Method for manufacturing resist compositions and resist patterns

Abstract

To provide a resist composition from which a resist pattern having a good pattern collapse margin (PCM) can be produced.SOLUTION: A resist composition contains a compound represented by Formula (I), a resin having an acid-labile group, and an acid generator. [In the formula, W represents an optionally substituted (m1+m2+m3)-valent aliphatic hydrocarbon group, provided that -CH2- contained in the aliphatic hydrocarbon group may be substituted with -O- or -CO-; R1 represents *-R10 or *-L2-CO-O-R10; R2 represents *-R10, *-CO-R10, *-CO-O-R10 or the like; R10 represents a base-labile group; and L2 represents an optionally substituted alkanediyl group.]SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Patent Document 1 describes a resist composition containing a compound with the following structural formula, a resin having an acid-unstable group, and an acid generator. TIFF0007878912000001.tif1852 [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2019 / 064976 [Overview of the project] [Problems that the invention aims to solve]

[0004] The object of the present invention is to provide a resist composition that forms a resist pattern with better pattern deformation resistance (PCM) than a resist pattern formed from the above-mentioned resist composition. [Means for solving the problem]

[0005] This invention includes the following inventions. [1] A resist composition containing a compound represented by formula (I), a resin having an acid-unstable group, and an acid generator. TIFF0007878912000002.tif3962 [In formula (I), W represents an aliphatic hydrocarbon group having 1 to 24 carbon atoms with (m1+m2+m3) valency, which may have substituents, and the -CH2- contained in the aliphatic hydrocarbon group may be replaced with -O- or -CO-. R 1 is, *-R 10 or *-L 2 -CO-OR10 represents, and * represents the bonding site with -O-. R 2 is *-R 10 , *-CO-R 10 , *-CO-O-R 10 , *-L 2 -CO-O-R 10 or *-CO-O-L 2 -CO-O-R 10 represents, and * represents the bonding site with -O-. R 10 represents a base-labile group. L 2 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent. m1 represents any integer from 1 to 6. When m1 is 2 or more, the plurality of R 1 may be the same as or different from each other. m2 represents any integer from 1 to 6. When m2 is 2 or more, the plurality of R 2 may be the same as or different from each other. R 3 represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and -CH2- contained in the alkyl group may be replaced by -O- or -CO-. Two R 3 may together form a group having an acetal ring structure. m3 represents any integer from 0 to 4. When m3 is 2 or more, the plurality of R 3 may be the same as or different from each other. [2] The resist composition according to [1], wherein the base-labile group of R 10 is a group represented by formula (1b). TIFF0007878912000003.tif2056 [In formula (1b), R ba1 and R ba2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 6 carbon atoms having a fluorine atom. R ba3 represents a fluorine atom or an alkyl group having 1 to 6 carbon atoms having a fluorine atom. * represents a bonding site. [3] The resist composition according to [1] or [2], wherein W is an aliphatic hydrocarbon group having 3 to 18 carbon atoms and having a (m1+m2+m3) valency. [4] The resist composition according to any one of [1] to [3], wherein the resin having an acid-unstable group comprises at least one selected from the group consisting of structural units represented by formula (a1-0), structural units represented by formula (a1-1), and structural units represented by formula (a1-2). TIFF0007878912000004.tif44144[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents a bond, where k1 is an integer from 1 to 7, and * represents the bond site with -CO-. R a01 , R a4 and R a5 Each of these independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a02 , R a03 and R a04 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R a6 and R a7 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination of 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] A resist composition according to any one of [1] to [4], wherein the resin having an acid-unstable group comprises a structural unit represented by formula (a2-A). TIFF0007878912000005.tif3843[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-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy 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 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 -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, multiple R a51 They may be the same or different from each other. [6] A resist composition according to any one of [1] to [5], wherein the acid generator comprises a salt represented by formula (B1). TIFF0007878912000006.tif2862[In formula (B1), Q b1 and Q b2 Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, wherein -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 24 carbon atoms which may have a substituent, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-. Z1 + represents an organic cation. 〔7〕The resist composition according to any one of 〔1〕~〔6〕, further containing a salt that generates an acid having a lower acidity than the acid generated from the acid generator. 〔8〕(1) A step of applying the resist composition according to any one of 〔1〕~〔7〕 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 exposed composition layer, and (5) A step of developing the heated composition layer, which is a method for manufacturing a resist pattern.

Advantages of the Invention

[0006] By using the resist composition of the present invention, a resist pattern can be manufactured with good pattern collapse resistance (PCM).

Modes for Carrying Out the Invention

[0007] In this specification, the term “(meth)acrylic monomer” means “at least one of acrylic monomers and methacrylic monomers”. Similarly, notations such as “(meth)acrylate” and “(meth)acrylic acid” represent the same meaning. For groups described in this specification that can take both linear and branched structures, either one is acceptable. When -CH2- contained in a hydrocarbon group or the like is replaced by -O-, -S-, -CO-, -SO- or -SO2-, the same examples apply to each group. The term “combined group” means a group formed by bonding two or more of the exemplified groups, and the valences of these groups may be appropriately changed depending on the bonding form. The terms “derived from” or “derived” refer to the fact that the polymerizable C═C bond contained in the molecule becomes a single bond (-C-C- group) by polymerization. When stereoisomers exist, all stereoisomers are included. In this specification, the “solid content of the resist composition” means the total of the components excluding the solvent (E) described later from the total amount of the resist composition.

[0008] 〔Resist Composition〕 The resist composition of the present invention contains a compound represented by formula (I) (hereinafter sometimes referred to as “compound (I)”), a resin having an acid-labile group (hereinafter sometimes referred to as “resin (A)”), and an acid generator (hereinafter sometimes referred to as “acid generator (B)”). Here, the “acid-labile group” has a leaving group, and by contact with an acid, the leaving group is eliminated and converted into a structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). The resist composition of the present invention may further contain a resin other than resin (A). The resist composition of the present invention preferably contains a quencher (hereinafter sometimes referred to as “quencher (C)”) such as a salt that generates an acid having a lower acidity than the acid generated from the acid generator, and preferably contains a solvent (hereinafter sometimes referred to as “solvent (E)”).

[0009] 〈Compound (I)〉 The resist composition of the present invention contains compound (I). TIFF0007878912000007.tif3962[In formula (I), all symbols have the same meaning as described above.]

[0010] Aliphatic hydrocarbon groups with a (m1+m2+m3) valency in W include chain hydrocarbon groups, alicyclic hydrocarbon groups, and groups that combine these. Examples of chain hydrocarbon groups include alkane-(m1+m2+m3)valent-yl groups, alkene-(m1+m2+m3)valent-yl groups, and alkyne-(m1+m2+m3)valent-yl groups, which represent groups in which (m1+m2+m3-1) hydrogen atoms are replaced at the bonding site from alkyl groups, alkenyl groups, and alkynyl groups. The number of carbon atoms in the chain hydrocarbon group is preferably 1 to 18, more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 9, even more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, and nonyl groups. Examples of alkenyl groups include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. Examples of alkynyl groups include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, tert-butynyl, pentynyl, hexynyl, octinyl, and noninyl groups. The alicyclic hydrocarbon group may be monocyclic, polycyclic, or spirocyclic, and may be saturated or unsaturated. Examples of alicyclic hydrocarbon groups include the following groups. The bonding site can be at any position. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, even more preferably 3 to 12, and even more preferably 3 to 10. Specifically, examples of alicyclic hydrocarbon groups include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl groups, and polycyclic cycloalkyl groups such as norbornyl and adamantyl groups, in which (m1+m2+m3-1) hydrogen atoms are replaced at the bonding site. TIFF0007878912000008.tif47169

[0011] The combined bases are, This represents a group formed by combining an alicyclic hydrocarbon group with a chain-like hydrocarbon group such as an alkyl group, alkenyl group, and / or alkynyl group, in which (m1 + m2 + m3 - 1) hydrogen atoms are replaced at the bonding site. Note that in the combined group, two or more types of chain-like hydrocarbon groups such as alicyclic hydrocarbon groups, alkyl groups, alkenyl groups, and alkynyl groups may be combined. Groups in which the -CH2- contained in an aliphatic hydrocarbon group is replaced with -O- or -CO- include alkoxy groups (groups in which -CH2- at any position in an alkyl group is replaced with -O-), alkoxycarbonyl groups (groups in which -CH2-CH2- at any position in an alkyl group is replaced with -O-CO-), alkylcarbonyl groups (groups in which -CH2- at any position in an alkyl group is replaced with -CO-), alkylcarbonyloxy groups (groups in which -CH2-CH2- at any position in an alkyl group is replaced with -CO-O-), cycloalkoxy groups, cycloalkylalkoxy groups, alkoxycarbonyloxy groups, and groups formed by combining two or more of these groups, in which (m1+m2+m3-1) hydrogen atoms are replaced at the bonding site. Examples of alkoxy groups include alkoxy groups having 1 to 17 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and undecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 11, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups represent groups in which a carbonyl group or carbonyloxy group is bonded to an alkyl group or alkoxy group as described above. Examples of alkoxycarbonyl groups include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of alkylcarbonyl groups include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl, propionyl, and butyryl groups. Examples of alkylcarbonyloxy groups include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy, propionyloxy, and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 8, even more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 8, even more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 8, even more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 or 3. Examples of cycloalkoxy groups include cycloalkoxy groups having 3 to 17 carbon atoms, such as the cyclohexyloxy group. Examples of cycloalkylalkoxy groups include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as the cyclohexylmethoxy group. Examples of alkoxycarbonyloxy groups include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as the butoxycarbonyloxy group. Furthermore, groups in which the -CH2- group in an alicyclic hydrocarbon group is replaced by -O- or -CO- include the groups shown below. The bonding site can be at any position. TIFF0007878912000009.tif47167 When an -CH2- group in an aliphatic hydrocarbon group is replaced by an -O- or -CO- group, the number of carbon atoms before the replacement is considered the total number of carbon atoms in the aliphatic hydrocarbon group. This number may be one or two or more. The aliphatic hydrocarbon group of W may have substituents such as halogen atoms, hydroxyl groups, cyano groups, carboxyl groups, C1-C12 alkyl groups, C1-C12 haloalkyl groups, C1-C12 alkoxy groups, and groups formed by combining two or more of these groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Haloalkyl groups having 1 to 12 carbon atoms represent alkyl groups containing halogen atoms, and include alkyl fluorides, alkyl chlorides, alkyl bromides, and alkyl iodides. Examples of haloalkyl groups include perfluoroalkyl groups (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, perfluoropentyl group, perfluorohexyl group, etc.), fluoromethyl group, difluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, chloromethyl group, bromomethyl group, and iodomethyl group. The number of carbon atoms in the haloalkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of groups formed by combining two or more types include alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and alkylcarbonyloxy groups having 2 to 13 carbon atoms. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and alkylcarbonyloxy groups having 2 to 13 carbon atoms represent groups in which a carbonyl group or carbonyloxy group is bonded to the alkyl or alkoxy group mentioned above. Examples of alkoxycarbonyl groups having 2 to 13 carbon atoms include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of alkylcarbonyl groups having 2 to 13 carbon atoms include acetyl, propionyl, and butyryl groups. Examples of alkylcarbonyloxy groups having 2 to 13 carbon atoms include acetyloxy, propionyloxy, and butyryloxy groups.

[0012] Examples of the aliphatic hydrocarbon group of W include the groups shown below. Among these, the aliphatic hydrocarbon group of W is preferably a 2-6 valent aliphatic hydrocarbon group, more preferably a 2-5 valent aliphatic hydrocarbon group, even more preferably a 2-4 valent aliphatic hydrocarbon group, and even more preferably a 2-3 valent aliphatic hydrocarbon group. * indicates a bonding site. TIFF0007878912000010.tif173164

[0013] In particular, W is preferably an aliphatic hydrocarbon group with (m1+m2+m3) valency containing an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aliphatic hydrocarbon group with (m1+m2+m3) valency containing a chain hydrocarbon group having 1 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group with (m1+m2+m3) valency containing an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and even more preferably an aliphatic hydrocarbon group with (m1+m2+m3) valency containing an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group with (m1+m2+m3) valency combining an alicyclic hydrocarbon group having 3 to 18 carbon atoms and a chain hydrocarbon group having 1 to 4 carbon atoms. Furthermore, the aforementioned group is preferably a di- to hexavalent aliphatic hydrocarbon group containing a 3- to 18 carbon atom alicyclic hydrocarbon group or a di- to hexavalent aliphatic hydrocarbon group containing a 1- to 12 carbon atom chain hydrocarbon group, more preferably a di- to hexavalent aliphatic hydrocarbon group containing a 3- to 18 carbon atom alicyclic hydrocarbon group, even more preferably a di, tri, or tetravalent aliphatic hydrocarbon group containing a 3- to 18 carbon atom alicyclic hydrocarbon group, even more preferably a di, tri, or tetravalent group combining a 3- to 18 carbon atom alicyclic hydrocarbon group and a 1- to 4 carbon atom chain hydrocarbon group, and even more preferably a di or trivalent alicyclic hydrocarbon group containing a 3- to 18 carbon atom.

[0014] R 1 and R 2 L contained in 2 The alkanediyl groups in this include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group; and Examples of branched alkanediyl groups include 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 group, and 2-methylbutane-1,4-diyl group. The number of carbon atoms in the alkanediyl group is preferably 1 to 4, and more preferably 1 to 3. L 2 The substituents that the alkanediyl group may have include halogen atoms, hydroxyl groups, cyano groups, carboxyl groups, C1-C12 alkyl groups, C1-C12 haloalkyl groups, C1-C12 alkoxy groups, and groups formed by combining two or more of these groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Haloalkyl groups having 1 to 12 carbon atoms represent alkyl groups containing halogen atoms, and include alkyl fluorides, alkyl chlorides, alkyl bromides, and alkyl iodides. Examples of haloalkyl groups include perfluoroalkyl groups (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, perfluoropentyl group, perfluorohexyl group, etc.), fluoromethyl group, difluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, chloromethyl group, bromomethyl group, and iodomethyl group. The number of carbon atoms in the haloalkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. Examples of groups formed by combining two or more types include alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and alkylcarbonyloxy groups having 2 to 13 carbon atoms. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and alkylcarbonyloxy groups having 2 to 13 carbon atoms represent groups in which a carbonyl group or carbonyloxy group is bonded to the alkyl or alkoxy group mentioned above. Examples of alkoxycarbonyl groups having 2 to 13 carbon atoms include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of alkylcarbonyl groups having 2 to 13 carbon atoms include acetyl, propionyl, and butyryl groups. Examples of alkylcarbonyloxy groups having 2 to 13 carbon atoms include acetyloxy, propionyloxy, and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. L 2 It is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms, and even more preferably a methylene group.

[0015] R 1 R included 10 The base-unstable group is one that, when in contact with a base (for example, a 2.38% aqueous solution of tetramethylammonium hydroxide), R 10 A leaving group containing the group represented by R is eliminated, 1 *-R 10 or *-L 2 -CO-OR 10 If the group is represented by R 1 This refers to a group on which a carboxyl group is formed. R 2 R included 10 The base-unstable group is one that, when in contact with a base (for example, a 2.38% aqueous solution of tetramethylammonium hydroxide), R 10 A leaving group containing the group represented by R is eliminated, 2 *-R 10 *-CO-R 10 Or *-CO-OR 10 If the group is represented by R 2 A hydroxyl group is formed on R 2 *-L 2-CO-O-R 10 or *-CO-O-L 2 -CO-O-R 10 When it is a group represented by, R 2 means a group in which a carboxy group is formed. As the base-labile group, a group represented by the formula (1b) (hereinafter, sometimes referred to as "base-labile group (1b)") is preferable. TIFF0007878912000011.tif2056[In the formula (1b), R ba1 and R ba2 each independently represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 6 carbon atoms and having a fluorine atom. R ba3 represents a fluorine atom or an alkyl group having 1 to 6 carbon atoms and having a fluorine atom. * represents a bonding site.]

[0016] R ba1 , R ba2 and R ba3 Examples of the alkyl group having a fluorine atom for R R ba1 are, for example, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 1-trifluoromethyl-2,2,2-trifluoroethyl group, a perfluoropropyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a perfluorobutyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a perfluoropentyl group, a perfluorohexyl group and the like. The number of carbon atoms of the alkyl group having a fluorine atom is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 to 3. R ba1 is preferably a hydrogen atom or a fluorine atom. R ba2 is preferably a hydrogen atom, a fluorine atom or a trifluoromethyl group. R ba3 is preferably a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a perfluoroalkylmethyl group having 2 to 5 carbon atoms, and more preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. -C(R ba1 )(R ba2 )(R ba3 ) is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, a perfluoroalkylmethyl group having 1 to 4 carbon atoms or a 1-trifluoromethyl-2,2,2-trifluoroethyl group, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms or a perfluoroalkylmethyl group having 1 to 4 carbon atoms. R 1 is preferably *-R 10 . R 2 is preferably *-CO-R 10 or *-CO-O-R 10 . m1 is preferably any integer from 1 to 5, more preferably any integer from 1 to 4, still more preferably any integer from 1 to 3, and even more preferably 1 or 2. m2 is preferably any integer from 1 to 5, more preferably any integer from 1 to 4, still more preferably any integer from 1 to 3, and even more preferably 1 or 2.

[0017] R 3 Examples of the halogen atom of R include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. R 3A C1-C12 haloalkyl group refers to an alkyl group having a halogen atom and containing C1-C12 atoms. Examples include C1-C12 alkyl fluorides, C1-C12 alkyl chlorides, C1-C12 alkyl bromides, and C1-C12 alkyl iodides. Examples of haloalkyl groups include perfluoroalkyl groups having 1 to 12 carbon atoms (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, perfluoropentyl group, perfluorohexyl group, etc.), fluoromethyl group, difluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc. The number of carbon atoms in the haloalkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. R 3 Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. If the -CH2- group in an alkyl group is replaced by -O- or -CO-, the number of carbon atoms before the replacement shall be considered the total number of carbon atoms in the alkyl group. Groups in which the -CH2- contained in an alkyl group is replaced with -O- or -CO- include hydroxyl groups (groups in which the -CH2- contained in a methyl group is replaced with -O-), carboxyl groups (groups in which the -CH2-CH2- contained in an ethyl group is replaced with -O-CO-), alkoxy groups (groups in which the -CH2- at any position in an alkyl group is replaced with -O-), alkoxycarbonyl groups (groups in which the -CH2-CH2- at any position in an alkyl group is replaced with -O-CO-), alkylcarbonyl groups (groups in which the -CH2- at any position in an alkyl group is replaced with -CO-), alkylcarbonyloxy groups (groups in which the -CH2-CH2- at any position in an alkyl group is replaced with -CO-O-), and groups that combine two or more of these groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, and undecyloxy groups. The number of carbon atoms in the alkoxy group is typically 1 to 11, preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups represent groups in which a carbonyl group or carbonyloxy group is bonded to an alkyl group or alkoxy group as described above. Examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples of alkylcarbonyloxy groups include acetyloxy, propionyloxy, and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl group is typically 2 to 11, preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is typically 2 to 12, preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is typically 2 to 11, preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. Two R's 3 When these groups combine to form a group having an acetal ring structure, examples of such groups include the group represented by formula (3b) (hereinafter sometimes referred to as "group (3b)"). TIFF0007878912000012.tif18148[In formula (3b), L 4 This represents an alkanediyl group having 1 to 6 carbon atoms, which may have a single bond or substituents. R ab1 and R ab2 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ab1 and R ab2 These atoms bond to each other to form a cyclic hydrocarbon group having 3 to 20 carbon atoms, and the alkyl group and the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O- or -CO-. * indicates the bonding site with W. Examples of alkanediyl groups, alkyl groups, and alicyclic hydrocarbon groups include the same groups as those listed above. Examples of group (3b) include the following groups. * indicates the bonding site with W. More specifically, examples of the base represented by TIFF0007878912000013.tif22138 include the following: TIFF0007878912000014.tif231202 R 3 When these groups combine to form a group having an acetal ring structure, examples of compound (I) include compounds (Ia), (Ib), (Ic), (Id), and (Ie) as shown below. Of these, compound (Ia) is preferred. More specifically, examples of compounds represented below can be found in TIFF0007878912000015.tif49154. TIFF0007878912000016.tif48155R 3 This includes a halogen atom, a hydroxyl group, a carboxyl group, a C1-C6 haloalkyl group, a C1-C6 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), or two R 3 Preferably, the group is one in which the atoms together form a group having an acetal ring structure, and may be a halogen atom, a hydroxyl group, a carboxyl group, a C1-C4 alkyl fluoride, a C1-C4 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), or two R 3 It is more preferable that the group is formed by combining the atoms to form an acetal ring structure, and may be a fluorine atom, an iodine atom, a hydroxyl group, a carboxyl group, a C1-C4 alkyl fluoride group, a C1-C4 alkyl group (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), or two R 3 It is even more preferable that the group is formed by the combination of these elements to form a group having an acetal ring structure, and that the elements are a fluorine atom, an iodine atom, a hydroxyl group, a carboxyl group, a C1-C3 perfluoroalkyl group, a C1-C3 alkyl group, a C1-C3 alkoxy group, or two R 3 It is even more preferable that the group is formed by combining with a group having an acetal ring structure, and that the group is a fluorine atom, an iodine atom, a hydroxyl group, a carboxyl group, a trifluoromethyl group, a methyl group, a methoxy group, or two R groups3 It is even more preferable that the groups together form a group having an acetal ring structure. m3 is preferably an integer between 0 and 3, more preferably 0, 1, or 2, and even more preferably 0 or 1.

[0018] Compound (I) includes compounds represented by the following formula. TIFF0007878912000017.tif254166

[0019] TIFF0007878912000018.tif213164

[0020] TIFF0007878912000019.tif241165

[0021] TIFF0007878912000020.tif238165

[0022] TIFF0007878912000021.tif104170

[0023] The content of compound (I) is typically 0.001 to 20% by mass, preferably 0.005 to 15% by mass, and more preferably 0.01 to 10% by mass, based on the solid content of the resist composition.

[0024] <Resin (A)> Resin (A) contains structural units having acid-unstable groups (hereinafter sometimes referred to as "structural unit (a1)"). Preferably, resin (A) further contains structural units other than structural unit (a1). Examples of structural units other than structural unit (a1) include structural units that do not have acid-unstable groups (hereinafter sometimes referred to as "structural unit (s)"), structural units other than structural unit (a1) and structural unit (s) (for example, structural units having halogen atoms as described later (hereinafter sometimes referred to as "structural unit (a4)"), structural units having non-eliminating hydrocarbon groups as described later (hereinafter sometimes referred to as "structural unit (a5)"), and structural units derived from other monomers known in the art.

[0025] <Structural unit (a1)> The structural unit (a1) is derived from a monomer having an acid-unstable group (hereinafter sometimes referred to as "monomer (a1)"). The acid-unstable group contained in resin (A) is preferably the group represented by formula (1) (hereinafter also referred to as group (1)) and / or the group represented by formula (2) (hereinafter also referred to as group (2)). TIFF0007878912000022.tif1988[In formula (1), R a1 , R a2 and R a3 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. a1 and R a2 These atoms bond with each other, forming a non-aromatic hydrocarbon ring with 3 to 20 carbon atoms, along with the carbon atoms to which they bond. ma and na each independently represent either 0 or 1, and at least one of ma and na represents 1. * indicates a connection site. TIFF0007878912000023.tif2171[In formula (2), R a1’ and R a2’ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a3’ R represents a hydrocarbon group with 1 to 20 carbon atoms. a2’ and R a3’ These atoms bond to each other, forming a heterocycle with 3 to 20 carbon atoms together with the carbon atoms to which they are bonded and X, and the -CH2- contained in the hydrocarbon group and the heterocycle may be replaced with -O- or -S-. X represents either an oxygen atom or a sulfur atom. 'na' represents either 0 or 1. * indicates a connection site.

[0026] R a1 , R a2 and R a3Examples of alkyl groups in this context include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. R a1 , R a2 and R a3 Examples of alkenyl groups in this context include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, tert-butenyl, pentenyl, hexenyl, heptenyl, octenyl, isooctenyl, and nonenyl groups. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site). a1 , R a2 and R a3 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16. TIFF0007878912000024.tif10150R a1 , R a2 and R a3 Examples of aromatic hydrocarbon groups in this context include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Examples of combined groups include groups that combine alkyl groups and alicyclic hydrocarbon groups as described above (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having alkyl 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 groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as phenylcyclohexyl group. Preferably, ma is 0 and na is 1. R a1 and R a2 -C(R a1 )(R a2 )(R a3 Examples of non-aromatic hydrocarbon rings include the following rings. The non-aromatic hydrocarbon rings preferably have 3 to 12 carbon atoms. * indicates a bond site with -O-. TIFF0007878912000025.tif31139

[0027] R a1’ , R a2’ and R a3’ Examples of hydrocarbon groups in this context include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Alkyl and alicyclic hydrocarbon groups are R a1 , R a2 and R a3 The same types of elements mentioned above can be cited. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Examples of combined groups include groups that combine alkyl groups and alicyclic hydrocarbon groups as described above (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having alkyl 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 groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as phenylcyclohexyl group. R a2’ and R a3’ When they bond with each other and form a heterocycle with the carbon atoms and X to which they are bonded, -C(R a1’ )(R a2’ )-XR a3’ The following rings are examples. * indicates a bonding site. TIFF0007878912000026.tif18130R a1’ and R a2’ Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0028] The following are examples of base (1): In equation (1), R a1 , R a2 and R a3 A group in which the parentheses is an alkyl group, ma=0, and na=1. A tert-butoxycarbonyl group is preferred as the group. In equation (1), R a1 , R a2 However, these combine with the carbon atoms to which they bond to form an adamantyl group, R a3 A group that is an alkyl group, with ma=0 and na=1. In equation (1), R a1 and R a2Each of them is an alkyl group independently, and R a3 This is an adamantyl group with ma=0 and na=1. The following are specific examples of group (1). * indicates a bonding site. TIFF0007878912000027.tif154163

[0029] The following are specific examples of group (2). * indicates a bonding site. TIFF0007878912000028.tif55153

[0030] The monomer (a1) is preferably a monomer having an acid-unstable group and an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer having an acid-unstable group.

[0031] Among (meth)acrylic monomers having acid-unstable groups, those having alicyclic hydrocarbon groups with 5 to 20 carbon atoms are preferred. If a resin (A) having structural units derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

[0032] Structural units derived from (meth)acrylic monomers having group (1) include structural units represented by formula (a1-0) (hereinafter sometimes referred to as structural unit (a1-0)), structural units represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)), or structural units represented by formula (a1-2) (hereinafter sometimes referred to as structural unit (a1-2)). Preferably, it is at least one structural unit selected from the group consisting of structural unit (a1-0), structural unit (a1-1), and structural unit (a1-2), and more preferably, it is at least one or two structural units selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). These may be used individually or in combination of two or more. TIFF0007878912000029.tif46151[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 -CO-O- represents a bond, where k1 is an integer from 1 to 7, and * represents the bond site with -CO-. R a01 , R a4 and R a5 Each of these independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a02 , R a03 and R a04 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R a6 and R a7 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination of 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.

[0033] R a01 , R a4 and R a5 Preferably, it is a hydrogen atom or a methyl group, and more preferably a methyl group. L a01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 It is -CO-O- (where k01 is preferably an integer from 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7The alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof in group (1) are R a1 , R a2 and R a3 Similar groups to those listed above can be cited. R a02 , R a03 , and R a04 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. 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, an isopropyl group, or a t-butyl group, and even more preferably an ethyl group, an isopropyl group, or a t-butyl group. R a6 and R a7 The alkenyl group in is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an ethenyl group, a propenyl group, an isopropenyl group, or a butenyl group. 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 12, and more preferably 5 to 10. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 12, and more preferably 6 to 10. In groups formed by combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms in the combined alkyl group and alicyclic hydrocarbon group is 18 or less. In groups formed by combining an alkyl group and an aromatic hydrocarbon group, it is preferable that the total number of carbon atoms in the combined alkyl group and aromatic hydrocarbon group is 18 or less. R a02 and R a03The group is preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a phenyl group, or a naphthyl group. R a04 The group is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. R a6 and R a7 Each of these groups is independently preferably a C1-C6 alkyl group, a C2-C6 alkenyl group, or a C6-C12 aromatic hydrocarbon group, more preferably a methyl group, ethyl group, isopropyl group, t-butyl group, ethenyl group, phenyl group, or naphthyl group, and even more preferably an ethyl group, isopropyl group, t-butyl group, ethenyl group, or phenyl group. m1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0034] Examples of structural units (a1-0) include structural units represented by any of the formulas (a1-0-1) to (a1-0-18) and R in structural unit (a1-0). a01 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group (an alkyl group having a halogen atom), or another alkyl group are given, with structural units represented by any of the formulas (a1-0-1) to (a1-0-10), (a1-0-13), or (a1-0-14) being preferred. TIFF0007878912000030.tif88160

[0035] Examples of structural units (a1-1) include structural units derived from monomers described in Japanese Patent Publication No. 2010-204646. In particular, structural units represented by any of formulas (a1-1-1) to (a1-1-7) and R in structural unit (a1-1) a4A structural unit in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group is preferred, and a structural unit represented by any of formulas (a1-1-1) to (a1-1-4) is more preferred. TIFF0007878912000031.tif40165

[0036] The structural unit (a1-2) is a structural unit represented by any of the formulas (a1-2-1) to (a1-2-14) and R in the structural unit (a1-2). a5 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group include structural units represented by any of the formulas (a1-2-2), (a1-2-5), (a1-2-6), and (a1-2-10) to (a1-2-14). TIFF0007878912000032.tif69165

[0037] If resin (A) contains structural unit (a1-0), its content is typically 5 to 80 mol%, preferably 5 to 75 mol%, and more preferably 10 to 70 mol%, relative to the total structural units of resin (A). If resin (A) contains structural unit (a1-1) and / or structural unit (a1-2), the total content of these is usually 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol%, even more preferably 20 to 75 mol%, and even more preferably 20 to 70 mol%, relative to the total structural units of resin (A).

[0038] Examples of structural units having a base (2) in structural unit (a1) include the structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF0007878912000033.tif4564[In formula (a1-4), R a32 This represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R a33This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a30 is a single bond or * -X a31 -(A a32 -X a32 ) nc - represents -R a32 This represents the bonding site with the carbon atom to which it is bonded. A a32 This represents an alkanediyl group with 1 to 6 carbon atoms. X a31 and X a32 These represent -O-, -CO-O-, or -O-CO- independently. nc represents 0 or 1. la represents an integer between 0 and 4. If la is an integer greater than or equal to 2, multiple R a33 They may be the same or different from each other. R a34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R a36 R represents a hydrocarbon group with 1 to 20 carbon atoms. a35 and R a36 These atoms bond with each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the -CH2- contained in this hydrocarbon group and the divalent hydrocarbon group may be replaced with -O- or -S-.

[0039] R a32 and R a33 Examples of halogen atoms in this context include fluorine atoms, chlorine atoms, and bromine atoms. R a32Examples of C1-C6 alkyl groups that may have halogen atoms include trifluoromethyl, difluoromethyl, methyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, and perfluorohexyl groups. R a32 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom, a methyl group, or an ethyl group is more preferred, and a hydrogen atom or a methyl group is even more preferred. R a33 Examples of alkyl groups in this context include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. The alkyl group is preferably a C1-C4 alkyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group. R a33 Examples of alkoxy groups in this compound include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, and hexyloxy groups. The alkoxy group is preferably a carbon-1 to carbon-4 alkoxy group, more preferably a methoxy or ethoxy group, and even more preferably a methoxy group. R a33 Examples of alkoxyalkyl groups in this context include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably a carbon-2 to carbon-8 alkoxyalkyl group, more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group. R a33Examples of alkoxyalkoxy groups in this context include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. The alkoxyalkoxy group is preferably one having 2 to 8 carbon atoms, with methoxyethoxy or ethoxyethoxy being more preferred. R a33 Examples of alkylcarbonyl groups in this compound include acetyl, propionyl, and butyryl groups. The alkylcarbonyl group is preferably one having 2 to 3 carbon atoms, with acetyl being more preferred. R a33 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The alkylcarbonyloxy group is preferably one having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a33 The group is preferably a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0040] *-X a31 -(A a32 -X a32 ) nc - for example, *-O-, *-CO-O-, *-O-CO-, *-CO-OA a32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO- is one example. In particular, *-CO-O- and *-CO-OA a32 -CO-O- or *-OA a32-CO-O- is preferred.

[0041] A a32 Examples of alkanediyl groups in this compound include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. A a32 It is preferable that this is a methylene group or an ethylene group.

[0042] A a30 These are single bonds, *-CO-O- or *-CO-OA a32 It is preferably -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0043] la is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. R a34 , R a35 and R a36 Examples of hydrocarbon groups in this context include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining these. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Alicyclic hydrocarbon groups may be monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site). TIFF0007878912000034.tif10151 Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Examples of combined groups include groups that combine alkyl groups and alicyclic hydrocarbon groups as described above (for example, alkylcycloalkyl groups or cycloalkylalkyl groups such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl groups such as benzyl group, aromatic hydrocarbon groups having alkyl 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 groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as phenylcyclohexyl group. In particular, R a36 Examples include alkyl groups having 1 to 18 carbon atoms, alicyclic hydrocarbon groups having 3 to 18 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or groups formed by combining these.

[0044] R a34 Preferably, it is a hydrogen atom. R a35 Preferably, this is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination thereof, and more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. a36 The alkyl group and alicyclic hydrocarbon group in R are preferably unsubstituted. a36In this context, the aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms. -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36 It is eliminated upon contact with an acid (e.g., p-toluenesulfonic acid) to form a hydroxyl group. -OC(R a34 )(R a35 )-OR a36 It is preferable that the atom is bonded to the ortho- or para-position of the benzene ring, and more preferably to the para-position.

[0045] Examples of structural units (a1-4) include monomer-derived structural units described in Japanese Patent Publication No. 2010-204646. Preferably, structural units represented by formulas (a1-4-1) to (a1-4-24) and R in structural unit (a1-4). a32 Examples of structural units in which the hydrogen atom corresponding to is replaced by a halogen atom, a haloalkyl group, or an alkyl group are given, and more preferably, structural units represented by formulas (a1-4-1) to (a1-4-5), (a1-4-10), (a1-4-13), (a1-4-14), (a1-4-19), and (a1-4-20), respectively. TIFF0007878912000035.tif127160

[0046] If resin (A) contains structural units (a1-4), the content of these units is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, even more preferably 7 to 70 mol%, even more preferably 7 to 65 mol%, and particularly preferably 10 to 60 mol%, relative to the total amount of all structural units of resin (A).

[0047] Structural units derived from (meth)acrylic monomers having group (2) include the structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007878912000036.tif4558 formula (a1-5), R a8 This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. Z a1 This is a single bond or *-(CH2) h3 -CO-L 54 - represents, h3 represents an integer from 1 to 4, and * represents 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.

[0048] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of C1-C6 alkyl groups that may contain halogen atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, fluoromethyl, and trifluoromethyl groups. In equation (a1-5), R a8 The preferred element is a hydrogen atom, a methyl group, or a trifluoromethyl group. 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.

[0049] Examples of structural units (a1-5) include monomer-derived structural units described in Japanese Patent Publication No. 2010-61117. Among these, structural units represented by formulas (a1-5-1) to (a1-5-4) are preferred, and structural units represented by formula (a1-5-1) or (a1-5-2) are more preferred. TIFF0007878912000037.tif33133

[0050] If resin (A) contains structural units (a1-5), the content of these units is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, even more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol%, relative to the total structural units of resin (A).

[0051] In addition, the following structural units (a1) can also be listed. TIFF0007878912000038.tif31162

[0052] If resin (A) contains structural units such as (a1-3-1) to (a1-3-7) above, the content of these structural units is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, even more preferably 20 to 85 mol%, even more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol% relative to the total structural units of resin (A).

[0053] In addition, the following structural units (a1) can also be listed. TIFF0007878912000039.tif4994 When resin (A) contains structural units such as (a1-6-1) to (a1-6-3) above, the content thereof is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, even more preferably 20 to 50 mol%, even more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol% relative to the total structural units of resin (A).

[0054] <Structural unit (s)> Structural units (s) are derived from monomers that do not have acid-unstable groups (hereinafter sometimes referred to as "monomer(s)"). Monomers known in the resist field that do not have acid-unstable groups can be used to derive structural units (s). The structural unit (s) preferably has a hydroxyl group or a lactone ring. If a resin containing a structural unit having a hydroxyl group and not having an acid-unstable group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and not having an acid-unstable group (hereinafter sometimes referred to as "structural unit (a3)") is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0055] <Structural Unit (a2)> The hydroxyl group in structural unit (a2) may be either an alcoholic hydroxyl group or a phenolic hydroxyl group. When manufacturing a resist pattern from the resist composition of the present invention, if a high-energy beam such as a KrF excimer laser (248 nm), electron beam, or EUV (ultra-ultraviolet light) is used as the exposure light source, a structural unit (a2) having a phenolic hydroxyl group is preferred, and it is more preferable to use the structural unit (a2-A) described later. Furthermore, if an ArF excimer laser (193 nm) or the like is used, a structural unit (a2) having an alcoholic hydroxyl group is preferred, and it is more preferable to use the structural unit (a2-1) described later. The structural unit (a2) may consist of one type alone, or it may consist of two or more types.

[0056] A structural unit having a phenolic hydroxyl group in structural unit (a2) is the structural unit represented by formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). TIFF0007878912000040.tif4653[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 a51This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy 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 -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, multiple R a51 They may be the same or different from each other.

[0057] R a50 and R a51 Examples of halogen atoms in this context include fluorine atoms, chlorine atoms, and bromine atoms. R a50 Examples of C1-C6 alkyl groups that may have halogen atoms include trifluoromethyl, difluoromethyl, methyl, perfluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, and perfluorohexyl groups. R a50The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, a hydrogen atom, a methyl group, or an ethyl group is more preferred, and a hydrogen atom or a methyl group is even more preferred. R a51 Examples of alkyl groups in this context include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. The alkyl group is preferably a C1-C4 alkyl group, more preferably a methyl or ethyl group, and even more preferably a methyl group. R a51 Examples of alkoxy groups in this compound include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, and tert-butoxy groups. The alkoxy group is preferably a carbon-1 to carbon-4 alkoxy group, more preferably a methoxy or ethoxy group, and even more preferably a methoxy group. R a51 Examples of alkoxyalkyl groups in this context include methoxymethyl, ethoxyethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, sec-butoxymethyl, and tert-butoxymethyl groups. The alkoxyalkyl group is preferably a carbon-2 to carbon-8 alkoxyalkyl group, more preferably a methoxymethyl or ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of alkoxyalkoxy groups in this context include methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy, isopropoxymethoxy, butoxymethoxy, sec-butoxymethoxy, and tert-butoxymethoxy. The alkoxyalkoxy group is preferably one having 2 to 8 carbon atoms, with methoxyethoxy or ethoxyethoxy being more preferred. R a51 Examples of alkylcarbonyl groups in this compound include acetyl, propionyl, and butyryl groups. The alkylcarbonyl group is preferably one having 2 to 3 carbon atoms, with acetyl being more preferred. R a51Examples of alkylcarbonyloxy groups in this context include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The alkylcarbonyloxy group is preferably one having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a51 The group is preferably a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C2-C8 alkoxyalkoxy group; more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, an ethoxy group, an ethoxyethoxy group, or an ethoxymethoxy group; and even more preferably a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0058] *-X a51 -(A a52 -X a52 ) nb - for example, *-O-, *-CO-O-, *-O-CO-, *-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- is one example. In particular, *-CO-O- and *-CO-OA a52 -CO-O- or *-OA a52 -CO-O- is preferred.

[0059] A a52 Examples of alkanediyl groups in this compound include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl. A a52 It is preferable that this is a methylene group or an ethylene group.

[0060] Aa50 These are single bonds, *-CO-O- or *-CO-OA a52 It is preferably -CO-O-, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0061] mb is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. The hydroxyl group is preferably bonded to the m- or p-position of the benzene ring, and more preferably to the m-position. If the phenyl group has two or more hydroxyl groups, it is preferable that the two hydroxyl groups are bonded to the m- and p-positions, respectively.

[0062] Examples of structural units (a2-A) include monomer-derived structural units described in Japanese Patent Publication No. 2010-204634 and Japanese Patent Publication No. 2012-12577. The structural unit (a2-A) is the structural unit represented by formulas (a2-2-1) to (a2-2-24), and the R in the structural unit (a2-A) in the structural unit (a2-A) represented by formulas (a2-2-1) to (a2-2-24). a50 Examples of structural units in which the methyl group corresponding to is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. Structural unit (a2-A) is a structural unit represented by formulas (a2-2-1) to (a2-2-4), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), a structural unit represented by formulas (a2-2-12) to (a2-2-18), and a structural unit represented by formulas (a2-2-1) to (a2-2-4), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), and a structural unit represented by formulas (a2-2-12) to (a2-2-18), in which R a50Preferably, the structural unit is one in which the corresponding methyl group is replaced by a hydrogen atom, and in the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-4), the structural unit represented by formula (a2-2-8), the structural unit represented by formulas (a2-2-12) to (a2-2-14), the structural unit represented by formula (a2-2-18), and the structural unit represented by formula (a2-2-3), the structural unit represented by formula (a2-2-4), the structural unit represented by formula (a2-2-8), the structural unit represented by formulas (a2-2-12) to (a2-2-14), and the structural unit represented by formula (a2-2-18), the R in structural unit (a2-A) a50 It is more preferable that the corresponding methyl group is replaced by a hydrogen atom in the structural unit represented by formula (a2-2-3), formula (a2-2-4), formula (a2-2-8), and in the structural unit represented by formula (a2-2-3), formula (a2-2-4), and formula (a2-2-8), the R in structural unit (a2-A) a50 It is even more preferable that the corresponding methyl group is replaced by a hydrogen atom in the structural unit. TIFF0007878912000041.tif79169

[0063] When the resin (A) contains structural units (a2-A), the content of structural units (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, even more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol%, relative to the total number of structural units. The structural unit (a2-A) can be incorporated into resin (A) by polymerizing using structural unit (a1-4), for example, and then treating with an acid such as p-toluenesulfonic acid. Alternatively, the structural unit (a2-A) can be incorporated into resin (A) by polymerizing using acetoxystyrene, for example, and then treating with an alkali such as tetramethylammonium hydroxide.

[0064] A structural unit having an alcoholic hydroxyl group in structural unit (a2) is the structural unit represented by formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). TIFF0007878912000042.tif4562 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.

[0065] In equation (a2-1), L a3 Preferably, -O-, -O-(CH2) f1 The result is -CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-. R a14 The group is preferably a methyl group. R a15 Preferably, it is a hydrogen atom. R a16 This is preferably a hydrogen atom or a hydroxyl group. o1 is preferably an integer between 0 and 3, more preferably 0 or 1.

[0066] Examples of structural units (a2-1) include structural units derived from monomers described in Japanese Patent Publication No. 2010-204646. Structural units represented by any of formulas (a2-1-1) to (a2-1-6) are preferred, structural units represented by any of formulas (a2-1-1) to (a2-1-4) are more preferred, and structural units represented by formula (a2-1-1) or (a2-1-3) are even more preferred. TIFF0007878912000043.tif47132

[0067] If resin (A) contains structural unit (a2-1), its content is typically 1 to 45 mol%, preferably 1 to 40 mol%, more preferably 1 to 35 mol%, even more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol%, relative to the total structural units of resin (A).

[0068] <Structural unit (a3)> The lactone ring of the structural unit (a3) ​​may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or it may be a fused ring of a monocyclic lactone ring and another ring. Preferably, it may be a γ-butyrolactone ring, an adamantane lactone ring, or a bridging ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)).

[0069] The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), formula (a3-2), formula (a3-3), or formula (a3-4). One of these may be included alone, or two or more may be included. TIFF0007878912000044.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 This represents a base represented by -CO-O-(where k3 is an integer from 1 to 7). L a7 is -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 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 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 This represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. R a22 , R a23 and R a25 Each of these independently represents a carboxyl group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. 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 or different from each other.

[0070] R a21 , R a22 , R a23 and R a25 Examples of aliphatic hydrocarbon groups in this context include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tert-butyl groups. R a24 Examples of halogen atoms in this context include fluorine, chlorine, bromine, and iodine atoms. R a24 Examples of alkyl groups in this context include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups, with alkyl groups having 1 to 4 carbon atoms being preferred, and methyl or ethyl groups being more preferred. R a24 Examples of alkyl groups having halogen atoms in this context include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl groups.

[0071] L a8 and L a9 Examples of alkanediyl groups in this compound include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl.

[0072] In equations (a3-1) to (a3-3), L a4 ~L a6 Each is independently, preferably -O- or *-O-(CH2) k3 In -CO-O-, k3 is an integer from 1 to 4, more preferably -O- and *-O-CH2-CO-O-, and even more preferably 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. p1, q1, and r1 are each independently, preferably integers from 0 to 2, and more preferably 0 or 1.

[0073] In equation (a3-4), R a24Preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom or a methyl group. R a25 The group is preferably a carboxyl group, a cyano group, or a methyl group. L a7 Preferably -O- or *-OL a8 It is -CO-O-, and more preferably -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). TIFF0007878912000045.tif3849 (in the formula, R a24 , L a7 (This expresses the same meaning as above.)

[0074] Examples of structural units (a3) ​​include those derived from monomers described in Japanese Patent Publication No. 2010-204646, Japanese Patent Publication No. 2000-122294, and Japanese Patent Publication No. 2012-41274. Examples of structural units (a3) ​​include those represented by any of the formulas (a3-1-1), (a3-1-2), (a3-2-1), (a3-2-2), (a3-3-1), (a3-3-2), and (a3-4-1) to (a3-4-12), and in the said structural units, R in formulas (a3-1) to (a3-4). a18 , R a19 , R a20 and R a24 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom is preferred.

[0075] TIFF0007878912000046.tif116165

[0076] When resin (A) contains structural units (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, and more preferably 10 to 60 mol%, relative to the total structural units of resin (A). Furthermore, the content of structural unit (a3-1), structural unit (a3-2), structural unit (a3-3), or structural unit (a3-4) is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and even more preferably 10 to 50 mol%, relative to the total structural units of resin (A).

[0077] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF0007878912000047.tif2862[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 This represents a saturated hydrocarbon group having a halogen atom with 1 to 24 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. R 42 The saturated hydrocarbon groups represented by include chain-type saturated hydrocarbon groups, monocyclic or polycyclic alicyclic saturated hydrocarbon groups, and groups formed by combining these.

[0078] Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates the bonding site). TIFF0007878912000048.tif10146 Examples of groups formed by combinations include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group.

[0079] Examples of structural units (a4) include the structural unit represented by formula (a4-0), the structural unit represented by formula (a4-1), and the structural unit represented by formula (a4-4). TIFF0007878912000049.tif4551[In formula (a4-0), R 54 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 represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms. R 64 This represents a hydrogen atom or a fluorine atom.

[0080] L 4a Examples of alkanediyl groups in this context include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group, and branched alkanediyl groups such as ethane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, and 2-methylpropane-1,2-diyl group.

[0081] L 3aThe perfluoroalkanediyl groups in this product include difluoromethylene, perfluoroethylene, perfluoroethylfluoromethylene, perfluoropropane-1,3-diyl, perfluoropropane-1,2-diyl, perfluoropropane-2,2-diyl, perfluorobutane-1,4-diyl, perfluorobutane-2,2-diyl, perfluorobutane-1,2-diyl, perfluoropentane-1,5-diyl, perfluoropentane-2,2-diyl, and perfluoropentane-3 Examples include 3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3-diyl group, and perfluorooctane-4,4-diyl group. L 3a Examples of perfluorocycloalkanediyl groups in this context include perfluorocyclohexanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group, and perfluoroadamantanediyl group.

[0082] L 4a Preferably, it is a single bond, a methylene group, or an ethylene group, and more preferably a single bond and a methylene group. L 3a The group is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0083] The structural units (a4-0) are the structural units shown below and the R in the structural units (a4-0) within the structural units below. 54 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom. JPEG0007878912000050.jpg95166

[0084] TIFF0007878912000051.tif4866[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, which may have substituents, and the -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. A a41 This represents an alkanediyl group having 1 to 6 carbon atoms, which may have substituents, or a group represented by formula (a-g1). However, A a41 and R a42 At least one of these atoms has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007878912000052.tif1488 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44 Each of these independently represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, which may have substituents. A a43 This represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, which may have single bonds or substituents. X a41 and X a42 These represent -O-, -CO-, -CO-O-, or -O-CO-, respectively, independently. 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 a42 This is the junction site.

[0085] R a42 Examples of saturated hydrocarbon groups in this context include chain-type saturated hydrocarbon groups, monocyclic or polycyclic alicyclic saturated hydrocarbon groups, and groups formed by combining these.

[0086] Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups; and polycyclic alicyclic saturated hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates the bonding site). TIFF0007878912000053.tif10160 Examples of groups formed by combinations include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, such as -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group.

[0087] R a42 The substituents on the compound include at least one selected from the group consisting of a halogen atom and a group represented by formula (a-g3). Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine being preferred. TIFF0007878912000054.tif855[In formula (a-g3), X a43 * represents an oxygen atom, a carbonyl group, *-O-CO-, or *-CO-O-. A a45 This represents a saturated 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 a45 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms and containing at least one halogen atom.

[0088] A a45 Examples of saturated hydrocarbon groups in this context include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups; Examples include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, as well as polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, norbornyl, and the following groups (* indicates a bonding site). TIFF0007878912000055.tif10160 Examples of groups formed by combinations include groups formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, such as -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, and -alkanediyl group-alicyclic hydrocarbon group-alkyl group.

[0089] R a42 A saturated hydrocarbon group which may have a halogen atom is preferred, and a saturated hydrocarbon group which has an alkyl group having a halogen atom and / or a group represented by formula (a-g3) is more preferred. R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, even more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of perfluoroalkyl groups include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, and perfluorooctyl group. Examples of perfluorocycloalkyl groups include perfluorocyclohexyl group. R a42However, if it is a saturated hydrocarbon group having a group represented by formula (a-g3), then R is calculated including the number of carbon atoms in the group represented by formula (a-g3). a42 The total number of carbon atoms is preferably 15 or less, and more preferably 12 or less. If the atom has a substituent represented by formula (a-g3), the number of substituents is preferably one.

[0090] R a42 If is a saturated hydrocarbon group having a group represented by formula (a-g3), then R a42 More preferably, the group is represented by formula (a-g2). TIFF0007878912000056.tif871[In formula (a-g2), A a46 This represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. X a44 This represents **-O-CO- or **-CO-O- (where ** is A a46 This represents the connection site. A a47 This represents a saturated 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 At least one of them has at least one halogen atom. * indicates a bonding site with a carbonyl group.

[0091] 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 saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 12, A a47 A cyclohexyl group or an adamantyl group is more preferable.

[0092] The preferred structure of the group represented by formula (a-g2) is as follows (* indicates the bonding site with the carbonyl group). TIFF0007878912000057.tif14160

[0093] A a41 Examples of alkanediyl groups in this context include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group; and branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. A a41 Examples of substituents on the alkanediyl group represented by include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. A a41 The group is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and even more preferably an ethylene group.

[0094] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Examples of divalent saturated hydrocarbon groups represented by include linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated hydrocarbon groups, as well as divalent saturated hydrocarbon groups formed by combining alkanediyl groups and divalent alicyclic saturated hydrocarbon groups. Specifically, examples include methylene groups, ethylene groups, propane-1,3-diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, 1-methylpropane-1,3-diyl groups, 2-methylpropane-1,3-diyl groups, and 2-methylpropane-1,2-diyl groups. A a42 , A a43 and A a44 Examples of substituents on the divalent saturated hydrocarbon group represented by include hydroxyl groups and alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0095] In the group represented by formula (a-g1), X a42The following are examples of groups whose -O-, -CO-, -CO-O-, or -O-CO-. In the following examples, * and ** represent the bonding site, and ** is -O-CO-R a42 This is the junction site. TIFF0007878912000058.tif46140

[0096] The structural units represented by formula (a4-1) are the structural units shown below and the R in the structural units represented by formula (a4-1) in the structural units below. a41 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom. JPEG0007878912000059.jpg92135

[0097] TIFF0007878912000060.tif132150

[0098] Examples of structural units represented by formula (a4-1) include the structural units represented by formula (a4-2) and the structural units represented by formula (a4-3). TIFF0007878912000061.tif4256[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 -CH2- contained in the alkanediyl group may be replaced with -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.

[0099] L 44 The alkanediyl group with 1 to 6 carbon atoms is A a41 Similar to the examples given earlier, the same types of bases can be cited. R f6 The saturated hydrocarbon group is R 42 Similar to the examples given earlier, the same types of bases can be cited. L44 In this compound, an alkanediyl group having 2 to 4 carbon atoms is preferred, and an ethylene group is more preferred.

[0100] Examples of structural units represented by equation (a4-2) include those represented by equations (a4-1-1) to (a4-1-11), respectively. f5 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom can also be cited as a structural unit represented by formula (a4-2).

[0101] TIFF0007878912000062.tif5671[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. X f12 This represents *-O-CO- or *-CO-O- (* is A f13 This represents the connection site. 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.

[0102] L 5 The alkanediyl group in A is a41 Examples of groups similar to those exemplified by the alkanediyl group include the following.

[0103] A f13The divalent saturated hydrocarbon group which may have a fluorine atom is preferably a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent alicyclic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group. Examples of divalent chain-type saturated hydrocarbon groups that may contain a fluorine atom include methylene groups, ethylene groups, propanediyl groups, butanediyl groups, and pentanediyl groups, as well as perfluoroalkanediyl groups such as difluoromethylene groups, perfluoroethylene groups, perfluoropropanediyl groups, perfluorobutanediyl groups, and perfluoropentanediyl groups. The divalent alicyclic saturated hydrocarbon group, which may contain a fluorine atom, may be monocyclic or polycyclic. Examples of monocyclic groups include cyclohexanediyl and perfluorocyclohexanediyl groups. Examples of polycyclic groups include adamantanediyl, norbornanediyl, and perfluoroadamantanediyl groups.

[0104] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42The same groups as those exemplified above can be cited. Among them, trifluoromethyl group, difluoromethyl 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, Preferred groups include alkyl fluorides such as hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, and perfluorooctyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, and perfluoroadamantylmethyl group.

[0105] In equation (a4-3), L 5 An ethylene group is preferred. A f13 The divalent saturated hydrocarbon group is preferably a group containing a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a divalent chain saturated hydrocarbon group having 2 to 3 carbon atoms. A f14 The saturated hydrocarbon group is preferably a group containing a chain-type saturated hydrocarbon group having 3 to 12 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a group containing a chain-type saturated hydrocarbon group having 3 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. Among these, A f14 The group is preferably a group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0106] Examples of structural units represented by equation (a4-3) include those represented by equations (a4-1'-1) to (a4-1'-11), respectively. f7 A structural unit in which the corresponding methyl group is replaced by a hydrogen atom can also be cited as a structural unit represented by formula (a4-3).

[0107] As a structural unit (a4), the structural unit represented by formula (a4-4) can also be cited. TIFF0007878912000063.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.

[0108] R f22 The saturated hydrocarbon group is R a42 Examples include saturated hydrocarbon groups similar to those represented by R. f22 The C1-C10 alkyl group having a fluorine atom or the C1-C10 alicyclic saturated hydrocarbon group having a fluorine atom is preferred, the C1-C10 alkyl group having a fluorine atom is more preferred, and the C1-C6 alkyl group having a fluorine atom is even more preferred.

[0109] In equation (a4-4), A f21 As for, -(CH2) j1 - is preferred, an ethylene group or a methylene group is more preferred, and a methylene group is even more preferred.

[0110] As a structural unit represented by formula (a4-4), for example, the following structural unit and the structural unit represented by the following formula, R in structural unit (a4-4) f21 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom. JPEG0007878912000064.jpg87160

[0111] If resin (A) has structural units (a4), the content of these units is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total structural units of resin (A).

[0112] <Structural Unit (a5)> Examples of non-eliminating hydrocarbon groups in structural unit (a5) include groups having linear, branched, or cyclic hydrocarbon groups. Among these, structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. An example of a structural unit (a5) is the structural unit represented by formula (a5-1). TIFF0007878912000065.tif3555[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 hydrogen atoms contained in this alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group 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 -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.

[0113] R 52 The alicyclic hydrocarbon group in this compound may be either monocyclic or polycyclic. Examples of monocyclic alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include adamantyl and norbornyl groups. Examples of aliphatic hydrocarbon groups having 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. Examples of substituted alicyclic hydrocarbon groups include the 3-methyladamantyl group. R 52 Preferably, it is an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably, an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0114] L 55 Examples of divalent saturated hydrocarbon groups in this context include divalent chain-type saturated hydrocarbon groups and divalent alicyclic saturated hydrocarbon groups, with divalent chain-type saturated hydrocarbon groups being preferred. Examples of divalent chain-type saturated hydrocarbon groups include methylene groups, ethylene groups, propanediyl groups, butanediyl groups, and pentanediyl groups, which are all types of alkanediyl groups. The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of monocyclic alicyclic saturated hydrocarbon groups include cycloalkanediyl groups such as cyclopentanediyl and cyclohexanediyl. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include adamantanediyl and norbornanediyl.

[0115] L 55 Groups in which the -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO- include, for example, the groups represented by formulas (L1-1) to (L1-4). In the following formulas, * and ** represent bonding sites, respectively, and * represents the bonding site with the oxygen atom. TIFF0007878912000066.tif18164 formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is L x1 This represents the connection site. 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 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. 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.

[0116] L x1 Preferably, this is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x2 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond. L x3Preferably, 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, this is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x6 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x7 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 Preferably, it is 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. L x9 Preferably, it is 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. W x1 Preferably, this is a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0117] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF0007878912000067.tif53135

[0118] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF0007878912000068.tif23130

[0119] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF0007878912000069.tif15145

[0120] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF0007878912000070.tif26114

[0121] L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0122] The structural units (a5-1) are the structural units shown below and the R in the structural unit (a5-1) within the structural units below. 51 One example is a structural unit in which the corresponding methyl group is replaced by a hydrogen atom. TIFF0007878912000071.tif111150 If resin (A) has structural units (a5), the content of these units is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 3 to 15 mol%, relative to the total structural units of resin (A).

[0123] <Structural Unit (a6)> Structural unit (a6) is a structural unit having an -SO2- group, and it is preferable that it has an -SO2- group in its side chain. A structural unit having an -SO2- group may have a linear structure having an -SO2- group, a branched structure having an -SO2- group, or a cyclic structure (monocyclic and polycyclic) having an -SO2- group. Preferably, it is a structural unit having a cyclic structure having an -SO2- group, and more preferably, it is a structural unit having a cyclic structure (sultone ring) containing -SO2-O-.

[0124] As a sultone ring, the following equation (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 A ring represented by (T-4) is an example. The bonding site can be at any position. The sultone ring may be monocyclic, but it is preferably polycyclic. A polycyclic sultone ring means a bridging ring containing -SO2-O- as the atomic group constituting the ring, and is represented by formula (T 1 -1) and formula (T1 A ring represented by equation (T) is an example. A Sultone ring is given by equation (T 1 As shown in (2), the ring may contain heteroatoms in addition to -SO2-O- as a group of atoms constituting the ring. Examples of heteroatoms include oxygen atoms, sulfur atoms, or nitrogen atoms, with oxygen atoms being preferred. TIFF0007878912000072.tif3186

[0125] The sultone ring may have substituents, and examples of substituents include C1-C12 alkyl groups which may have a halogen atom or a hydroxyl group, halogen atoms, hydroxyl groups, cyano groups, C1-C12 alkoxy groups, C6-C12 aryl groups, C7-C12 aralkyl groups, glycidyloxy groups, C2-C12 alkoxycarbonyl groups, and C2-C4 alkylcarbonyl groups.

[0126] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl groups, preferably alkyl groups having 1 to 6 carbon atoms, and more preferably methyl groups. Examples of alkyl groups having a halogen atom include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl, with trifluoromethyl being preferred. Examples of alkyl groups having a hydroxyl group include hydroxymethyl groups and 2-hydroxyethyl groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and dodecyloxy groups. Examples of aryl groups include phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl. Examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, naphthylmethyl, and naphthylethyl groups. Examples of alkoxycarbonyl groups include groups in which an alkoxy group such as a methoxycarbonyl group or an ethoxycarbonyl group is bonded to a carbonyl group, preferably an alkoxycarbonyl group having 6 or fewer carbon atoms, and more preferably a methoxycarbonyl group. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups.

[0127] From the viewpoint of ease of production of monomers that lead to structural unit (a6), a sultone ring without substituents is preferred. As the sultone ring, the ring represented by the following formula (T1') is preferred. TIFF0007878912000073.tif3172[In formula (T1'), X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 This represents a C1-C12 alkyl group which may have a halogen atom or a hydroxyl group, a halogen atom, a hydroxyl group, a cyano group, a C1-C12 alkoxy group, a C6-C12 aryl group, a C7-C12 aralkyl group, a glycidyloxy group, a C2-C12 alkoxycarbonyl group, or a C2-C4 alkylcarbonyl group. ma represents an integer from 0 to 9. When ma is 2 or greater, multiple R 41 They may be the same or different. The connection point can be at any location. X 11 This is preferably an oxygen atom or a methylene group, and more preferably a methylene group. R41 Examples include substituents similar to those of a sultone ring, and C1-C12 alkyl groups which may have a halogen atom or a hydroxyl group are preferred.

[0128] As a sultone ring, the ring represented by formula (T1) is more preferable. TIFF0007878912000074.tif3148[In formula (T1), R 8 This represents a C1-C12 alkyl group which may have a halogen atom or a hydroxyl group, a halogen atom, a hydroxyl group, a cyano group, a C1-C12 alkoxy group, a C6-C12 aryl group, a C7-C12 aralkyl group, a glycidyloxy group, a C2-C12 alkoxycarbonyl group, or a C2-C4 alkylcarbonyl group. m represents an integer from 0 to 9. When m is 2 or greater, multiple R 8 They may be the same or different. The connection point can be at any location.

[0129] R 8 R 41 Similar examples include the above. In formula (T1'), ma and in formula (T1), m are preferably 0 or 1, and more preferably 0.

[0130] The following rings are examples of rings represented by formula (T1') and formula (T1). The bonding site is at an arbitrary position. TIFF0007878912000075.tif47145

[0131] Structural units having a sultone ring preferably have the following groups. * in the following groups indicates a bonding site. TIFF0007878912000076.tif45144

[0132] The structural unit having the -SO2- group preferably further has a group derived from a polymerizable group. Examples of polymerizable groups include vinyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, acryloylthio group, and methacryloylthio group. In particular, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, and more preferably a (meth)acrylic monomer.

[0133] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007878912000077.tif4956 [In formula (Ix), R x This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. A xx is an oxygen atom, -N(R c )- or represents a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, or -N(R d )- may be replaced with this. X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 This represents a C1-C12 alkyl group which may have a halogen atom or a hydroxyl group, a halogen atom, a hydroxyl group, a cyano group, a C1-C12 alkoxy group, a C6-C12 aryl group, a C7-C12 aralkyl group, a glycidyloxy group, a C2-C12 alkoxycarbonyl group, or a C2-C4 alkylcarbonyl group. ma represents an integer from 0 to 9. When ma is 2 or greater, multiple R 41 They may be the same or different. R c and R d Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0134] R x Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. R x Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl groups, preferably alkyl groups having 1 to 4 carbon atoms, and more preferably methyl or ethyl groups. R x Examples of alkyl groups having a halogen atom include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl, and triiodomethyl. R x Preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom or a methyl group.

[0135] A x Examples of divalent saturated hydrocarbon groups include linear alkanediyl groups, branched alkanediyl groups, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations of two or more of these groups are also acceptable. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group Linear alkanediyl groups such as 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, heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, and propane-2,2-diyl group; Branched alkanediyl groups such as butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group; Monocyclic, divalent, alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0136] R 41 , X 11 And ma can be the same as in equation (T1'). Examples of sultone rings include those mentioned above, and among them, those with specified bonding positions are preferred.

[0137] The following are examples of structural units (a6): TIFF0007878912000078.tif93150 Among these, structural units represented by formulas (a6-1), (a6-2), (a6-6), (a6-7), (a6-8), and (a6-12) are preferred, and structural units represented by formulas (a6-1), (a6-2), (a6-7), and (a6-8) are more preferred. If resin (A) has structural units (a6), the content of these units is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and even more preferably 3 to 30 mol%, relative to the total structural units of resin (A).

[0138] <Structural Unit (II)> The resin (A) may further contain structural units that decompose upon exposure to generate acid (hereinafter sometimes referred to as "structural unit (II)"). Specifically, structural unit (II) is the structural unit described in Japanese Patent Application Publication No. 2016-79235, and is preferably a structural unit having a sulfonate group or carboxylate group and an organic cation in its side chain, or a structural unit having a sulfonio group and an organic anion in its side chain.

[0139] The structural unit having a sulfonate group or carboxylate group and an organic cation in its side chain is preferably the structural unit represented by formula (II-2-A'). TIFF0007878912000079.tif3189 [In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the saturated hydrocarbon group may be replaced with -O-, -S-, or -CO-, and the hydrogen atom contained in the saturated hydrocarbon group may be replaced with a halogen atom, an alkyl group having 1 to 6 carbon atoms which may contain a halogen atom, or a hydroxyl group. A x1 This represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atoms contained in the alkanediyl group 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 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. ZA + This represents an organic cation.

[0140] R III3 Examples of halogen atoms represented by this formula include fluorine, chlorine, bromine, and iodine atoms. R III3 A C1-C6 alkyl group which may have a halogen atom represented by R is: a8 Examples include alkyl groups having 1 to 6 carbon atoms that may contain a halogen atom represented by . A x1 Examples of C1-C8 alkanediyl groups represented by 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, 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 group, and 2-methylbutane-1,4-diyl group. A x1 Examples of C1-C6 perfluoroalkyl groups that may be substituted include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, and perfluorohexyl groups.

[0141] X III3 Examples of divalent saturated hydrocarbon groups having 1 to 18 carbon atoms represented by include linear or branched alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and combinations thereof. Specifically, linear alkane diyl groups such as methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Examples include branched alkanediyl groups such as 1,4-diyl, pentane-1,4-diyl, and 2-methylbutane-1,4-diyl; divalent monocyclic alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; and divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl.

[0142] Examples of groups in which the -CH2- group in a saturated hydrocarbon group is replaced by -O-, -S-, or -CO- include the divalent groups represented by formulas (X1) to (X53). However, the number of carbon atoms before the -CH2- group in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO- is 17 or less. In the following formulas, * and ** represent bonding sites, and * is A x1 This represents the connection point. TIFF0007878912000080.tif145161

[0143] X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6 This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7This 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.

[0144] ZA + Examples of organic cations represented by the formulas (b2-1) to (b2-4) described later include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, examples include cations represented by any of the formulas (b2-1) to (b2-4) described later (hereinafter, depending on the formula number, they may be referred to as "cation (b2-1)," etc.).

[0145] The structural unit represented by formula (II-2-A') is preferably the structural unit represented by formula (II-2-A). JPEG0007878912000081.jpg37109 [In formula (II-2-A), R III3 , X III3 and ZA + This expresses the same meaning as above. z represents an integer between 0 and 6. R III2 and R III4 Each of these independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms, and when z is 2 or greater, multiple R III2 and R III4 They may be the same or different from each other. Q a and Q b Each of these independently represents either a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0146] R III2 , R III4 Q a and Q b As perfluoroalkyl groups having 1 to 6 carbon atoms, the following Q will be described later. b1Examples include perfluoroalkyl groups with 1 to 6 carbon atoms, represented by [the formula shown].

[0147] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF0007878912000082.tif5576 [In formula (II-2-A-1), R III2 , R III3 , R III4 Q a Q b , z and ZA + This expresses the same meaning as above. R III5 This represents a saturated hydrocarbon group with 1 to 12 carbon atoms. X I2 This represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, where the -CH2- group may be replaced with -O-, -S-, or -CO-, and the hydrogen atoms in the saturated hydrocarbon group may be substituted with halogen atoms or hydroxyl groups.

[0148] R III5 Examples of saturated hydrocarbon groups having 1 to 12 carbon atoms represented by include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. X I2 As a divalent saturated hydrocarbon group represented by , X III3 Examples include divalent saturated hydrocarbon groups represented by .

[0149] The structural unit represented by formula (II-2-A-2) is preferred over the structural unit represented by formula (II-2-A-1). TIFF0007878912000083.tif5287 [In formula (II-2-A-2), R III3 , R III5 and ZA + This expresses the same meaning as above. m and nA each independently represent either 1 or 2.

[0150] Examples of structural units represented by formula (II-2-A') include the following structural unit, R III3 Examples include structural units in which the group corresponding to the methyl group is replaced by a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a C1-C6 alkyl group which may have a halogen atom (e.g., a trifluoromethyl group), and structural units described in International Publication No. 2012 / 050015. ZA + This represents an organic cation. TIFF0007878912000084.tif86163

[0151] The structural unit having a sulfonio group and an organic anion in its side chain is preferably the structural unit represented by formula (II-1-1). JPEG0007878912000085.jpg3381 [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 and R II3 These atoms may bond to each other, forming a ring with the sulfur atom to which they are bonded. R II4 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. A - This represents an organic anion. R II1 Examples of divalent aromatic hydrocarbon groups having 6 to 18 carbon atoms, represented by this formula, include phenylene groups and naphthylene groups. R II2 and R II3 Examples of hydrocarbon groups represented by this symbol include alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of alkyl groups and alicyclic hydrocarbon groups are the same as those described above. Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, naphthyl, anthryl, biphenyl, and phenanthryl groups. Examples of combined groups include groups combining alkyl groups and alicyclic hydrocarbon groups as described above, aralkyl groups such as benzyl groups, aromatic hydrocarbon groups having alkyl 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 groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and aryl-cycloalkyl groups such as phenylcyclohexyl group. R II4 Examples of halogen atoms represented by this formula include fluorine, chlorine, bromine, and iodine atoms. R II4 A C1-C6 alkyl group which may have a halogen atom represented by R is: a8 Examples include alkyl groups having 1 to 6 carbon atoms that may contain a halogen atom represented by . A II1 Examples of divalent linking groups represented by include divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O-, -S-, or -CO-. Specifically, X III3 Examples include divalent saturated hydrocarbon groups with 1 to 18 carbon atoms, represented by .

[0152] The cation-containing structural unit in formula (II-1-1) is the structural unit represented below, R II4 Examples include structural units in which the group corresponding to the methyl group is replaced by a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a C1-C6 alkyl group that may have a halogen atom (e.g., a trifluoromethyl group). TIFF0007878912000086.tif85130

[0153] A - Examples of organic anions represented by include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, and carboxylic acid anions. - The organic anion represented by is preferably a sulfonate anion, and examples of sulfonate anions include those similar to the anion represented by formula (B1) described later.

[0154] A - Examples of sulfonylimid anions represented by the formula include the following: TIFF0007878912000087.tif36136

[0155] Examples of sulfonylmethide anions include the following: TIFF0007878912000088.tif29123

[0156] Examples of carboxylic acid anions include the following: TIFF0007878912000089.tif51152

[0157] Examples of structural units represented by formula (II-1-1) include the following structural units: JPEG0007878912000090.jpg88149

[0158] When resin (A) contains structural unit (II), the content of structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol%, relative to the total structural units of resin (A).

[0159] The resin (A) may have structural units other than those described above, and examples of such structural units include structural units well known in the art.

[0160] The resin (A) is preferably a resin consisting of structural units (a1) and structural units (s), that is, a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably at least one selected from the group consisting of structural unit (a1-0), structural unit (a1-1), and structural unit (a1-2), more preferably at least one selected from the group consisting of structural unit (a1-1) and structural unit (a1-2), and even more preferably at least two selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). The structural unit (s) is preferably at least one selected from the group consisting of structural units (a2) and structural units (a3). The structural unit (a2) is preferably a structural unit represented by formula (a2-1) or a structural unit represented by formula (a2-A). The structural unit (a3) ​​is preferably at least one selected from the group consisting of a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2), and a structural unit represented by formula (a3-4).

[0161] Each structural unit constituting resin (A) may be used individually or in combination of two or more types, and these structural units can be produced by known polymerization methods (e.g., radical polymerization) using monomers that derive these structural units. The content of each structural unit in resin (A) can be adjusted by the amount of monomer used in polymerization. The weight-average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,500 or more, even more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, even more preferably 15,000 or less). In this specification, the weight-average molecular weight is the value obtained by gel permeation chromatography under the conditions described in the examples.

[0162] <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 resins containing structural unit (a4) or structural unit (a5) (hereinafter sometimes referred to as resin (X)).

[0163] Among the resins (X), resins containing structural units (a4) are preferred. In resin (X), the content of structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 45 mol% or more, relative to the total amount of all structural units in resin (X). Further structural units that resin (X) may have include structural unit (a2), structural unit (a3), and structural units derived from other known monomers. In particular, resin (X) is preferably a resin consisting only of structural unit (a4) and / or structural unit (a5), and more preferably a resin consisting only of structural unit (a4). Each structural unit constituting resin (X) may be used individually or in combination of two or more types, and these structural units can be produced by known polymerization methods (e.g., radical polymerization) using monomers that induce these structural units. The content of each structural unit in resin (X) can be adjusted by the amount of monomer used in polymerization. The weight-average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight-average molecular weight of resin (X) is the same as in the case of resin (A). If the resist composition contains resin (X), its content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1 to 40 parts by mass, even more preferably 1 to 30 parts by mass, and even more preferably 1 to 8 parts by mass, per 100 parts by mass of resin (A).

[0164] The content of resin (A) in the resist composition is preferably 80% to 99% by mass, and more preferably 90% to 99% by mass, relative to the solid content of the resist composition. Furthermore, if resins other than resin (A) are included, the total content of resin (A) and the other resins is preferably 80% to 99% by mass, and more preferably 90% to 99% by mass, relative to the solid content of the resist composition. The solid content of the resist composition and the resin content thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0165] <Acid Generator (B)> The acid generator (B) may be either nonionic or ionic. Examples of nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxiimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate) and sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane). Typical ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of onium salt anions include sulfonic acid anions, sulfonylimide anions, and sulfonylmethide anions.

[0166] As the acid generator (B), compounds that generate acid by radiation as described in Japanese Patent Publication Nos. 63-26653, 55-164824, 62-69263, 63-146038, 63-163452, 62-153853, 63-146029, U.S. Patent Nos. 3,779,778 and 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc., can be used. Compounds manufactured by known methods may also be used. Two or more types of acid generators (B) may be used in combination.

[0167] The acid generator (B) is preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007878912000091.tif2961[In formula (B1), Q b1 and Q b2 Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y represents a methyl group which may have substituents or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the -CH2- contained in the alicyclic hydrocarbon group may be replaced with -O-, -SO2-, or -CO-. Z1 + This represents an organic cation.

[0168] Q b1 and Q b2 Examples of perfluoroalkyl groups include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluorosec-butyl, perfluorotert-butyl, perfluoropentyl, and perfluorohexyl groups. Q b1 and Q b2 Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and hexyl groups. The acid generator (B) is preferably a fluorine-containing acid generator, Q b1 and Q b2Preferably, at least one of them contains a fluorine atom or a perfluoroalkyl group, more preferably at least one is a fluorine atom or a perfluoroalkyl group, even more preferably a fluorine atom or a trifluoromethyl group, and even more preferably both are fluorine atoms.

[0169] L b1 Examples of divalent saturated hydrocarbon groups in this context include linear alkanediyl groups, branched alkanediyl groups, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. Groups formed by combining two or more of these groups may also be used. Specifically, linear alkane diyl groups such as 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-diyl group; Branched alkanediyl groups such as 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 group, and 2-methylbutane-1,4-diyl group; Monocyclic, divalent, alicyclic saturated hydrocarbon groups such as cycloalkanediyl groups, cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl; Examples include polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group.

[0170] L b1Examples of groups in which the -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO- include the group represented by any of the formulas (b1-1) to (b1-3). In the groups represented by formulas (b1-1) to (b1-3) and their specific examples, the groups represented by formulas (b1-4) to (b1-11), * and ** represent bonding sites, and * represents the bonding site with -Y.

[0171] TIFF0007878912000092.tif26117 [In formula (b1-1), L b2 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the 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, wherein the hydrogen atoms in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 This 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 b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, wherein the hydrogen atoms in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, wherein the hydrogen atoms in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0172] In groups represented by formulas (b1-1) to (b1-3), if the -CH2- contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before the replacement shall be the number of carbon atoms of the saturated hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups. L b2 These are preferably a single bond, a methylene group, -CH(CF3)-, and -C(CF3)2-. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atoms in the divalent saturated hydrocarbon group may be substituted with fluorine atoms, and it is preferably a methylene group, -CH(CF3)-, or -C(CF3)2-. L b5 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b7 Preferably, the saturated hydrocarbon group is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups, and the -CH2- groups in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-.

[0173] Lb1 As for the group in which the -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced with -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferred. The groups represented by formula (b1-1) include those represented by formulas (b1-4) to (b1-8), respectively. TIFF0007878912000093.tif48120[In formula (b1-4), L b8 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group 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 the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms in the divalent saturated hydrocarbon 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, and the hydrogen atoms in the divalent saturated hydrocarbon 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, and the -CH2- contained in the divalent saturated hydrocarbon 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, and the hydrogen atoms in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -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, and the hydrogen atoms in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. L b8 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably 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 b15Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 This is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0174] The groups represented by formula (b1-3) include those represented by formulas (b1-9) to (b1-11), respectively. TIFF0007878912000094.tif22140[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 hydrogen atoms contained in the saturated hydrocarbon 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 hydrogen atoms in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. The -CH2- in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms in the alkylcarbonyloxy group may be substituted with a hydroxyl group. 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 hydrogen atoms contained in the saturated hydrocarbon 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 hydrogen atoms in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. The -CH2- in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms in the alkylcarbonyloxy group may be substituted with a hydroxyl group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon 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 hydrogen atoms in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. The -CH2- in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms in the alkylcarbonyloxy group may be substituted with a hydroxyl group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less.

[0175] Furthermore, in the case of the groups represented by formulas (b1-9) to (b1-11), if a hydrogen atom in a saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before the substitution shall be the number of carbon atoms in the saturated hydrocarbon group. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, butyryloxy group, cyclohexylcarbonyloxy group, and adamantylcarbonyloxy group.

[0176] The following are examples of bases represented by formula (b1-4): TIFF0007878912000095.tif17150

[0177] The following are examples of bases represented by formula (b1-5): TIFF0007878912000096.tif72149

[0178] The following are examples of bases represented by formula (b1-6): TIFF0007878912000097.tif30150

[0179] The following are examples of bases represented by formula (b1-7): TIFF0007878912000098.tif64150

[0180] The following are examples of bases represented by formula (b1-8): TIFF0007878912000099.tif23150

[0181] The following are examples of bases represented by formula (b1-2): TIFF0007878912000100.tif31161

[0182] The following are examples of bases represented by formula (b1-9): TIFF0007878912000101.tif44137

[0183] The following are examples of bases represented by formula (b1-10): TIFF0007878912000102.tif89157

[0184] The following are examples of bases represented by formula (b1-11): TIFF0007878912000103.tif82158

[0185] Examples of alicyclic hydrocarbon groups in which the -CH2- contained in the alicyclic hydrocarbon group represented by Y is not replaced by -O-, -S-, -SO2-, or -CO- include the groups represented by formulas (Y1) to (Y11) and (Y36) to (Y38). When the -CH2- in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -S-, -SO2-, or -CO-, the number of replacements may be one or two or more. Examples of such groups include those represented by formulas (Y12) to (Y35) and (Y39) to (Y43). The -O- or -CO- in the groups represented by formulas (Y12) to (Y35) and (Y39) to (Y43) may also be replaced by -S- or -SO2-. * is L b1 This represents the connection point. The alicyclic hydrocarbon group represented by TIFF0007878912000104.tif84165Y is preferably a group represented by any of the following formulas: (Y1) to (Y20), (Y26), (Y27), (Y30), (Y31), (Y39) to (Y43), and more preferably (Y11), (Y15), (Y16), (Y20), ( The group is represented by formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43), and more preferably by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43). When the alicyclic hydrocarbon group represented by Y is a spiro ring containing an oxygen atom, such as formulas (Y28) to (Y35), (Y39), (Y40), (Y42), or (Y43), it is preferable that the alkanediyl group between the two oxygen atoms has one or more fluorine atoms. Furthermore, it is preferable that the methylene group adjacent to the oxygen atom among the alkanediyl groups contained in the ketal structure is not substituted with a fluorine atom.

[0186] The substituents of the methyl group represented by Y include halogen atoms, hydroxyl groups, alicyclic hydrocarbon groups with 3 to 16 carbon atoms, aromatic hydrocarbon groups with 6 to 18 carbon atoms, glycidyloxy groups, and -(CH2) ja-CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 ) represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and the -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O-, -SO2-, or -CO-, and the hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced with a hydroxyl group or a fluorine atom. ja represents an integer from 0 to 4. ) are some examples. Substituents for the alicyclic hydrocarbon group represented by Y include halogen atoms, hydroxyl groups, C1-C16 alkyl groups that may be substituted with hydroxyl groups (the -CH2- contained in the alkyl group may be replaced with -O- or -CO-), C3-C16 alicyclic hydrocarbon groups, C6-C18 aromatic hydrocarbon groups, C7-C21 aralkyl groups, glycidyloxy groups, and -(CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 ) represents an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, and the -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced with -O-, -SO2-, or -CO-, and the hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced with a hydroxyl group or a fluorine atom. ja represents an integer from 0 to 4. ) are some examples.

[0187] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, and adamantyl group. Alicyclic hydrocarbon groups may also have chain hydrocarbon groups, such as methylcyclohexyl group and dimethylcyclohexyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, and more preferably 3 to 10. Examples of aromatic hydrocarbon groups include phenyl groups, naphthyl groups, anthryl groups, biphenyl groups, phenanthryl groups, and other aryl groups. Aromatic hydrocarbon groups may have a chain-type hydrocarbon group or an alicyclic hydrocarbon group, and examples include aromatic hydrocarbon groups having a chain-type hydrocarbon group with 1 to 18 carbon atoms (tolyl group, xylyl group, cumenyl group, mesityl group, p-methylphenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), and aromatic hydrocarbon groups having an alicyclic hydrocarbon group with 3 to 18 carbon atoms (p-adamantylphenyl group, p-cyclohexylphenyl group, etc.). The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, and dodecyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkyl groups substituted with a hydroxyl group include hydroxymethyl groups, hydroxyethyl groups, and other hydroxyalkyl groups. Examples of aralkyl groups include benzyl groups, phenethyl groups, phenylpropyl groups, naphthylmethyl groups, and naphthylethyl groups. Groups in which the -CH2- group in an alkyl group is replaced with -O-, -SO2-, or -CO- include alkoxy groups, alkylsulfonyl groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, or combinations thereof. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and dodecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkylsulfonyl groups include methylsulfonyl groups, ethylsulfonyl groups, and propylsulfonyl groups. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkoxycarbonyl groups include methoxycarbonyl groups, ethoxycarbonyl groups, and butoxycarbonyl groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkylcarbonyl groups include acetyl groups, propionyl groups, and butyryl groups. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkylcarbonyloxy groups include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of combined groups include groups combining an alkoxy group and an alkyl group, groups combining two alkoxy groups, groups combining an alkoxy group and an alkylcarbonyl group, and groups combining an alkoxy group and an alkylcarbonyloxy group. Examples of groups combining an alkoxy group and an alkyl group include alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxyethyl, and ethoxymethyl groups. The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of groups formed by combining alkoxy groups include alkoxyalkoxy groups such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of groups combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as methoxyacetyl group, methoxypropionyl group, ethoxyacetyl group, and ethoxypropionyl group. The number of carbon atoms in the alkoxyalkylcarbonyl group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Examples of groups combining an alkoxy group and an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as methoxyacetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, and ethoxypropionyloxy group. The number of carbon atoms in the alkoxyalkylcarbonyloxy group is preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. Groups in which the -CH2- group in an alicyclic hydrocarbon group is replaced with -O-, -SO2-, or -CO- include the groups represented by formulas (Y12) to (Y35) and (Y39) to (Y43).

[0188] The following are examples of Y: TIFF0007878912000105.tif128165

[0189] TIFF0007878912000106.tif55155

[0190] Y is preferably a substituted alicyclic hydrocarbon group having 3 to 24 carbon atoms, more preferably a substituted alicyclic hydrocarbon group having 3 to 20 carbon atoms, even more preferably a substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and even more preferably a substituted adamantyl group or a substituted norbornyl group, wherein the -CH2- constituting the alicyclic hydrocarbon group, adamantyl group or norbornyl group may be replaced with -O-, -SO2-, or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, a norbornane lactone group, or a group represented by formulas (Y42), (Y100) to (Y114), (Y134) to (Y139).

[0191] The anions in the salt represented by formula (B1) are preferably those represented by formulas (B1-A-1) to (B1-A-62) (hereinafter, they may be referred to as "anion (B1-A-1)" etc. depending on the formula number), and more preferably those represented by any of formulas (B1-A-1) to (B1-A-4), (B1-A-9), (B1-A-10), (B1-A-24) to (B1-A-33), (B1-A-36) to (B1-A-40), or (B1-A-47) to (B1-A-62). TIFF0007878912000107.tif231165

[0192] TIFF0007878912000108.tif247165

[0193] TIFF0007878912000109.tif184163

[0194] Here R i2 ~R i7 These are, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. i8For example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by a combination thereof, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. A41 This is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 This expresses the same meaning as above. Specific examples of anions in the salt represented by formula (B1) include those described in Japanese Patent Publication No. 2010-204646.

[0195] Preferred anions in the salt represented by formula (B1) are the anions represented by formulas (B1a-1) to (B1a-40), respectively. TIFF0007878912000110.tif89153

[0196] TIFF0007878912000111.tif92139

[0197] TIFF0007878912000112.tif142155

[0198] TIFF0007878912000113.tif103164

[0199] Among these, anions represented by any of the following formulas are preferred: (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), and (B1a-22) to (B1a-40).

[0200] Z1 +Examples of organic cations include organic onium cations, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, and organic phosphonium cations. Among these, organic sulfonium cations and organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, examples include cations represented by any of formulas (b2-1) to (b2-4) (hereinafter, depending on the formula number, they may be referred to as "cation (b2-1)," etc.). In formulas (b2-1) to (b2-4) of TIFF0007878912000114.tif46164, R b4 ~R b6 Each of these independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms. The hydrogen atoms in the chain hydrocarbon group may be substituted with a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atoms in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkyl fluoride group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5 These atoms may bond with each other and form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b7 and R b8 Each of these independently represents a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer between 0 and 5. When m2 is 2 or more, multiple R b7They may be the same or different, and when n2 is 2 or greater, multiple R b8 They may be the same or different. R b9 and R b10 Each of these independently represents either a chain-like hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 These atoms may bond with each other and form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. R b11 This represents a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 This represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the chain hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 These may be bonded to each other and form a ring including the -CH-CO- groups to which they are bonded, and the -CH2- groups included in the ring may be replaced by -O-, -S-, or -CO-. R b13 ~R b18 Each of these independently represents a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b13 and R b14 These atoms may bond with each other and together with the benzene ring to which they are bonded, form a ring containing a sulfur atom, and the -CH2- contained in the ring may be replaced with -O-, -S-, or -CO-. 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, and when r2 is 2 or more, multiple R b16 They are the same or different, and when s2 is 2 or more, multiple R b17 They are the same or different, and when t2 is 2 or more, multiple R b18 They are either the same or different. When u2 is 0, then at least one of o2, p2, q2, and r2 is 1 or greater, and R b13 ~R b16 Preferably, at least one of them is a halogen atom, and when u2 is 1, then one of o2, p2, s2, t2, q2 and r2 is 1 or more, and R b13 ~R b18 Preferably, at least one of them is a halogen atom. Furthermore, when u2 is 0, it is preferable that r2 is 1 or greater, and more preferably 1. Also, when u2 is 0 and r2 is 1 or greater, R b16 It is preferable that the atom is a halogen atom.

[0201] Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain-like hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2-ethylhexyl. 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. Examples of monocyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following groups. TIFF0007878912000115.tif11158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

[0202] Examples of alicyclic hydrocarbon groups in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include methylcyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, 2-isopropyladamantan-2-yl group, methylnorbornyl group, and isobornyl group. In alicyclic hydrocarbon groups in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. A fluorinated alkyl group refers to an alkyl group having 1 to 12 carbon atoms and containing a fluorine atom, such as a fluoromethyl group, difluoromethyl group, trifluoromethyl group, or perfluorobutyl group. The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4.

[0203] Examples of aromatic hydrocarbon groups include aryl groups such as phenyl, biphenyl, naphthyl, and phenanthryl groups. Aromatic hydrocarbon groups may have a chain-like hydrocarbon group or an alicyclic hydrocarbon group, and examples include aromatic hydrocarbon groups having a chain-like hydrocarbon group (tolyl, xylyl, cumenyl, mesityl, p-ethylphenyl, p-tert-butylphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.) and aromatic hydrocarbon groups having an alicyclic hydrocarbon group (p-cyclohexylphenyl, p-adamantylphenyl, etc.). Furthermore, if the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which a hydrogen atom is substituted with an alkoxy group include the p-methoxyphenyl group. Examples of chain-like hydrocarbon groups in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl, and naphthylethyl groups.

[0204] Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, and dodecyloxy groups. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of alkylcarbonyloxy groups include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, and 2-ethylhexylcarbonyloxy group.

[0205] R b4 and R b5 The ring formed by the bonding of these atoms to each other and the sulfur atoms to which they are bonded may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. Examples of such rings include those with 3 to 18 carbon atoms, preferably those with 4 to 18 carbon atoms. Furthermore, examples of sulfur atom-containing rings include those with 3 to 12 membered rings, preferably those with 3 to 7 membered rings, and the following rings are examples. * indicates a bonding site. TIFF0007878912000116.tif23143

[0206] R b9 and R b10 The ring formed by the combination of these elements may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. Examples include a thiolan-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxatian-4-ium ring. R b11 and R b12 The ring formed by the combination of these elements may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. Examples include oxocycloheptane rings, oxocyclohexane rings, oxonorbornane rings, and oxoadamantane rings.

[0207] Among cations (b2-1) to (b2-4), cation (b2-1) is preferred. The following cations can be considered as cations (b2-1): TIFF0007878912000117.tif80158

[0208] TIFF0007878912000118.tif107164

[0209] The following cations can be considered as cations (b2-2): TIFF0007878912000119.tif18150

[0210] The following cations can be considered as cations (b2-3): TIFF0007878912000120.tif26140

[0211] The following cations can be considered as cations (b2-4): TIFF0007878912000121.tif153161

[0212] The acid generator (B) is a combination of the anion and the organic cation described above, and these can be combined arbitrarily. Preferred examples of the acid generator (B) include a combination of an anion represented by any of the formulas (B1a-1) to (B1a-3), (B1a-7) to (B1a-16), (B1a-18), (B1a-19), (B1a-22) to (B1a-38) and a cation (b2-1), cation (b2-2), cation (b2-3), or cation (b2-4).

[0213] Preferably, the acid generator (B) is represented by formulas (B1-1) to (B1-60). Among these, those containing arylsulfonium cations are preferred, and those represented by formulas (B1-1) to (B1-3), (B1-5) to (B1-7), (B1-11) to (B1-14), (B1-20) to (B1-26), (B1-29), and (B1-31) to (B1-60) are particularly preferred. TIFF0007878912000122.tif191167

[0214] TIFF0007878912000123.tif250153

[0215] TIFF0007878912000124.tif237166

[0216] In the resist composition of the present invention, the content of the acid generator is preferably 1 to 45 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the aforementioned resin (A).

[0217] <Solvent (E)> The solvent (E) content in the resist composition is usually 90% to 99.9% by mass, preferably 92% to 99% by mass, and more preferably 94% to 99% by mass. The solvent (E) content can be measured by known analytical means such as liquid chromatography or gas chromatography. Examples of solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and cyclic esters such as γ-butyrolactone. One of solvents (E) may be used alone, or two or more may be used.

[0218] <Quencher (C)> Quencher (C) can be a basic nitrogen-containing organic compound or a salt that generates an acid weaker than the acid generated from the acid generator (B). When the resist composition contains quencher (C), the quencher (C) content is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, even more preferably about 0.1 to 8% by mass, and even more preferably about 0.1 to 7% by mass, based on the solid content of the resist composition. Basic nitrogen-containing organic compounds include amines and ammonium salts. Amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, trib Tylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldi Decylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridine, 4-methylpyridine, 1,2-di(2-P Examples include lysyl)ethane, 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Diisopropylaniline is preferred, and 2,6-diisopropylaniline is more preferred. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, and the like.

[0219] The acidity of a salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is represented by the acid dissociation constant (pKa). A salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is a salt having an acid dissociation constant of the acid generated from the salt usually of -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid weaker in 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 "weak acid inner salt (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, and JP-A-2011-191745. Preferably, it is a salt that generates a carboxylic acid weaker in acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), more preferably a weak acid inner salt (D), and still more preferably a diphenyliodonium salt containing a phenyl group substituted with a carboxylic acid anion among the weak acid inner salts (D). TIFF0007878912000125.tif116167

[0220] The weak acid inner salt (D) is preferably a diphenyliodonium salt having an iodonium cation to which two phenyl groups are bonded and a carboxylic acid anion substituted for at least one of the two phenyl groups bonded to the iodonium cation, and specifically, examples thereof include salts represented by the following formula.

[0221] TIFF0007878912000126.tif1593 [In formula (D), R D1 and R D2 Each of these independently represents a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group, or a halogen atom. m' and n' each independently represent an integer from 0 to 4, and if m' is 2 or greater, multiple R D1 They may be the same or different, and if n' is 2 or more, there may be multiple R D2 They may be the same or different. R D1 and R D2 Examples of hydrocarbon groups include chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. Examples of chain-type hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and nonyl groups. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and may be saturated or unsaturated. Examples include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and cyclododecyl groups, as well as norbonyl and adamantyl groups. Examples of aromatic hydrocarbon groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, and other aryl groups. Groups formed by combining these include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, and aralkyl groups (for example, phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group, etc.). Examples of alkoxy groups include methoxy groups and ethoxy groups. Examples of acyl groups include acetyl groups, propanoyl groups, benzoyl groups, and cyclohexanecarbonyl groups. Examples of acyloxy groups include groups in which an oxy group (-O-) is bonded to the above-mentioned acyl group. Examples of alkoxycarbonyl groups include groups in which a carbonyl group (-CO-) is bonded to the above-mentioned alkoxy group. Examples of halogen atoms include fluorine, chlorine, and bromine atoms. R D1 and R D2 Each of these is preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or a halogen atom. m' and n' are each independently preferably integers between 0 and 2, and more preferably 0. If m' is 2 or greater, multiple R D1 They may be the same or different, and if n' is 2 or more, there may be multiple R D2 They may be the same or different.

[0222] More specifically, the following salts are examples: TIFF0007878912000127.tif72165

[0223] <Other ingredients> The resist composition of the present invention may optionally contain components other than those described above (hereinafter sometimes referred to as "other components (F)"). There are no particular limitations on other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc., can be used.

[0224] <Preparation of resist composition> The resist composition of the present invention can be prepared by mixing compound (I), resin (A), and acid generator (B), and optionally resins other than resin (A), solvent (E), quencher (C), and other components (F). The mixing order is arbitrary and not particularly limited. The mixing temperature can be selected from 10 to 40°C, depending on the type of resin, etc., and the solubility of the resin, etc., in the solvent (E). The mixing time can be selected from 0.5 to 24 hours, depending on the mixing temperature. There are no particular restrictions on the mixing method, and stirring or other methods can be used. After mixing the components, it is preferable to filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm.

[0225] <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. The resist composition can be applied to a substrate using commonly used equipment such as a spin coater. Examples of substrates include inorganic substrates such as silicon wafers, and organic substrates with a resist film or the like formed on their surface. Before applying the resist composition, the substrate may be cleaned, or an anti-reflective film or the like may be formed on the substrate. The solvent is removed and a composition layer is formed by drying the coated composition. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or by using a vacuum device. The heating temperature is preferably 50 to 200°C, and the heating time is preferably 10 to 180 seconds. The pressure when drying under reduced pressure is 1 to 1.0 × 10⁻⁶. 5 It is preferable that the pressure be around Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Various types of exposure light sources can be used, including those that emit ultraviolet laser light such as KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm), those that emit far-ultraviolet or vacuum-ultraviolet harmonic laser light by wavelength conversion of laser light from a solid-state laser light source (such as a YAG or semiconductor laser), electron beams, and those that irradiate with ultra-ultraviolet (EUV) light. In this specification, the irradiation of these radiations is sometimes collectively referred to as "exposure." During exposure, exposure is usually performed through a mask corresponding to the desired pattern. If the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is subjected to heat treatment (so-called post-exposure bake) to promote the deprotection reaction at acid-unstable groups. The heating temperature is usually around 50 to 200°C, preferably around 70 to 150°C. After heating, a chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition. Alternatively, before development, the process of coating the resist composition, drying, exposure, and heating may be repeated on the composition layer after exposure. The heated composition layer is typically developed using a developing apparatus and a developing solution. Development methods include the dip 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 preferably, for example, 5 to 300 seconds. By selecting the type of developing solution as described below, a positive-type resist pattern or a negative-type resist pattern can be manufactured. When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer can be any alkaline aqueous solution used in this field. For example, aqueous solutions of tetramethylammonium hydroxide or (2-hydroxyethyl)trimethylammonium hydroxide (commonly known as choline) can be used. The alkaline developer may also contain a surfactant. It is preferable to wash the resist pattern with ultrapure water after development, and then remove any remaining water on the substrate and pattern. When manufacturing a negative-type resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used as the developer. Examples of organic solvents contained in organic developers include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and even more preferably substantially composed of only organic solvents. Among these, organic developers containing butyl acetate and / or 2-heptanone are preferred. The total content of butyl acetate and 2-heptanone in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and even more preferably substantially butyl acetate and / or 2-heptanone alone. Organic developers may contain surfactants. Furthermore, organic developers may contain trace amounts of water. During development, the development process may be stopped by substituting a different type of solvent for the organic developer. It is preferable to wash the developed resist pattern with a rinsing solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent 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.

[0226] <Application> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, an ArF excimer laser exposure, an electron beam (EB) exposure, or an EUV exposure, and is particularly suitable as a resist composition for electron beam (EB) exposure or an EUV exposure, and is useful for semiconductor microfabrication. [Examples]

[0227] The present invention will be described in more detail with reference to examples. In the examples, "%" and "parts" representing the content or amount used are based on mass unless otherwise specified. The weight-average molecular weight was determined by gel permeation chromatography under the following conditions. Equipment: HLC-8120GPC model (manufactured by Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guardcolumn (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)

[0228] Furthermore, the structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: Agilent 1100, MASS: Agilent LC / MSD). In the following examples, the value of this molecular ion peak is indicated as "MASS".

[0229] Synthesis Example 1: Synthesis of the compound represented by formula (I-1) TIFF0007878912000128.tif41140 Mix 2.40 parts of the compound represented by formula (I-1-a) and 40 parts of chloroform and stir at 23°C for 30 minutes. Add 4.86 parts of the compound represented by formula (I-1-b) to the resulting mixed solution and stir at 50°C for 2 hours. Add 3.00 parts of the compound represented by formula (I-1-c) to the resulting mixed solution and stir at 50°C for 3 hours, then cool to 23°C. Add 20 parts of 5% oxalic acid aqueous solution to the resulting mixture and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 20 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and the concentrated mixture was parsed using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to obtain 4.18 parts of the compound represented by formula (I-1). MASS (mass spectrometry):531.1[M+H] +

[0230] Synthesis Example 2: Synthesis of the compound represented by formula (I-3) TIFF0007878912000129.tif41141 Mix 2.40 parts of the compound represented by formula (I-1-a) and 40 parts of chloroform and stir at 23°C for 30 minutes. Add 4.86 parts of the compound represented by formula (I-1-b) to the resulting mixed solution and stir at 50°C for 2 hours. Add 5.04 parts of the compound represented by formula (I-3-c) to the resulting mixed solution and stir at 50°C for 3 hours, then cool to 23°C. Add 20 parts of 5% oxalic acid aqueous solution to the resulting mixture and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 20 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and the concentrated mixture was parsed using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to obtain 5.92 parts of the compound represented by formula (I-3). MASS (mass spectrometry):735.1[M+H] +

[0231] Synthesis Example 3: Synthesis of the compound represented by formula (I-6) TIFF0007878912000130.tif28144 1.96 parts of the compound represented by formula (I-6-a) and 40 parts of chloroform were mixed and stirred at 23°C for 30 minutes. 3.36 parts of the compound represented by formula (I-1-b) were added to the resulting mixed solution and stirred at 50°C for 2 hours. 3.00 parts of the compound represented by formula (I-3-c) were added to the resulting mixed solution and stirred at 50°C for 3 hours, after which it was cooled to 23°C. 20 parts of 5% aqueous oxalic acid were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was separated. 20 parts of deionized water were added to the resulting organic layer and stirred at 23°C for 30 minutes, after which the organic layer was separated. This washing procedure was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was parsed using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to obtain 4.33 parts of the compound represented by formula (I-6). MASS (mass spectrometry):541.1[M+H] +

[0232] Synthesis Example 4: Synthesis of the compound represented by formula (I-13) TIFF0007878912000131.tif38144 Two-tenths of the compound represented by formula (I-13-a) and forty parts of chloroform were mixed and stirred at 23°C for 30 minutes. Four-tenths of the compound represented by formula (I-1-b) were added to the resulting mixed solution and stirred at 50°C for 2 hours. Three-tenths of the compound represented by formula (I-1-c) were added to the resulting mixed solution and stirred at 50°C for 3 hours, after which it was cooled to 23°C. Twenty-tenths of 5% aqueous oxalic acid solution were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was separated. Twenty-tenths of deionized water were added to the resulting organic layer and stirred at 23°C for 30 minutes, after which the organic layer was separated. This washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was parsed using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to obtain 4.42 parts of the compound represented by formula (I-13). MASS (mass spectrometry):547.1[M+H] +

[0233] Synthesis Example 5: Synthesis of the compound represented by formula (I-14) TIFF0007878912000132.tif31128 Mix 4.24 parts of the compound represented by formula (I-13-a) and 40 parts of chloroform and stir at 23°C for 30 minutes. Add 3.24 parts of the compound represented by formula (I-1-b) to the resulting mixed solution and stir at 50°C for 2 hours. Add 2.00 parts of the compound represented by formula (I-1-c) to the resulting mixed solution and stir at 50°C for 3 hours, then cool to 23°C. Add 20 parts of 5% oxalic acid aqueous solution to the resulting mixture and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 20 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and the concentrated mixture was parsed using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to obtain 3.94 parts of the compound represented by formula (I-14-a). TIFF0007878912000133.tif34142 2.94 parts of the compound represented by formula (I-14-a), 40 parts of dimethylformamide, and 3.10 parts of diisopropylethylamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. 2.64 parts of the compound represented by formula (I-14-b) were added dropwise to the resulting mixture, the temperature was raised to 70°C, stirred at 70°C for 2 hours, and then cooled to 23°C. 100 parts of chloroform and 50 parts of deionized water were added to the resulting mixture, stirred at 23°C for 30 minutes, and the organic layer was obtained by liquid-liquid extraction. 50 parts of 5% oxalic acid aqueous solution were added to the obtained organic layer, stirred at 23°C for 30 minutes, and the organic layer was obtained by liquid-liquid extraction. 50 parts of deionized water were added to the obtained organic layer, stirred at 23°C for 30 minutes, and the organic layer was obtained by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was fractionated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 3.98 parts of the compound represented by formula (I-14). MASS (mass spectrometry):487.1[M+H] +

[0234] Synthesis Example 6: Synthesis of the compound represented by formula (I-72) TIFF0007878912000134.tif43147 Mix 2.40 parts of the compound represented by formula (I-1-a) and 40 parts of chloroform and stir at 23°C for 30 minutes. Add 4.86 parts of the compound represented by formula (I-1-b) to the resulting mixed solution and stir at 50°C for 2 hours. Add 4.50 parts of the compound represented by formula (I-72-c) to the resulting mixed solution and stir at 50°C for 3 hours, then cool to 23°C. Add 20 parts of 5% oxalic acid aqueous solution to the resulting mixture and stir at 23°C for 30 minutes, then separate to remove the organic layer. Add 20 parts of deionized water to the resulting organic layer and stir at 23°C for 30 minutes, then separate to remove the organic layer. Repeat this washing procedure five times. The obtained organic layer was concentrated, and the concentrated mixture was parsed using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to obtain 4.92 parts of the compound represented by formula (I-72). MASS (mass spectrometry):681.1[M+H] +

[0235] Synthesis Example 7: Synthesis of the compound represented by formula (I-73) TIFF0007878912000135.tif45149 2.40 parts of the compound represented by formula (I-1-a) and 40 parts of chloroform were mixed and stirred at 23°C for 30 minutes. 4.86 parts of the compound represented by formula (I-1-b) were added to the resulting mixed solution and stirred at 50°C for 2 hours. 6.00 parts of the compound represented by formula (I-73-c) were added to the resulting mixed solution and stirred at 50°C for 3 hours, after which it was cooled to 23°C. 20 parts of 5% aqueous oxalic acid were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was separated. 20 parts of deionized water were added to the resulting organic layer and stirred at 23°C for 30 minutes, after which the organic layer was separated. This washing procedure was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was parsed using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to obtain 4.68 parts of the compound represented by formula (I-73). MASS (mass spectrometry):831.1[M+H] +

[0236] Synthesis Example 8: Synthesis of the compound represented by formula (I-74) TIFF0007878912000136.tif50151 2.40 parts of the compound represented by formula (I-1-a) and 40 parts of chloroform were mixed and stirred at 23°C for 30 minutes. 4.86 parts of the compound represented by formula (I-1-b) were added to the resulting mixed solution and stirred at 50°C for 2 hours. 7.50 parts of the compound represented by formula (I-74-c) were added to the resulting mixed solution and stirred at 50°C for 3 hours, after which it was cooled to 23°C. 20 parts of 5% aqueous oxalic acid were added to the resulting mixture and stirred at 23°C for 30 minutes, after which the organic layer was separated. 20 parts of deionized water were added to the resulting organic layer and stirred at 23°C for 30 minutes, after which the organic layer was separated. This washing procedure was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was parsed using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to obtain 4.19 parts of the compound represented by formula (I-74). MASS (mass spectrometry):981.1[M+H] +

[0237] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. Hereafter, these compounds will be referred to as "monomers (a1-1-3)," etc., according to their formula numbers. TIFF0007878912000137.tif43156

[0238] Synthesis Example 9 [Synthesis of Resin A1] Monomers (a1-4-2), (a1-1-3), and (a1-2-6) were used as monomers, and they were mixed in a molar ratio [monomer (a1-4-2):monomer (a1-1-3):monomer (a1-2-6)] of 38:24:38. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. Azobisisobutyronitrile was added to the resulting mixture as an initiator in an amount of 7 mol% relative to the total moles of all monomers, and polymerization was carried out by heating at 85°C for approximately 5 hours. Subsequently, 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5 wt%) relative to the total mass of all monomers was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.3 × 10⁻⁶. 3 Resin A1 (polymer) was obtained in a yield of 78%. This resin A1 has the following structural units. TIFF0007878912000138.tif30126

[0239] Synthesis Example 10 [Synthesis of Resin A2] Monomers (a1-4-2) and (a1-2-6) were used as monomers, and they were mixed in a molar ratio [monomer (a1-4-2):monomer (a1-2-6)] of 38:62. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. Azobisisobutyronitrile was added to the resulting mixture as an initiator in an amount of 7 mol% relative to the total moles of all monomers, and polymerization was carried out by heating at 85°C for approximately 5 hours. Subsequently, 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5 wt%) relative to the total mass of all monomers was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.4 × 10⁻⁶. 3 Resin A2 (polymer) was obtained in a yield of 89%. This resin A2 has the following structural units. TIFF0007878912000139.tif2886

[0240] Synthesis Example 11 [Synthesis of Resin A3] Monomers (a1-4-19) and (a1-2-6) were used as monomers, and they were mixed in a molar ratio [monomer (a1-4-19):monomer (a1-2-6)] of 38:62. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. Azobisisobutyronitrile was added to the resulting mixture as an initiator in an amount of 7 mol% relative to the total moles of all monomers, and polymerization was carried out by heating at 85°C for approximately 5 hours. Subsequently, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) equal to 2.0 times the total mass of all monomers was added to the polymerization reaction solution, and after stirring for 6 hours, the solution was separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.2 × 10⁻⁶. 3 Resin A3 (polymer) was obtained in a yield of 86%. This resin A3 has the following structural units. TIFF0007878912000140.tif2686

[0241] Synthesis Example 12 [Synthesis of Resin A4] Monomers (a1-4-13) and (a1-2-6) were used as monomers, and they were mixed in a molar ratio [monomer (a1-4-13):monomer (a1-2-6)] of 38:62. Furthermore, methyl isobutyl ketone was added to this monomer mixture in an amount equal to 1.5 times the total mass of all monomers. Azobisisobutyronitrile was added to the resulting mixture as an initiator in an amount of 7 mol% relative to the total moles of all monomers, and polymerization was carried out by heating at 85°C for approximately 5 hours. Subsequently, 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5 wt%) relative to the total mass of all monomers was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and recovered, yielding a weight-average molecular weight of approximately 5.1 × 10⁻⁶. 3 Resin A4 (polymer) was obtained in a yield of 77%. This resin A4 has the following structural units. TIFF0007878912000141.tif2886

[0242] <Preparation of the resist composition> As shown in Table 1, the following components were mixed, and the resulting mixture was filtered through a polyethylene resin filter with a pore size of 0.001 μm to prepare a resist composition. [Table 1]

[0243] <Resin> A1~A4: Resin A1~Resin A4 <Acid Generator> B1-43: Salt represented by formula (B1-43) (synthesized according to the examples in Japanese Patent Publication No. 2016-47815) TIFF0007878912000143.tif4381<Compound (I)> I-1: Compound represented by formula (I-1) I-3: Compound represented by formula (I-3) I-6: Compound represented by formula (I-6) I-13: Compound represented by formula (I-13) I-14: Compound represented by formula (I-14) I-72: Compound represented by formula (I-72) I-73: Compound represented by formula (I-73) I-74: Compound represented by formula (I-74) <Compound (IX)> IX-1: TIFF0007878912000144.tif1544<Quencher(C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 TIFF0007878912000145.tif4347<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0244] (Electron beam exposure evaluation of resist composition: Alkaline development) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90°C for 60 seconds. A resist composition was spin-coated onto this silicon wafer to a thickness of 0.04 μm. Subsequently, the composition layer was formed by pre-baking on a direct hot plate at the temperature shown in the "PB" column of Table 1 for 60 seconds. A line-and-space pattern (pitch 60 nm / line width 30 nm) was directly drawn onto the composition layer formed on the wafer using an electron beam lithography machine [ELS-F125 125 keV, manufactured by Elionix Co., Ltd.] by gradually changing the exposure amount. After exposure, post-exposure baking was performed on a hot plate at the temperature shown in the "PEB" column of Table 1 for 60 seconds, and then paddle development was performed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 60 seconds to obtain the resist pattern. In the obtained resist pattern, the effective sensitivity was defined as the exposure amount at which the line width and space width of the line-and-space pattern were in a 1:1 ratio.

[0245] <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 the minimum line width (nm) of a resist pattern in which pattern disappearance due to collapse or peeling is not observed in line patterns formed at exposure levels above the effective sensitivity. The results are shown in Table 2. [Table 2] [Industrial applicability]

[0246] The resist composition of the present invention exhibits excellent pattern deformation resistance (PCM) of the resulting resist pattern, making it suitable for semiconductor microfabrication and extremely useful in industry.

Claims

1. A resist composition comprising a compound represented by formula (I), a resin having an acid-unstable group represented by formula (1) or formula (2), and an acid generator. [In formula (I), W represents an aliphatic hydrocarbon group having 1 to 24 carbon atoms and having a (m1 + m2 + m3) valency, which may have substituents, and the aliphatic hydrocarbon group contains -CH ２ The - may be replaced by -O- or -CO-. However, among the -CH2- contained in the aliphatic hydrocarbon group, the -CH2- to which -O-R2 is bonded will not be replaced by -CO-. R １ is *-R １０ or *-L ２ -CO-O-R １０ This represents the bond site with -O-. R ２ represents *-R １０ , *-CO-R １０ , *-CO-O-R １０ , *-L ２ -CO-O-R １０ or *-CO-O-L ２ -CO-O-R １０ , where * represents the bonding site with -O. R １０ This represents the base expressed by formula (1b). L ２ This represents an alkanediyl group having 1 to 6 carbon atoms, which may have substituents. m1 represents an integer from 1 to 6, and when m1 is 2 or greater, multiple R １ They may be identical or different from one another. m2 represents an integer from 1 to 6, and when m2 is 2 or greater, multiple R ２ They may be identical or different from one another. R ３ This represents a halogen atom, a hydroxyl group, a C1-C12 haloalkyl group, or a C1-C12 alkyl group, and the alkyl group contains -CH 2 The - can be replaced with -O- or -CO-. Two R ３ These may together form a group having an acetal ring structure. m3 represents an integer from 0 to 4, and when m3 is 2 or greater, multiple R ３ They may be identical or different from one another. [In formula (1b), R ba1 and R ba2 each independently represent a hydrogen atom, a fluorine atom, or a C1-C6 alkyl group having a fluorine atom. R ba3 represents a fluorine atom or an alkyl group having 1 to 6 carbon atoms that contains a fluorine atom. * indicates a connection site. [In formula (1), Ra1, Ra2, and Ra3 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group having a combination thereof. Alternatively, Ra1 and Ra2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded. ma and na each independently represent either 0 or 1, and at least one of ma and na represents 1. * indicates a connection site. [In formula (2), Ra1' and Ra2' each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Ra3' represents a hydrocarbon group having 1 to 20 carbon atoms, or Ra2' and Ra3' are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded and X, and the -CH2- contained in the hydrocarbon group and the heterocycle may be replaced with -O- or -S-. X represents either an oxygen atom or a sulfur atom. 'na' represents 0 or 1. * indicates a connection site.

2. The resist composition according to claim 1, wherein W is an aliphatic hydrocarbon group having 3 to 18 carbon atoms and having an (m1 + m2 + m3) valency.

3. The resist composition according to claim 1 or 2, wherein the resin having an acid-unstable group comprises at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2). [In formulas (a1-0), (a1-1), and (a1-2), L ａ０１ , 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 ａ０１ , R ａ４ and R ａ５ Each of these independently represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R ａ０２ , R ａ０３ and R ａ０４ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R ａ６ and R ａ７ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination of 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.

4. The resist composition according to any one of claims 1 to 3, wherein the resin having an acid-unstable group comprises a structural unit represented by formula (a2-A). [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-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy 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 the same or different from each other.

5. The resist composition according to any one of claims 1 to 4, wherein the acid generator comprises a salt represented by formula (B1). [In formula (B1), Q ｂ１ and Q ｂ２ Each of these independently represents a hydrogen atom, a fluorine atom, a C1-C6 alkyl group, or a C1-C6 perfluoroalkyl group. L ｂ１ This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the -CH contained in this divalent saturated hydrocarbon group is ２ The - may be replaced by -O- or -CO-, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group. Y represents a methyl group which may have substituents or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have substituents, and the alicyclic hydrocarbon group contains -CH ２ - is -O-, -S-, -SO ２ It may be replaced with - or -CO-. Z1 ＋ This represents an organic cation.

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

7. (1) A step of applying the resist composition according to any one of claims 1 to 6 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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