Salt, acid generator, resist composition, and method for producing resist pattern

Abstract

To provide a salt, an acid generator, and a resist composition which allow a resist pattern having good CD uniformity (CDU) to be produced.SOLUTION: The salt represented by formula (I), the acid generator, and the resist composition are provided. [In the formula, Q1 and Q2 each represent a fluorine atom or a perfluoroalkyl group; R11 and R12 each represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group; z represents an integer of 0-6; X1 and X2 each represent *-CO-O-, *-O-CO- or the like; L1 represents a single bond or an optionally substituted hydrocarbon group; A1 represents a group having an optionally substituted lactone structure; L2 and L3 each represent a single bond or an alkanediyl group; R1 represents an iodine atom or a haloalkyl group; R2 represents a halogen atom, a hydroxy group, a haloalkyl group or an alkyl group; m2 represents an integer of 0-4; and Z+ represents an organic cation.]SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a salt, an acid generator, a resist composition, and a method for producing a resist pattern.

Background Art

[0002] Patent Document 1 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator, respectively. TIFF0007714438000001.tif26124 Patent Document 2 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator, respectively. TIFF0007714438000002.tif2570

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a salt that forms a resist pattern having better CD uniformity (CDU) than a resist pattern formed from a resist composition containing the above salt.

Means for Solving the Problems

[0005] The present invention includes the following inventions. [1] An acid generator containing a salt represented by formula (I). TIFF0007714438000003.tif35124 [In formula (I), Q 1 and Q 2Each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. z represents any integer from 0 to 6. When z is 2 or more, the plurality of R 11 and R 12 may be the same as or different from each other. X 1 and X 2 each independently represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O-, where * represents a bond to C(R 11 )(R 12 ) or C(Q 1 )(Q 2 ) or A 1 or L 2 and represents the bonding site therewith. L 1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-. A 1 represents a group having a lactone structure which may have a substituent. L 2 and L 3 each independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. R 1 represents an iodine atom or a haloalkyl group having 1 to 12 carbon atoms. R 2 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 haloalkyl group and the alkyl group may be replaced by -O- or -CO-. m2 represents any integer from 0 to 4. When m2 is 2 or more, the plurality of R 2 may be the same as or different from each other. Z + represents an organic cation. [2]L 1is a single bond or *-L 4 -CO-O-(L 4 represents a cyclic hydrocarbon group having 3 to 18 carbon atoms or a group combining a cyclic hydrocarbon group having 3 to 18 carbon atoms and an alkanediyl group having 1 to 4 carbon atoms. The cyclic hydrocarbon group may have a substituent, and -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-. -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. * represents the bonding site with X 1 ). The acid generator according to [1]. [3]A 1 is a group represented by formula (R 10 -1), formula (R 10 -2), formula (R 10 -3) or formula (R 10 -4). The acid generator according to [1] or [2]. TIFF0007714438000004.tif36166[In formula (R 10 -1) to formula (R 10 -4), * represents the bonding site. Z 12 represents an oxygen atom, a sulfur atom or a methylene group. R 11 、R 12 、R 13 and R 14 each independently represent a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms or a group combining these. m11 represents any integer from 0 to 5. When m11 is 2 or more, a plurality of R 11 may be the same as or different from each other. m12 represents any integer from 0 to 5. When m12 is 2 or more, a plurality of R 12 may be the same as or different from each other. m13 represents any integer from 0 to 5. When m13 is 2 or more, a plurality of R 13They may be the same as or different from each other. m14 represents any integer from 0 to 5. When m14 is 2 or more, a plurality of Rs 14 may be the same as or different from each other. n10 represents an integer from 1 to 3. [4]A 1 is a group represented by the following formula (L 4 -1), formula (L 4 -2) or formula (L 4 -3) (the group may have a substituent. * represents a bonding site.), which is the acid generator according to [1] or [2]. TIFF0007714438000005.tif2970[5]L 2 and L 3 are each independently a single bond or an alkanediyl group having 1 to 3 carbon atoms, which is the acid generator according to any one of [1] to [4]. [6]R 1 is an iodine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, which is the acid generator according to any one of [1] to [5]. [7]R 2 is an iodine atom, a fluorine atom, a hydroxy group, a perfluoroalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, which is the acid generator according to any one of [1] to [6]. [8]A resist composition containing the acid generator according to any one of [1] to [7] and a resin having an acid-labile group. [9]The resin having an acid-labile group contains 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), which is the resist composition according to [8]. TIFF0007714438000006.tif44141[In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 L a1 and L a2 each independently represent -O- or *-O-(CH2) k1 -CO-O-, k1 represents any integer from 1 to 7, and * represents a bonding site with -CO-. Ra01 , R a4 and R a5 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 , R a03 and R a04 each 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 formed by combining these. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1’ represents any integer from 0 to 3.

[10] A resist composition according to [8] or [9], wherein the resin having an acid-labile group contains a structural unit represented by formula (a2-A). TIFF0007714438000007.tif4349 [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 represents a single bond or * -X a51 -(A a52 -X a52 ) nb - and * represents the bonding site with the carbon atom to which -R a50 is bonded. Aa52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represent -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of R a51 may be the same as or different from each other. The resist composition according to any one of [8] to

[10] , further containing a salt that generates an acid having a lower acidity than the acid generated from the

[11] acid generator.

[12] (1) A step of applying the resist composition according to any one of [8] to

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

[13] The salt represented by formula (I). TIFF0007714438000008.tif35124 [In formula (I), Q 1 and Q 2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R 11 and R 12 each independently represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. z represents any integer from 0 to 6. When z is 2 or more, a plurality of R 11 and R 12 may be the same as or different from each other. X 1 and X 2 each independently represent *-CO-O-, *-O-CO-, *-O-CO-O- or *-O-, where * is C(R 11 )(R 12 ) or C(Q 1 )(Q 2) or A 1 or L 2 represents a binding site with it. L 1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-. A 1 represents a group having a lactone structure which may have a substituent. L 2 and L 3 each independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. R 1 represents an iodine atom or a haloalkyl group having 1 to 12 carbon atoms. R 2 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 haloalkyl group and the alkyl group may be replaced by -O- or -CO-. m2 represents any integer from 0 to 4, and when m2 is 2 or more, a plurality of R 2 may be the same as or different from each other. Z + represents an organic cation.

Advantages of the Invention

[0006] By using the resist composition containing the salt of the present invention, a resist pattern can be produced with good CD uniformity (CDU).

Embodiments for Carrying Out the Invention

[0007] In this specification, the term "(meth)acrylic monomer" means "at least one of acrylic monomers and methacrylic monomers". Expressions such as "(meth)acrylate" and "(meth)acrylic acid" also represent the same meaning. Among the groups described in this specification, those that can take both a linear structure and a branched structure may be either. When -CH2- contained in a hydrocarbon group or the like is replaced by -O-, -S-, -CO- or -SO2-, the same examples shall 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 term "derived from" or "derived" refers 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.

[0008] [Salt represented by formula (I)] The present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). Among salts (I), the side having a negative charge may be referred to as "anion (I)", and the side having a positive charge may be referred to as "cation (I)". TIFF0007714438000009.tif35124[Wherein all symbols have the same meanings as described above respectively.]

[0009] In formula (I), Q 1 , Q 2 , R 11 and R 12 Examples of the perfluoroalkyl group of are trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoropentyl group, perfluorohexyl group and the like. The number of carbon atoms of the perfluoroalkyl group is preferably 1 to 4, more preferably 1 to 3. Q 1 and Q 2 are each independently preferably a trifluoromethyl group or a fluorine atom, more preferably a fluorine atom. R 11 and R 12 is each independently preferably a hydrogen atom, a fluorine atom or a trifluoromethyl group, more preferably a hydrogen atom or a trifluoromethyl group. z is preferably 0 or 1. X 1 is preferably *-CO-O-, *-O-CO-O- or *-O-CO- (* represents the bonding site with C(R 11 )(R 12 ) or C(Q 1 )(Q 2 ), and more preferably *-CO-O- or *-O-CO-).

[0010] L 1 Examples of the hydrocarbon group in include divalent chain hydrocarbon groups such as alkanediyl groups, divalent alicyclic hydrocarbon groups which are monocyclic or polycyclic (including spiro rings), and divalent aromatic hydrocarbon groups, and groups formed by combining two or more of these groups (for example, divalent hydrocarbon groups formed from an alicyclic hydrocarbon group and an alkanediyl group) may also be used. Examples of the alkanediyl group 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, 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, and 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, 2-methylbutane-1,4-diyl group. The number of carbon atoms in the chain hydrocarbon group is preferably from 1 to 18, more preferably from 1 to 12, still more preferably from 1 to 9, even more preferably from 1 to 6, and even more preferably from 1 to 4. Examples of the monocyclic or polycyclic divalent alicyclic hydrocarbon group include the following groups. The bonding site can be at any position. TIFF0007714438000010.tif43167Specifically, examples of the alicyclic hydrocarbon group include monocyclic divalent alicyclic hydrocarbon groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, and polycyclic divalent alicyclic hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group. The number of carbon atoms in the alicyclic hydrocarbon group is preferably from 3 to 18, more preferably from 3 to 16, and still more preferably from 3 to 12. Examples of the divalent aromatic hydrocarbon group include aromatic hydrocarbon groups such as arylene groups such as phenylene group, naphthylene group, anthrylene group, biphenylene group, phenanthrylene group. The number of carbon atoms in the aromatic hydrocarbon group is preferably from 6 to 18, more preferably from 6 to 14, and still more preferably from 6 to 10. Examples of the group formed by combining two or more types include a group formed by combining an alicyclic hydrocarbon group and an alkanediyl group, a group formed by combining an aromatic hydrocarbon group and an alkanediyl group, and a group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group. In the combination, two or more types of alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups may be combined respectively. Also, any group may be bonded to X 1 here. Examples of the group formed by combining an alicyclic hydrocarbon group and an alkanediyl group include, for example, -divalent alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent alicyclic hydrocarbon group-. Examples of the group formed by combining an aromatic hydrocarbon group and an alkanediyl group include, for example, -divalent aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-, and the like. Examples of the group formed by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group include -aromatic hydrocarbon group-alicyclic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-, -alicyclic hydrocarbon group-aromatic hydrocarbon group-alicyclic hydrocarbon group-, and the like. L 1 The -CH2- contained in the hydrocarbon group having 1 to 28 carbon atoms of L may be replaced by -O-, -S-, -SO2- or -CO-. L 1 When the -CH2- contained in the hydrocarbon group having 1 to 28 carbon atoms of L is replaced by -O-, -S-, -SO2- or -CO-, the carbon number before replacement is regarded as the carbon number of the hydrocarbon group. Examples of groups in which -CH2- contained in a hydrocarbon group is replaced by -O-, -S-, -SO2- or -CO- include a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), a thiol group (a group in which -CH2- contained in a methyl group is replaced by -S-), an alkoxy group (a group in which -CH2- at any position contained in an alkyl group is replaced by -O-), an alkylthio group (a group in which -CH2- at any position contained in an alkyl group is replaced by -S-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -CO-), an alkylsulfonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -SO2-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -CO-O-), an alkanedioxy group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -O-), an alkanedioxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkanediyl group is replaced by -O-CO-), an alkanediylcarbonyl group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -CO-), an alkanediylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkanediyl group is replaced by -CO-O-), an alkanediylsulfonyl group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -SO2-), an alkanediylthio group (a group in which -CH2- at any position contained in an alkanediyl group is replaced by -S-), a cycloalkoxy group, a cycloalkylalkoxy group, an alkoxycarbonyloxy group, an aromatic hydrocarbon group-carbonyl-oxy group, a group formed by combining two or more of these groups, and the like. Examples of the alkoxy group include alkoxy groups having 1 to 17 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkylthio group include alkylthio groups having 1 to 17 carbon atoms, such as methylthio group, ethylthio group, propylthio group, butylthio group and the like. The number of carbon atoms of the alkylthio group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group represent groups in which a carbonyl group or carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 17 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group and the like. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 18 carbon atoms, such as acetyl group, propionyl group and butyryl group and the like. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 17 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group and the like. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. Examples of the alkylsulfonyl group include alkylsulfonyl groups having 1 to 17 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group and the like. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyl-oxy group include alkanediyl-oxy groups having 1 to 17 carbon atoms, such as methyleneoxy group, ethyleneoxy group, propanediyl-oxy group, butanediyl-oxy group, pentanediyl-oxy group and the like. The number of carbon atoms of the alkanediyl-oxy group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediyl-oxycarbonyl group include alkanediyl-oxycarbonyl groups having 2 to 17 carbon atoms, such as methyleneoxycarbonyl group, ethyleneoxycarbonyl group, propanediyl-oxycarbonyl group, butanediyl-oxycarbonyl group and the like. Examples of the alkanediylcarbonyl group include alkanediylcarbonyl groups having 2 to 18 carbon atoms, such as methylenecarbonyl group, ethylenecarbonyl group, propanediylcarbonyl group, butanediylcarbonyl group, pentanediylcarbonyl group and the like. Examples of the alkanediylcarbonyloxy group include alkanediylcarbonyloxy groups having 2 to 17 carbon atoms, such as methylenecarbonyloxy group, ethylenecarbonyloxy group, propanediylcarbonyloxy group, butanediylcarbonyloxy group and the like. The number of carbon atoms of the alkanediyl-oxycarbonyl group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkanediylcarbonyl group is preferably 2 to 12, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms of the alkanediylcarbonyloxy group is preferably 2 to 11, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2 or 3. Examples of the alkanediylsulfonyl group include alkanediylsulfonyl groups having 1 to 17 carbon atoms, such as a methylenesulfonyl group, an ethylenesulfonyl group, and a propylenesulfonyl group. The number of carbon atoms of the alkanediylsulfonyl group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the alkanediylthio group include alkanediylthio groups having 1 to 17 carbon atoms, such as a methylenethio group, an ethylenethio group, and a propylenethio group. The number of carbon atoms of the alkanediylthio group is preferably 1 to 11, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. Examples of the cycloalkoxy group include cycloalkoxy groups having 3 to 17 carbon atoms, such as a cyclohexyloxy group. Examples of the cycloalkylalkoxy group include cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as a cyclohexylmethoxy group. Examples of the alkoxycarbonyloxy group include alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as a butoxycarbonyloxy group. Examples of the aromatic hydrocarbon group-carbonyl-oxy group include aromatic hydrocarbon group-carbonyl-oxy groups having 7 to 17 carbon atoms, such as a benzoyloxy group. In addition, examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -S-, -CO- or -SO2- include the following groups. -O- or -CO- in the groups represented below may be replaced by -S- or -SO2, respectively. The bonding site can be at any position. TIFF0007714438000011.tif46165

[0011] L 1Examples of the substituent which may be included are a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group combining these. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and the like. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, and the like. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent a group in which a carbonyl group or a carbonyl-oxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, and the like. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group, and the like. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like. The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group, or a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms or a halogen atom, and even more preferably a methyl group or a fluorine atom.

[0012] L 1is preferably a group formed by combining a single bond, an alkanediyl group having 1 to 8 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-), or a group formed by combining an alkanediyl group having 1 to 6 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-); more preferably, it is a single bond, an alkanediyl group having 1 to 6 carbon atoms (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-), a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-), or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent (provided that -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-). Also, L 1 is a single bond, *-L 4 -CO-O- or *-L 4 -O-CO-O-(L 4 represents a cyclic hydrocarbon group having 3 to 18 carbon atoms or a group formed by combining a cyclic hydrocarbon group having 3 to 18 carbon atoms and an alkanediyl group having 1 to 4 carbon atoms. The cyclic hydrocarbon group may have a substituent, -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. * represents the bonding site with X 1 . It is also preferable that it is as such. In addition, the combinations of the alkandiyl group and the alicyclic hydrocarbon group or the aromatic hydrocarbon group herein include *-alkandiyl group-alicyclic hydrocarbon group or aromatic hydrocarbon group-, *-alicyclic hydrocarbon group or aromatic hydrocarbon group-alkandiyl group-, *-alkandiyl group-alicyclic hydrocarbon group or aromatic hydrocarbon group-alkandiyl group-, and the like. * represents X 1 represents the bonding site with L 4 As the cyclic hydrocarbon group and the alkandiyl group in L 4 are preferably a polycyclic divalent cyclic hydrocarbon group having 6 to 12 carbon atoms or a group combining a polycyclic divalent cyclic hydrocarbon group having 6 to 12 carbon atoms and an alkandiyl group having 1 to 4 carbon atoms (the cyclic hydrocarbon group may have a substituent, and -CH2- contained in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO2-, and -CH2- contained in the alkandiyl group may be replaced by -O- or -CO-), more preferably a polycyclic divalent alicyclic hydrocarbon group having 7 to 11 carbon atoms or a group combining a polycyclic divalent alicyclic hydrocarbon group having 7 to 11 carbon atoms and an alkandiyl group having 1 to 3 carbon atoms (the -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O- or -CO-, and the -CH2- contained in the alkandiyl group may be replaced by -O- or -CO-), and a group selected from the group consisting of the group represented by the following formula (L 4 -1), the group represented by the formula (L 4 -2), the group represented by the formula (L 4 -3) and the group represented by the formula (L 4 -4), or a group selected from the group consisting of the group represented by the following formula (L 4 -1), the group represented by the formula (L 4 -2), the group represented by the formula (L 4 -3) and the group represented by the formula (L 4 -4) and an alkandiyl group having 1 to 3 carbon atoms (the -CH2- contained in the alkandiyl group may be replaced by -O- or -CO-), and is more preferably a group represented by the formula (L 4A group represented by -2) is more preferable. * represents a bonding site. TIFF0007714438000012.tif3096

[0013] A 1 represents a group having a lactone structure which may have a substituent. The lactone structure refers to a structure obtained by removing one or more hydrogen atoms bonded to an atomic group constituting a lactone ring. The lactone ring is a cyclic ester and is a ring containing -CO-O- as an atomic group constituting the ring. The lactone structure may contain, as an atomic group constituting the ring, one or more heteroatoms such as a nitrogen atom, an oxygen atom, and a sulfur atom in addition to -CO-O-, and a hydrogen atom bonded to an atomic group constituting the lactone ring may be replaced by a substituent. The lactone ring may be a monocyclic lactone ring such as a β-propiolactone ring, a γ-butyrolactone ring, and a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. Among these lactone rings, a γ-butyrolactone ring, an adamantanlactone ring, and a condensed ring of a γ-butyrolactone ring and another ring are preferable. Examples of the lactone ring corresponding to the structure before the hydrogen atom is removed in the above lactone structure include lactone rings having 2 to 36 carbon atoms. For example, a ring in which -CH2-CH2- contained in an alicyclic hydrocarbon ring having 3 to 37 carbon atoms is replaced by -CO-O- can be mentioned. The carbon number of the group having a lactone structure or the lactone ring is 2 to 36, preferably 3 to 36, more preferably 3 to 30, still more preferably 3 to 24, even more preferably 3 to 18, and even more preferably 3 to 12. A 1 Specific examples of A include groups represented by the following (the group may have a substituent. * represents a bonding site), etc. TIFF0007714438000013.tif45105A 1 More preferably, A is a group represented by the following (the group may have a substituent. * represents a bonding site). TIFF0007714438.jpg000014.tif2372 Among them, the following formula (L4 -1), a group represented by formula (L 4 -2) or formula (L 4 -3) (the group may have a substituent. * represents a bonding site.) is more preferable. TIFF0007714438000015.tif2970

[0014] A 1 Examples of the substituent that A may have include a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group combining these. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, etc. The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms represent a group in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group, etc. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, a butyryloxy group, etc.

[0015] A1 The substituent that may be present is preferably an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a hydroxyalkyl group having 1 to 6 carbon atoms, a carboxy group, a cyano group or a halogen atom, more preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a carboxy group, a cyano group or a halogen atom, and even more preferably an alkyl group having 1 to 4 carbon atoms, a hydroxy group, a cyano group or a halogen atom.

[0016] A 1 Examples of A include a group represented by the following formula (R 10 -1), formula (R 10 -2), formula (R 10 -3) or formula (R 10 -4). TIFF0007714438000016.tif36166[In formulas (R 10 -1) to (R 10 -4), * represents a bonding site. Z 12 represents an oxygen atom, a sulfur atom or a methylene group. R 11 , R 12 , R 13 and R 14 each independently represent a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms or a group combining these. m11 represents any integer from 0 to 5, and when m11 is 2 or more, the plurality of R 11 may be the same as or different from each other. m12 represents any integer from 0 to 5, and when m12 is 2 or more, the plurality of R 12 may be the same as or different from each other. m13 represents any integer from 0 to 5, and when m13 is 2 or more, the plurality of R 13 may be the same as or different from each other. m14 represents any integer from 0 to 5. When m14 is 2 or more, a plurality of Rs 14 may be the same as or different from each other. n10 represents an integer from 1 to 3.] R 11 、R 12 、R 13 and R 14 Examples of the halogen atom, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkoxycarbonyl group having 2 to 13 carbon atoms, alkylcarbonyl group having 2 to 13 carbon atoms, alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group formed by combining these are the same groups as those described above. m11, m12, m13, and m14 are each preferably independently 0 to 2, and more preferably 0.

[0017] L 2 and L 3 Examples of the alkanediyl group having 1 to 6 carbon atoms for 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, hexane-1,6-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, 2-methylbutane-1,4-diyl group; cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group are included. The number of carbon atoms of the alkanediyl group is preferably 1 to 4, and more preferably 1 to 3. L 2 is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms, and more preferably a single bond. 3is preferably a single bond or an alkanediyl group having 1 to 4 carbon atoms, and more preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms.

[0018] X 2 is preferably *-CO-O-, *-O-CO- or *-O-CO-O- (* represents the bonding site with A 1 or L 2 .).

[0019] R 2 Examples of the halogen atom of R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 1 and R 2 The haloalkyl group having 1 to 12 carbon atoms in R and R represents an alkyl group having 1 to 12 carbon atoms having a halogen atom, and examples thereof include a fluoroalkyl group having 1 to 12 carbon atoms, a chloroalkyl group having 1 to 12 carbon atoms, a bromoalkyl group having 1 to 12 carbon atoms, and an iodoalkyl group having 1 to 12 carbon atoms. Examples of the haloalkyl group include a perfluoroalkyl group having 1 to 12 carbon atoms (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, etc.), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group, chloromethyl group, bromomethyl group, iodomethyl group, etc. The number of carbon atoms of the haloalkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. R 2 Examples of the alkyl group having 1 to 12 carbon atoms in R include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and nonyl group. The number of carbon atoms of the alkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3. R 2When -CH2- contained in the haloalkyl group or alkyl group represented by is replaced by -O- or -CO-, the number of carbon atoms before replacement shall be the total number of carbon atoms of the haloalkyl group or the alkyl group. Examples of the replaced groups include a hydroxy group (a group in which -CH2- contained in a methyl group is replaced by -O-), a carboxy group (a group in which -CH2-CH2- contained in an ethyl group is replaced by -O-CO-), an alkoxy group (a group in which -CH2- at any position contained in an alkyl group is replaced by -O-), an alkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -O-CO-), an alkylcarbonyl group (a group in which -CH2- at any position contained in an alkyl group is replaced by -CO-), an alkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in an alkyl group is replaced by -CO-O-), a haloalkoxy group (a group in which -CH2- at any position contained in a haloalkyl group is replaced by -O-), a haloalkoxycarbonyl group (a group in which -CH2-CH2- at any position contained in a haloalkyl group is replaced by -O-CO-), a haloalkylcarbonyl group (a group in which -CH2- at any position contained in a haloalkyl group is replaced by -CO-), a haloalkylcarbonyloxy group (a group in which -CH2-CH2- at any position contained in a haloalkyl group is replaced by -CO-O-), and groups formed by combining two or more of these groups.

[0020] Examples of the alkoxy group include alkoxy groups having 1 to 11 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, and an undecyloxy group. The number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3. The alkoxycarbonyl group, the alkylcarbonyl group, and the alkylcarbonyloxy group represent groups in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 2 to 11 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, etc. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 12 carbon atoms, such as acetyl group, propionyl group and butyryl group, etc. Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having 2 to 11 carbon atoms, such as acetyloxy group, propionyloxy group, butyryloxy group, etc. The number of carbon atoms of 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 of 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 of the alkylcarbonyloxy group is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. Examples of the haloalkoxy group, haloalkoxycarbonyl group, haloalkylcarbonyl group and haloalkylcarbonyloxy group include haloalkoxy groups having 1 to 11 carbon atoms, haloalkoxycarbonyl groups having 2 to 11 carbon atoms, haloalkylcarbonyl groups having 2 to 12 carbon atoms, and haloalkylcarbonyloxy groups having 2 to 11 carbon atoms. For example, groups in which one or more hydrogen atoms of the groups exemplified above are replaced by halogen atoms can be mentioned. R 1 is preferably an iodine atom or a haloalkyl group having 1 to 6 carbon atoms, more preferably an iodine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, even more preferably an iodine atom or a trifluoromethyl group, and even more preferably an iodine atom. m2 is preferably 0, 1, 2 or 4, and more preferably 0, 1 or 2. R 2is preferably an iodine atom, a fluorine atom, a hydroxy group, a haloalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms (wherein -CH2- contained in the haloalkyl group and the alkyl group may be replaced by -O- or -CO-), more preferably an iodine atom, a fluorine atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, still more preferably an iodine atom, a fluorine atom, a hydroxy group, a perfluoroalkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and even more preferably an iodine atom, a fluorine atom, a hydroxy group, a trifluoromethyl group or a methoxy group. R 1 The bonding position of 3 to the benzene ring of L 2 or X 1 may be any of the ortho, meta and para positions with respect to the bonding position of. In particular, when m2 is 0, the bonding position of R 3 to the benzene ring of L 2 or X R 2 The bonding position of 3 to the benzene ring of L 2 or X 2 may be any of the ortho, meta and para positions with respect to the bonding position of. In particular, when m2 is 1, the bonding position of R 3 to the benzene ring of L 2 or X 3 is preferably the meta or para position with respect to the bonding position of. When m2 is 2, one of the bonding positions of L 2 or X 3 is preferably the ortho or meta position, and the other is preferably the ortho or para position. When m2 is 4, two of the bonding positions of L 2 or X

[0021] Examples of the anion (I) include the following anions. Among them, anions represented by formula (Ia-1) to formula (Ia-16), formula (Ia-26) to formula (Ia-30) are preferred. JPEG0007714438000017.jpg214169

[0022] JPEG0007714438000018.jpg232165

[0023] TIFF0007714438000019.tif145170

[0024] Z + Examples of the organic cation 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 arylsulfonium cations are more preferred. Specifically, cations represented by any of formula (b2-1) to formula (b2-4) (hereinafter, may be referred to as "cation (b2-1)" etc. according to the formula number) can be mentioned.

[0025] TIFF0007714438000020.tif49170In formula (b2-1) to formula (b2-4), R b4 ~R b6 each 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, and the hydrogen atom contained in the chain hydrocarbon group may be substituted with a hydroxy 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, and the hydrogen atom contained 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, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. R b4 and R b5They may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b7 and R b8 each independently represents a halogen atom, a hydroxy 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 any integer from 0 to 5. When m2 is 2 or more, the plurality of R b7 may be the same or different, and when n2 is 2 or more, the plurality of R b8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms. R b9 and R b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b11 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 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, and the hydrogen atom contained in the chain hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyloxy group having 1 to 12 carbon atoms. R b11 and R b12 may be bonded to each other to form a ring including -CH-CO- to which they are bonded, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. R b13 ~R b18Each independently represents a halogen atom, a hydroxy 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. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent any integer from 0 to 5. q2 and r2 each independently represent any integer from 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, the plurality of R b13 are the same or different, and when p2 is 2 or more, the plurality of R b14 are the same or different, and when q2 is 2 or more, the plurality of R b15 are the same or different, and when r2 is 2 or more, the plurality of R b16 are the same or different, and when s2 is 2 or more, the plurality of R b17 are the same or different, and when t2 is 2 or more, the plurality of R b18 are the same or different. When u2 is 0, any one of o2, p2, q2, and r2 is 1 or more, and at least one of R b13 ~R b16 is preferably a halogen atom. When u2 is 1, any one of o2, p2, s2, t2, q2, and r2 is 1 or more, and at least one of R b13 ~R b18 is preferably a halogen atom. Furthermore, when u2 is 0, r2 is preferably 1 or more, and more preferably 1. Also, when u2 is 0 and r2 is 1 or more, R b16 is preferably a halogen atom.

[0026] The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. In particular, Rb9 ~R b12 The chain hydrocarbon group of ~R preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, etc. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups, etc. TIFF0007714438000021.tif11157 In particular, R b9 ~R b12 The alicyclic hydrocarbon group of ~R preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

[0027] Examples of the alicyclic hydrocarbon group 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, isobornyl group, etc. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less. The alkyl fluoride group represents an alkyl group having 1 to 12 carbon atoms and having a fluorine atom, and examples thereof include fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl group, etc. The number of carbon atoms of the alkyl fluoride group is preferably 1 to 9, more preferably 1 to 6, and still more preferably 1 to 4.

[0028] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, biphenyl group, naphthyl group, and phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and examples of the aromatic hydrocarbon group having a chain hydrocarbon group include tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc., and examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group include p-cyclohexylphenyl group, p-adamantylphenyl group, etc. When 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 preferable. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include p-methoxyphenyl group, etc. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc.

[0029] Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, and dodecyloxy group, etc. Examples of the alkylcarbonyl group include acetyl group, propionyl group, and butyryl group, etc. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom, etc. Examples of the alkylcarbonyloxy group 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, etc.

[0030] Rb4 and R b5 The ring formed by the combination of and the sulfur atom to which they are attached may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of such rings include rings having 3 to 18 carbon atoms, preferably rings having 4 to 18 carbon atoms. Further, examples of the ring containing a sulfur atom include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings, and examples thereof include the following rings. * represents a bonding site. TIFF0007714438000022.tif24142

[0031] R b9 and R b10 The ring formed by the combination of and may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of such rings include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples thereof include thiolan-1-ium ring (tetrahydrothiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring and the like. R b11 and R b12 The ring formed by the combination of and may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of such rings include 3-membered to 12-membered rings, preferably 3-membered to 7-membered rings. Examples thereof include oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring, oxoadamantane ring and the like.

[0032] Among cations (b2-1) to (b2-4), preferably, it is cation (b2-1). Examples of cation (b2-1) include the following cations. TIFF0007714438000023.tif79158

[0033] TIFF0007714438000024.tif109165

[0034] Examples of cation (b2-2) include the following cations. TIFF0007714438000025.tif18150

[0035] Examples of the cation (b2-3) include the following cations. TIFF0007714438000026.tif26140

[0036] Examples of the cation (b2-4) include the following cations. TIFF0007714438000027.tif127165

[0037] The salt (I) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. Preferred examples of the salt (I) include a combination of an anion represented by any of Formula (Ia-1) to Formula (Ia-16) and Formula (Ia-26) to Formula (Ia-30), and the cation (b2-1), the cation (b2-2), the cation (b2-3) or the cation (b2-4).

[0038] Examples of the salt (I) include the salts described in Table 1. In the following table, each symbol represents the symbol attached to the structure representing the above-mentioned anion or cation. For example, the salt (I-1) means a salt composed of an anion represented by Formula (Ia-1) and a cation represented by Formula (b2-c-1), and represents the salts shown below. TIFF0007714438000028.tif3297 [Table 1] TIFF0007714438000030.tif223154 TIFF0007714438000031.tif223154 TIFF0007714438000032.tif223154 TIFF0007714438000033.tif223154 TIFF0007714438000034.tif223154 TIFF0007714438000035.tif223154 TIFF0007714438000036.tif223154 TIFF0007714438000037.tif223154 TIFF0007714438000038.tif223154 TIFF0007714438000039.tif223154 TIFF0007714438000040.tif223154 TIFF0007714438000041.tif223154 TIFF0007714438000042.tif223154 TIFF0007714438000043.tif140152 Among them, the salt (I) is preferably the salt (I-1) to salt (I-16), salt (I-26) to salt (I-241), salt (I-51) to salt (I-66), salt (I-76) to salt (I-91), salt (I-101) to salt (I-116), salt (I-126) to salt (I-141), salt (I-151) to salt (I-166), salt (I-176) to salt (I-191), salt (I-201) to salt (I-216), salt (I-226) to salt (I-241), salt (I-251) to salt (I-266), salt (I-276) to salt (I-346), salt (I-356) to salt (I-376), salt (I-386) to salt (I-406), salt (I-416) to salt (I-436), salt (I-446) to salt (I-450).

[0039] <Method for producing salt (I)> In the salt (I), X 0 is, *-CO-O- (* represents a bonding site with C(R 11 )(R 12 ) or C(Q 1 )(Q 2 ).) The salt represented by the formula (I1) can be produced, for example, by reacting the salt represented by the formula (I1-a) with carbonyldiimidazole in a solvent and then further reacting with the compound represented by the formula (I1-b). TIFF0007714438000044.tif67162 (In the formula, all symbols have the same meanings as described above.) Examples of the solvent in this reaction include chloroform and acetonitrile. The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 hour to 24 hours.

[0040] Examples of the salt represented by the formula (I1-a) include salts represented below, and it can be produced by the method described in JP-A-2008-127367. TIFF0007714438000045.tif87134 Examples of the compound represented by the formula (I1-b) include compounds represented by the following formula, etc., which can be easily obtained from the market and can also be easily produced by known production methods. TIFF0007714438000046.tif110166

[0041] In salt (I), X 0 being *-O-CO-O- (the salt represented by formula (I2)) can be produced, for example, by reacting the salt represented by formula (I2-a) with carbonyldiimidazole in a solvent and then further reacting with the compound represented by formula (I1-b). Also, the salt represented by formula (I2) can be produced, for example, by reacting the compound represented by formula (I1-b) with carbonyldiimidazole in a solvent and then further reacting with the salt represented by formula (I2-a). JPEG0007714438000047.jpg92163 (wherein all symbols have the same meanings as described above). Examples of the solvent in this reaction include chloroform and acetonitrile. The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 hour to 24 hours. Examples of the salt represented by formula (I2-a) include salts represented below and can be produced by the method described in JP-A-2012-193170. TIFF0007714438000048.tif88138

[0042] In salt (I), X 0 being *-O-CO- (the salt represented by formula (I3)) can be produced, for example, by reacting the compound represented by formula (I3-b) with carbonyldiimidazole in a solvent and then further reacting with the salt represented by formula (I2-a). TIFF0007714438000049.tif34161 (wherein all symbols have the same meanings as described above). Examples of the solvent in this reaction include chloroform and acetonitrile. The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 hour to 24 hours.

[0043] The compound represented by formula (I3-b) includes, for example, the compounds represented below, can be easily obtained from the market, and can also be easily produced by known production methods. TIFF0007714438000050.tif70167

[0044] In salt (I), X 0 The salt in which *-O- (the salt represented by formula (I4)) can be obtained by reacting the salt represented by formula (I2-a) with the compound represented by formula (I1-b) in a solvent in the presence of a base. TIFF0007714438000051.tif53144 (wherein all the symbols have the same meanings as described above.) Examples of the base in this reaction include potassium hydroxide. Examples of the solvent in this reaction include acetonitrile. The reaction temperature is usually 5°C to 80°C, and the reaction time is usually 0.5 hour to 24 hours.

[0045] In salt (I), L 1 The salt in which is a group formed by combining an alkanediyl group having 1 to 4 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms (however, -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-, and -CH2- contained in the alicyclic hydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-) can be produced by replacing the salt represented by formula (I1-a) or the salt represented by formula (I2-a) when synthesizing the salts represented by formulas (I1) to (I4) with the salt represented below. JPEG0007714438000052.jpg96161

[0046] JPEG0007714438000053.jpg244155

[0047] JPEG0007714438000054.jpg141142

[0048] [Acid generator] The acid generator of the present invention is an acid generator containing salt (I). It may contain one kind of salt (I) or may contain two or more kinds of salt (I). In addition to salt (I), the acid generator of the present invention may contain an acid generator known in the resist field (hereinafter sometimes referred to as "acid generator (B)"). The acid generator (B) may be used alone or in combination of two or more.

[0049] As the acid generator (B), either a nonionic or ionic one may be used. Examples of nonionic acid generators include sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxy ketone, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, ketosulfone, sulfonyldiazomethane), etc. Representative examples of ionic acid generators include onium salts containing onium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of anions of onium salts include sulfonic acid anions, sulfonylimide anions, sulfonylmethide anions, etc.

[0050] As the acid generator (B), compounds that generate acid by radiation described in, for example, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712, etc. can be used. Also, compounds produced by known methods may be used. The acid generator (B) may be used in combination of two or more.

[0051] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a salt represented by formula (B1) (hereinafter sometimes referred to as "acid generator (B1)"). In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, wherein -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-, and a hydrogen atom contained in the 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-, -SO2- or -CO-. Z1 + represents an organic cation.]

[0052] Q b1 and Q b2 Examples of the perfluoroalkyl group represented by include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. Q b1 and Q b2 each independently is preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

[0053] L b1 Examples of the divalent saturated hydrocarbon group in include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a group formed by combining two or more of these groups. Specifically, linear alkanediyl 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, 2-methylbutane-1,4-diyl group; Monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. may be mentioned.

[0054] L b1 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by L is replaced by -O- or -CO- include groups represented by any of formula (b1-1) to formula (b1-3). In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) which are specific examples thereof, * and ** represent bonding sites, and * represents the bonding site with -Y.

[0055] TIFF0007714438000056.tif26117[In formula (b1-1), L b2represents 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, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms of and is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, 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, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms of and is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups, and -CH2- contained in the saturated hydrocarbon group may be replaced with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms of and is 23 or less.

[0056] In the groups represented by formulas (b1-1) to (b1-3), when -CH2- contained in the saturated hydrocarbon group is replaced by -O- or -CO-, the number of carbon atoms before replacement is defined as the number of carbon atoms of the saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L b1 as defined above.

[0057] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-.

[0058] L b1 As the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by L is replaced by -O- or -CO-, the group represented by formula (b1-1) or formula (b1-3) is preferable. Examples of the group represented by formula (b1-1) include the groups represented by formulas (b1-4) to (b1-8), respectively. TIFF0007714438000057.tif49119 [In formula (b1-4), L b8represents 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 hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b9 L b10 and the total carbon number of In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b11 L b12 and the total carbon number of In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced with -O- or -CO-. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atoms contained in the divalent saturated hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. However, b13 L b15 to In formula (b1-8), L b16represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted by a fluorine atom or a hydroxy group. However, L b16 ~L b18 The total number of carbon atoms of is 19 or less.] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0059] Examples of the group represented by the formula (b1-3) include the groups represented by the formulas (b1-9) to (b1-11). TIFF0007714438000058.tif24140[In the formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, the total number of carbon atoms of L b19 and L b20 is 23 or less. In the formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group. However, L b21 , L b22 and Lb23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon group may be substituted with fluorine atoms, hydroxy groups or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be replaced with -O- or -CO-, and the hydrogen atoms contained in the alkylcarbonyloxy group may be substituted with hydroxy groups. However, the total number of carbon atoms of L b24 , L b25 and L b26 is 21 or less.

[0060] In the group represented by formula (b1-9) to the group represented by formula (b1-11), when the hydrogen atoms contained in the saturated hydrocarbon group are substituted with alkylcarbonyloxy groups, the number of carbon atoms before replacement is taken as the number of carbon atoms of the saturated hydrocarbon group. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group and the like.

[0061] Examples of the group represented by formula (b1-4) include the following. TIFF0007714438000059.tif17151

[0062] Examples of the group represented by formula (b1-5) include the following. TIFF0007714438000060.tif72149

[0063] Examples of the group represented by formula (b1-6) include the following. TIFF0007714438000061.tif30151

[0064] Examples of the group represented by formula (b1-7) include the following. TIFF0007714438000062.tif64151

[0065] Examples of the group represented by formula (b1-8) include the following. TIFF0007714438000063.tif24151

[0066] Examples of the group represented by formula (b1-2) include the following. TIFF0007714438000064.tif30159

[0067] Examples of the group represented by formula (b1-9) include the following. TIFF0007714438000065.tif45136

[0068] Examples of the group represented by formula (b1-10) include the following. TIFF0007714438000066.tif87159

[0069] Examples of the group represented by formula (b1-11) include the following. TIFF0007714438000067.tif81157

[0070] Examples of the alicyclic hydrocarbon group represented by Y include the groups represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y38). When -CH2- contained in the alicyclic hydrocarbon group represented by Y is replaced by -O-, -SO2- or -CO-, the number thereof may be one or two or more. Examples of such groups include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43). * represents the bonding site to L b1 represents the bonding site to As the alicyclic hydrocarbon group represented by TIFF0007714438000068.tif82165Y, a group represented by any of formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43) is preferable, a group represented by formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) is more preferable, and a group represented by formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) is still more preferable. When the alicyclic hydrocarbon group represented by Y is a spiro ring having an oxygen atom such as formula (Y28) to formula (Y35), formula (Y39), formula (Y40), formula (Y42), formula (Y43), etc., the alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom preferably has no fluorine atom substituted thereon.

[0071] Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 group or -(CH2) ja -O-CO-R b1 group (wherein, 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. ja represents any integer from 0 to 4. The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and the hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.). Examples of the substituent of the alicyclic hydrocarbon group represented by Y include a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms which may be substituted by a hydroxy group (in the alkyl group, -CH2- may be replaced by -O- or -CO-), an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a glycidyloxy group, -(CH2) ja -CO-O-R b1 -group or -(CH2) ja -O-CO-R b1 -group (wherein 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. ja represents any integer from 0 to 4. -CH2- contained in the alkyl group and the alicyclic hydrocarbon group may be replaced by -O-, -SO2- or -CO-, and a hydrogen atom contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by a hydroxy group or a fluorine atom.).

[0072] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like. The alicyclic hydrocarbon group may have a chain hydrocarbon group, such as a methylcyclohexyl group and a dimethylcyclohexyl group. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group. Examples of the aromatic hydrocarbon group having a chain hydrocarbon group include tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc. Examples of the aromatic hydrocarbon group having an alicyclic hydrocarbon group include p-cyclohexylphenyl group, p-adamantylphenyl group, etc. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, more preferably 6 to 10. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkyl group substituted with a hydroxy group include hydroxyalkyl groups such as hydroxymethyl group, hydroxyethyl group, etc. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, etc. Examples of the group in which -CH2- contained in the alkyl group is replaced with -O-, -SO2- or -CO- etc. include alkoxy group, alkylsulfonyl group, alkoxycarbonyl group, alkylcarbonyl group, alkylcarbonyloxy group or a group combining these, etc. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, dodecyloxy group, etc. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 4. Examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a propylsulfonyl group. The number of carbon atoms in the alkylsulfonyl group is preferably from 1 to 12, more preferably from 1 to 6, and even more preferably from 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. The number of carbon atoms in the alkoxycarbonyl group is preferably from 2 to 12, more preferably from 2 to 6, and even more preferably from 2 to 4. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The number of carbon atoms in the alkylcarbonyl group is preferably from 2 to 12, more preferably from 2 to 6, and even more preferably from 2 to 4. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferably from 2 to 12, more preferably from 2 to 6, and even more preferably from 2 to 4. Examples of the combined group include a group formed by combining an alkoxy group and an alkyl group, a group formed by combining an alkoxy group and an alkoxy group, a group formed by combining an alkoxy group and an alkylcarbonyl group, and a group formed by combining an alkoxy group and an alkylcarbonyloxy group. Examples of the group formed by combining an alkoxy group and an alkyl group include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and an ethoxymethyl group. The number of carbon atoms in the alkoxyalkyl group is preferably from 2 to 12, more preferably from 2 to 6, and even more preferably from 2 to 4. Examples of the group formed by combining an alkoxy group and an alkoxy group include an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, and an ethoxyethoxy group. The number of carbon atoms in the alkoxyalkoxy group is preferably from 2 to 12, more preferably from 2 to 6, and even more preferably from 2 to 4. Examples of the group combining an alkoxy group and an alkylcarbonyl group include alkoxyalkylcarbonyl groups such as a methoxyacetyl group, a methoxypropionyl group, an ethoxyacetyl group, and an ethoxypropionyl group. The number of carbon atoms in the alkoxyalkylcarbonyl group is preferably from 3 to 13, more preferably from 3 to 7, and still more preferably from 3 to 5. Examples of the group combining an alkoxy group and an alkylcarbonyloxy group include alkoxyalkylcarbonyloxy groups such as a methoxyacetyloxy group, a methoxypropionyloxy group, an ethoxyacetyloxy group, and an ethoxypropionyloxy group. The number of carbon atoms in the alkoxyalkylcarbonyloxy group is preferably from 3 to 13, more preferably from 3 to 7, and still more preferably from 3 to 5. Examples of the group in which -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2- or -CO- etc. include the groups represented by formula (Y12) to formula (Y35), formula (Y39) to formula (Y43).

[0073] Examples of Y include the following. TIFF0007714438000069.tif160165

[0074] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, still more preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and even more preferably an adamantyl group which may have a substituent, and -CH2- constituting the alicyclic hydrocarbon group or adamantyl group may be replaced by -CO-, -SO2- or -CO-. Specifically, Y is preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or the groups represented by formula (Y42), formula (Y100) to formula (Y114).

[0075] As the anion in the salt represented by formula (B1), anions represented by formula (B1-A-1) to formula (B1-A-59) [hereinafter, may be referred to as "anion (B1-A-1)" etc. according to the formula number] are preferable, and an anion represented by any of formula (B1-A-1) to formula (B1-A-4), formula (B1-A-9), formula (B1-A-10), formula (B1-A-24) to formula (B1-A-33), formula (B1-A-36) to formula (B1-A-40), and formula (B1-A-47) to formula (B1-A-59) is more preferable. TIFF0007714438000070.tif231164

[0076] TIFF0007714438000071.tif238165

[0077] TIFF0007714438000072.tif168160Here, R i2 ~R i7 are, independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R i8 is, for 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 combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group. L A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Q b2 represent the same meaning as described above. Specific examples of the anion in the salt represented by formula (B1) include the anions described in JP-A-2010-204646.

[0078] Preferably, as the anion in the salt represented by formula (B1), anions represented by formula (B1a-1) to formula (B1a-38) are exemplified. TIFF0007714438000073.tif238158

[0079] TIFF0007714438000074.tif130154

[0080] Among them, anions represented by any of Formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), and Formula (B1a-22) to Formula (B1a-38) are preferable. Z1 + Examples of the organic cation of [Z1] + 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 preferable, and arylsulfonium cations are more preferable. Examples of the arylsulfonium cation include those similar to the cation of Z + in Formula (I).

[0081] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), combinations of anions preferably represented by any of Formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), and Formula (B1a-22) to Formula (B1a-38) with cation (b2-1), cation (b2-3), or cation (b2-4) are exemplified.

[0082] As the acid generator (B), those preferably represented by Formula (B1-1) to Formula (B1-57) are exemplified. Among them, those containing an arylsulfonium cation are preferable, and those represented by Formula (B1-1) to Formula (B1-3), Formula (B1-5) to Formula (B1-7), Formula (B1-11) to Formula (B1-14), Formula (B1-20) to Formula (B1-26), Formula (B1-29), Formula (B1-31) to Formula (B1-57) are particularly preferable. TIFF0007714438000075.tif190167

[0083] TIFF0007714438000076.tif250153

[0084] TIFF0007714438000077.tif205166

[0085] When containing salt (I) and acid generator (B) as the acid generator, the ratio of the content of salt (I) to the content of acid generator (B) (mass ratio; salt (I): acid generator (B)) is usually 1:99 to 99:1, preferably 2:98 to 98:2, more preferably 5:95 to 95:5, still more preferably 10:90 to 90:10, and particularly preferably 15:85 to 85:15.

[0086] Resist composition The resist composition of the present invention contains an acid generator containing salt (I) and a resin having an acid-labile group (hereinafter sometimes referred to as "resin (A)"). Here, the "acid-labile group" means a group having a leaving group, and when in contact with an acid, the leaving group leaves and the structural unit is 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 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)").

[0087] Acid generator In the resist composition of the present invention, the total content rate of the acid generator is preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, still more preferably 3 parts by mass or more and 40 parts by mass or less, even more preferably 3 parts by mass or more and 35 parts by mass or less, and still even more preferably 5 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin (A) described later.

[0088] Resin (A) Resin (A) contains a structural unit having an acid-labile group (hereinafter sometimes referred to as "structural unit (a1)"). Resin (A) preferably further contains a structural unit other than structural unit (a1). Examples of the structural unit other than structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit other than structural unit (a1) and structural unit (s) (for example, a structural unit having a halogen atom described later (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit having a non-leaving hydrocarbon group described later (hereinafter sometimes referred to as "structural unit (a5)"), and a structural unit derived from other monomers known in the art, etc.).

[0089] 〈Structural unit (a1)〉 Structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter sometimes referred to as "monomer (a1)"). The acid-labile group contained in resin (A) is preferably a group represented by formula (1) (hereinafter also referred to as group (1)) and / or a group represented by formula (2) (hereinafter also referred to as group (2)). TIFF0007714438000078.tif1988[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these, or R a1 and R a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bonding site.] TIFF0007714438000079.tif2171[In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’are bonded to each other to form a heterocyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X, and -CH2- contained in the hydrocarbon group and the heterocyclic ring may be replaced with -O- or -S-. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * denotes a binding site.]

[0090] R a1 , R a2 and R a3 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 Examples of the alkenyl group in the formula (I) 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 either 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, and norbornyl groups, as well as the following groups (* indicates a bonding site): a1 , R a2 and R a3 The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms. TIFF0007714438000080.tif10150R a1 , R a2 and R a3 Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group (e.g., an alkylcycloalkyl group or cycloalkylalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), an aralkyl group such as benzyl group, an aromatic hydrocarbon group having an alkyl group (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.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), an aryl-cycloalkyl group such as phenylcyclohexyl group, and the like. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form a non-aromatic hydrocarbon ring, examples of -C(R a1 )(R a2 )(R a3 ) include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * represents the bonding site with -O-. TIFF0007714438000081.tif30138

[0091] R a1’ 、R a2’ and R a3’ Examples of the hydrocarbon group in R include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. a1 、R a2 and R a3 include the same groups as those exemplified for R Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group, etc. Examples of the combined group include a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (e.g., alkylcycloalkyl group or cycloalkylalkyl group such as methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornil group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl group such as benzyl group, aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group, etc. R a2’ and R a3’ When they are bonded to each other to form a heterocyclic ring together with the carbon atom to which they are bonded and X, -C(R a1’ )(R a2’ )-X-R a3’ includes the following rings. * represents the bonding site. TIFF0007714438000082.tif18130R a1’ and R a2’ Among them, at least one is preferably a hydrogen atom. na' is preferably 0.

[0092] Examples of the group (1) include the following groups. In formula (1), R a1 , R a2 and R a3 are alkyl groups, ma = 0, and na = 1. As such a group, a tert-butoxycarbonyl group is preferable. In formula (1), R a1 , R a2 together with the carbon atom to which they are bonded form an adamantyl group, R a3 is an alkyl group, ma = 0, and na = 1. In formula (1), R a1 and R a2is each independently an alkyl group, R a3 is an adamantyl group, a group where ma = 0 and na = 1. Specific examples of the group (1) include the following groups. * represents the bonding site. TIFF0007714438000083.tif154163

[0093] Specific examples of the group (2) include the following groups. * represents the bonding site. TIFF0007714438000084.tif55153

[0094] The monomer (a1) is preferably a monomer having an acid-labile group and an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer having an acid-labile group.

[0095] Among the (meth)acrylic monomers having an acid-labile group, those having an alicyclic hydrocarbon group with 5 to 20 carbon atoms are preferably mentioned. If a resin (A) having a structural unit 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.

[0096] As the structural unit derived from the (meth)acrylic monomer having the group (1), a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as the structural unit (a1-0)), a structural unit represented by the formula (a1-1) (hereinafter sometimes referred to as the structural unit (a1-1)), or a structural unit represented by the formula (a1-2) (hereinafter sometimes referred to as the structural unit (a1-2)) can be mentioned. Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2), more preferably at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more. TIFF0007714438000085.tif44144[In the formula (a1-0), the formula (a1-1), and the formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or -O-(CH2) k1 represents —CO—O—, k1 represents an integer of 1 to 7, and * represents the bonding site with —CO—. R a01 , R a4 and R a5 each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 , R a03 and R a04 each 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 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 combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0097] R a01 , R a4 and R a5 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or —O—(CH2) k01 It is —CO—O— (wherein k01 is preferably an integer of any one of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 and R a04 The alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group and combination thereof in the group (1) Ra1 , R a2 and R a3 include groups similar to those exemplified by R a6 and R a7 As the alkyl group, alkenyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and groups combining these in R a1 , R a2 and R a3 include groups similar to those exemplified by R a02 , R a03 , and R a04 The alkyl group in R a6 and R a7 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 R a02 , R a03 , R a04 , R a6 and R a7 The alicyclic hydrocarbon group of R a02 , R a03 , R a04 , R a6 and R a7 preferably has 5 to 12 carbon atoms, and more preferably 5 to 10 carbon atoms. For the group combining an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total number of carbon atoms of these alkyl group and alicyclic hydrocarbon group is 18 or less. The group combining an alkyl group and an aromatic hydrocarbon group preferably has a total carbon number of 18 or less for the combined alkyl group and aromatic hydrocarbon group. R a02 and R a03 are preferably an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a phenyl group or a naphthyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R a6 and R a7 are each independently preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group, a phenyl group or a naphthyl group, still more preferably an ethyl group, an isopropyl group, a t-butyl group, an ethenyl group or a phenyl group. m1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1 is preferably any integer from 0 to 3, more preferably 0 or 1. n1’ is preferably 0 or 1.

[0098] Examples of the structural unit (a1-0) include structural units represented by any of formula (a1-0-1) to formula (a1-0-18) and structural units in which the methyl group corresponding to R a01 in the structural unit (a1-0) is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group, and structural units represented by any of formula (a1-0-1) to formula (a1-0-10), formula (a1-0-13), formula (a1-0-14) are preferred. TIFF0007714438000086.tif88161

[0099] Examples of the structural unit (a1-1) include structural units derived from the monomers described in JP-A-2010-204646. Among them, the structural units represented by any of formula (a1-1-1) to formula (a1-1-7) and the methyl group corresponding to R in the structural unit (a1-1) a4 in which is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group are preferred, and the structural units represented by any of formula (a1-1-1) to formula (a1-1-4) are more preferred. TIFF0007714438000087.tif38168

[0100] Examples of the structural unit (a1-2) include structural units represented by any of formula (a1-2-1) to formula (a1-2-14) and structural units in which the methyl group corresponding to R in the structural unit (a1-2) a5 is replaced by a hydrogen atom, a halogen atom, a haloalkyl group or another alkyl group, and the structural units represented by any of formula (a1-2-2), formula (a1-2-5), formula (a1-2-6) and formula (a1-2-10) to formula (a1-2-14) are preferred. TIFF0007714438000088.tif67163

[0101] When the resin (A) contains the structural unit (a1-0), its content is usually 5 to 80 mol%, preferably 5 to 75 mol%, more preferably 10 to 70 mol% based on all the structural units of the resin (A). When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is usually 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol%, still more preferably 20 to 75 mol%, and even more preferably 20 to 70 mol% based on all the structural units of the resin (A).

[0102] Examples of the structural unit having the group (2) in the structural unit (a1) include the structural unit represented by formula (a1-4) (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF0007714438000089.tif4766; in formula (a1-4), R a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a33 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a30 represents a single bond or * -X a31 -(A a32 -X a32 ) nc - and * represents the bonding site with the carbon atom to which -R a32 is bonded. A a32 represents an alkanediyl group having 1 to 6 carbon atoms. X a31 and X a32 each independently represents -O-, -CO-O- or -O-CO-. nc represents 0 or 1. la represents any integer from 0 to 4. When la is any integer of 2 or more, a plurality of R a33 may be the same as or different from each other. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -C-O- to which they are bonded, and -CH2- contained in the hydrocarbon group and the divalent hydrocarbon group may be replaced by -O- or -S-.

[0103] R a32 and R a33Examples of the halogen atom in [compound name] include a fluorine atom, a chlorine atom, and a bromine atom. R a32 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in [compound name] include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a32 R is preferably 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 a33 Examples of the alkyl group in [compound name] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a33 Examples of the alkoxy group in [compound name] include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a33 Examples of the alkoxyalkyl group in [compound name] include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. Ra33 Examples of the alkoxyalkoxy group in [description] include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group. R a33 Examples of the alkylcarbonyl group in [description] include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, more preferably an acetyl group. R a33 Examples of the alkylcarbonyloxy group in [description] include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, more preferably an acetyloxy group. R a33 R is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy 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 hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0104] *-X a31 -(A a32 -X a32 ) nc Examples of - include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a32 -CO-O-, *-O-CO-A a32 -O-, *-O-A a32 -CO-O-, *-CO-O-A a32 -O-CO-, *-O-CO-A a32 -O-CO-, are included. Among them, *-CO-O-, *-CO-O-A a32 -CO-O- or *-O-Aa32 -CO-O- is preferred.

[0105] A a32 Examples of the alkanediyl group in A include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. A a32 A is preferably a methylene group or an ethylene group.

[0106] A a30 A is a single bond, *-CO-O- or *-CO-O-A a32 -CO-O- is preferred, more preferably a single bond, *-CO-O- or *-CO-O-CH2-CO-O-, and even more preferably a single bond or *-CO-O-.

[0107] 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 the hydrocarbon group in R, R and R include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, etc. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents the bonding site). As the aromatic hydrocarbon group, aryl groups such as phenyl group, naphthyl group, anthryl group, biphenyl group, phenanthryl group and the like can be mentioned. As the combined group, a group combining the above-mentioned alkyl group and alicyclic hydrocarbon group (for example, alkyl cycloalkyl group or cycloalkyl alkyl group such as methyl cyclohexyl group, dimethyl cyclohexyl group, methyl norbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc.), aralkyl group such as benzyl group, aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group such as phenylcyclohexyl group and the like can be mentioned. In particular, R a36 Examples thereof include 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 combining these.

[0108] R a34 is preferably a hydrogen atom. R a35 is preferably 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 of R 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 combining these, 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. The alkyl group and alicyclic hydrocarbon group in R a36 are preferably unsubstituted. R a36The aromatic hydrocarbon group in [the compound] preferably has an aromatic ring having an aryloxy group with 6 to 10 carbon atoms. -OC(R a34 )(R a35 )-O-R a36 in the structural unit (a1-4) eliminates upon contact with an acid (for example, p-toluenesulfonic acid) to form a hydroxy group. -OC(R a34 )(R a35 )-O-R a36 is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

[0109] Examples of the structural unit (a1-4) include structural units derived from the monomers described in JP-A-2010-204646. Preferably, the structural units represented by formula (a1-4-1) to formula (a1-4-24) and the structural unit (a1-4) in which the hydrogen atom corresponding to R a32 is replaced with a halogen atom, a haloalkyl group or an alkyl group are included, and more preferably, the structural units represented by formula (a1-4-1) to formula (a1-4-5), formula (a1-4-10), formula (a1-4-13), and formula (a1-4-14) are included. TIFF0007714438000091.tif131165

[0110] When the resin (A) contains the structural unit (a1-4), its content is preferably 3 to 80 mol%, more preferably 5 to 75 mol%, still more preferably 7 to 70 mol%, still more preferably 7 to 65 mol%, and particularly preferably 10 to 60 mol% based on the total of all the structural units of the resin (A).

[0111] Examples of the structural unit derived from the (meth)acrylic monomer having the group (2) also include the structural unit represented by formula (a1-5) (hereinafter sometimes referred to as "structural unit (a1-5)"). TIFF0007714438000092.tif4558In formula (a1-5), R a8represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Z a1 represents a single bond or *-(CH2) h3 -CO-L 54 -, h3 represents an integer of any one of 1 to 4, and * represents the bonding site with 51 L. L 51 L 52 L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of any one of 1 to 3. s1’ represents an integer of any one of 0 to 3.

[0112] Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. In formula (a1-5), R a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group. L 51 is preferably an oxygen atom. L 52 and L 53 Among them, it is preferable that one is -O- and the other is -S-. s1 is preferably 1. s1’ is preferably an integer of any one of 0 to 2. Z a1 is preferably a single bond or *-CH2-CO-O-.

[0113] Examples of the structural unit (a1-5) include structural units derived from monomers described in JP-A-2010-61117. Among them, the structural units represented by formula (a1-5-1) to formula (a1-5-4) are preferred, and the structural unit represented by formula (a1-5-1) or formula (a1-5-2) is more preferred. TIFF0007714438000093.tif33133

[0114] When the resin (A) contains the structural unit (a1-5), its content is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, still more preferably 5 to 40 mol%, and even more preferably 5 to 30 mol% based on all the structural units of the resin (A).

[0115] In addition, examples of the structural unit (a1) also include the following structural units. TIFF0007714438000094.tif31162

[0116] When the resin (A) contains structural units such as (a1-3-1) to (a1-3-7) above, its content is preferably 10 to 95 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol%, even more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol% based on all the structural units of the resin (A).

[0117] In addition, examples of the structural unit (a1) also include the following structural units. TIFF0007714438000095.tif5295 When the resin (A) contains structural units such as (a1-6-1) to (a1-6-3) above, its content is preferably 10 to 60 mol%, more preferably 15 to 55 mol%, still more preferably 20 to 50 mol%, even more preferably 20 to 45 mol%, and particularly preferably 20 to 40 mol% based on all the structural units of the resin (A).

[0118] 〈Structural unit (s)〉 The structural unit (s) is derived from a monomer having no acid-labile group (hereinafter sometimes referred to as "monomer (s)"). As the monomer that leads to the structural unit (s), a monomer having no acid-labile group known in the resist field can be used. As the structural unit(s), it is preferable to have a hydroxy group or a lactone ring. By using a resin containing a structural unit having a hydroxy group and no acid-labile group (hereinafter sometimes referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid-labile group (hereinafter sometimes referred to as "structural unit (a3)") in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0119] 〈Structural unit (a2)〉 The hydroxy group possessed by the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. When producing a resist pattern from the resist composition of the present invention, when using a high-energy ray such as a KrF excimer laser (248 nm), an electron beam, or EUV (extreme ultraviolet light) as the exposure light source, as the structural unit (a2), a structural unit (a2) having a phenolic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-A) described later. Further, when using an ArF excimer laser (193 nm) or the like, as the structural unit (a2), a structural unit (a2) having an alcoholic hydroxy group is preferable, and it is more preferable to use the structural unit (a2-1) described later. The structural unit (a2) may be included alone or in combination of two or more.

[0120] Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as "structural unit (a2-A)"). TIFF0007714438000096.tif4753[In the formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - and * represents the bonding site with the carbon atom to which -R a50 is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of R a51 may be the same as or different from each other.]

[0121] R a50 and R a51 Examples of the halogen atom in include a fluorine atom, a chlorine atom, and a bromine atom. R a50 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, an ethyl group, a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a propyl group, a perfluorobutyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a butyl group, a perfluoropentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a pentyl group, a hexyl group, and a perfluorohexyl group. R a50is preferably 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 a51 Examples of the alkyl group in a51 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R a51 Examples of the alkoxy group in a51 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group. R a51 Examples of the alkoxyalkyl group in a51 include a methoxymethyl group, an ethoxyethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxymethyl group, and a tert-butoxymethyl group. The alkoxyalkyl group is preferably an alkoxyalkyl group having 2 to 8 carbon atoms, more preferably a methoxymethyl group or an ethoxyethyl group, and even more preferably a methoxymethyl group. R a51 Examples of the alkoxyalkoxy group in a51 include a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group, an ethoxyethoxy group, a propoxymethoxy group, an isopropoxymethoxy group, a butoxymethoxy group, a sec-butoxymethoxy group, and a tert-butoxymethoxy group. The alkoxyalkoxy group is preferably an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a methoxyethoxy group or an ethoxyethoxy group. R a51 Examples of the alkylcarbonyl group in a51 include an acetyl group, a propionyl group, and a butyryl group. The alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 3 carbon atoms, and more preferably an acetyl group. R a51Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkylcarbonyloxy group is preferably an alkylcarbonyloxy group having 2 to 3 carbon atoms, and more preferably an acetyloxy group. R a51 is preferably a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkoxyalkoxy group having 2 to 8 carbon atoms, more preferably a fluorine atom, an iodine atom, a hydroxy 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 hydroxy group, a methyl group, a methoxy group, or an ethoxyethoxy group.

[0122] *-X a51 -(A a52 -X a52 ) nb Examples of - include *-O-, *-CO-O-, *-O-CO-, *-CO-O-A a52 -CO-O-, *-O-CO-A a52 -O-, *-O-A a52 -CO-O-, *-CO-O-A a52 -O-CO-, *-O-CO-A a52 -O-CO-, etc. Among them, *-CO-O-, *-CO-O-A a52 -CO-O- or *-O-A a52 -CO-O- is preferred.

[0123] A a52 Examples of the alkanediyl group in A include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group, etc. A a52 is preferably a methylene group or an ethylene group.

[0124] Aa50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- is preferred, a single bond, *-CO-O- or *-CO-O-CH2-CO-O- is more preferred, and a single bond or *-CO-O- is even more preferred.

[0125] mb is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0. The hydroxy group is preferably bonded to the o- or p-position of the benzene ring, more preferably to the p-position.

[0126] Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A Nos. 2010-204634 and 2012-12577.

[0127] The structural unit (a2-A) includes structural units represented by formulas (a2-2-1) to (a2-2-24) and R in the structural unit (a2-A) in the structural units represented by formulas (a2-2-1) to (a2-2-24). a50 The structural unit (a2-A) is a structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), and a structural unit represented by formula (a2-2-12) to (a2-2-14), and the structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6), a structural unit represented by formula (a2-2-8), and a structural unit represented by formula (a2-2-12) to (a2-2-14), a50It is preferable that the structural unit in which the methyl group corresponding to R is replaced by a hydrogen atom, and in the structural unit represented by the formula (a2-2-3), the structural unit represented by the formula (a2-2-8), the structural units represented by the formulas (a2-2-12) to (a2-2-14), and the structural unit represented by the formula (a2-2-3) or the structural unit represented by the formula (a2-2-8), the structural units represented by the formulas (a2-2-12) to (a2-2-14), R in the structural unit (a2-A) a50 More preferably, it is a structural unit in which the methyl group corresponding to R is replaced by a hydrogen atom, and in the structural unit represented by the formula (a2-2-8) and the structural unit represented by the formula (a2-2-8), R in the structural unit (a2-A) a50 It is even more preferable that the methyl group corresponding to R is replaced by a hydrogen atom. TIFF0007714438000097.tif79169

[0128] When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 15 to 65 mol%, and even more preferably 20 to 65 mol% with respect to all the structural units. The structural unit (a2-A) can be contained in the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. Also, after polymerizing using acetoxystyrene or the like and then treating with an alkali such as tetramethylammonium hydroxide, the structural unit (a2-A) can be contained in the resin (A).

[0129] Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include the structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)"). TIFF0007714438000098.tif4461In the formula (a2-1), L a3 represents -O- or *-O-(CH2) k2 -CO-O-, k2 represents an integer from 1 to 7. * represents the bonding site with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group. o1 represents an integer from 0 to 10.

[0130] In formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer from 1 to 4), more preferably -O-. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer from 0 to 3, more preferably 0 or 1.

[0131] Examples of the structural unit (a2-1) include structural units derived from the monomers described in JP-A-2010-204646. The structural unit represented by any of formulas (a2-1-1) to (a2-1-6) is preferable, the structural unit represented by any of formulas (a2-1-1) to (a2-1-4) is more preferable, and the structural unit represented by formula (a2-1-1) or formula (a2-1-3) is even more preferable. TIFF0007714438000099.tif50139

[0132] When the resin (A) contains the structural unit (a2-1), its content is usually 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% based on all the structural units of the resin (A).

[0133] <Structural unit (a3)> The lactone ring possessed by 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 may be a condensed ring of a monocyclic lactone ring and another ring. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) can be mentioned.

[0134] The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or the formula (a3-4). These may be contained alone or in combination of two or more. TIFF0007714438000100.tif49159[In the formula (a3-1), the formula (a3-2), the formula (a3-3), and the formula (a3-4), L a4 、L a5 and L a6 each independently represents a group represented by -O- or *-O-(CH2) k3 -CO-O- (where k3 represents an integer from 1 to 7). L a7 represents -O-, *-O-L a8 -O-, *-O-L a8 -CO-O-, *-O-L a8 -CO-O-L a9 -CO-O- or *-O-L a8 -O-CO-L a9 -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents the bonding site with the carbonyl group. R a18 、R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. X a3 represents -CH2- or an oxygen atom. Ra21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. p1 represents any integer from 0 to 5. q1 represents any integer from 0 to 3. r1 represents any integer from 0 to 3. w1 represents any integer from 0 to 8. When p1, q1, r1 and / or w1 is 2 or more, the plurality of R a21 , R a22 , R a23 and / or R a25 may be the same as or different from each other.

[0135] R a21 , R a22 , R a23 and R a25 Examples of the aliphatic hydrocarbon group in R , R a24 , R , R a24 , R , R a24 include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group.

[0136] L a8 and L a9 Examples of the alkanediyl group in include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like.

[0137] In formulas (a3-1) to (a3-3), L a4 ~L a6 is each independently preferably -O- or, *-O-(CH2) k3 -CO-O- where 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 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group, or a methyl group. p1, q1, and r1 are each independently preferably an integer from 0 to 2, more preferably 0 or 1.

[0138] In formula (a3-4), R a24 is preferably 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 is preferably a carboxy group, a cyano group, or a methyl group. L a7 is preferably -O- or *-O-L a8 -CO-O-, more preferably -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably any integer from 0 to 2, more preferably 0 or 1. In particular, formula (a3-4) is preferably formula (a3-4)'. TIFF0007714438000101.tif3848 (wherein R a24 , L a7 represents the same meaning as described above.)

[0139] Examples of the structural unit (a3) include structural units derived from the monomers described in JP-A-2010-204646, the monomers described in JP-A-2000-122294, and the monomers described in JP-A-2012-41274. Examples of the structural unit (a3) include structural units represented by any of formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2), formula (a3-3-1), formula (a3-3-2), and formula (a3-4-1) to formula (a3-4-12), and, in the above structural units, structural units in which the methyl groups corresponding to R a18 , R a19 , R a20 and R a24 are replaced with hydrogen atoms are preferred.

[0140] TIFF0007714438000102.tif116165

[0141] When the resin (A) contains the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, more preferably 10 to 60 mol% with respect to all the structural units of the resin (A). Further, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3), or the structural unit (a3-4) is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, still more preferably 10 to 50 mol% with respect to all the structural units of the resin (A).

[0142] 〈Structural unit (a4)〉 Examples of the structural unit (a4) include the following structural units. TIFF0007714438000103.tif2758[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having a halogen atom with 1 to 24 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.] R 42 The saturated hydrocarbon group represented by is exemplified by a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

[0143] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; polycyclic alicyclic saturated hydrocarbon groups such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bonding site). TIFF0007714438000104.tif10146Examples of the group formed by combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, and -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, etc.

[0144] Examples of the structural unit (a4) include a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), and a structural unit represented by formula (a4-4). TIFF0007714438000105.tif4349[In formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms. R 64 represents a hydrogen atom or a fluorine atom.]

[0145] L 4a Examples of the alkanediyl group in L include linear alkanediyl groups such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group, and branched alkanediyl groups such as an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, and a 2-methylpropane-1,2-diyl group.

[0146] L 3a Examples of the perfluoroalkanediyl group in L include a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2-diyl group, a perfluorobutane-1,4-diyl group, a perfluorobutane-2,2-diyl group, a perfluorobutane-1,2-diyl group, a perfluoropentane-1,5-diyl group, a perfluoropentane-2,2-diyl group, a perfluoropentane-3,3-diyl group, a perfluorohexane-1,6-diyl group, a perfluorohexane-2,2-diyl group, a perfluorohexane-3,3-diyl group, a perfluoroheptane-1,7-diyl group, a perfluoroheptane-2,2-diyl group, a perfluoroheptane-3,4-diyl group, a perfluoroheptane-4,4-diyl group, a perfluorooctane-1,8-diyl group, a perfluorooctane-2,2-diyl group, a perfluorooctane-3,3-diyl group, and a perfluorooctane-4,4-diyl group. L 3aExamples of the perfluorocycloalkanediyl group include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

[0147] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0148] Examples of the structural unit (a4-0) include the structural units shown below and the structural units in the following structural units where the methyl group corresponding to R in the structural unit (a4-0) is replaced by a hydrogen atom. 54 are mentioned. TIFF0007714438000106.tif95166

[0149] TIFF0007714438000107.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 a substituent, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent or a group represented by formula (a-g1). However, at least one of A a41 and R a42 has a halogen atom (preferably a fluorine atom) as a substituent. TIFF0007714438000108.tif1487[In formula (a-g1), s represents 0 or 1. A a42 and A a44Each independently represents a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. A a43 represents a single bond or a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. X a41 and X a42 each independently represents -O-, -CO-, -CO-O- or -O-CO-. However, A a42 、A a43 、A a44 、X a41 and X a42 The total number of carbon atoms of is 7 or less. ] * is a bonding site, and the * on the right is the bonding site with -O-CO-R a42

[0150] R a42 Examples of the saturated hydrocarbon group in include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

[0151] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, etc. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group; a polycyclic alicyclic saturated hydrocarbon group such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bonding site). Examples of the group formed by the combination in TIFF0007714438000109.tif10160 include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, and -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl group, -alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, etc. ​

[0152] R a42 Examples of the substituent that R has include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. TIFF0007714438000110.tif855[In the formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * is the bonding site with R a42 .] However, in R a42 -X a43 -A a45 , when R a42 does not have a halogen atom, A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which has at least one halogen atom.

[0153] A a45 Examples of the saturated hydrocarbon group in A include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; and polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl group, adamantyl group, norbornyl group, and the following group (* represents the bonding site). TIFF0007714438000111.tif10160Examples of the group formed by the combination include a group 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, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, and the like.

[0154] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3). R a42 When it 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, still 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 the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group. R a42 When it is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the carbon atoms contained in the group represented by the formula (a-g3), the total carbon atoms of R a42 are preferably 15 or less, more preferably 12 or less. When having a group represented by the formula (a-g3) as a substituent, the number thereof is preferably 1.

[0155] R a42 When it is a saturated hydrocarbon group having a group represented by the formula (a-g3), R a42 is more preferably a group represented by the formula (a-g2). TIFF0007714438000112.tif871[In the formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. X a44 represents **-O-CO- or **-CO-O- (** represents the bonding site with A a46 ).). A a47represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. However, A a46 , A a47 and X a44 The total number of carbon atoms of is 18 or less, and A a46 and A a47 Among them, at least one has at least one halogen atom. * represents the bonding site with the carbonyl group.]

[0156] A a46 The number of carbon atoms of the saturated hydrocarbon group of is preferably 1 to 6, more preferably 1 to 3. A a47 The number of carbon atoms of the saturated hydrocarbon group of is preferably 4 to 15, more preferably 5 to 12, and A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0157] The preferred structure of the group represented by the formula (a-g2) is the following structure (* is the bonding site with the carbonyl group). TIFF0007714438000113.tif14160

[0158] A a41 Examples of the alkanediyl group in 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, hexane-1,6-diyl group; 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, 2-methylbutane-1,4-diyl group. A a41 Examples of the substituent in the alkanediyl group represented by include hydroxy group and alkoxy group having 1 to 6 carbon atoms. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

[0159] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Examples of the divalent saturated hydrocarbon group represented by A a42 , A a43 and A a44 include linear or branched alkanediyl groups, monocyclic divalent alicyclic saturated hydrocarbon groups, and divalent saturated hydrocarbon groups formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group. Specifically, examples include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, and the like. A a42 , A a43 and A a44 Examples of the substituent of the divalent saturated hydrocarbon group represented by A a42 , A a43 and A a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. s is preferably 0.

[0160] In the group represented by formula (a-g1), examples of the group in which X a42 is -O-, -CO-, -CO-O- or -O-CO- include the following groups. In the following examples, * and ** each represent a bonding site, and ** is the bonding site with -O-CO-R a42 . a42 Examples of the group in which X a42 is -O-, -CO-, -CO-O- or -O-CO- in the group represented by formula (a-g1) include the following groups. In the following examples, * and ** each represent a bonding site, and ** is the bonding site with -O-CO-R a42 . a42 is the bonding site with it. TIFF0007714438000114.tif47140

[0161] Examples of the structural unit represented by formula (a4-1) include the following structural units and structural units in which the methyl group corresponding to R a41 in the following structural units represented by formula (a4-1) is replaced by a hydrogen atom. a41 include structural units in which the methyl group corresponding to R a41 in the structural unit represented by formula (a4-1) in the following structural units and the following structural units is replaced by a hydrogen atom. TIFF0007714438000115.tif99146

[0162] TIFF0007714438000116.tif132150

[0163] Examples of the structural unit represented by formula (a4-1) include the structural unit represented by formula (a4-2) and the structural unit represented by formula (a4-3). TIFF0007714438000117.tif4356[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, and -CH2- contained in the alkanediyl group may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having a fluorine atom and 1 to 20 carbon atoms. However, 44 L f6 and the total carbon number of R

[0164] L 44 The alkanediyl group having 1 to 6 carbon atoms is the same as the group exemplified by A a41 R f6 The saturated hydrocarbon group of R 42 is the same as the group exemplified by R L 44 The alkanediyl group in is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

[0165] Examples of the structural unit represented by formula (a4-2) include the structural units represented by formulas (a4-1-1) to (a4-1-11), respectively. The structural unit in which the methyl group corresponding to R f5 in the structural unit (a4-2) is replaced by a hydrogen atom is also included as the structural unit represented by formula (a4-2).

[0166] TIFF0007714438000118.tif5671[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 ​represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. X f12 represents *-O-CO- or *-CO-O- (* represents the bonding site with A f13 .). A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom. However, at least one of A f13 and A f14 has a fluorine atom, and the upper limit of the total carbon number of L 5 , A f13 and A f14 is 20.]

[0167] L 5 As the alkanediyl group in, groups similar to those exemplified as the alkanediyl group of A a41 can be mentioned.

[0168] A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in 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 the divalent chain saturated hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group. The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include cyclohexanediyl group and perfluorocyclohexanediyl group. Examples of the polycyclic group include adamantanediyl group, norbornanediyl group, perfluoroadamantanediyl group.

[0169] A f14The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 The groups similar to those exemplified by a42 can be mentioned. Among them, alkyl fluoride groups such as 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, 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, perfluoroadamantylmethyl group, etc. are preferable.

[0170] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group of A 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 of A is preferably a group containing a chain 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 saturated hydrocarbon group having 3 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms. Among them, A f14 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.

[0171] Examples of the structural unit represented by formula (a4-3) include structural units represented by formulas (a4-1'-1) to (a4-1'-11), respectively. In the structural unit (a4-3), the methyl group corresponding to R f7 in which the methyl group is replaced by a hydrogen atom is also included as a structural unit represented by formula (a4-3).

[0172] Examples of the structural unit (a4) also include a structural unit represented by formula (a4-4). TIFF0007714438000119.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 represents -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 - or -(CH2) j4 -CO-O-(CH2) j5 -. j1 to j5 each independently represent an integer from 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom.]

[0173] R f22 The saturated hydrocarbon group of is the same as the saturated hydrocarbon group represented by R a42 . R f22 is preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, and still more preferably an alkyl group having 1 to 6 carbon atoms and having a fluorine atom.

[0174] In formula (a4-4), A f21 is preferably -(CH2) j1 -, more preferably an ethylene group or a methylene group, and still more preferably a methylene group.

[0175] Examples of the structural unit represented by formula (a4-4) include structural units represented by the following structural units and the following formulas, in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom. f21 Examples include structural units in which the methyl group corresponding to R in structural unit (a4-4) is replaced by a hydrogen atom. TIFF0007714438000120.tif86160

[0176] When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and even more preferably 3 to 10 mol% based on all the structural units of the resin (A).

[0177] 〈Structural unit (a5)〉 Examples of the non-leaving hydrocarbon group in the structural unit (a5) include groups having a linear, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) preferably has a group having an alicyclic hydrocarbon group. Examples of the structural unit (a5) include a structural unit represented by formula (a5-1). TIFF0007714438000121.tif3554[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the hydrogen atoms contained in the alicyclic hydrocarbon group may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O- or -CO-.]

[0178] R 52 Examples of the alicyclic hydrocarbon group in R include both monocyclic and polycyclic groups. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group, etc. The aliphatic hydrocarbon groups having 1 to 8 carbon atoms include, for example, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include 3-methyladamantyl group. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

[0179] L 55 Examples of the divalent saturated hydrocarbon group in L include divalent chain saturated hydrocarbon groups and divalent alicyclic saturated hydrocarbon groups, and preferably divalent chain saturated hydrocarbon groups. Examples of the divalent chain saturated hydrocarbon group include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adamantanediyl group and norbornanediyl group.

[0180] L 55 Examples of the group in which -CH2- contained in the divalent saturated hydrocarbon group represented by L is replaced by -O- or -CO- include the groups represented by formula (L1-1) to formula (L1-4). In the following formulas, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. In formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents a bonding site with L x1 .). L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, the total number of carbon atoms in L x1 and L x2 is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, the total number of carbon atoms in L x3 and L x4 is 17 or less. In formula (L1-3), L x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms. However, the total number of carbon atoms in L x5 , L x6 and L x7 is 15 or less. In formula (L1-4), L x8 and L x9 each represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, the total number of carbon atoms in L x8 , L x9 and W x1 is 15 or less.

[0181] L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond. L x3is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

[0182] Examples of the group represented by the formula (L1-1) include the following divalent groups. TIFF0007714438000123.tif53136

[0183] Examples of the group represented by the formula (L1-2) include the following divalent groups. TIFF0007714438000124.tif23130

[0184] Examples of the group represented by the formula (L1-3) include the following divalent groups. TIFF0007714438000125.tif16146

[0185] Examples of the group represented by formula (L1-4) include, for example, the following divalent groups. TIFF0007714438000126.tif26114

[0186] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0187] Examples of the structural unit (a5-1) include the following structural units and the structural units in the following structural units where the methyl group corresponding to R in the structural unit (a5-1) is replaced by a hydrogen atom. 51 is replaced by a hydrogen atom. TIFF0007714438000127.tif111150 When the resin (A) has the structural unit (a5), its content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 3 to 15 mol% with respect to all the structural units of the resin (A).

[0188] 〈Structural unit (a6)〉 The structural unit (a6) is a structural unit having a -SO2- group, and preferably has a -SO2- group in the side chain. The structural unit having a -SO2- group may have a linear structure having a -SO2- group, a branched structure having a -SO2- group, or a cyclic structure (monocyclic and polycyclic structures) having a -SO2- group. Preferably, it is a structural unit having a cyclic structure having a -SO2- group, and more preferably, it is a structural unit having a cyclic structure containing -SO2-O- (sultone ring).

[0189] Examples of the sultone ring include the rings represented by the following formula (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula (T 1 -4). The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. The polycyclic sultone ring means a bridged ring containing -SO2-O- as an atomic group constituting the ring, and formula (T 1 -1) and formula (T1 Examples of the ring represented by the formula (T-2) include sultone rings. The sultone ring may contain a heteroatom in addition to -SO2-O- as an atomic group constituting the ring, like the ring represented by the formula (T-2). Examples of the heteroatom include an oxygen atom, a sulfur atom, or a nitrogen atom, preferably an oxygen atom. 1 The sultone ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkylcarbonyl group having 2 to 4 carbon atoms, etc. TIFF0007714438000128.tif3087

[0190] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0191] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group. Preferably, it is an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group. Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group. Preferably, a trifluoromethyl group is mentioned. Examples of the alkyl group having a hydroxy group include a hydroxymethyl group and a hydroxyalkyl group such as a 2-hydroxyethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. ​Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumyl group, a mesityl group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxycarbonyl group include a group 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 less carbon atoms, and more preferably a methoxycarbonyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

[0192] From the viewpoint that the production of the monomer leading to the structural unit (a6) is easy, a sultone ring having no substituent is preferable. As the sultone ring, a ring represented by the following formula (T1') is preferable. TIFF0007714438000129.tif3072[In the formula (T1'), X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. The bonding site is an arbitrary position.] X 11 is preferably an oxygen atom or a methylene group, and more preferably a methylene group. R41 Examples thereof include the same as the substituents of the sultone ring, and an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group is preferable.

[0193] As the sultone ring, a ring represented by the formula (T1) is more preferable. TIFF0007714438000130.tif3049[In the formula (T1), R 8 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. m represents any integer from 0 to 9. When m is 2 or more, a plurality of R 8 may be the same or different. The bonding site is at an arbitrary position.]

[0194] R 8 is the same as R 41 Examples thereof include the same as those of R. ma in the formula (T1') and m in the formula (T1) are preferably 0 or 1, more preferably 0.

[0195] Examples of the ring represented by the formula (T1') and the ring represented by the formula (T1) include the following rings. The bonding site is at an arbitrary position. TIFF0007714438000131.tif47144

[0196] The structural unit having a sultone ring preferably has the following group. * in the following group represents a bonding site. TIFF0007714438000132.tif45144

[0197] The structural unit having a -SO2- group preferably further has a group derived from a polymerizable group. Examples of the polymerizable group include a vinyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an acryloylthio group, a methacryloylthio group, and the like. Among them, the monomer that leads to the structural unit (a6) is preferably a monomer having an ethylenically unsaturated bond, more preferably a (meth)acrylic monomer.

[0198] The structural unit (a6) is preferably a structural unit represented by the formula (Ix). TIFF0007714438000133.tif4956[In the formula (Ix), R x represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. A xx represents an oxygen atom, -N(R c )- or a sulfur atom. A x represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -CO- or -N(R d )-. X 11 represents an oxygen atom, a sulfur atom or a methylene group. R 41 represents an alkyl group having 1 to 12 carbon atoms which may have a halogen atom or a hydroxy group, a halogen atom, a hydroxy group, a cyano group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, a glycidyloxy group, an alkoxycarbonyl group having 2 to 12 carbon atoms or an alkylcarbonyl group having 2 to 4 carbon atoms. ma represents any integer from 0 to 9. When ma is 2 or more, a plurality of R 41 may be the same or different. R c and R d each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.]

[0199] R x Examples of the halogen atom of R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R x Examples of the alkyl group of R include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group, etc. Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. R x Examples of the alkyl group having a halogen atom of R include, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group, etc. R x R is preferably 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.

[0200] A x Examples of the divalent saturated hydrocarbon group of A include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and those obtained by combining two or more of these groups may also be used. Specifically, linear alkanediyl 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, 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, 2-methylbutane-1,4-diyl group; Monocyclic divalent alicyclic saturated hydrocarbon groups which are cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Polycyclic divalent alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. may be mentioned.

[0201] R 41 、X 11 And ma are the same as those in formula (T1'). Examples of the sultone ring include those described above, and among them, those with specific bonding positions are preferred.

[0202] Examples of the structural unit (a6) include the following structural units. TIFF0007714438000134.tif93150

[0203] Among them, the structural units represented by formula (a6-1), formula (a6-2), formula (a6-6), formula (a6-7), formula (a6-8) and formula (a6-12) are preferable, and the structural units represented by formula (a6-1), formula (a6-2), formula (a6-7) and (a6-8) are more preferable. When the resin (A) has the structural unit (a6), its content is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and still more preferably 3 to 30 mol% with respect to all the structural units of the resin (A).

[0204] <Structural unit (II)> The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter sometimes referred to as "structural unit (II)"). Specific examples of the structural unit (II) include the structural units described in JP-A-2016-79235, and a structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain or a structural unit having a sulfonio group and an organic anion in the side chain is preferable.

[0205] The structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF0007714438000135.tif3089[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted by a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. RA - represents a sulfonate group or a carboxylate group. R III3represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. ZA + represents an organic cation.

[0206] R III3 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R III3 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R include the same ones as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, etc. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted in A include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, etc.

[0207] X III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by X include a linear or branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and combinations thereof may also be possible. Specifically, linear alkanediyl 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; 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, 2-methylbutane-1,4-diyl group; divalent monocyclic alicyclic saturated hydrocarbon groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; divalent polycyclic alicyclic saturated hydrocarbon groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. can be mentioned.

[0208] Examples of those in which -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- include divalent groups represented by formula (X1) to formula (X53). However, the number of carbon atoms before -CH2- contained in the saturated hydrocarbon group is replaced by -O-, -S- or -CO- is 17 or less respectively. In the following formula, * and ** represent bonding sites, and * represents the bonding site with A x1 represents the bonding site with A. TIFF0007714438000136.tif145161

[0209] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0210] ZA + Examples of the organic cation represented by ZA 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 arylsulfonium cations are more preferred. Specifically, cations represented by any of the above-described formulas (b2-1) to (b2-4) (hereinafter, may be referred to as "cation (b2-1)" etc. according to the formula number) can be mentioned.

[0211] The structural unit represented by the formula (II-2-A') is preferably the structural unit represented by the formula (II-2-A). JPEG0007714438000137.jpg37109 [In the formula (II-2-A), R III3 、X III3 and ZA + represent the same meanings as described above. z represents any integer from 0 to 6. R III2 and R III4 each independently represent a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. When z is 2 or more, a plurality of R III2 and R III4 may be the same as or different from each other. Q a and Q b each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.

[0212] R III2 、R III4 、Q a and Q bExamples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by are the same as the aforementioned Q. b1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by are the same as those described above.

[0213] The structural unit represented by formula (II-2-A) is preferably the structural unit represented by formula (II-2-A-1). TIFF0007714438000138.tif5576 [In formula (II-2-A-1), R III2 、R III3 、R III4 、Q a 、Q b 、z and ZA + have the same meanings as described above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, in which -CH2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom or a hydroxy group.

[0214] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. X I2 Examples of the divalent saturated hydrocarbon group represented by are the same as those of the divalent saturated hydrocarbon group represented by X III3 .

[0215] As the structural unit represented by formula (II-2-A-1), the structural unit represented by formula (II-2-A-2) is preferable. TIFF0007714438000139.tif5287 [In formula (II-2-A-2), R III3 、RIII5 and ZA + has the same meaning as described above. m and nA each independently represent 1 or 2.

[0216] Examples of the structural unit represented by formula (II-2-A’) include the following structural units, R III3 wherein the group corresponding to the methyl group of R is replaced with a hydrogen atom, a halogen atom (e.g., a fluorine atom), or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (e.g., a trifluoromethyl group, etc.), and the structural units described in International Publication No. 2012 / 050015. ZA + represents an organic cation. TIFF0007714438000140.tif86163

[0217] The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by formula (II-1-1). TIFF0007714438000141.tif3689[In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, and R II2 and R II3 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. R II4 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R include a phenylene group and a naphthylene group, etc. R II2 and R II3Examples of the hydrocarbon group represented by [ ] include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups. Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those described above. Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. Examples of the combined group include a group formed by combining the above-described alkyl group and alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, an aromatic hydrocarbon group having an alkyl group (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.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), and an aryl-cycloalkyl group such as a phenylcyclohexyl group. R II4 Examples of the halogen atom represented by [ ] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R II4 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by [ ] are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by [ ]. a8 Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by [ ] are the same as those of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by [ ]. A II1 Examples of the divalent linking group represented by [ ] include, for example, a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH2- contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. Specifically, examples are the same as those of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by [ ]. III3 Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by [ ] are the same as those of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by [ ].

[0218] Examples of the structural unit containing the cation in formula (II-1-1) include the structural unit represented by the following, R II4Examples of the structural unit in which the group corresponding to the methyl group is replaced with a hydrogen atom, a halogen atom (e.g., fluorine atom), or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom (e.g., trifluoromethyl group) etc. can be mentioned. TIFF0007714438000142.tif85130

[0219] A - Examples of the organic anion represented by A include sulfonate anion, sulfonylimide anion, sulfonylmethide anion, and carboxylate anion etc. A - The organic anion represented by A is preferably a sulfonate anion, and examples of the sulfonate anion include the same ones as the anion represented by the aforementioned formula (B1).

[0220] A - Examples of the sulfonylimide anion represented by A include the following. TIFF0007714438000143.tif36136

[0221] Examples of the sulfonylmethide anion include the following. TIFF0007714438000144.tif29123

[0222] Examples of the carboxylate anion include the following. TIFF0007714438000145.tif51152

[0223] Examples of the structural unit represented by the formula (II-1-1) include the structural unit represented by the following etc. TIFF0007714438000146.tif88149

[0224] When the resin (A) contains the structural unit (II), the content of the structural unit (II) is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and still more preferably 3 to 10 mol% with respect to all the structural units of the resin (A).

[0225] Resin (A) may have structural units other than the above-described structural units, and examples of such structural units include structural units well-known in the art.

[0226] Resin (A) is preferably a resin composed of structural unit (a1) and structural unit (s), that is, a copolymer of monomer (a1) and monomer (s). 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) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), more preferably at least two, and still more preferably at least two selected from the group consisting of structural unit (a1-1) and structural unit (a1-2). Structural unit (s) is preferably at least one selected from the group consisting of structural unit (a2) and structural unit (a3). Structural unit (a2) is preferably a structural unit represented by formula (a2-1) or a structural unit represented by formula (a2-A). 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).

[0227] Each structural unit constituting resin (A) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using monomers that lead to these structural units. The content of each structural unit of resin (A) can be adjusted by the amount of monomers used in the polymerization. The weight average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more) and 50,000 or less (more preferably 30,000 or less, still more preferably 15,000 or less). In this specification, the weight average molecular weight is a value determined by gel permeation chromatography under the conditions described in the examples.

[0228] <Resin other than resin (A)> The resist composition of the present invention may contain a resin other than resin (A). Examples of the resin other than resin (A) include resins containing structural unit (a4) or structural unit (a5) (hereinafter sometimes referred to as resin (X)).

[0229] Among them, as resin (X), a resin containing structural unit (a4) is preferable. 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 based on the total of all structural units of resin (X). Examples of the structural units that resin (X) may further have include structural unit (a2), structural unit (a3), and structural units derived from other known monomers. Among them, resin (X) is preferably a resin composed of only structural unit (a4) and / or structural unit (a5), and more preferably a resin composed of only structural unit (a4). Each structural unit constituting resin (X) may be used alone or in combination of two or more, and can be produced by a known polymerization method (for example, radical polymerization method) using the monomers that induce these structural units. The content of each structural unit of resin (X) can be adjusted by the amount of the monomers used in the 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 measuring means of the weight average molecular weight of resin (X) is the same as that of resin (A). When 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, still more preferably 1 to 30 parts by mass, and even more preferably 1 to 8 parts by mass with respect to 100 parts by mass of resin (A).

[0230] The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. When a resin other than the resin (A) is included, the total content of the resin (A) and the resin other than the resin (A) is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, based on the solid content of the resist composition. The solid content of the resist composition and the content of the resin relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0231] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, more preferably 94% by mass or more and 99% by mass or less. The content of the solvent (E) can be measured by known analytical means such as liquid chromatography or gas chromatography. Examples of the 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; cyclic esters such as γ-butyrolactone; and the like. One kind of the solvent (E) may be used alone, or two or more kinds may be used.

[0232] <Quencher (C)> Examples of the quencher (C) include salts that generate an acid having a lower acidity than the acid generated from the acid generator (B), and basic nitrogen-containing organic compounds. The content of the quencher (C) is preferably about 0.01 to 15% by mass, more preferably about 0.01 to 10% by mass, still 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.

[0233] The acidity of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "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. As the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B), preferably, it is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), more preferably, it is a weak acid inner salt (D), and still more preferably, among the weak acid inner salts (D), it is a diphenyliodonium salt containing a phenyl group substituted with a carboxylic acid anion. JPEG0007714438000147.jpg121167

[0234] 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 on at least one of the two phenyl groups bonded to the iodonium cation. Specifically, examples include salts represented by the following formula.

[0235] TIFF0007714438000148.tif2362[In formula (D), R D1 and R D2Each 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 of any one of 0 to 4. When m’ is 2 or more, a plurality of R D1 may be the same or different. When n’ is 2 or more, a plurality of R D2 may be the same or different.] R D1 and R D2 Examples of the hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. Examples of the chain hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, nonyl group and the like. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and may be either saturated or unsaturated. Examples thereof include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group, adamantyl group and the like. Examples of the aromatic hydrocarbon group include aryl groups such as 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 and the like. Examples of groups formed by combining these include alkyl-cycloalkyl groups, cycloalkyl-alkyl groups, aralkyl groups (e.g., 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 group, ethoxy group, etc. Examples of acyl groups include acetyl group, propanoyl group, benzoyl group, cyclohexanecarbonyl group, etc. Examples of acyloxy groups include groups in which an oxy group (-O-) is bonded to the above acyl group, etc. Examples of alkoxycarbonyl groups include groups in which a carbonyl group (-CO-) is bonded to the above alkoxy group, etc. Examples of halogen atoms include fluorine atom, chlorine atom, bromine atom, etc. R D1 and R D2 are each independently 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 any integer from 0 to 2, more preferably 0. When m' is 2 or more, the plurality of R D1 may be the same or different, and when n' is 2 or more, the plurality of R D2 may be the same or different.

[0236] More specifically, the following salts can be mentioned. TIFF0007714438000149.tif72165

[0237] Examples of the basic nitrogen-containing organic compounds include amines and ammonium salts. Examples of the amines include aliphatic amines and aromatic amines. Examples of the aliphatic amines include primary amines, secondary amines, and tertiary amines. Examples of the amine 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, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, 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-pyridyl)ethane, 1,2-di(4-pyridyl)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di(2-pyridyl)ketone, 4,4'-dipyridylsulfide, 4,4'-dipyridyldisulfide, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine and the like. Aromatic amines such as diisopropylaniline are preferable, and 2,6-diisopropylaniline is more preferable. 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, and choline.

[0238] <Other Components> The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes referred to as "other components (F)"). There is no particular limitation on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, etc. can be used.

[0239] <Preparation of Resist Composition> The resist composition of the present invention can be prepared by mixing the salt (I), the resin (A), and, if necessary, the acid generator (B), a resin other than the resin (A), the solvent (E), the quencher (C), and the other components (F). The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can be appropriately selected from 10 to 40°C according to the type of resin, etc. and the solubility of the resin, etc. in the solvent (E). The mixing time can be appropriately selected from 0.5 to 24 hours according to the mixing temperature. Note that the mixing means is not particularly limited, and stirring and mixing, etc. can be used. After mixing the respective components, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

[0240] <Method for Producing Resist Pattern> The method for producing 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, and (5) A step of developing the composition layer after heating. To apply the resist composition onto a substrate, it can usually be carried out by a commonly used apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers and organic substrates with a resist film formed on the surface. Before applying the resist composition, the substrate may be cleaned, or an antireflection film or the like may be formed on the substrate. By drying the applied composition, the solvent is removed to form a composition layer. Drying is carried out, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-bake), or by using a decompression device. The heating temperature is preferably 50 to 200 °C, and the heating time is preferably 10 to 180 seconds. Also, the pressure during decompression drying is preferably about 1 to 1.0×10 5 Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As the exposure light source, those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), those that convert laser light from a solid laser light source (such as YAG or semiconductor laser) to emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams, extreme ultraviolet light (EUV), etc., various ones can be used. In this specification, irradiating these radiations may be collectively referred to as "exposure" in some cases. During exposure, usually, exposure is carried out through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be carried out 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 the acid-labile groups. The heating temperature is usually about 50 to 200 °C, preferably about 70 to 150 °C. Chemical treatment (silylation) may be performed to adjust the hydrophilicity or hydrophobicity of the resin on the surface side of the composition after heating. Also, before development, the steps of coating, drying, exposing, and heating the resist composition may be repeatedly performed on the composition layer after exposure. The composition layer after heating is usually developed using a developing solution with a developing apparatus. Examples of the developing method include dip method, paddle method, spray method, dynamic dispense method, etc. The developing temperature is preferably, for example, 5 to 60 °C, and the developing time is preferably, for example, 5 to 300 seconds. By selecting the type of the developing solution as follows, a positive resist pattern or a negative resist pattern can be manufactured. When manufacturing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developing solution. The alkaline developer may be various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (commonly called choline) etc. may be mentioned. The alkaline developer may contain a surfactant. It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern. When manufacturing a negative resist pattern from the resist composition of the present invention, a developing solution containing an organic solvent (hereinafter sometimes referred to as an "organic-based developing solution") is used as the developing solution. Examples of the organic solvent contained in the organic-based developing solution 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; aromatic hydrocarbon solvents such as anisole, etc. In the organic developing solution, 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 still more preferably substantially only the organic solvent. Among them, as the organic developing solution, a developing solution containing butyl acetate and / or 2-heptanone is preferable. In the organic developing solution, the total content of butyl acetate and 2-heptanone 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 still more preferably substantially only butyl acetate and / or 2-heptanone. The organic developing solution may contain a surfactant. Further, the organic developing solution may contain a small amount of water. During development, development may be stopped by substituting with a solvent of a different type from the organic developing solution. It is preferable to wash the resist pattern after development with a rinse solution. The rinse 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 washing, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

[0241] <Usage> The resist composition of the present invention is suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, particularly as a resist composition for electron beam (EB) exposure or a resist composition for EUV exposure, and is useful for semiconductor microfabrication.

Examples

[0242] The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or the amount used are based on mass unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows. Column: TSKgel Multipore HXL-M x 3 + guard column (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI detector Column temperature: 40 °C Injection volume: 100 μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC is Agilent 1100 type, MASS is Agilent LC / MSD type). In the following examples, the value of this molecular ion peak is indicated by "MASS".

[0243] Example 1: Synthesis of the salt represented by formula (I-1) 3.96 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. To the resulting mixed solution, 3.24 parts of the compound represented by formula (I-1-b) were added, and the mixture was further stirred at 50 °C for 2 hours. To the resulting mixed solution, 4.40 parts of the compound represented by formula (I-1-c) were added, and the mixture was further stirred at 50 °C for 3 hours and then cooled to 23 °C. To the resulting mixture, 20 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and the mixture was stirred at 23 °C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was fractionated using a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 3 / 1) to obtain 6.98 parts of the compound represented by formula (I-1-d). 4.38 parts of the salt represented by formula (I-1-e) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes. Then, 1.62 parts of the compound represented by formula (I-1-b) were added. After heating to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting reaction mixture, 4.00 parts of the compound represented by formula (I-1-d) were added and the mixture was stirred at 50°C for 3 hours, and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes. Then, the layers were separated and the organic layer was taken out. To the obtained organic layer, 10 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. Then, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. The obtained organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether were added and the mixture was stirred at 23°C for 30 minutes. Then, the supernatant was removed and the residue was concentrated to obtain 7.22 parts of the salt represented by formula (I-1). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 556.9

[0244] Example 2: Synthesis of the salt represented by formula (I-2) 3.96 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. To the resulting mixed solution, 3.24 parts of the compound represented by formula (I-1-b) were added, and the mixture was further stirred at 50°C for 2 hours. To the resulting mixed solution, 9.44 parts of the compound represented by formula (I-2-c) were added, and the mixture was further stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 20 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was fractionated using a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 3 / 1) to obtain 6.96 parts of the compound represented by formula (I-2-d). 4.38 parts of the salt represented by formula (I-1-e) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes, then 1.62 parts of the compound represented by formula (I-1-b) were added, and after raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting reaction mixture, 6.52 parts of the compound represented by formula (I-2-d) were added, and the mixture was stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 7.81 parts of the salt represented by formula (I-2). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 808.7

[0245] Example 3: Synthesis of the salt represented by formula (I-10) 3.96 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. To the resulting mixed solution, 3.24 parts of the compound represented by formula (I-1-b) were added, and the mixture was further stirred at 50°C for 2 hours. To the resulting mixed solution, 4.68 parts of the compound represented by formula (I-10-c) were added, and the mixture was further stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 20 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was fractionated using a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 3 / 1) to obtain 7.28 parts of the compound represented by formula (I-10-d). 4.38 parts of the salt represented by formula (I-1-e) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes, then 1.62 parts of the compound represented by formula (I-1-b) were added, and after raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting reaction mixture, 4.14 parts of the compound represented by formula (I-10-d) were added, and the mixture was stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 7.68 parts of the salt represented by formula (I-10). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 570.9

[0246] Example 4: Synthesis of the salt represented by formula (I-11) 3.96 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. To the resulting mixed solution, 3.24 parts of the compound represented by formula (I-1-b) were added, and the mixture was further stirred at 50°C for 2 hours. To the resulting mixed solution, 4.96 parts of the compound represented by formula (I-11-c) were added, and the mixture was further stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 20 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to extract the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was fractionated using a column (silica gel 60N (spherical, neutral), 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 3 / 1) to obtain 6.97 parts of the compound represented by formula (I-11-d). 4.38 parts of the salt represented by formula (I-1-e) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes, then 1.62 parts of the compound represented by formula (I-1-b) were added, and after raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting reaction mixture, 4.28 parts of the compound represented by formula (I-11-d) were added, and the mixture was stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to extract the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 7.44 parts of the salt represented by formula (I-11). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M -585.0

[0247] Example 5: Synthesis of the salt represented by formula (I-12) 3.96 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. To the resulting mixed solution, 3.24 parts of the compound represented by formula (I-1-b) were added, and the mixture was further stirred at 50°C for 2 hours. To the resulting mixed solution, 5.24 parts of the compound represented by formula (I-12-c) were added, and the mixture was further stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 20 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 20 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was fractionated using a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 3 / 1) to obtain 4.43 parts of the compound represented by formula (I-12-d). 4.38 parts of the salt represented by formula (I-1-e) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes, then 1.62 parts of the compound represented by formula (I-1-b) were added, and after raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting reaction mixture, 4.42 parts of the compound represented by formula (I-12-d) were added, and the mixture was stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether were added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 7.19 parts of the salt represented by formula (I-12). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum): M - 599.0

[0248] Example 6: Synthesis of the salt represented by formula (I-13) 3.96 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. 3.24 parts of the compound represented by formula (I-1-b) was added to the obtained mixed solution, and the mixture was further stirred at 50°C for 2 hours. 7.20 parts of the compound represented by formula (I-13-c) was added to the obtained mixed solution, and the mixture was further stirred at 50°C for 3 hours and then cooled to 23°C. 20 parts of a 5% aqueous oxalic acid solution was added to the obtained mixture, and the mixture was stirred at 23°C for 30 minutes, followed by liquid separation to take out the organic layer. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by liquid separation to take out the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was fractionated using a column (silica gel 60N (spherical, neutral) 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 3 / 1) to obtain 6.09 parts of the compound represented by formula (I-13-d). 4.38 parts of the salt represented by formula (I-1-e) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes. 1.62 parts of the compound represented by formula (I-1-b) was added thereto, and after raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. 5.40 parts of the compound represented by formula (I-13-d) was added to the obtained reaction mixture, and the mixture was stirred at 50°C for 3 hours and then cooled to 23°C. 10 parts of a 5% aqueous oxalic acid solution was added to the obtained mixture, and the mixture was stirred at 23°C for 30 minutes, followed by liquid separation to take out the organic layer. 10 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by liquid separation to take out the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23°C for 30 minutes. Then, the supernatant was removed and concentrated to obtain 6.17 parts of the salt represented by formula (I-13). MASS(ESI(+)Spectrum): M +263.1 MASS(ESI(-) Spectrum): M - 696.8

[0249] Example 7: Synthesis of the salt represented by formula (I-16) JPEG0007714438000162.jpg51158 3.96 parts of the compound represented by formula (I-16-a) and 20 parts of chloroform were mixed and stirred at 23°C for 30 minutes. To the resulting mixed solution, 3.24 parts of the compound represented by formula (I-1-b) were added, and the mixture was further stirred at 50°C for 2 hours. To the resulting mixed solution, 9.84 parts of the salt represented by formula (I-16-e) were added, and the mixture was further stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. To the obtained organic layer, 10 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 5 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added, and the mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 6.78 parts of the salt represented by formula (I-16-d). JPEG0007714438000163.jpg35170 6.72 parts of the salt represented by formula (I-16-d) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes, then 1.62 parts of the compound represented by formula (I-1-b) were added, and after raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting reaction mixture, 4.72 parts of the compound represented by formula (I-2-c) were added, and the mixture was stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. To the obtained organic layer, 10 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes, then separated and the organic layer was taken out. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 30 parts of tert-butyl methyl ether were added, and the mixture was stirred at 23°C for 30 minutes, then the supernatant was removed and concentrated to obtain 7.11 parts of the salt represented by formula (I-16). MASS(ESI(+) Spectrum): M+ 263.1 MASS(ESI(-)Spectrum):M - 906.7

[0250] Example 8: Synthesis of the salt represented by formula (I-266) 3.96 parts of the compound represented by formula (I-16-a) and 20 parts of chloroform were mixed and stirred at 23°C for 30 minutes. To the resulting mixed solution, 3.24 parts of the compound represented by formula (I-1-b) were added, and the mixture was further stirred at 50°C for 2 hours. To the resulting mixed solution, 10.20 parts of the salt represented by formula (I-266-e) were added, and the mixture was further stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 5 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes, and then the supernatant was removed and concentrated to obtain 7.02 parts of the salt represented by formula (I-266-d). 6.90 parts of the salt represented by formula (I-266-d) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes, and then 1.62 parts of the compound represented by formula (I-1-b) were added. After raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting reaction mixture, 4.72 parts of the compound represented by formula (I-2-c) were added, and the mixture was stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes, and then the layers were separated to obtain the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and to the concentrated residue, 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes, and then the supernatant was removed and concentrated to obtain 6.39 parts of the salt represented by formula (I-266). MASS(ESI(+)Spectrum): M + 281.0 MASS(ESI(-)Spectrum): M - 906.7

[0251] Example 9: Synthesis of the salt represented by formula (I-276) 3.96 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. 3.24 parts of the compound represented by formula (I-1-b) were added to the resulting mixed solution, and the mixture was further stirred at 50°C for 2 hours. 7.24 parts of the compound represented by formula (I-276-c) were added to the resulting mixed solution, and the mixture was further stirred at 50°C for 3 hours and then cooled to 23°C. 20 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes. Then, liquid separation was performed to extract the organic layer. 20 parts of ion-exchanged water were added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. Then, liquid separation was performed to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mixture was fractionated using a column (silica gel 60N (spherical, neutral), 100 - 210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 3 / 1) to obtain 7.42 parts of the compound represented by formula (I-276-d). 4.38 parts of the salt represented by formula (I-1-e) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes. Then, 1.62 parts of the compound represented by formula (I-1-b) were added. After heating to 50°C, the mixture was stirred at 50°C for 2 hours. To the resulting reaction mixture, 5.42 parts of the compound represented by formula (I-276-d) were added, and the mixture was stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and stirred at 23°C for 30 minutes. Then, the layers were separated and the organic layer was taken out. To the obtained organic layer, 10 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes. Then, the layers were separated and the organic layer was taken out. This washing operation with water was repeated 5 times. The obtained organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether were added and stirred at 23°C for 30 minutes. Then, the supernatant was removed and the residue was concentrated to obtain 7.89 parts of the salt represented by formula (I-276). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 698.8

[0252] Example 10: Synthesis of the salt represented by formula (I-277) 3.96 parts of a compound represented by formula (I-1-a) and 40 parts of chloroform were mixed and stirred at 23°C for 30 minutes. 3.24 parts of a compound represented by formula (I-1-b) were added to the resulting mixed solution, and the mixture was further stirred at 50°C for 2 hours. 7.24 parts of a compound represented by formula (I-277-c) were added to the resulting mixed solution, and the mixture was further stirred at 50°C for 3 hours, and then cooled to 23°C. 20 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 20 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was separated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate=3 / 1) to obtain 6.89 parts of the compound represented by formula (I-277-d). 4.38 parts of the salt represented by formula (I-1-e) and 30 parts of chloroform were mixed and stirred at 23°C for 30 minutes, after which 1.62 parts of the compound represented by formula (I-1-b) were added, the mixture was heated to 50°C, and stirred at 50°C for 2 hours. 5.42 parts of the compound represented by formula (I-277-d) were added to the resulting reaction mixture, stirred at 50°C for 3 hours, and then cooled to 23°C. 10 parts of a 5% aqueous oxalic acid solution were added to the resulting mixture, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. 10 parts of ion-exchanged water was added to the resulting organic layer, and the mixture was stirred at 23°C for 30 minutes, followed by separation to separate the organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the concentrated residue. After stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain 7.94 parts of the salt represented by formula (I-277). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 698.8

[0253] Example 11: Synthesis of the salt represented by formula (I-417) 7.00 parts of the salt represented by formula (I-417-e) and 30 parts of chloroform were mixed and stirred at 23 °C for 30 minutes. Then, 1.62 parts of the compound represented by formula (I-1-b) were added. After raising the temperature to 50 °C, the mixture was stirred at 50 °C for 2 hours. To the resulting reaction mixture, 5.42 parts of the compound represented by formula (I-277-d) were added, and the mixture was stirred at 50 °C for 3 hours and then cooled to 23 °C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. 10 parts of ion-exchanged water were added to the obtained organic layer and stirred at 23 °C for 30 minutes. Then, the layers were separated and the organic layer was taken out. This water washing operation was repeated 5 times. The obtained organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether were added and stirred at 23 °C for 30 minutes. Then, the supernatant was removed and concentrated to obtain 9.96 parts of the salt represented by formula (I-417). MASS(ESI(+)Spectrum):M + 525.0 MASS(ESI(-)Spectrum):M - 698.8

[0254] Example 12: Synthesis of the salt represented by formula (I-447) 6.56 parts of the salt represented by JPEG0007714438000171.jpg34170 (I-447-e) and 30 parts of chloroform were mixed and stirred at 23 °C for 30 minutes. Then, 1.62 parts of the compound represented by formula (I-1-b) were added. After raising the temperature to 50 °C, the mixture was stirred at 50 °C for 2 hours. To the resulting reaction mixture, 5.42 parts of the compound represented by formula (I-277-d) were added, and the mixture was stirred at 50 °C for 3 hours and then cooled to 23 °C. To the resulting mixture, 10 parts of a 5% aqueous oxalic acid solution were added and stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer. To the obtained organic layer, 10 parts of ion-exchanged water were added and stirred at 23 °C for 30 minutes. Then, liquid separation was performed to extract the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether were added and stirred at 23 °C for 30 minutes. Then, the supernatant was removed and concentrated to obtain 9.01 parts of the salt represented by formula (I-447). MASS(ESI(+)Spectrum):M + 481.0 MASS(ESI(-)Spectrum):M - 698.8

[0255] Synthesis of Resin The compounds (monomers) used in the synthesis of resin (A) are shown below. Hereinafter, these compounds will be referred to as "monomer (a1-2-6)" etc. according to their formula numbers. TIFF0007714438000172.tif48154

[0256] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a1-4-2) were used, and their molar ratio [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-2)] was mixed at a ratio of 53:3:12:32. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol% respectively with respect to the total monomer amount, and these were heated at 73 °C for about 5 hours. Thereafter, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the mass of the total monomers was added to the polymerization reaction solution, and after stirring for 12 hours, liquid separation was performed. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, and resin A1 having a weight average molecular weight of about 5.3×10 3 was obtained at a yield of 88%. This resin A1 has the following structural units. TIFF0007714438000173.tif37129

[0257] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer (a3-4-2) and monomer (a1-4-13) were used and mixed so that the molar ratio [monomer (a1-2-6): monomer (a2-1-3): monomer (a3-4-2): monomer (a1-4-13)] was 53:3:12:32. Further, 1.5 times the mass of methyl isobutyl ketone with respect to the total mass of all monomers was mixed into this monomer mixture. To the obtained mixture, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators at 1.2 mol% and 3.6 mol%, respectively, with respect to the total monomer amount, and these were heated at 73 °C for about 5 hours. Then, an aqueous solution of p-toluenesulfonic acid (2.5 wt%) 2.0 times the mass of the total monomers was added to the polymerization reaction solution, stirred for 12 hours, and then separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and the resin was obtained by filtration and recovery, and resin A2 having a weight average molecular weight of about 5.1×10 3 was obtained at a yield of 79%. This resin A2 has the following structural units. TIFF0007714438000174.tif38129

[0258] <Preparation of resist composition> As shown in Table 2, the following components were mixed, and the obtained mixture was filtered through a fluororesin filter with a pore size of 0.2 μm to prepare a resist composition.

Table 2

[0259] <Resin> A1, A2: Resin A1, Resin A2 <Salt (I)> I-1: Salt represented by formula (I-1) I-2: Salt represented by formula (I-2) I-10: Salt represented by formula (I-10) I-11: Salt represented by formula (I-11) I-12: Salt represented by formula (I-12) I-13: Salt represented by formula (I-13) I-16: Salt represented by formula (I-16) I-266: Salt represented by formula (I-266) I-276: Salt represented by formula (I-276) I-277: Salt represented by formula (I-277) I-417: Salt represented by formula (I-417) I-447: Salt represented by formula (I-447) <Acid generator> IX-1 IX-2 IX-3 TIFF0007714438000176.tif33167<Quencher> C1: Synthesized by the method described in JP-A-2011-39502 TIFF0007714438000177.tif4355D1: (manufactured by Tokyo Chemical Industry Co., Ltd.) TIFF0007714438000178.tif1932<Solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0260] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 °C for 60 seconds. The resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, it was prebaked on a direct hot plate at the temperature shown in the "PB" column of Table 2 for 60 seconds to form a composition layer. A contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn on the composition layer formed on the wafer using an electron beam lithography machine ["ELS-F125 125 keV" manufactured by Elionix, Inc.] while changing the exposure dose stepwise. After exposure, post-exposure baking was performed on a hot plate for 60 seconds at the temperature shown in the "PEB" column in Table 2. Next, the composition layer on this silicon wafer was developed by a dynamic dispensing method using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer at 23°C for 20 seconds to obtain a resist pattern.

[0261] In the resist pattern obtained after development, the exposure amount at which the diameter of the formed hole was 17 nm was defined as the effective sensitivity.

[0262] <CD均一性(CDU)評価> For the effective sensitivity, the hole diameter of a pattern formed with a hole diameter of 17 nm was measured 24 times per hole, and the average of these measurements was taken as the average hole diameter for one hole.The standard deviation was calculated using the population of 400 measurements of the average hole diameter of patterns formed with a hole diameter of 17 nm on the same wafer. The results are shown in Table 3. The values in the table indicate the standard deviation (nm). [Table 3] Compared with the comparative compositions 1 to 3, the standard deviations of the compositions 1 to 14 were small, and the CD uniformity (CDU) evaluation was good. [Industrial Applicability]

[0263] A resist composition containing the salt of the present invention has good CD uniformity (CDU) and is useful for semiconductor microfabrication.

Claims

1. An acid generator containing a salt represented by formula (I). [In formula (I), Q １ and Q ２ each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. z represents any integer from 0 to 6, and when z is 2 or more, a plurality of Rs 11 and Rs 12 may be the same as or different from each other. X 1 and X ２ each independently represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O-, * represents C(R 11 ) (R 12 ) or C(Q １ ) (Q ２ ) or A １ Or L ２ represents the binding site with L 1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and —CH 2 - is -O-, -S-, -SO ２ It may be replaced by - or -CO-. A １ represents a group having a lactone structure which may have a substituent. L ２ and L ３ each independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. R １ represents an iodine atom. R ２ represents an iodine atom or a hydroxy group, and at least one of R2 is a hydroxy group. m2 represents an integer of 1 to 4, and when m2 is 2 or more, a plurality of R ２ may be the same or different from each other. Z ＋ represents an organic cation.

2. L １ is a single bond or *-L ４ -CO-O-(L ４ represents a cyclic hydrocarbon group having 3 to 18 carbon atoms or a group combining a cyclic hydrocarbon group having 3 to 18 carbon atoms and an alkanediyl group having 1 to 4 carbon atoms. The cyclic hydrocarbon group may have a substituent, and -CH 2 - in the cyclic hydrocarbon group may be replaced by -O-, -S-, -CO- or -SO ２ -, and -CH 2 - in the alkanediyl group may be replaced by -O- or -CO-. * represents the bonding site with X 1 . The acid generator according to claim 1, wherein it is as described above.)

3. A １ is a group represented by formula (R １０ -1), formula (R １０ -2), formula (R １０ -3) or formula (R １０ -4) The acid generator according to claim 1 or 2. [Formula (R １０ -1) to formula (R １０ -4), * represents a bonding site. Z 12 represents an oxygen atom, a sulfur atom or a methylene group. R １１ 、 R １２ 、 R １３ and R １４ each independently represents a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group combining these. m11 represents any integer from 0 to 5, and when m11 is 2 or more, the plurality of Rs １１ may be the same as or different from each other. m12 represents any integer from 0 to 5, and when m12 is 2 or more, the plurality of Rs １２ may be the same as or different from each other. m13 represents any integer from 0 to 5. When m13 is 2 or more, the plurality of Rs １３ may be the same as or different from each other. m14 represents any integer from 0 to 5, and when m14 is 2 or more, the plurality of Rs １４ may be the same as or different from each other. n10 represents an integer of 1 to 3.]

4. A １ is expressed by the following formula (L ４ -1), formula (L ４ -2) or formula (L ４ 3. The acid generator according to claim 1, wherein the acid generator is a group represented by the formula:

5. L ２ and L ３ and each independently represent a single bond or an alkanediyl group having 1 to 3 carbon atoms.

6. R ２ The acid generator according to any one of claims 1 to 5, wherein R is an iodine atom, a fluorine atom, a hydroxy group, a C1-C3 perfluoroalkyl group or a C1-C3 alkoxy group.

7. A resist composition containing the acid generator according to any one of Claims 1 to 6 and a resin having an acid-labile group.

8. The resist composition according to Claim 7, wherein the resin having an acid-labile group contains 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 formula (a1-0), formula (a1-1), and formula (a1-2), L a01 , L ａ１ and L ａ２ each independently represents -O- or *-O-(CH ２ ), ｋ１ -CO-O-, k1 represents any integer from 1 to 7, and * represents the bonding site with -CO-. R a01 , R ａ４ and R ａ５ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 , R a03 and R a04 each 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 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 combining these. m1 represents any integer from 0 to 14. n1 represents any integer from 0 to 10. n1' represents any integer from 0 to 3.]

9. The resist composition according to Claim 7 or 8, wherein the resin having an acid-labile group contains a structural unit represented by formula (a2-A). [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group. A a50 is a single bond or *-X a51 - (A a52 -X a52 ) nｂ -, * represents -R a50 represents the bonding site with the carbon atom to which it is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents —O—, —CO—O—, or —O—CO—. nb represents 0 or 1. mb represents any integer from 0 to 4. When mb is any integer of 2 or more, a plurality of Rs a51 may be the same as or different from each other.]

10. The resist composition according to any one of Claims 7 to 9, further containing a salt that generates an acid having a lower acidity than the acid generated from the acid generator.

11. (1) A step of applying the resist composition according to any one of Claims 7 to 10 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, A method for manufacturing a resist pattern including these steps.

12. A salt represented by formula (I). [In formula (I), Q １ and Q ２ each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. z represents any integer from 0 to 6, and when z is 2 or more, a plurality of R 11 and R 12 may be the same as or different from each other. X 1 and X ２ each independently represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O-, where * represents a bonding site with C(R 11 )(R 12 ) or C(Q １ )(Q ２ ) or A １ or L ２ and represents the binding site with it. L 1 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a single bond or a substituent, and the -CH 2 - in the hydrocarbon group may be replaced by -O-, -S-, -SO ２ - or -CO-. A １ represents a group having a lactone structure which may have a substituent. L ２ and L ３ each independently represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. R １ represents an iodine atom. R ２ represents an iodine atom or a hydroxy group, and at least one of R2 is a hydroxy group. m2 represents any integer from 1 to 4, and when m2 is 2 or more, a plurality of Rs ２ may be the same as or different from each other. Z ＋ represents an organic cation.

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