (a3) ​​is , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , equation (a3-3-1), equation (a3-3-2), and equation (a3-4-1) ~ equation (a3-4-1 2) A structural unit represented by any of the above, and in the said structural unit, formula (a3-1) to formula ( R in a3-4) a18 , R a19 , R a20 and R a24 A methyl group corresponding to this is placed on the hydrogen atom. The altered structural units are preferable.

[0139] TIFF0007848299000087.tif112162

[0140] If resin (A) contains structural units (a3), the total content of these units is the total structural unit content of resin (A). The amount is usually 5-70 mol%, preferably 10-65 mol%, and more preferably More specifically, it is between 10 and 60 mol%. Also, structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structure The content of units (a3-4) is 5 to 60 units relative to the total structural units of resin (A), respectively. % is preferred, 5 to 50 mol% is more preferred, and 10 to 50 mol% is even more preferred.

[0141] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF0007848299000088.tif3167[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 This represents a saturated hydrocarbon group having fluorine atoms with 1 to 24 carbon atoms, and the saturated hydrocarbon The -CH2- group in the group may be replaced by -O- or -CO-. R 42 The saturated hydrocarbon group represented by this term includes chain hydrocarbon groups and monocyclic or polycyclic alicyclic hydrocarbon groups. Examples include bases, and bases formed by combining them.

[0142] Chain hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include decyl groups, heptadecyl groups, and octadecyl groups. Monocyclic or polycyclic alicyclic carbides. Examples of hydrogen groups include cyclopentyl group, cyclohexyl group, cycloheptyl group, and cycloocyl group. Cycloalkyl groups such as tyl groups; decahydronaphthyl group, adamantyl group, norbornyl group Examples include polycyclic alicyclic hydrocarbon groups such as the following groups (* indicates a bonding site). TIFF0007848299000089.tif11158 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic hydrocarbon groups include -Alkanediyl group-alicyclic hydrocarbon group, -Alkanediyl group-alkyl group, -Al Examples include candiyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0143] As structural units (a4), equation (a4-0), equation (a4-1), equation (a4-2), equation ( Structures represented by at least one selected from the group consisting of a4-3) and formula (a4-4) The units are listed. TIFF0007848299000090.tif4651[In formula (a4-0), R 5 represents a hydrogen atom or a methyl group. L 4a This represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a This refers to a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. Represents an orocycloalkanediyl group. R 6 This represents a hydrogen atom or a fluorine atom.

[0144] L 4a The alkanediyl groups in this context include methylene, ethylene, and propane-1,3. -Diyl group, linear alkane diyl 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 alkaned groups such as n-1,3-diyl groups and 2-methylpropane-1,2-diyl groups An example is the yl group. L 3a In this context, the perfluoroalkanediyl group is a difluoromethylene group, perf Perfluoroethylene 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 Examples include diyl groups and perfluorooctane-4,4-diyl groups. L 3a In this context, the perfluorocycloalkanediyl group is perfluorocyclohex Sandiyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl Examples include the yl group and the perfluoroadamantanediyl group.

[0145] L 4a The is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond It is a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably k is a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0146] The structural units (a4-0) include the structural units shown below and the structural units within the following structural units ( a4-0) R 5Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007848299000091.tif94165

[0147] TIFF0007848299000092.tif4466[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 This represents a saturated hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. A a41 This is an alkanediyl group having 1 to 6 carbon atoms, which may have substituents, or a compound of formula (ag 1) represents the base. However, A a41 and R a42 At least one of them is a substituent. It has a halogen atom (preferably a fluorine atom). TIFF0007848299000093.tif1384 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44 Each of these is independently a divalent carbon atom having 1 to 5 carbon atoms, which may have substituents. This represents a saturated hydrocarbon group. A a43 This is a divalent aliphatic hydrocarbon having 1 to 5 carbon atoms, which may have single bonds or substituents. It represents the base. X a41 and X a42 These are, independently, -O-, -CO-, -CO-O-, or -O-CO - represents However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates a binding site, and the * on the right is -O-CO-R a42This is the junction site.

[0148] R a42 The saturated hydrocarbon groups in this context include chain-type saturated hydrocarbon groups and monocyclic or polycyclic alicyclic groups. Examples include saturated hydrocarbon groups and groups formed by combining them. ru. Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, and pentyl groups. Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, Examples include xadecyl groups, heptadecyl groups, and octadecyl groups. Monocyclic or polycyclic alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, and cyclopentyl groups. Cycloalkyl groups such as chloroheptyl and cyclooctyl groups; decahydronaphthyl groups, ada Polycyclic alicyclic groups such as mantyl groups, norbornyl groups, and the following groups (* indicates a bonding site). Examples include saturated hydrocarbon groups. TIFF0007848299000094.tif11158 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic saturated hydrocarbon groups include -Alkanediyl group-alicyclic saturated hydrocarbon group, -Alkanediyl group-alkyl Examples include AL groups, -alkanediyl groups, -alicyclic saturated hydrocarbon groups, -alkyl groups, etc.

[0149] R a42 The substituents it possesses include halogen atoms and groups represented by formula (a-g3). At least one selected from the group is mentioned. Examples of halogen atoms include fluorine atoms, Examples include chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. TIFF0007848299000095.tif965[In formula (a-g3), Xa43 * represents an oxygen atom, a carbonyl group, *-O-CO-, or *-CO-O-. A a45 This represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. . * is R a42 This represents the connection point with [the other element]. However, R a42 -X a43 -A a45 In R a42 If it does not have a halogen atom, then A a4 5 This represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and containing at least one halogen atom. .

[0150] A a45 The aliphatic hydrocarbon groups in this context include methyl, ethyl, propyl, and butyl groups. Group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, penta Alkyl groups such as decyl, hexadecyl, heptadecyl, and octadecyl groups; Monocyclic groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups Alicyclic hydrocarbon groups; as well as decahydronaphthyl groups, adamantyl groups, norbornyl groups and Examples include polycyclic alicyclic hydrocarbon groups such as the following groups (* indicates a bonding site). TIFF0007848299000096.tif11158 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic hydrocarbon groups include -Alkanediyl group-alicyclic hydrocarbon group, -Alkanediyl group-alkyl group, -Al Examples include candiyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0151] R a42The preferably is a saturated hydrocarbon group which may have halogen atoms, and has halogen atoms A saturated hydrocarbon group having an alkyl group and / or a group represented by formula (a-g3) is preferred. It seems so. R a42 If it is a saturated hydrocarbon group having a halogen atom, it preferably has a fluorine atom. A saturated hydrocarbon group, more preferably a perfluoroalkyl group or perfluoroalkyl group. It is a chloroalkyl group, and more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. The perfluoromethyl group, perfluoroethyl group, and perfluoropropyl group are examples of perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples include oroheptyl groups and perfluorooctyl groups. Examples of the 'l' group include the perfluorocyclohexyl group. R a42 However, if it is a saturated hydrocarbon group having a group represented by formula (a-g3), then formula (a- Including the number of carbon atoms in the group represented by g3), R a42 The total number of carbon atoms should preferably be 15 or less. Furthermore, 12 or less is more preferable. When the group represented by formula (a-g3) is used as a substituent, The number should preferably be one.

[0152] R a42 If is a saturated hydrocarbon group having a group represented by formula (a-g3), then R a42 is, More preferably, the group is represented by the formula (a-g2). TIFF0007848299000097.tif879[In formula (a-g2), A a46 This comprises a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, which may have a halogen atom. represent. X a44 This represents **-O-CO- or **-CO-O- (where ** is A a46 The connection site represent). A a47 This represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. . However, A a46 , A a47 and X a44 The total number of carbon atoms is 18 or less, A a46 and A a47 of Of these, at least one has at least one halogen atom. * indicates a bonding site with a carbonyl group.

[0153] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3. A a47 The number of carbon atoms in the aliphatic hydrocarbon group is preferably 4 to 15, more preferably 5 to 12. A a47 A cyclohexyl group or an adamantyl group is more preferable.

[0154] The preferred structure of the group represented by formula (a-g2) is as follows (* represents a carbonyl group) (This is the junction site.) TIFF0007848299000098.tif13161

[0155] A a41 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 Linear alkanediyl groups such as ,6-diyl groups; propane-1,2-diyl groups, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- Examples include branched alkanediyl groups such as diyl groups and 2-methylbutane-1,4-diyl groups. ru. A a41 The substituents on the alkanediyl group include a hydroxyl group and a carbon-1 to carbon-6 group. Examples include alkoxy groups. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a carbon number The group is an alkanediyl group of type 2 to 4, and more preferably an ethylene group.

[0156] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Divalent saturated carbonized water The elemental groups include linear or branched alkanediyl groups and monocyclic or polycyclic divalent alicyclic water carbon. Formed by combining an elementary group with an alkanediyl group and a divalent alicyclic hydrocarbon group. Examples of such groups include methylene groups, ethylene groups, and propane-1,3-di Iyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane -1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1 Examples include 2-diyl groups. A a42 , A a43 and A a44 The substituents of the divalent saturated hydrocarbon group represented by are hydroxyl groups. Examples include alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0157] In the group represented by formula (a-g1), X a42 -O-, -CO-, -CO-O- or The following are examples of groups that are -O-CO-. In the following examples, * and ** represents a binding site, and ** is -O-CO-R a42 This is the junction site. TIFF0007848299000099.tif54163

[0158] The structural units represented by formula (a4-1) are the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to this is placed on a hydrogen atom. Examples of replaced structural units include: TIFF0007848299000100.tif165143

[0159] TIFF0007848299000101.tif67132

[0160] An example of a structural unit (a4) is the structural unit represented by formula (a4-2). TIFF0007848299000102.tif4364[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 This represents an alkanediyl group having 1 to 6 carbon atoms, and the -C contained in the alkanediyl group H2- may be replaced by -O- or -CO-. R f6 This represents a saturated hydrocarbon group having 1 to 20 fluorine atoms. However, L 44 and R f6 The upper limit for the total number of carbon atoms is 21.

[0161] L 44 The alkanediyl group with 1 to 6 carbon atoms is A a41 An example using the alkanediyl group in Similar to the above, the same type of group can be cited. R f6 The saturated hydrocarbon group is R a42 Similar to the examples given earlier, the same types of bases can be cited. L 44 As for the alkanediyl groups with 1 to 6 carbon atoms, the alkanediyl groups with 2 to 4 carbon atoms are A ru group is preferred, and an ethylene group is more preferred.

[0162] Examples of structural units represented by formula (a4-2) include formulas (a4-1-1) to (a4 The structural units represented in (a4-2) are as follows: R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It can be cited as a structural unit.

[0163] An example of a structural unit (a4) is the structural unit represented by formula (a4-3). TIFF0007848299000103.tif5672[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 This represents an alkanediyl group with 1 to 6 carbon atoms. A f13 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, which may contain a fluorine atom. vinegar. X f12 This represents *-O-CO- or *-CO-O- (* is A f13 This represents the connection point. ). A f14 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a fluorine atom. However, A f13 and A f14 At least one of them has a fluorine atom, L 5 , A f13 and A f14 The upper limit for the total number of carbon atoms is 20.

[0164] L 5 The alkanediyl group in A is a41 The example given is the alkanediyl group in Similar bases can be cited. A f13A preferred divalent saturated hydrocarbon group which may have a fluorine atom is A divalent chain-type saturated hydrocarbon group which may have a fluorine atom and a fluorine atom A divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanedi It is a lu group. Examples of divalent chain hydrocarbon groups that may contain a fluorine atom include methylene groups and ethylene groups. Alkanediyl groups such as propanediyl, butanediyl and pentanediyl groups; di Fluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perf Perfluoroalkanediyl groups such as ruolobutanediyl and perfluoropentanediyl groups Examples include the 'L' group. A divalent alicyclic hydrocarbon group that may contain a fluorine atom can be monocyclic or polycyclic. But that's fine too. Examples of monocyclic groups include the cyclohexanediyl group and the perfluorocyclohexa Examples include the nucleotide group. Polycyclic groups include the adamantanediyl group and norbornane. Examples include diyl groups and perfluoroadamantanediyl groups. A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 in Similar groups to those exemplified can be cited. Among them, the trifluoromethyl group and the difluoromethyl group are particularly noteworthy. Tyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-Pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and per Fluoroctyl groups and other alkyl fluorides, cyclopropylmethyl groups, cyclopropyl groups Cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group Xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbol Nyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl A methyl group is preferred.

[0165] In equation (a4-3), L 5 An ethylene group is preferred. A f13 The divalent saturated hydrocarbon groups are divalent chain hydrocarbon groups with 1 to 6 carbon atoms and 3 carbon atoms. A group containing a divalent alicyclic hydrocarbon group of ~12 is preferred, and a divalent chain-type carbon dioxide group having 2 to 3 carbon atoms is preferred. A more preferable base material is available. A f14 The saturated hydrocarbon group consists of a chain-like hydrocarbon group with 3 to 12 carbon atoms and a lipid group with 3 to 12 carbon atoms. Groups containing cyclic hydrocarbon groups are preferred, including chain hydrocarbon groups having 3 to 10 carbon atoms and groups having 3 to 1 carbon atoms. Groups containing 0 alicyclic hydrocarbon groups are even more preferred. Among them, A f14 Preferably carbon The group contains 3 to 12 alicyclic hydrocarbon groups, and more preferably cyclopropylmethyl These are the cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group.

[0166] Examples of structural units represented by equation (a4-3) include equation (a4-1'-1) ~ equation (a The structural units represented in 4-1'-11) are listed below. Keru R f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also shown in formula (a4-3). It can be cited as a structural unit.

[0167] As a structural unit (a4), the structural unit represented by formula (a4-4) can also be cited. TIFF0007848299000104.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is, -(CH2) j1 -,-(CH2) j2 -O-(CH2) j3 - or - (CH2) j4 - CO-O-(CH2) j5 - represents j1 through j5 each independently represent an integer from 1 to 6. R f22 This represents a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom.

[0168] R f22 The saturated hydrocarbon group is R a42 Examples include the same saturated hydrocarbon group represented by . R f22 This refers to an alkyl group having 1 to 10 carbon atoms and containing a fluorine atom, or a carbon atom containing a fluorine atom. A cycloaliphatic hydrocarbon group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms and a fluorine atom is preferred. A fluorine group is more preferred, and an alkyl group having 1 to 6 carbon atoms and containing a fluorine atom is even more preferred.

[0169] In equation (a4-4), A f21 As for, -(CH2) j1 - is preferred, ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0170] Examples of structural units represented by formula (a4-4) include the following structural units and the following formula In the structural unit shown, R in structural unit (a4-4) f21 The methyl group corresponding to One example is a structural unit in which a hydrogen atom has been replaced. TIFF0007848299000105.tif87160

[0171] If resin (A) has structural units (a4), the content of these units is the total structural unit content of resin (A). A percentage of the position is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and 3 to 10 mol%. A percentage is even more preferable.

[0172] <Structural Unit (a5)> The non-eliminating hydrocarbon groups of structural unit (a5) include linear, branched, or cyclic hydrocarbons. Groups having a group are examples. In particular, structural unit (a5) has an alicyclic hydrocarbon group. The base is preferable. Examples of structural units (a5) include the structural unit represented by formula (a5-1). . TIFF0007848299000106.tif3871[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in this alicyclic hydrocarbon group The elementary atoms may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- group contained in may be replaced by -O- or -CO-.

[0173] R 52 The alicyclic hydrocarbon group in this can be either monocyclic or polycyclic. Examples of alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, and cyclopene. Examples include chill groups and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include, for example, Examples include adamantyl groups and norbornyl groups. Aliphatic hydrocarbon groups with 1 to 8 carbon atoms include, for example, methyl, ethyl, propyl, and iso groups. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl Examples include alkyl groups such as the octyl group and the 2-ethylhexyl group. Examples of alicyclic hydrocarbon groups with substituents include the 3-methyladamantyl group. ru. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably k is an adamantyl group, a norbornyl group, or a cyclohexyl group. L 55 In this context, divalent saturated hydrocarbon groups include divalent chain saturated hydrocarbon groups and divalent lipids. Examples include cyclic saturated hydrocarbon groups, preferably divalent chain saturated hydrocarbon groups. Examples of divalent chain-type saturated hydrocarbon groups include methylene groups, ethylene groups, and propanedi groups. Examples include alkanediyl groups such as the yl group, butanediyl group, and pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl groups and cyclohexanediyl groups. Examples include the roalkanediyl group. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include ada Examples include mantanediyl groups and norbornanediyl groups.

[0174] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by can be replaced with -O- or -CO-. Examples of the replaced groups include those represented by formulas (L1-1) to (L1-4). In the following formula, * and ** represent bonding sites, respectively, with * representing the bonding site with the oxygen atom. TIFF0007848299000107.tif18165 formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is L x1 (This represents the connection point with [another element].) . L x1 This represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 Each of these independently consists of a single bond or a divalent aliphatic saturated carbon with 1 to 14 carbon atoms. It represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 This represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0175] L x1 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x2 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a single bond. L x3 Preferably, it is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x6 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably The group is either a methylene group or an ethylene group. L x7 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. L x9 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. W x1 Preferably, a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably It is either a cyclohexanediyl group or an adamantanediyl group.

[0176] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF0007848299000108.tif54136

[0177] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF0007848299000109.tif23130

[0178] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF0007848299000110.tif15145

[0179] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF0007848299000111.tif26115

[0180] L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0181] Structural units (a5-1) include the structural units shown below and the structural units within the following structural units ( a5-1) R 51 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007848299000112.tif112150 If resin (A) has structural units (a5), the content of these units is the total structural unit content of resin (A). A value of 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 3 to 15 mol% is preferred. A percentage is even more preferable.

[0182] <Structural Unit (II)> Resin (A) further decomposes upon exposure to generate acid, forming structural units (hereinafter referred to as "structural units") It may contain (II) (in some cases). Specifically, structural unit (II) is Examples include the structural unit described in Japanese Patent Publication No. 2016-79235, with a sulfonate group in the side chain. Alternatively, a structural unit having a carboxylate group and an organic cation, or a side chain with a sulfonio group. It is preferable that the structural unit has an organic anion.

[0183] Structural units having a sulfonate group or carboxylate group in the side chain are defined by formula (II-2 It is preferable that the structural unit is represented by -A'). TIFF0007848299000113.tif36105[In formula (II-2-A'), X III3 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and contains -CH2- may be replaced with -O-, -S-, or -CO- in the saturated carbonized water. The hydrogen atoms contained in the elementary group are halogen atoms, or C1-C2 atoms which may contain halogen atoms. It may be replaced by an alkyl group or hydroxyl group of 6. A X1 This represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen contained in the alkanediyl group The atoms may be substituted with fluorine atoms or perfluoroalkyl groups having 1 to 6 carbon atoms. . RA - This represents a sulfonate group or a carboxylate group. R III3 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents the alkyl group. ZA + This represents an organic cation.

[0184] R III3 The halogen atoms represented by include fluorine, chlorine, bromine, and iodine. Examples include atoms, etc. R III3 A C1-C6 alkyl group which may have a halogen atom represented by the following is: , R a8The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by These are some examples. A X1 Examples of alkanediyl groups with 1 to 8 carbon atoms, represented by the following: methylene group, ethylene group, Propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group Iyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples include the group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. . A X1 The perfluoroalkyl groups having 1 to 6 carbon atoms that may be substituted in the above are: Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Isopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert Examples include butyl groups, perfluoropentyl groups, and perfluorohexyl groups.

[0185] X III3 As a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, the following are examples: linear or branched a Examples include lucandiyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of these groups. They can be placed together. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, do Linear alkanediyl groups such as decane-1,12-diyl groups; butane-1,3-diyl groups, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen Branched alkanedi such as tan-1,4-diyl group and 2-methylbutane-1,4-diyl group cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclo Cycloalkanes such as xane-1,4-diyl groups and cyclooctane-1,5-diyl groups Divalent monocyclic or alicyclic saturated hydrocarbon groups such as the 1,4-diyl group; norbornane-1,4-diyl group, Lunan-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6- Examples include divalent polycyclic and alicyclic saturated hydrocarbon groups such as diyl groups.

[0186] The -CH2- group in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. Examples include the divalent groups represented by equations (X1) to (X53). However, Furthermore, the -CH2- group contained in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. The number of carbon atoms in each preceding element is 17 or less. In the following formula, * and ** represent bonding sites. * is A X1 This represents the connection point. TIFF0007848299000114.tif145161

[0187] X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 This represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0188] ZA in equation (II-2-A') + This is the cation Z in salt (I). + Similar examples can be given. It can be done.

[0189] The structural unit represented by formula (II-2-A') is the structural unit represented by formula (II-2-A) It is preferable that this be the case. TIFF0007848299000115.tif38110[In formula (II-2-A), R III3 , X III3 and ZA + This expresses the same meaning as above. z2A represents an integer between 0 and 6. R III2 and R III4 Each of these is independently a hydrogen atom, a fluorine atom, or a carbon atom with 1 to 6 carbon atoms. Represents a fluoroalkyl group, and when z2A is 2 or more, multiple R III2 and R III4 they They can be the same or different. Q a and Q b Each is independently a fluorine atom or a perfluoroal with 1 to 6 carbon atoms. [Represents the kill group.]

[0190] R III2 , R III4 Q a and Q b As a perfluoroalkyl group having 1 to 6 carbon atoms, So, the aforementioned Q b1 Examples include perfluoroalkyl groups with 1 to 6 carbon atoms, as shown below. It is possible.

[0191] The structural unit represented by formula (II-2-A) is the same as the structural unit represented by formula (II-2-A-1). It is preferable that it be in that position. TIFF0007848299000116.tif5677 [In formula (II-2-A-1), R III2 , R III3 , R III4 Q a Q b and ZA + This expresses the same meaning as above. R III5 This represents a saturated hydrocarbon group with 1 to 12 carbon atoms. z2A1 represents an integer between 0 and 6. X I2 This represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and the saturated hydrocarbon group contains -CH2- may be replaced by -O-, -S-, or -CO-, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with halogen atoms or hydroxyl groups.

[0192] R III5 Examples of saturated hydrocarbon groups with 1 to 12 carbon atoms include methyl group, ethyl group, and propyl group. Ropyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentium hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and do Examples include linear or branched alkyl groups such as decyl groups. X I2 As a divalent saturated hydrocarbon group represented by , X III3 Divalent saturated hydrocarbons represented by Similar examples can be given.

[0193] The structural unit represented by formula (II-2-A-1) is represented by formula (II-2-A-2). A structural unit that can be made into a structure is preferable. TIFF0007848299000117.tif5187 [In formula (II-2-A-2), R III3 , R III5 and ZA + This expresses the same meaning as above. m and n each independently represent either 1 or 2.

[0194] Examples of structural units represented by formula (II-2-A') include the following structural unit, R III3 The group corresponding to the methyl group is a hydrogen atom, a halogen atom (for example, a fluorine atom), or a halogen. A C1-C6 alkyl group that may contain atoms (e.g., a trifluoromethyl group). Examples include structural units that have been replaced and structural units described in International Publication No. 2012 / 050015. It can be done. ZA + This represents an organic cation. TIFF0007848299000118.tif87163

[0195] A structural unit having a sulfonio group and an organic anion in its side chain is represented by formula (II-1-1). It is preferable that the structural unit is such that it can be formed. TIFF0007848299000119.tif3692[In formula (II-1-1), A II1 This represents a single bond or a divalent linking group. R II1 This represents a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms. R II2 and R II3 Each of these independently represents a hydrocarbon group with 1 to 18 carbon atoms, and R II2 Reach biR II3 These atoms may bond to each other, forming a ring with the sulfur atom to which they are bonded. R II4 This is a hydrogen atom, a halogen atom, or a C1-C6 atom which may have a halogen atom. This represents a luquill group. A -This represents an organic anion. R II1 Divalent aromatic hydrocarbon groups with 6 to 18 carbon atoms, as represented by the phenylene group, Examples include naphthylene groups. R II2 and R II3 Examples of hydrocarbon groups represented include alkyl groups, alicyclic hydrocarbon groups, and aromatic groups. Examples include hydroxyl groups and groups formed by combining them. R a1’ , R a2’ and R a3’ Examples include the same hydrocarbon groups as in [the relevant context]. R II4 The halogen atoms represented by include fluorine, chlorine, bromine, and iodine. Examples include atoms, etc. R II4 A C1-C6 alkyl group which may have a halogen atom represented by the following is: , R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by These are some examples. A II1 Examples of divalent linking groups represented by this formula include divalent saturated carbon dioxide with 1 to 18 carbon atoms. Examples include the elemental group, and the -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or It may be replaced with -CO-. Specifically, X III3 Two carbon atoms represented by 1 to 18 Examples include the same saturated hydrocarbon groups as those with a valence.

[0196] The structural units containing cations in formula (II-1-1) are the structural units represented below and biR II4 The group equivalent to the methyl group is a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. Examples include replaced structural units. TIFF0007848299000120.tif84130

[0197] A - Examples of organic anions represented by this include sulfonic acid anions and sulfonylimido anions. Examples include sulfonylmethide anions and carboxylic acid anions. - It is represented The organic anion is preferably a sulfonate anion, and as for the sulfonate anion, as mentioned above. It is more preferable that the anion is contained in the salt represented by formula (B1).

[0198] A - Examples of sulfonylimid anions represented by the formula include the following: TIFF0007848299000121.tif35134

[0199] Examples of sulfonylmethide anions include the following: TIFF0007848299000122.tif29123

[0200] Examples of carboxylic acid anions include the following: TIFF0007848299000123.tif41155

[0201] Examples of structural units represented by formula (II-1-1) include the following structural units. It is possible. TIFF0007848299000124.tif94155

[0202] When resin (A) contains structural unit (II), the content of structural unit (II) is: The amount is preferably 1 to 20 mol%, and more preferably 2 to 1 mol%, relative to the total structural units of fat (A). The percentage is 15 mol%, and more preferably 3 to 10 mol%.

[0203] Resin (A) may have structural units other than those described above, and such structural units In terms of rank, well-known structural units in this field can be cited.

[0204] The resin (A) is preferably a resin consisting of structural unit (a1) and structural unit (s), In other words, it is a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably structural unit (a1-0), structural unit (a1-1) and structural unit (a1-0) Manufacturing unit (a1-2) (preferably having a cyclohexyl group and a cyclopentyl group) At least one, more preferably at least two, selected from the group consisting of (production units). More preferably, a group consisting of structural unit (a1-1) and structural unit (a1-2). It consists of at least two types selected from the following. The structural unit (s) is preferably from the group consisting of structural unit (a2) and structural unit (a3). At least one of the selected structural units (a2) is preferably structural unit (a2-1). Alternatively, it is a structural unit (a2-A). The structural unit (a3) ​​is preferably expressed by formula (a3-1). The structural units that are formed, the structural units represented by formula (a3-2) and the structural units represented by formula (a3-4) It is at least one of the units selected from the group. Each structural unit constituting resin (A) may be used individually or in combination of two or more types. Furthermore, using monomers that derive these structural units, known polymerization methods (e.g., radical polymerization) can be used. Therefore, it can be manufactured. The content of each structural unit in resin (A) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,5 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 (less than 15,000, more preferably less than 15,000). In this specification, weight average fraction The amount of molecules was determined by gel permeation chromatography under the conditions described in the examples. That is the case.

[0205] <Resins other than resin (A)> The resist composition of the present invention may contain resins other than resin (A). Examples of resins other than resin (A) include structural unit (a4) or structural unit (a5). Examples include resins (hereinafter sometimes referred to as resin(X)). Among the resins (X), resins containing structural units (a4) are preferred. It is preferable that the resin contains structural units having oxyatoms. In resin (X), the content of structural unit (a4) is equal to the sum of all structural units in resin (X). In contrast, it is preferable that the amount be 30 mol% or more, and more preferably 40 mol% or more. Furthermore, it is more preferable that the amount be 45 mol% or more. The structural units that resin (X) may further possess include structural unit (a1) and structural unit (a2) Structural units (a3) ​​and structural units derived from other known monomers are examples. In particular, resin (X) consists only of structural unit (a4) and / or structural unit (a5). It is preferable that it be made of resin. Each structural unit constituting the resin (X) may be used individually or in combination of two or more types. These monomers that induce structural units can be used in known polymerization methods (e.g., radical polymerization). Therefore, it can be manufactured. The content of each structural unit in resin (X) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000). The value is 0 or greater, and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight-average molecular weight is the same as in the case of resin (A).

[0206] If the resist composition of the present invention contains resin (X), its content is such that resin (A) 100 Preferably 1 to 60 parts by mass, and more preferably 1 to 50 parts by mass, relative to the mass. More preferably 1 to 40 parts by mass, and particularly preferably 1 to 30 parts by mass, Preferably, the amount is 1 to 8 parts by mass.

[0207] The content of resin (A) in the resist composition is 8 in relation to the solid content of the resist composition. Preferably, it is 0% by mass or more and 99% by mass or less, and preferably 90% by mass or more and 99% by mass or less. It is preferable. Also, if it contains resins other than resin (A), then resin (A) and resins other than resin (A) The total content of the resin is 80% by mass or more and 99% by mass or less relative to the solid content of the resist composition. It is preferable that the amount be less than 90% by mass or more and more than 99% by mass or less. Furthermore, "solid content of the resist composition" refers to the amount of solvent (E) described later, calculated from the total amount of the resist composition. This refers to the total of the components excluding ). Solid content of the resist composition and the resin content thereof. The rate is measured by known analytical means such as liquid chromatography or gas chromatography. It is possible.

[0208] <Solvent (E)> The solvent (E) content is typically 90% by mass or more and 99.9% by mass or less in the resist composition. Yes, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of solvent (E) is 99% by mass or less. The content of solvent (E) is determined, for example, by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as chromatography. The solvent (E) includes ethyl cellosolve acetate, methyl cellosolve acetate, and Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, vinegar Esters such as butyl acid, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl Ketones such as lucetone, 2-heptanone, and cyclohexanone; γ-butyrolactone, etc. Examples include cyclic esters; etc. One of the solvents (E) may be used alone. You may use two or more types.

[0209] <Quencher (C)> Quencher (C) is generated from a basic nitrogen-containing organic compound and an acid generator (B). Examples include salts that produce acids with weaker acidity than the acid that produces the quencher. If (C) is included, the amount of quencher (C) is based on the solid content of the resist composition. Preferably, it is about 0.01 to 15% by mass, and more preferably about 0.1 to 10% by mass. It is more preferable that it be about 0.1 to 5% by mass, and even more preferable that it be about 0.1 to 3% by mass. It is even more preferable that it be in mass percent. Basic nitrogen-containing organic compounds include amines and ammonium salts. Examples include aliphatic amines and aromatic amines. Aliphatic amines include primary amines. Examples include amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, and diisopropylamine. Ruaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine Octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine mine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, methyldinonylamine, methylddecylamine, ethyl dibuty Luamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine Ethyl dioctylamine, ethyl dinonylamine, ethyl didecylamine, dicyclo Xylmethylamine, Tris[2-(2-methoxyethoxy)ethyl]amine, Triiso Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine Mine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmeth , 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridazole 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl (Lu)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-Pyridyl)ketone, 4,4'-dipyridylsulfide, 4,4'-dipyridyldisulfide Examples include phyto, 2,2'-dipyridylamine, 2,2'-dipicolylamine, and bipyridine. Preferably, diisopropylaniline is cited, and more preferably 2,6-diiso Examples include propylaniline. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethyl ammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, and the like.

[0210] The acidity of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt with an acid dissociation constant of the acid generated from the salt usually being -3 < pKa, preferably a salt with -1 < pKa < 7, and more preferably a salt with 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as " intramolecular salt of weak acid (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. As the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B), preferably, a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylate anion ), and more preferably, an intramolecular salt of weak acid (D). (D) TIFF0007848299000125.tif85165​

[0211] Examples of intramolecular salts (D) of weak acids include the following salts: TIFF0007848299000126.tif72165

[0212] <Other ingredients> The resist composition of the present invention may optionally include components other than those described above (hereinafter referred to as "other components"). It may be referred to as "F (F)". It may contain other components (F) in particular. There are no known additives in the resist field, such as sensitizers, dissolution inhibitors, surfactants, and stabilizers. Agents, dyes, etc. can be used.

[0213] <Preparation of resist composition> The resist composition of the present invention comprises a salt (I), a resin (A), an acid generator (B), and necessary Depending on the resin used, a resin other than resin (A), solvent (E), quencher (C), and its It can be prepared by mixing with other components (F). The mixing order is arbitrary, and in particular It is not limited to this. The mixing temperature can range from 10 to 40°C, depending on the type of resin, etc. An appropriate temperature can be selected depending on the solubility in solvents (E), etc. The mixing time is Depending on the mixing temperature, you can choose an appropriate time from 0.5 to 24 hours. There are no particular restrictions on the mixing method, and stirring and mixing can be used. After mixing each component, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable to do so.

[0214] <Method for manufacturing resist patterns> The method for manufacturing a resist pattern of the present invention is: (1) A step of applying the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) Includes a step of developing the composition layer after heating. To coat the resist composition onto the substrate, a commonly used device such as a spin coater is used. Therefore, it can be done. Examples of substrates include inorganic substrates such as silicon wafers. Before applying the Dist composition, the substrate may be cleaned, and an anti-reflective film or the like may be formed on the substrate. It's fine if you do that. By drying the applied composition, the solvent is removed and a composition layer is formed. Drying is performed. For example, evaporating a solvent using a heating device such as a hot plate (so-called private heating) This is done by (k) or by using a vacuum device. The heating temperature is 50-200°C. It is preferable that the heating time be 10 to 180 seconds. Also, vacuum drying The pressure used during this process is 1 to 1.0 × 10 5 It is preferable that the pressure be around Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine is an immersion exposure machine. This is also good. As exposure light sources, KrF excimer laser (wavelength 248nm), ArF excimer Ultraviolet lasers such as lasers (wavelength 193nm) and F2 excimer lasers (wavelength 157nm) Laser light is emitted from solid-state laser sources (such as YAG or semiconductor lasers). These devices emit high-harmonic laser light in the far-ultraviolet or vacuum-ultraviolet region by wavelength conversion, such as electron beams and ultra-high-frequency lasers. Various methods can be used, such as those that irradiate with ultraviolet light (EUV). In some cases, the act of irradiating with these radiations is collectively referred to as "exposure." Typically, exposure is performed through a mask corresponding to the desired pattern. The exposure light source is electron In the case of lines, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is heat-treated to promote the deprotection reaction at the acid-unstable groups. Perform a loose post-exposure bake. The heating temperature is usually around 50-200°C, or as preferred. The temperature is approximately 70-150°C. The heated composition layer is typically developed using a developing device and a developing solution. Examples include the dipping method, paddle method, spray method, and dynamic dispensing method. The development temperature is preferably, for example, 5 to 60°C, and the development time is, for example, 5 It is preferable that the developing time is ~300 seconds. By selecting the type of developer as follows: Positive-type resist patterns or negative-type resist patterns can be manufactured. When producing a positive-type resist pattern from the resist composition of the present invention, the developer is used as follows: An alkaline developer is used. The alkaline developer is a type of alkaline water used in this field. Any solution will do. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). Alkaline developers may contain surfactants. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is washed away. It is preferable to remove it. When manufacturing a negative-type resist pattern from the resist composition of the present invention, the developer is used as A developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used. Organic solvents contained in organic developers include ketosols such as 2-hexanone and 2-heptanone. Solvents; glycol ethers such as propylene glycol monomethyl ether acetate Sterling solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole Examples include aromatic hydrocarbon solvents such as the like. In organic developer solutions, the content of organic solvents is preferably 90% by mass or more and 100% by mass or less. It is more preferable that the concentration be 95% by mass or more and 100% by mass or less, and that it be substantially composed of only organic solvents. It is preferable. Among organic developers, those containing butyl acetate and / or 2-heptanone are Preferred. The total content of butyl acetate and 2-heptanone in the organic developer is 50% by mass. Preferably, the amount is 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the composition consists solely of butyl acetate and / or 2-heptanone. Organic developers may contain surfactants. Also, organic developers may contain trace amounts of surfactants. It may contain moisture. During development, by substituting a different type of solvent than the organic developer, development can be stopped. That's good too. It is preferable to wash the resist pattern with a rinsing solution after development. The rinsing solution can be: There are no particular restrictions as long as it does not dissolve the resist pattern, including general organic solvents. A liquid can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove any remaining rinse solution from the substrate and patterns.

[0215] <Application> The resist composition of the present invention is a resist composition for KrF excimer laser exposure, and ArF Resist compositions for Kishima laser exposure, resist compositions for electron beam (EB) exposure, or EU Resist compositions for V exposure, particularly resist compositions for electron beam (EB) exposure or EUV exposure It is suitable as a resist composition for use and is useful for semiconductor microfabrication. [Examples]

[0216] The present invention will be described in more detail with reference to examples. In the examples, the content or amount used is expressed Unless otherwise specified, "%" and "parts" refer to mass. The weight-average molecular weight is a value obtained by gel permuration chromatography. The analytical conditions for gel permuration chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The compound structure was determined by mass spectrometry (LC: Agilent 1100, MASS: Agil This was confirmed by measuring molecular ion peaks using an ent LC / MSD (manufactured by ent). In the examples, the value of this molecular ion peak is indicated by "MASS".

[0217] Example 1: Synthesis of the salt represented by formula (I-1) TIFF0007848299000127.tif35157 3 parts of salt represented by formula (I-1-a), 1.55 parts of potassium carbonate and dimethylformamine 30 parts of the mixture were mixed and stirred at 23°C for 30 minutes, then the temperature was raised to 50°C. The resulting mixed solution Then, 5.43 parts of the compound represented by formula (I-1-b) and 0.46 parts of potassium iodide are added. Furthermore, the mixture was stirred at 50°C for 20 hours and then cooled to 23°C. Add 50 parts of Loloform and 25 parts of deionized water, stir at 23°C for 30 minutes, then separate the liquid. The organic layer was then removed. This washing procedure was repeated five times. The resulting organic layer was then concentrated. This yielded 7.35 parts of the salt represented by formula (I-1-c). TIFF0007848299000128.tif37166 7.35 parts of salt represented by formula (I-1-c), 3.23 parts of salt represented by formula (I-1-d) Mix 10 parts of deionized water, 50 parts of chloroform, and 25 parts of ethyl acetate, and heat at 23°C. The mixture was stirred for 8 hours. To the resulting mixed solution, 25 parts of a 5% oxalic acid aqueous solution were added and the mixture was heated at 23°C for 30 minutes. After stirring for several minutes, the organic layer was separated and the organic layer was removed. 25 parts of deionized water were added to the resulting organic layer. After adding and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was repeated 5 times. The process was repeated several times. To the obtained concentrated residue, 30 parts of tert-butyl methyl ether were added. After stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is concentrated to obtain the product shown in formula (I-1). We obtained 7.02 parts of the salt expressed. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 657.2

[0218] Example 2: Synthesis of the salt represented by formula (I-16) TIFF0007848299000129.tif25158 2.51 parts of salt represented by formula (I-16-a), 0.78 parts of potassium carbonate and dimethyl phosphate 30 parts of lumamide were mixed and stirred at 23°C for 30 minutes, then the temperature was raised to 50°C. To the mixed solution, add 2.72 parts of the compound represented by formula (I-1-b) and 0.23 parts of potassium iodide. The mixture was added, stirred at 50°C for 20 hours, and then cooled to 23°C. After adding 50 parts chloroform and 25 parts deionized water to the mixture and stirring at 23°C for 30 minutes, The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was then concentrated. By doing so, 4.71 parts of the salt represented by formula (I-16-c) were obtained. TIFF0007848299000130.tif34166 4.65 parts of salt represented by formula (I-16-c), 3.2 parts of salt represented by formula (I-1-d) Mix 3 parts of [unclear], 10 parts of deionized water, 50 parts of chloroform, and 25 parts of ethyl acetate, and heat at 23°C. The mixture was stirred for 8 hours. To the resulting mixed solution, 25 parts of a 5% oxalic acid aqueous solution were added and the mixture was heated at 23°C for 3 hours. After stirring for 0 minutes, the organic layer was separated and the organic layer was removed. 25% deionized water was added to the resulting organic layer. After adding the liquid and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was then performed. The process was repeated five times. 30 parts of tert-butyl methyl ether were added to the resulting concentrated residue. After stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is concentrated to obtain formula (I-16 4.29 parts of the salt represented by ) were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 407.1

[0219] Example 3: Synthesis of the salt represented by formula (I-100) TIFF0007848299000131.tif43157 7.35 parts of salt represented by formula (I-1-c), 3 parts of salt represented by formula (I-100-d). 81 parts of the mixture, 50 parts of chloroform, and 25 parts of ethyl acetate were mixed and stirred at 23°C for 8 hours. To the resulting mixed solution, add 25 parts of a 5% oxalic acid aqueous solution and stir at 23°C for 30 minutes, The organic layer was separated by liquid-liquid extraction. 25 parts of deionized water were added to the obtained organic layer and incubated at 23°C. After stirring for 30 minutes, the organic layer was separated and removed. This washing procedure was repeated 5 times. To the concentrated residue, add 30 parts of tert-butyl methyl ether and incubate at 23°C for 30 minutes. After stirring, the supernatant is removed and the liquid is concentrated to obtain salt 7 represented by formula (I-100). 72 copies were obtained. MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 657.2

[0220] Example 4: Synthesis of the salt represented by formula (I-15) TIFF0007848299000132.tif32152 3 parts of salt represented by formula (I-1-a), 1.55 parts of potassium carbonate and dimethylformamine 30 parts of the mixture were mixed and stirred at 23°C for 30 minutes, then the temperature was raised to 50°C. The resulting mixed solution To this, add 4.27 parts of the compound represented by formula (I-15-b) and 0.46 parts of potassium iodide. The mixture was then stirred at 50°C for 20 hours, and then cooled to 23°C. Add 50 parts chloroform and 25 parts deionized water, stir at 23°C for 30 minutes, then separate the liquid-liquid solution. Then the organic layer was removed. This washing operation was repeated five times. The obtained organic layer was concentrated. This yielded 6.25 parts of the salt represented by formula (I-15-c). TIFF0007848299000133.tif40163 6.23 parts of salt represented by formula (I-15-c), 3.2 parts of salt represented by formula (I-1-d) Mix 3 parts of [unclear], 10 parts of deionized water, 50 parts of chloroform, and 25 parts of ethyl acetate, and heat at 23°C. The mixture was stirred for 8 hours. To the resulting mixed solution, 25 parts of a 5% oxalic acid aqueous solution were added and the mixture was heated at 23°C for 3 hours. After stirring for 0 minutes, the organic layer was separated and the organic layer was removed. 25% deionized water was added to the resulting organic layer. After adding the liquid and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was then performed. The process was repeated five times. 30 parts of tert-butyl methyl ether were added to the resulting concentrated residue. After stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is concentrated to obtain formula (I-15 5.89 parts of the salt represented by ) were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 553.2

[0221] Example 5: Synthesis of the salt represented by formula (I-6) TIFF0007848299000134.tif41163 3 parts of salt represented by formula (I-1-a), 1.55 parts of potassium carbonate, and dimethylformamine 30 parts of the mixture were mixed and stirred at 23°C for 30 minutes, then the temperature was raised to 50°C. The resulting mixed solution Then, 8.65 parts of the compound represented by formula (I-6-b) and 0.46 parts of potassium iodide are added. Furthermore, the mixture was stirred at 50°C for 20 hours and then cooled to 23°C. Add 50 parts of Loloform and 25 parts of deionized water, stir at 23°C for 30 minutes, then separate the liquid. The organic layer was then removed. This washing procedure was repeated five times. The resulting organic layer was then concentrated. This yielded 10.75 parts of the salt represented by formula (I-6-c). TIFF0007848299000135.tif46168 10.46 parts of salt represented by formula (I-6-c), 3.2 parts of salt represented by formula (I-1-d) Mix 3 parts of [unclear], 10 parts of deionized water, 50 parts of chloroform, and 25 parts of ethyl acetate, and heat at 23°C. The mixture was stirred for 8 hours. To the resulting mixed solution, 25 parts of a 5% oxalic acid aqueous solution were added and the mixture was heated at 23°C for 3 hours. After stirring for 0 minutes, the organic layer was separated and the organic layer was removed. 25% deionized water was added to the resulting organic layer. After adding the liquid and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was then performed. The process was repeated five times. 30 parts of tert-butyl methyl ether were added to the resulting concentrated residue. After stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is concentrated to obtain formula (I-6). 10.22 parts of the salt represented by [formula] were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 945.2

[0222] Example 6: Synthesis of the salt represented by formula (I-114) TIFF0007848299000136.tif45163 6.23 parts of salt represented by formula (I-15-c), 3 parts of salt represented by formula (I-100-d) Mix 0.81 parts, 10 parts deionized water, 50 parts chloroform, and 25 parts ethyl acetate, 2 The mixture was stirred at 3°C ​​for 8 hours. 25 parts of a 5% oxalic acid aqueous solution were added to the resulting mixed solution and heated to 23°C. After stirring for 30 minutes, the mixture was separated to remove the organic layer. Deionized water was added to the resulting organic layer. 25 parts were added and stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing procedure was performed. The process was repeated five times. To the resulting concentrated residue, 30 parts of tert-butyl methyl ether were added. After stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is concentrated to obtain the formula (I- 6.74 parts of the salt represented by 114) were obtained. MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 553.2

[0223] Example 7: Synthesis of the salt represented by formula (I-105) TIFF0007848299000137.tif45162 10.46 parts of salt represented by formula (I-5-c), 3 parts of salt represented by formula (I-100-d) Mix 0.81 parts, 10 parts deionized water, 50 parts chloroform, and 25 parts ethyl acetate, 2 The mixture was stirred at 3°C ​​for 8 hours. 25 parts of a 5% oxalic acid aqueous solution were added to the resulting mixed solution and heated to 23°C. After stirring for 30 minutes, the mixture was separated to remove the organic layer. Deionized water was added to the resulting organic layer. 25 parts were added and stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing procedure was performed. The process was repeated five times. To the resulting concentrated residue, 30 parts of tert-butyl methyl ether were added. After stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is concentrated to obtain the formula (I- 10.62 parts of the salt represented by 105) were obtained. MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 945.2

[0224] Example 8: Synthesis of the salt represented by formula (I-4) TIFF0007848299000138.tif36163 3 parts of salt represented by formula (I-1-a), 1.55 parts of potassium carbonate and dimethylformamine 30 parts of the mixture were mixed and stirred at 23°C for 30 minutes, then the temperature was raised to 50°C. The resulting mixed solution Then, 5.47 parts of the compound represented by formula (I-4-b) and 0.46 parts of potassium iodide are added. Furthermore, the mixture was stirred at 50°C for 20 hours and then cooled to 23°C. Add 50 parts of Loloform and 25 parts of deionized water, stir at 23°C for 30 minutes, then separate the liquid. The organic layer was then removed. This washing procedure was repeated five times. The resulting organic layer was then concentrated. This yielded 7.53 parts of the salt represented by formula (I-4-c). TIFF0007848299000139.tif35167 7.39 parts of salt represented by formula (I-4-c), 3.23 parts of salt represented by formula (I-1-d) Mix 10 parts of deionized water, 50 parts of chloroform, and 25 parts of ethyl acetate, and heat at 23°C. The mixture was stirred for 8 hours. To the resulting mixed solution, 25 parts of a 5% oxalic acid aqueous solution were added and the mixture was heated at 23°C for 30 minutes. After stirring for several minutes, the organic layer was separated and the organic layer was removed. 25 parts of deionized water were added to the resulting organic layer. After adding and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was repeated 5 times. The process was repeated several times. To the obtained concentrated residue, 30 parts of tert-butyl methyl ether were added. After stirring at 23°C for 30 minutes, the supernatant is removed and the mixture is concentrated to obtain the product shown in formula (I-4). 6.89 parts of salt were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 661.2

[0225] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. These are referred to as "monomers (a1-1-3)" etc., according to their formula numbers. TIFF0007848299000140.tif4179

[0226] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) is used, and its molar ratio [monomer (a1-4-2):monomer (a1-1 -3): Mix the monomers (a1-2-6) in a ratio of 38:24:38. Furthermore, this monomer mixture contains methyl methyl in an amount equal to 1.5 times the total mass of all monomers. Isobutyl ketone was mixed. To the resulting mixture, azobisisobutyronite was added as an initiator. Add lyl to a concentration of 7 mol% relative to the total number of moles of all monomers, and then heat at 85°C. Polymerization was carried out by heating for approximately 5 hours. Afterwards, p-toluenesulfone was added to the polymerization reaction solution. An acidic aqueous solution was added, and the mixture was stirred for 6 hours before being separated. The resulting organic layer contained a large amount of n-heptane. By pouring it into the solution and allowing the resin to precipitate, then filtering and recovering it, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 Resin A1 (polymer) was obtained in a yield of 78%. This resin A1 has the following structural units It is what it is. TIFF0007848299000141.tif29124

[0227] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) are used, The molar ratio [monomer(a1-4-2):monomer(a1-2-6)] is 38:62. Mix them together, and then add to this monomer mixture, relative to the total mass of all monomers. Then, 1.5 times the mass of methyl isobutyl ketone was mixed in. To the resulting mixture, as an initiator, Azobisisobutyronitrile is added in a quantity of 7 mol% relative to the total number of moles of all monomers. Polymerization was carried out by adding it to and heating it at 85°C for about 5 hours. After that, the polymerization reaction solution was added to Then, an aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 6 hours before being separated. The resulting organic layer This is poured into a large amount of n-heptane to precipitate the resin, which is then filtered and recovered, thereby obtaining the weight-averaged fraction. The amount of eggs is approximately 5.4 x 10 3 Resin A2 (polymer) was obtained in a yield of 89%. It has the following structural units: TIFF0007848299000142.tif2887

[0228] <Preparation of the resist composition> As shown in Table 2, the following components were mixed, and the resulting mixture contained fluorine with a pore size of 0.2 μm. The resist composition was prepared by filtering through a resin filter. [Table 2]

[0229] <Resin> A1, A2: Resin A1, Resin A2 <Salt (I)> I-1: Salt represented by formula (I-1) I-4: Salt represented by formula (I-4) I-6: Salt represented by formula (I-6) I-15: Salt represented by formula (I-15) I-16: Salt represented by formula (I-16) I-100: Salt represented by formula (I-100) I-105: Salt represented by formula (I-105) I-114: Salt represented by formula (I-114) <Acid Generator> IX-1 IX-2 IX-3 IX-4 IX-5 TIFF0007848299000144.tif68161<Quencher(C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 TIFF0007848299000145.tif3849<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0230] (Electron beam exposure evaluation of resist composition: Alkaline development) A 6-inch silicon wafer is subjected to hexamethyldisilaza on a direct hot plate. The silicon wafer was treated at 90°C for 60 seconds using a solvent. The resist composition was then applied to this silicon wafer. The layer was spin-coated to a thickness of 0.04 μm. Then, direct hot plated... On the grid, the composition layer was formed by pre-baking for 60 seconds at the temperature shown in the "PB" column of Table 2. A composition layer formed on the surface is subjected to electron beam lithography (ELS-F1 manufactured by Elionix Co., Ltd.). Using "25 125 keV", the exposure amount is changed in steps to create a line and space pattern. Lines (pitch 60nm / line width 30nm) were drawn directly. After exposure, post-exposure is performed on a hot plate at the temperature shown in the "PEB" column of Table 2 for 60 seconds. Jar baking was performed, and then 2.38% by mass of tetramethylammonium hydroxide aqueous solution was added. A resist pattern was obtained by paddle development with a solution for 60 seconds. In the resulting resist pattern, the line width and spacing of the line and space pattern The effective sensitivity was defined as the exposure amount at which the field width and exposure ratio were 1:1.

[0231] <Pattern Failure Evaluation (PCM) Evaluation> The line width of the line pattern becomes thinner with increasing exposure, and pattern disappearance becomes more likely. The numbers indicate line patterns formed with an exposure level exceeding the effective sensitivity, which may have fallen or peeled off. This shows the minimum line width (nm) of the resist pattern where turn disappearance is not observed. The results are shown in Table 3. This will be shown. [Table 3] Compared to comparative compositions 1-5, no pattern loss was observed in compositions 1-16. The minimum line width of the pattern was small, and the pattern collapse evaluation was good. Based on the above results, the salt of the present invention and the resist composition containing the salt have improved pattern deformation resistance. The PCM (Personal Computer Mass) is in good condition. [Industrial applicability]

[0232] The salt of the present invention and the resist composition containing the salt have good pattern deformation resistance (PCM). Therefore, it is useful for the microfabrication of semiconductors.

Claims

1. An acid generator containing a salt represented by formula (I) and A resist composition containing a resin comprising a structural unit having an acid-unstable group and a structural unit represented by formula (a2-A). [In formula (I), L 1 This represents an alkanediyl with 1 to 4 carbon atoms. X 1 * represents *-CO-O-, *-O-CO-, *-O-CO-O-, or *-O-, where * is L 1 This represents the connection point. R 1 represents a hydrocarbon group having 4 to 18 carbon atoms, which may have substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ - or -CO- may be replaced, and the substituent is a halogen atom, a cyano group, or an alkyl group having 1 to 12 carbon atoms, and the -CH2- contained in the alkyl group may be replaced with -O-, -S-, -CO- or -SO2-. m1 represents any integer from 1 to 3, and when m1 is 2 or more, a plurality of L 1 , X 1 and R 1 may be the same as or different from each other. R ２ This represents a halogen atom or an alkyl group having 1 to 6 carbon atoms. m2 represents an integer from 0 to 4, and when m2 is 2 or greater, multiple R ２ They may be identical or different from one another. Z ＋ This represents an organic cation. [In formula (a2-A), R a50 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a51 This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 - (A a52 -X a52 ) nｂ - represents -R a50 This represents the bonding site with the carbon atom to which it is bonded. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent, independently, -O-, -CO-O-, or -O-CO-. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, then multiple R a51 They may be identical or different from one another.

2. R 1 However, a hydrocarbon group containing a cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have substituents) (the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ The resist composition according to claim 1, wherein - or -CO- may be replaced.

3. The resist composition according to claim 1 or 2, wherein m1 is 2.

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

5. The resist composition according to any one of claims 1 to 4, further comprising a salt that generates an acid with a lower acidity than the acid generated from the acid generator.

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

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