Compounds and resins

Abstract

To provide a compound and a resin which allow a resist pattern having good line edge roughness (LER) to be produced.SOLUTION: There are provided a compound represented by formula (I) and a resin. [R0 represents an alkyl group which may have a halogen atom, H or the like; X1 represents a bond selected from an ether bond, an ester bond and a carbonate ester bond, or a linking group in which a bond selected from a single bond, an ether bond, an ester bond and a carbonate ester bond is combined with an optionally substituted arylene group; L1 represents a single bond, a substituted / unsubstituted hydrocarbon group or the like; Ar represents a substituted / unsubstituted aromatic hydrocarbon group; X2 represents O or S; R1 represents F, Br, I or a haloalkyl group; R2 represents a halogen atom, a hydroxy group, a haloalkyl group or the like; m1 represents an integer of 1-6; and m2 represents an integer of 0-4.]SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a compound and a resin comprising a structural unit derived from the compound, etc.

Background Art

[0002] Patent Document 1 discloses a resist composition comprising a resin containing a structural unit derived from the following compound . TIFF0007920396000001.tif2819

[0003] Patent Document 2 discloses a resist composition comprising a resin containing a structural unit derived from the following compound . TIFF0007920396000002.tif2819

Prior Art Literature

Patent Literature

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problem to be Solved by the Invention

[0005] An object of the present invention is to provide a compound that forms a resist pattern having better line edge roughness (LER) than a resist pattern formed from a resist composition comprising a resin containing a structural unit derived from the above-mentioned compound.

Means for Solving the Problem

[0006] The present invention includes the following inventions. 〔1〕 A resist composition comprising a resin containing a structural unit derived from a compound represented by formula (I), and an acid generator A resist composition according to claim 1. TIFF0007920396000003.tif4091[In formula (I), R 0 represents a C1-C6 alkyl group optionally having a halogen atom, a hydrogen atom or a halog en atom. X 1 is selected from the group consisting of an ether bond, an ester bond and a carbonate ester bond ; or a linking group formed by combining at least one or two binding species selected from the group consisting of said binding species or a single bond, an ether bond, an ester bond and a carbonate ester bond, and an optionally su bstituted arylene group. represents a linking group formed by combining at least one or two binding species selected from the group consisting of said binding species or a single bond, an ether bond, an ester bond and a carbonate ester bond, and an optionally substituted arylene group. L 1 represents a single bond or an optionally substituted C1-C28 hydrocarbon group, and -CH2- contained in the h ydrocarbon group may be replaced by -O-, -S-, -SO2- or -CO-[] . Ar represents an optionally substituted C6-C18 aromatic hydrocarbon group. X 2 represents an oxygen atom or a sulfur atom. R 1 represents a halogen atom or a C1-C12 haloalkyl group. R 2 represents a halogen atom, a hydroxy group, a C1-C12 haloalkyl group or a C1-C 12 alkyl group, and -CH2- contained in said haloalkyl group and said alkyl group m ay be replaced by -O- or -CO-. m1 represents an integer of any of 1 to 6, and when m1 is 2 or more, a plurality of groups in p arentheses may be the same or different from each other. m2 represents an integer of any of 0 to 4, and when m2 is 2 or more, a plurality of R 2 are the same as each oth er or may be different from each other.]] [2] X 1is a group represented by any one of Formula (X 1 -1) to Formula (X 1 -7) [1] The resist composition according to described above. TIFF0007920396000004.tif45141[In Formula (X 1 -1) to Formula (X 1 -7), * and ** each represent a binding site, and ** represents a binding site with L 1 .] [3] X 1 is a group represented by Formula (X 1 -1), Formula (X 1 -3) or Formula (X 1 -4) The resist composition according to [2]. [4] L 1 is a single bond or *-L 2 -CO-O-(L 2 is a cyclic hydrocarbon having 3 to 10 carbon atoms hydrogen group, 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, and -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2- , and -CH2- contained in the alkanediyl group may be replaced with -O- or -CO- . * represents a binding site to X 1 .) The resist composition according to any one of [1] to [3] described above. [5] The resist composition according to [1], wherein Ar is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent to [4]. [6] X 2 is an oxygen atom, the resist composition according to any one of [1] to [5]. [7] R 1 is an iodine atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms , the resist composition according to any one of [1] to [6]. [8] R 2 However, iodine atoms, fluorine atoms, hydroxyl groups, and perfluorocarbons with 1 to 3 carbon atoms are present. The following is an alkyl group or an alkoxy group having 1 to 3 carbon atoms, as described in any of [1] to [7]. Dyst composition. [9] The resin has acid-unstable groups other than structural units derived from the compound represented by formula (I). A resist composition according to any one of [1] to [8], further comprising the structural unit.

[10] The acid generator contains a salt represented by formula (B1) as described in any of [1] to [9]. A resist composition. TIFF0007920396000005.tif2855[In formula (B1), Q b1 and Q b2 Each of these independently comprises a fluorine atom or a perfluorinated atom having 1 to 6 carbon atoms. This represents a luquill group. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and this divalent saturated hydrocarbon group The -CH2- contained may be replaced by -O- or -CO-, and the divalent saturated carbon The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms or hydroxyl groups. Y is a methyl group which may have substituents or a C3-C2 group which may have substituents 4 represents an alicyclic hydrocarbon group, and the -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced with SO2- or -CO-. Z + This represents an organic cation.

[11] Further contains a salt that generates an acid that is less acidic than the acid generated by the acid generator. A resist composition according to any one of [1] to

[10] .

[12] (1) Apply the resist composition described in any of [1] to

[11] onto the substrate. The process, (2) A step of drying the applied composition to form a composition layer, (3) a step of exposing the composition layer, (4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating, which is a method for producing a resist pattern.

[13] A compound represented by formula (I). TIFF0007920396000006.tif4091[In formula (I), R 0 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a hal ogen atom. X 1 is a bonding species selected from the group consisting of an ether bond, an ester bond and a carbonate bond, or a linking group formed by combining at least one or two bonding species selected from the group consisting of a single bond, an ether bond, an ester bond and a carbonate bond with an arylene group which may have a substituent. L 1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and -CH2- contai ned in the hydrocarbon group may be replaced with -O-, -S-, -SO2- or -CO-. Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. X 2 represents an oxygen atom or a sulfur atom. R 1 represents a halogen 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 with -O- or -CO-. m1 represents an integer of any one of 1 to 6, and when m1 is 2 or more, a plurality of groups in the parenthes es may be the same as or different from each other.​​ m2 represents an integer between 0 and 4, and when m2 is 2 or greater, multiple R 2 They are the same It may be one or different. A resin containing structural units derived from the compounds described in

[14] and

[13] . [Effects of the Invention]

[0007] A resist composition containing a resin that includes structural units derived from the compound of the present invention is used. This allows for the creation of resist patterns with good line edge roughness (LER). Cut. [Modes for carrying out the invention]

[0008] In this specification, "(meth)acrylic monomer" means "acrylic monomer and This means "at least one methacrylate monomer." "(meth)acrylate" and " The notation "(meth)acrylic acid," etc., also has the same meaning. For hydrocarbons that can take both a linear and branched structure, either is acceptable. When the -CH2- contained in the group is replaced by -O-, -S-, -CO-, or -SO2- The same example shall apply to each group. "Combined groups" refers to the groups exemplified. This refers to a group formed by the bonding of two or more types of groups, and the valencies of these groups may be appropriately changed depending on the bonding configuration. "Derived from" or "induced from" means that the polymerizable C=C bonds contained in the molecule polymerize. This refers to the formation of a single bond (-CC- group). If stereoisomers exist, all Includes stereoisomers.

[0009] [Compounds represented by formula (I)] The compound of the present invention is a compound represented by formula (I) (hereinafter sometimes referred to as "compound (I)"). Regarding (ru). TIFF0007920396000007.tif4091[In formula (I), all symbols have the same meaning as described above.]

[0010] In equation (I), R 0 The alkyl groups include methyl, ethyl, and n-propyl groups. isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pteryl group Examples include C1-C4 alkyl groups and n-hexyl groups, and preferably C1-C4 alkyl groups. More preferably, it is a methyl group or an ethyl group. R 0 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. It is possible. R 0 Examples of alkyl groups having a halogen atom include trifluoromethyl group, perfluorinated group ethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl Perfluoro group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Pentyl group, perfluorohexyl group, perchloromethyl group, perbromomethyl group and pentyl group Examples include the iodomethyl group. R 0 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable.

[0011] In equation (I), X 1 However, single bonds, ether bonds, ester bonds and carbonate ester bonds It has at least one or two bond species and substituents selected from the group consisting of the combination In the case of a linking group that is combined with an arylene group, it is represented by the following formula (X10) It is preferable that the linking group is such that it can be linked. TIFF0007920396000008.tif3449 formula (X10), Ax is L 1 This represents the bond species that bond with a single bond, ether bond, ester bond, and carbonic acid. This represents one type of bond selected from the group of bonds composed of ester bonds. Ay is R 0 This represents the type of bond that forms with the bonded carbon atom, including single bonds, ether bonds, and ether bonds. This represents one type of bond selected from the group consisting of steric bonds and carbonate ester bonds. If Ax is a single bond, then Ay is an ether bond, an ester bond, or a carbonate ester bond. It is preferable that Ax is one type of compound species selected from the group consisting of A. One bond selected from the group consisting of ester bonds, ester bonds, and carbonate ester bonds. If it is a hybrid, Ay can be a single bond, ether bond, ester bond, or carbonate ester bond. It is preferable that the combined species is one selected from the group comprising the above. Rx is a halogen atom, a hydroxyl group, a C1-C6 alkyl fluoride, or a C1- It represents an 18-C18 alkyl group or an alkoxy group having 1 to 6 carbon atoms. In particular, fluorine atoms and iodine Atoms, trifluoromethyl groups, methyl groups, or ethyl groups are preferred. mx represents an integer from 0 to 4, preferably 0, 1, or 2. If they are numbers, multiple Rx values ​​may be the same or different from one another. The bond position of Ay in the arylene group is either m-position or p-position relative to the bond position of Ax. It is preferable that it be in position p, and more preferably in position p. X 1 For example, the following equation (X 1 -1), formula (X 1 -2')~expression(X 1 -7') and formula (X 1 The group represented by -8) is an example.0 Bonding with carbon atoms Represents a part. ** is L 1 This represents the connection point. TIFF0007920396000009.tif51156 expression (X 1 -2')~expression(X 1 Specific examples of the group represented by -7') include the following: It is possible. TIFF0007920396000010.tif78122 Among them, X 1 is the equation (X 1 -1)~Formula(X 1 The group is represented by one of the following (-7) This is preferable, and formula (X 1 The base represented by (X -1), formula (X 1 The base represented by -3), formula (X 1 - 4) The base or formula (X 1 It is more preferable that the group is represented by formula (X 1 The base represented by (X -1), formula (X 1 (X) is represented by a base or formula (X 1 The base represented by -4) It is even more preferable that the formula (X 1 (X) is represented by a base or formula (X 1 -4) It is even more preferable that the formula (X 1 It is especially preferable that the group be represented by (-1). stomach. L 1 Examples of hydrocarbon groups in this context include divalent chain hydrocarbon groups such as alkanediyl groups, and monocyclic hydrocarbon groups. Divalent alicyclic hydrocarbon groups of formula or polycyclic (including spiro rings), divalent aromatic hydrocarbon groups A group is listed, which is a combination of two or more of these groups (for example, an alicyclic hydrocarbon group and an aluminum group). It may also be a divalent hydrocarbon group formed from a candiyl group. Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, Butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,1 2-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, Pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane Linear alkanediyl groups such as n-1,17-diyl groups and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Examples include branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group. The number of carbon atoms in the chain-like hydrocarbon group is preferably 1 to 18, more preferably 1 to 12. More preferably 1 to 9, even more preferably 1 to 6, and even more preferably Or, it is 1 to 4. Examples of monocyclic or polycyclic divalent alicyclic hydrocarbon groups include the following groups: The location of the part can be any desired position. TIFF0007920396000011.tif43166 Specifically, examples of alicyclic hydrocarbon groups include cyclobutane-1,3-diyl group and cyclopene. Tan-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5 - Monocyclic divalent alicyclic hydrocarbon groups such as cycloalkanediyl groups and diyl groups and norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic hydrocarbons such as 1,5-diyl groups and adamantane-2,6-diyl groups The basis is cited. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16. Yes, and more preferably 3 to 12. Examples of divalent aromatic hydrocarbon groups include phenylene, naphthylene, anthrylene, and bivalent groups. Examples include aromatic hydrocarbon groups such as phenylene groups, phenanthrylene groups, and arylene groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14. Yes, and more preferably 6 to 10. As a group combining two or more types, a combination of an alicyclic hydrocarbon group and an alkanediyl group is used. Combined groups, groups combining aromatic hydrocarbon groups and alkanediyl groups, and alicyclic hydrocarbons. Examples include groups that combine a group with an aromatic hydrocarbon group. In combination, alicyclic carbon Hydrogen groups, aromatic hydrocarbon groups, and chain hydrocarbon groups can each be combined in pairs of two or more types. Also, which of the bases is X 1 They may be bound together. Examples of groups combining an alicyclic hydrocarbon group and an alkanediyl group include -2 valent groups. Alicyclic hydrocarbon group -alkanediyl group-,-alkanediyl group-divalent alicyclic hydrocarbon group Examples include -alkanediyl groups- and -alkanediyl group-divalent alicyclic hydrocarbon groups-. . Examples of groups combining an aromatic hydrocarbon group and an alkanediyl group include, for example, a -2 valent group. Aromatic hydrocarbon group -alkanediyl group-,-alkanediyl group-divalent aromatic hydrocarbon group Examples include -alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-, etc. . Groups that combine an alicyclic hydrocarbon group and an aromatic hydrocarbon group include: -aromatic hydrocarbons Base - alicyclic hydrocarbon group -, - alicyclic hydrocarbon group - aromatic hydrocarbon group -, - alicyclic hydrocarbon Examples include groups such as aromatic hydrocarbon groups and alicyclic hydrocarbon groups. L 1 The -CH2- groups in hydrocarbon groups with 1 to 28 carbon atoms are -O-, -S-, and -SO It may be replaced with 2- or -CO-. L 1 The -CH2- group in hydrocarbon groups with 1 to 28 carbon atoms is -O-, -S-, or -SO2 -If replaced by -CO-, the number of carbon atoms before replacement is equal to the number of carbon atoms in the hydrocarbon group. Let's assume that. The -CH2- contained in the hydrocarbon group is replaced by -O-, -S-, -SO2-, or -CO-. The replaced group is the hydroxyl group (where the -CH2- contained in the methyl group is replaced by -O-). (The replaced group), carboxyl group (the -CH2-CH2- contained in the ethyl group is -O-CO- (A group that has been replaced by a thiol group) (The -CH2- contained in the methyl group is replaced by an -S-) (A split group), an alkoxy group (where -CH2- is at any position within the alkyl group, -O- (a group replaced by), alkylthio group (a -CH2- at any position within the alkyl group) However, the group replaced by -S-, the alkoxycarbonyl group (any group contained within the alkyl group) (A group in which the -CH2-CH2- at the position is replaced by -O-CO-), alkylcarbonyl group (A group in which any -CH2- at any position within an alkyl group is replaced by -CO-), The hydroxyl sulfonyl group (where -CH2- at any position within the alkyl group is converted to -SO2-) (Replaced group), alkylcarbonyloxy group (any position contained within the alkyl group) (A group in which -CH2-CH2- is replaced by -CO-O-), an alkanediyloxy group (al A group in which any -CH2- at any position in the candiyl group is replaced by -O-, Candiyloxycarbonyl group (the -CH2- at any position within the alkanediyl group) CH2- is replaced by -O-CO-, an alkanediylcarbonyl group (alkane) (A group in which any -CH2- at any position in the diyl group is replaced by -CO-), Alka Alkanediylcarbonyloxy group (-CH2-C at any position within the alkanediyl group) (A group in which H2- is replaced by -CO-O-), an alkanediylsulfonyl group (alkanedi (A group in which any -CH2- at any position in the yl group is replaced by -SO2-), An alkanediylthio group (where any -CH2- is located at any position within the alkanediyl group is placed in the -S- group) (Replaced group), cycloalkoxy group, cycloalkylalkoxy group, alkoxycarb Nyloxy group, aromatic hydrocarbon group-carbonyloxy group, and combinations of two or more of these groups Examples of combined bases include: Examples of alkoxy groups include alkoxy groups having 1 to 17 carbon atoms, such as methoxy. Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, o Cutyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, un Examples include decyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 11. More preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 It is ~3. Examples of alkylthio groups include alkylthio groups having 1 to 17 carbon atoms, for example, methyl Examples include ruthio groups, ethylthio groups, propylthio groups, and butylthio groups. The number of carbon atoms in the group is preferably 1 to 11, more preferably 1 to 6, and even more preferably k is 1 to 4, and more preferably 1 to 3. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups are A carbonyl group or carbonyloxy group is bonded to the alkyl group or alkoxy group mentioned above. It represents the base. Examples of alkoxycarbonyl groups include alkoxycarbonyl groups having 2 to 17 carbon atoms. For example, methoxycarbonyl groups, ethoxycarbonyl groups, butoxycarbonyl groups, etc. Examples include alkylcarbonyl groups with 2 to 18 carbon atoms. Examples include acetyl groups, propionyl groups, and butyryl groups. Examples of carbonyloxy groups include alkylcarbonyloxy groups having 2 to 17 carbon atoms. Examples include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 11, and more preferably 2. ~6, more preferably 2~4, and even more preferably 2 or 3. The number of carbon atoms in the lucylcarbonyl group is preferably 2 to 12, more preferably 2 to 6. More preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the rubonyloxy group is preferably 2 to 11, more preferably 2 to 6. More preferably 2 to 4, and even more preferably 2 or 3. Examples of alkylsulfonyl groups include alkylsulfonyl groups having 1 to 17 carbon atoms. Examples include methylsulfonyl groups, ethylsulfonyl groups, and propylsulfonyl groups. The alkylsulfonyl group has preferably 1 to 11 carbon atoms, and more preferably 1 carbon atoms. It is ~6, more preferably 1~4, and even more preferably 1~3. Examples of alkanediyloxy groups include those with 1 to 17 carbon atoms. For example, methyleneoxy group, ethyleneoxy group, propanediyloxy group, butanedi Examples include yloxy groups and pentanediyloxy groups. The number is preferably 1 to 11, more preferably 1 to 6, and even more preferably 1 to It is 4, and more preferably 1 to 3. Alkanediyloxycarbonyl groups include those with 2 to 17 carbon atoms. Examples of carbonyl groups include methyleneoxycarbonyl groups and ethyleneoxycarbonyl groups. Examples include the nyl group, propanediyloxycarbonyl group, and butanediyloxycarbonyl group. It can be. As for the alkanediylcarbonyl group, alkanediylcarbonyl groups with 2 to 18 carbon atoms are available. Examples include the nyl group, such as the methylenecarbonyl group, ethylenecarbonyl group, and propanedi Examples include ylcarbonyl groups, butanediylcarbonyl groups, and pentanediylcarbonyl groups. Alkanediylcarbonyloxy groups include alkanediylcarbonyl groups with 2 to 17 carbon atoms. Examples of carbonyloxy groups include methylenecarbonyloxy groups and ethylenecarbonyloxy groups. Luoxy group, propanediylcarbonyloxy group, butanediylcarbonyloxy group, etc. For example, the number of carbon atoms in the alkanediyloxycarbonyl group is preferably 2 to 11. , more preferably 2 to 6, even more preferably 2 to 4, even more It is 2 or 3. The number of carbon atoms in the alkanediylcarbonyl group is preferably 2 to 12. More preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 Or 3. The number of carbon atoms in the alkanediylcarbonyloxy group is preferably 2 to 11. more preferably 2 to 6, even more preferably 2 to 4, and even more preferably It is either 2 or 3. Examples of alkanediylsulfonyl groups include alkanediylsulfonyl groups having 1 to 17 carbon atoms. Examples include methylene sulfonyl group, ethylene sulfonyl group, and propylene sulfonyl group. Examples include the nyl group. The number of carbon atoms in the alkanediylsulfonyl group is preferably 1 to 11. Yes, more preferably 1 to 6, even more preferably 1 to 4, even more preferably The values ​​are 1 to 3. Examples of alkanediylthio groups include those with 1 to 17 carbon atoms. Examples include methylenethio groups, ethylenethio groups, and propylenethio groups. The number of carbon atoms in the diylthio group is preferably 1 to 11, more preferably 1 to 6. More preferably, the values ​​are 1 to 4, and even more preferably, 1 to 3. Examples of cycloalkoxy groups include cycloalkoxy groups with 3 to 17 carbon atoms, for example Examples include cyclohexyloxy groups. Examples of cycloalkylalkoxy groups include carbon Examples include cycloalkylalkoxy groups with prime numbers 4 to 17, for example, cyclohexylmethyl Examples include alkoxycarbonyloxy groups, which have 2 to 16 carbon atoms. Examples include xycarbonyloxy groups, such as the butoxycarbonyloxy group. Aromatic hydrocarbon groups - carbonyloxy groups include aromatic hydrocarbons with 7 to 17 carbon atoms. Examples include carbonyloxy groups, such as the benzoyloxy group. Furthermore, the -CH2- contained in the alicyclic hydrocarbon group may be -O-, -S-, -CO-, or -S The following groups can be considered as examples of groups that have been replaced by O2-. The -O- of the groups shown below Alternatively, -CO- may be replaced with -S- or -SO2-, respectively. The bonding site is arbitrary. It can be positioned as follows: TIFF0007920396000012.tif46166

[0012] L 1 The substituents that may be present are a hydroxyl group, a carboxyl group, a halogen atom, and a hydroxyl group. A group, alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, group with 2 to 13 carbon atoms Alkoxycarbonyl groups, alkylcarbonyl groups with 2 to 13 carbon atoms, Examples include alkylcarbonyloxy groups or groups combining these. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, and isopropyl groups. butyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl Examples include the yl group and the nonyl group. Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, and b Toxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group These are some examples. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and The alkylcarbonyloxy group having 2 to 13 carbon atoms is the alkyl or alkoxy group described above. This represents a group to which a carbonyl group or a carbonyloxy group is bonded. Examples of alkoxycarbonyl groups with 2 to 13 carbon atoms include the methoxycarbonyl group and the ethoxycarbonyl group. Examples include carbonyl groups and butoxycarbonyl groups, which are alkylcarbonyl groups with 2 to 13 carbon atoms. Examples of acetyl groups include acetyl groups, propionyl groups, and butyryl groups, with 2 to 1 carbon atoms. 3. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, Examples include butyryloxy groups. The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. More preferably, it is an alkyl group or halogen atom having 1 to 4 carbon atoms, and methyl It is even more preferable that the group be a fluorine atom or a fluorine atom.

[0013] L 1 This refers to a single bond, an alkanediyl group having 1 to 8 carbon atoms (however, the alkanediyl group contains The -CH2- group may be replaced by -O- or -CO-. ) C1-6 A combination of an alkanediyl group and an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents. A group consisting of (however, the -CH2- contained in the alkanediyl group is -O- or -CO-) It may be replaced by -CH2-, and the -CH2- contained in the alicyclic hydrocarbon group may be -O-, -S -, -SO2- or -CO- may be replaced.) or alkanes having 1 to 6 carbon atoms. A diyl group and an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have substituents, are combined. The group (however, the -CH2- contained in the alkanediyl group is replaced with -O- or -CO-) It is preferable that it is divided, and has a single bond and an alkanediyl group having 1 to 6 carbon atoms. (However, the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-) (This may also be the case.) A carbon 1-4 alkanediyl group and a carbon 3- which may have substituents. A group formed by combining 18 alicyclic hydrocarbon groups (however, the alkanediyl group contains -CH2- may be replaced by -O- or -CO-, and the alicyclic hydrocarbon group may contain The -CH2- group may be replaced by -O- or -CO-. (or a group with 1 or more carbon atoms) A combination of a 4 alkanediyl group and an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have substituents. Groups formed by combining (however, the -CH2- contained in the alkanediyl group is -O- or -C It is preferable that it be replaced with O-. Also, L 1 This is a single bond, *-L 2 -CO-O- or *-L 2 -O-CO-O-(L 2 teeth , a cyclic hydrocarbon group having 3 to 18 carbon atoms, or a cyclic hydrocarbon group having 3 to 18 carbon atoms and a group having 1 to 4 carbon atoms It represents a group that is combined with an alkanediyl group, and the cyclic hydrocarbon group has substituents. It is also possible that the -CH2- contained in the cyclic hydrocarbon group is -O-, -S-, -CO- or - It may be replaced by SO2-, and the -CH2- contained in the alkanediyl group is -O - or -CO- may be used instead. * is X 1 This represents the bonding site. Both are preferable. Furthermore, the combination of an alkanediyl group and an alicyclic hydrocarbon group or an aromatic hydrocarbon group as used here Wase is an *-alkanediyl group-alicyclic hydrocarbon group or aromatic hydrocarbon group-, *-alicyclic Hydrocarbon group or aromatic hydrocarbon group - alkanediyl group - *-alkanediyl group - alicyclic Examples include hydrocarbon groups or aromatic hydrocarbon groups - alkanediyl groups - etc. * is X 1 The conclusion This indicates the joining point. L 2 The cyclic hydrocarbon group and alkanediyl group in these are the same as the groups exemplified above. The basis for this can be cited. L 2 This refers to a polycyclic divalent cyclic hydrocarbon group having 6 to 12 carbon atoms or a polycyclic group having 6 to 12 carbon atoms. A group formed by combining a divalent cyclic hydrocarbon group and an alkanediyl group having 1 to 4 carbon atoms (the cyclic The hydrocarbon group may have substituents, and the -CH2- contained in the cyclic hydrocarbon group is -O-, -S-, -CO-, or -SO2- may be substituted for the alkanediyl The -CH2- group contained in the group may be replaced by -O- or -CO-. Preferably, a polycyclic divalent alicyclic hydrocarbon group having 7 to 11 carbon atoms or a C7 to 11 carbon atom A group combining a polycyclic divalent alicyclic hydrocarbon group and an alkanediyl group having 1 to 3 carbon atoms. (The -CH2- contained in the alicyclic hydrocarbon group is replaced by -O- or -CO-) Often, the -CH2- contained in the alkanediyl group is replaced by -O- or -CO-. It is also possible that it is more preferable to be the following formula (L 2 The base represented by (-1), formula (L 2 The base represented by formula (L -2), formula (L 2 -3) The base and formula (L 2 -4) is a base represented by A group selected from the following group, or the following formula (L 2 The base represented by (-1), formula (L 2 -2) Table The base, formula (L 2 -3) The base and formula (L 2 From the group consisting of the group represented by -4) A group formed by combining a selected group with an alkanediyl group having 1 to 3 carbon atoms (the alkanediyl group The -CH2- contained in may be replaced by -O- or -CO-. More preferably, formula (L 2 The group represented by -2) is more preferred. * represents a binding site. . TIFF0007920396000013.tif3096

[0014] In Ar, the aromatic hydrocarbon groups include, in the case of divalent, phenylene groups, naphthylene groups, Aromatic carbonization of arylene groups such as anthrylene groups, biphenylene groups, and phenanthrylene groups. Examples include hydrogen groups. In the case of trivalent groups, these include benzenetriyl groups, naphthalentriyl groups, and ant groups. Aromatic carbonized water containing lacentryl groups, biphenyltriyl groups, phenanthrentriyl groups, etc. Examples of elemental groups include the benzenetetrayl group, naphthalenetetrayl group, and ammonium group. Fragrances of tracentetrayl groups, biphenyltetrayl groups, phenanthrenetetrayl groups, etc. Examples include hydroxyl groups (HQTs). In the case of pentavalent groups, these include benzenepentile groups and naphthalenepentile groups. Group, anthracene pentile group, biphenyl pentile group, phenanthrene pentile group Examples of aromatic hydrocarbon groups include benzenehexyl groups and naphthalene hexyl groups. In the case of hexavalent groups, these include benzenehexyl groups and naphthalene hexyl groups. Xyl group, anthracene hexyl group, biphenyl hexyl group, phenanthrene hexyl Examples include aromatic hydrocarbon groups such as silicic acid groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 14. Yes, more preferably 6 to 10, and even more preferably 6.

[0015] The substituents that Ar may have include a hydroxyl group, a carboxyl group, a halogen atom, and a hydroxyl group. A group, alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, group with 2 to 13 carbon atoms Alkoxycarbonyl groups, alkylcarbonyl groups with 2 to 13 carbon atoms, Examples include alkylcarbonyloxy groups or groups combining these. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, and isopropyl groups. butyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl Examples include the yl group and the nonyl group. Examples of alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, and b Toxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyl oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group These are some examples. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and The alkylcarbonyloxy group having 2 to 13 carbon atoms is the alkyl or alkoxy group described above. This represents a group to which a carbonyl group or a carbonyloxy group is bonded. Examples of alkoxycarbonyl groups with 2 to 13 carbon atoms include the methoxycarbonyl group and the ethoxycarbonyl group. Examples include carbonyl groups and butoxycarbonyl groups, which are alkylcarbonyl groups with 2 to 13 carbon atoms. Examples of acetyl groups include acetyl groups, propionyl groups, and butyryl groups, with 2 to 1 carbon atoms. 3. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, Examples include butyryloxy groups. Substituents include C1-C12 alkyl groups, C1-C12 alkoxy groups, and hydroxyl groups. A group, carboxyl group or halogen atom is preferred, and an alkyl group having 1 to 6 carbon atoms, or a group having 1 to 6 carbon atoms. It is more preferably a 6-carboxyl group, hydroxyl group, or halogen atom, and has 1 carbon atom. It is an alkyl group with 3 or more carbon atoms, an alkoxy group with 1 to 3 carbon atoms, a hydroxyl group, or a halogen atom. It would be even more preferable. Ar is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms, which may have substituents. More preferably, it is an aromatic hydrocarbon group having 6 to 10 carbon atoms, which may have substituents. It is further more preferred that the group is a C6 aromatic hydrocarbon group which may have a substituent, a substituted phenylene group which may have a substituent is even more preferred. Examples of preferred substituents include hydro- xy groups, carboxy groups, halogen atoms, alkyl groups having 1 to 12 carbon atoms or alkoxy groups having 1 to 1 2 carbon atoms. More preferred are hydroxy groups, halogen atoms, alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms. Even more preferred are hydroxy groups, halogen atoms, alkyl groups having 1 to 3 carbon atoms or alkoxy groups having 1 to 3 carbon atoms.

[0016] R 1 and R 2 Examples of the halogen atom for include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom and the like. R 1 and R 2 The haloalkyl group having 1 to 12 carbon atoms in refers to an alkyl group having 1 to 12 carbon atoms having one or more halogen atoms, and includes fluorinated alkyl groups having 1 to 12 carbon atoms, groups having 1 to 12 chlorinated alkyl groups having 1 to 12 carbon atoms, brominated alkyl groups having 1 to 12 carbon atoms, iodinated alkyl groups having 1 to 12 carbon atoms and the like. As the haloalkyl group, perfluoroalkyl groups having 1 to 12 carbon atoms (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonaf luorobutyl group, etc.), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropr opyl group, 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorob utyl group, chloromethyl group, bromomethyl group, iodomethyl group, and the like. The number of carbon atoms of the haloal kyl group is preferably 1 to 9, more preferably 1 to 6, still more prefe rably 1 to 4, and even more preferably 1 to 3. R 2Examples of alkyl groups with 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, iso Propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, Examples of alkyl groups include octyl groups and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, even more preferably 1 to 4, and even more Preferably, it is 1 to 3. R 2 The -CH2- contained in the haloalkyl group or alkyl group represented by is -O- or - If CO- is replaced, the number of carbon atoms before replacement will be the same as the haloalkyl group or the alkyl group. This refers to the total number of carbon atoms in the methyl group. The replaced group is a hydroxyl group (contained within the methyl group). A group in which -CH2- is replaced by -O-, a carboxyl group (containing -CH2 in the ethyl group) A group in which -CH2- is replaced by -O-CO-, an alkoxy group (contained within an alkyl group) (A group in which -CH2- at any position is replaced by -O-), an alkoxycarbonyl group ( A group in which any -CH2-CH2- at any position in the lukyl group is replaced by -O-CO-. ), alkylcarbonyl group (where -CH2- is at any position within the alkyl group, -CO - A group replaced by (), alkylcarbonyloxy group (any position contained in the alkyl group) (A group in which the -CH2-CH2- is replaced by -CO-O-), a haloalkoxy group (haloalkoxy group) (A group in which any -CH2- at any position in the lukyl group is replaced by -O-), haloal Coxycarbonyl group (where the -CH2-CH2- at any position within the haloalkyl group is - Groups replaced by O-CO-, haloalkylcarbonyl groups (contained within the haloalkyl group) (A group in which -CH2- at any position is replaced by -CO-), haloalkylcarbonylo The xy group (where any -CH2-CH2- in a haloalkyl group is converted to -CO-O-) Examples include replaced groups, and groups formed by combining two or more of these groups. Examples of alkoxy groups include alkoxy groups having 1 to 11 carbon atoms, such as methoxy. Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, o Cutyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, un Examples include decyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 6. Preferably, it is 1 to 4, and more preferably 1 to 3. Alkoxycarbonyl groups, alkylcarbonyl groups, and alkylcarbonyloxy groups are A carbonyl group or carbonyloxy group is bonded to the alkyl group or alkoxy group mentioned above. It represents the base. Examples of alkoxycarbonyl groups include alkoxycarbonyl groups having 2 to 11 carbon atoms. For example, methoxycarbonyl groups, ethoxycarbonyl groups, butoxycarbonyl groups, etc. Examples include alkylcarbonyl groups with 2 to 12 carbon atoms. Examples include acetyl groups, propionyl groups, and butyryl groups, and alkyl groups. Examples of carbonyloxy groups include alkylcarbonyloxy groups having 2 to 11 carbon atoms. Examples include acetyloxy groups, propionyloxy groups, and butyryloxy groups. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 6, more preferably 2 to 4. Yes, and more preferably 2 or 3. The number of carbon atoms in the alkylcarbonyl group is preferably It is 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The carbon number of the carbon-carbonyloxy group is preferably 2 to 6, more preferably 2 to 4. , more preferably 2 or 3. Haloalkoxy groups, haloalkoxycarbonyl groups, haloalkylcarbonyl groups, halo alkylcarbonyloxy groups include a haloalkoxy group having 1 to 11 carbon atoms, a haloalkoxycarbonyl group having 2 to 1 1 carbon atoms, a haloalkylcarbonyl group having 2 to 12 carbon atoms, a halo alkylcarbonyloxy group having 2 to 11 carbon atoms; examples include groups obtained by substituting one or more hydrogen atoms of the groups exemplified above with a halogen atom. are mentioned. X 2 is preferably an oxygen atom. When Ar is an aromatic hydrocarbon group having 6 carbon atoms that may have a substituent, the bonding position of X 2 to Ar relative to the bonding position of L 1 may be any of the ortho, meta, and para positions. Among these , when m1 is 1, X 1 is preferably bonded at the para position or meta position relative to the bonding position of L 1 , and more preferably bonded at the para position. When m1 is 2, X 1 is relative to the bonding position of L 1 , it is preferable that one is bonded at the ortho position or meta position and one is bonded at the ortho position or meta position , and it is more preferable that both are bonded at the meta position. When m1 is 3, X 1 is relative to the bonding position of L 1 , it is preferable that two are bonded at the ortho position or meta position, and one is bonded at the para position or meta position, and it is more preferable that two are bonded at the meta position and one is bonded at the para position . When m1 is 4, X 1 is relative to the bonding position of L 1 , it is preferable that two are bonded at the ortho position or meta position, and two are bonded at the para position or meta position, and more preferably two are ​​It is preferable that the two atoms are bonded at the O position, and more preferably that both are bonded at the m position. m1 is preferably 1, 2, 3, 4, or 5, and is 1, 2, 3, or 4. More preferably, it is 1, 2, or 4. m2 is preferably 0, 1, 2, or 4, and more preferably 0, 2, or 4. It's nice. R 1 It is preferable that it be an iodine atom, a fluorine atom, or a haloalkyl group having 1 to 6 carbon atoms. Furthermore, it must be an iodine atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms. More preferably, it is an iodine atom, a fluorine atom, or a trifluoromethyl group. It is even more preferable that it be an iodine atom or a fluorine atom. R 2 This includes an iodine atom, a fluorine atom, a hydroxyl group, a C1-C6 haloalkyl group, or Alkyl alkyl groups having 1 to 6 carbon atoms (the haloalkyl group and the -CH2- contained in the alkyl group are Preferably, iodine atoms and fluorine atoms (which may be replaced by -O- or -CO-) are present. , hydroxyl group, C1-C4 alkyl group, C1-C4 haloalkyl group or C4 1 to 3 alkoxy groups are more preferred, iodine atom, fluorine atom, hydroxyl group, carbon number A perfluoroalkyl group with 1 to 3 carbon atoms or an alkoxy group with 1 to 3 carbon atoms is more preferable. A fluorine atom, a fluorine atom, a hydroxyl group, a trifluoromethyl group, or a methoxy group may be further... It is preferable. R 1 The bond position to the benzene ring is X 1 With respect to the bonding position, the o position, m position, p position Any of these is fine. Among them, R 1 The bond position to the benzene ring is X 1 With respect to the bonding position, m It is preferable that the position be the p-position or the position of the first or second position. R 2 The bond position to the benzene ring is X 1 With respect to the bonding position, the o position, m position, p position This is also acceptable. In particular, if m2 is 1, R 2 The bond position to the benzene ring is X 1 The conclusion It is preferable that the position is m or p relative to the mating position. If m2 is 2, then X 1 bond position It is preferable that one of the positions is at position O or m, and the other is at position O or p. If 2 is 4, then X 1 With respect to the bonding position, two are at the O position or the m position, and two are at the m position or It is preferable that the position be p.

[0017] Examples of compound (I) include the following compounds. TIFF0007920396000014.tif159168

[0018] TIFF0007920396000015.tif252168

[0019] TIFF0007920396000016.tif221168

[0020] TIFF0007920396000017.tif112153

[0021] In the compounds represented by formulas (I-1) to (I-64), the R of formula (I) 1 Equivalent to The methyl group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. Compounds can also be given as specific examples of compound (I). Among them, formula (I-1) ~ Equations (I-3), (I-5), (I-7), (I-8), (I-10) ~ Equation (I- 30) Compounds represented by formulas (I-42) to (I-50) are preferred.

[0022] <Method for producing compound (I)> In compound (I), X 1 However, equation (X 1 -1), formula (X 1 -3) or formula (X 1 -4) A compound whose group is represented by any of the following formulas (hereinafter sometimes referred to as compound (I1)) is a compound whose group is represented by any of the following formulas. After reacting the compound represented by (I1-a) with carbonyldiimidazole in a solvent, Furthermore, it can be obtained by reacting it with the compound represented by formula (Ib). TIFF0007920396000018.tif45161(In the formula, all signs have the same meaning as above. X 1A This is a single bond, -Ar 1 - Or -CO-O-Ar 1 -* represents Ar 1 * represents a 1,4-phenylene group. * represents a carbony (This represents the bonding site between the carbon atom of the group.)

[0023] Examples of solvents include tetrahydrofuran, chloroform, and acetonitrile. ru. The reaction temperature is typically between 0°C and 80°C, and the reaction time is typically between 0.5 hours and 24 hours. Examples of compounds represented by formula (I1-a) include compounds represented by the following formulas, and the city It can be easily obtained from the field. TIFF0007920396000019.tif36163

[0024] Examples of compounds represented by formula (Ib) include those represented by the following formulas, and are available on the market. It can be obtained more easily. TIFF0007920396000020.tif113164

[0025] In compound (I), X 1 However, equation (X 1 -2) or formula (X1 The base represented by -5) The compound (compound represented by formula (I2)) is a compound represented by formula (I2-a) and formula ( It is obtained by reacting the compound represented by Ib) with a base in a solvent. It is possible. TIFF0007920396000021.tif50152(In the formula, all signs have the same meaning as above. X 1B is, -Ar 1 - or -C OO-Ar 1 -* represents the bond site with the oxygen atom.

[0026] Examples of solvents include tetrahydrofuran, chloroform, and acetonitrile. ru. Examples of bases include potassium hydroxide. The reaction temperature is typically between 0°C and 80°C, and the reaction time is typically between 0.5 hours and 24 hours. Examples of compounds represented by formula (I2-a) include compounds represented by the following formulas, and the city It can be easily obtained from the field. TIFF0007920396000022.tif36156

[0027] In compound (I), X 1 However, equation (X 1 -6) or formula (X 1 The base represented by -7) The compound (represented by formula (I3)) is a compound represented by formula (I2-a) and a carbo After reacting with nildiimidazole in a solvent, the compound represented by formula (Ib) is further reacted. It can be obtained by reacting with it. TIFF0007920396000023.tif52157(In this formula, all signs have the same meaning as above. X 1B is, -Ar 1 - or -C OO-Ar 1-* represents the bond site with the oxygen atom.

[0028] Examples of solvents include tetrahydrofuran, chloroform, and acetonitrile. ru. The reaction temperature is typically between 0°C and 80°C, and the reaction time is typically between 0.5 hours and 24 hours.

[0029] In compound (I), L 1 However, the alkanediyl group has 1 to 4 carbon atoms and the group has 3 to 18 carbon atoms. A group formed by combining with an alicyclic hydrocarbon group (however, the -CH contained in the alkanediyl group) 2- may be replaced with -O- or -CO-, and is contained in the alicyclic hydrocarbon group -CH2- may be replaced by -O-, -S-, -SO2-, or -CO-. The compound in question is the compound represented by formula (I1) to formula (I3) when synthesizing formula (I1-a Replace the compound represented by ) or the compound represented by formula (I2-a) with the compound represented below. It can be manufactured by replacing it. TIFF0007920396000024.tif30150

[0030] 〔resin〕 The resin of the present invention has structural units derived from compound (I) (hereinafter referred to as "structural unit (I)") It is a resin containing (which may be referred to as "Resin (A)" below). Resin (A) This may be a homopolymer of structural unit (I), or a copolymer consisting only of structural unit (I). It may be a polymer, or a polymer containing one or more structural units other than structural unit (I). This is also acceptable. Other structural units besides structural unit (I) include acid-unstable groups other than structural unit (I). A structural unit (hereinafter sometimes referred to as "structural unit (a1)"), a structure having an acid-unstable group Structural units other than units that contain halogen atoms (hereinafter referred to as "structural units (a4)") In some cases, a structural unit that does not have an acid-unstable group (hereinafter referred to as "structural unit (s)") (There is a combination), a structural unit having a non-leaved hydrocarbon group (hereinafter referred to as "structural unit (a5)") Examples include (which include). Here, an acid-unstable group is one that has a leaving group and leaves when in contact with an acid. A group that undergoes elimination to form a hydrophilic group (e.g., a hydroxyl group or a carboxyl group). It tastes good. The content of structural unit (I) is usually 1 mol% or less relative to the total structural units in resin (A). The amount is above, preferably 2 mol% or more, and more preferably 3 mol% or more. Typically 90 mol% or less, preferably 80 mol% or less, and more preferably 50 mol%. It is less than %. Also, it is usually 1 to 90 mol%, preferably 1 to 80 mol%, and Preferably, it is 3 to 50 mol%.

[0031] <Structural unit (a1)> Structural unit (a1) is a monomer having an acid-unstable group (hereinafter referred to as "monomer (a1)"). It is derived from (in some cases). The acid-unstable group contained in resin (A) is the group represented by formula (1) (hereinafter also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF0007920396000025.tif1988[In formula (1), R a1 , R a2 and R a3 These are, independently, alkyl groups with 1 to 8 carbon atoms. C1-C2 group, C2-C8 alkenyl group, C3-C20 alicyclic hydrocarbon group, C6-C1 8 represents aromatic hydrocarbon groups or groups formed by combining them, or R a1 and R a2 they are connected to each other They then form a non-aromatic hydrocarbon ring with 3 to 20 carbon atoms, together with the carbon atoms to which they bond. . ma and na each independently represent 0 or 1, and at least one of ma and na This represents 1. * indicates a connection site. TIFF0007920396000026.tif2171[In formula (2), R a1’ and R a2’ Each of these is independently a hydrogen atom or a carbon atom with 1 to 1 carbon atoms. Represents two hydrocarbon groups, R a3’ R represents a hydrocarbon group with 1 to 20 carbon atoms. a2’ Reach biR a3’ They bond with each other, and together with the carbon atoms and X they bond to, they have 3 to 20 carbon atoms. A heterocycle is formed, and the hydrocarbon group and the -CH2- contained in the heterocycle are -O- or -S- It can be replaced with this. X represents either an oxygen atom or a sulfur atom. 'na' represents either 0 or 1. * indicates a connection site.

[0032] R a1 , R a2 and R a3 Examples of alkyl groups in this context include methyl group, ethyl group, and propyl group. Examples include the hydroxyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group. R a1 , R a2 and R a3 The alkenyl groups in this context include the ethenyl group and the propenyl group. isopropenyl group, butenyl group, isobutenyl group, tert-butenyl group, pentenyl Examples include the hexenyl group, heptenyl group, octenyl group, isooctenyl group, and nonenyl group. It is possible. R a1 , R a2 and R a3 In this context, the alicyclic hydrocarbon group is either monocyclic or polycyclic. This is also acceptable. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl group, cyclohexyl group, and cyclopentyl group. Examples include cycloalkyl groups such as chloroheptyl and cyclooctyl groups. Polycyclic and alicyclic groups. The hydrocarbon groups include decahydronaphthyl, adamantyl, norbornyl, and the following: Examples include the base (* indicates a binding site). a1 , R a2 and R a3 Alicyclic carbonization The number of carbon atoms in the hydrogen group is preferably 3 to 16. TIFF0007920396000027.tif10150R a1 , R a2 and R a3 Aromatic hydrocarbon groups in this context include phenyl groups and naphthyl groups. Examples of aryl groups include anthryl, biphenyl, and phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) Cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbol Alkylcycloalkyl groups such as ylethyl groups or cycloalkylalkyl groups), benzyl Aralkyl groups such as p-methylphenyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc., alicyclic hydrocarbon group Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) Examples include aryl-cycloalkyl groups such as phenylcyclohexyl groups. Preferably, ma is 0 and na is 1. R a1 and R a2-C(R a1 )(R a2 )(R a3 Examples of such rings include the following: The non-aromatic hydrocarbon ring is preferably carbon The numbers range from 3 to 12. * represents the bonding site with -O-. TIFF0007920396000028.tif30138

[0033] R a1’ , R a2’ and R a3’ Examples of hydrocarbon groups in this context include alkyl groups and alicyclic carbon groups. Examples include hydrogenated groups, aromatic hydrocarbon groups, and groups formed by combining these. It is possible. Alkyl and alicyclic hydrocarbon groups are R a1 , R a2 and R a3 Similar to the base mentioned above This is one example. Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) Cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbol Alkylcycloalkyl groups such as ylethyl groups or cycloalkylalkyl groups), benzyl Aralkyl groups such as p-methylphenyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc., alicyclic hydrocarbon group Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) Examples include aryl-cycloalkyl groups such as phenylcyclohexyl groups. R a2’ and R a3’ They bond with each other and together with the carbon atoms and X they bond to, complex When forming a ring, -C(R a1’ )(R a2’ )-XR a3’ The following rings are examples: * indicates a bonding site. TIFF0007920396000029.tif18130R a1’ and R a2’ Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0034] The following are examples of base (1): In equation (1), R a1 , R a2 and R a3 is an alkyl group, ma=0, and n A group where a=1. A tert-butoxycarbonyl group is preferred as this group. In equation (1), R a1 , R a2 However, together with the carbon atoms to which these bond, adamant Forms a chill group, R a3 A group that is an alkyl group, with ma=0 and na=1. In equation (1), R a1 and R a2 Each of them is an alkyl group independently, and R a3 Adama A methyl group with ma=0 and na=1. The following are specific examples of group (1). * indicates a bonding site. TIFF0007920396000030.tif154163

[0035] The following are specific examples of group (2). * indicates a bonding site. TIFF0007920396000031.tif55153

[0036] The monomer (a1) preferably has an acid-unstable group and an ethylenically unsaturated bond. Mer, more preferably a (meth)acrylic monomer having an acid-unstable group.

[0037] Among (meth)acrylic monomers having an acid-unstable group, preferably those having 5 to 20 carbon atoms. Examples include those having alicyclic hydrocarbon groups. A resin (A) having structural units derived from monomer (a1) is used in the resist composition. This allows for an improvement in the resolution of the resist pattern.

[0038] As a structural unit derived from a (meth)acrylic monomer having group (1), formula (a1- A structural unit represented by (0) (hereinafter sometimes referred to as structural unit (a1-0)), formula (a1 A structural unit represented by -1) (hereinafter sometimes referred to as structural unit (a1-1)) or formula ( The structural units represented by a1-2) (hereinafter sometimes referred to as structural units (a1-2)) are listed below. It can be made. Preferably, structural unit (a1-0), structural unit (a1-1) and structural unit (a It is at least one structural unit selected from the group consisting of 1-2). More preferably, At least one selected from the group consisting of building units (a1-1) and structural units (a1-2) These are structural units. They may be used individually or in combination of two or more types. TIFF0007920396000032.tif44143[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 - CO-O- represents a bond, k1 is an integer from 1 to 7, and * is the bonding site with -CO-. represent. R a01 , R a4 and R a5 These are, independently, a hydrogen atom, a halogen atom, or a halogen. This represents an alkyl group having 1 to 6 carbon atoms, which may contain atoms. R a02 , R a03 and R a04 These are, independently, alkyl groups with 1 to 8 carbon atoms and alkyl groups with 3 to 8 carbon atoms. 18 alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof It represents the base. R a6 and R a7 These are, independently, alkyl groups with 1 to 8 carbon atoms and axyl groups with 2 to 8 carbon atoms. Lukenyl group, alicyclic hydrocarbon group having 3 to 18 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms or This represents the group formed by combining these elements. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

[0039] R a01 , R a4 and R a5 This is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. It is a chill group. L a01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 -C OO- (where k01 is preferably an integer from 1 to 4, more preferably It is 1, more preferably an oxygen atom. R a02 , R a03 and R a04Alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and And as a group formed by combining these, the R of group (1) a1 , R a2 and R a3 Similar to the bases mentioned above. The basis is cited. R a6 and R a7 alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic carbon groups As for hydrogen groups and groups formed by combining them, R in formula (1) a1 , R a2 and R a3 The basis mentioned above and Similar groups can be cited. R a02 , R a03 , and R a04 The alkyl group in this case is preferably an alkyl group having 1 to 6 carbon atoms. It is a group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. ru. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, and further Preferably, it is an ethyl group, an isopropyl group, or a t-butyl group. R a6 and R a7 The alkenyl group in is preferably an alkenyl group having 2 to 6 carbon atoms. Yes, more preferably an ethenyl group, propenyl group, isopropenyl group or butenyl group. ru. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably The range is 5 to 12, and more preferably 5 to 10. R a02 , R a03 , R a04 , R a6and R a7 The number of carbon atoms in the aromatic hydrocarbon group is preferably The range is 6 to 12, and more precisely, 6 to 10. Groups that combine alkyl groups and alicyclic hydrocarbon groups are formed by combining these alkyl groups and alicyclic hydrocarbon groups. It is preferable that the total number of carbon atoms in the combined group is 18 or less. Groups formed by combining alkyl groups and aromatic hydrocarbon groups are composed of these alkyl groups and aromatic hydrocarbon groups. It is preferable that the total number of carbon atoms in the combined group is 18 or less. R a02 and R a03 Preferably, an alkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms. A hydrocarbon group, more preferably a methyl group, an ethyl group, a phenyl group, or a naphthyl group. ru. R a04 Preferably, an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. The group is a methyl group, more preferably an ethyl group, a cyclohexyl group, or an adamantyl group. be. R a6 and R a7 Each is independently preferably an alkyl group having 1 to 6 carbon atoms, 2-6 alkenyl groups or 6-12 aromatic hydrocarbon groups, more preferably Tyl group, ethyl group, isopropyl group, t-butyl group, ethenyl group, phenyl group or naphthyl group It is a group, and more preferably an ethyl group, isopropyl group, t-butyl group, ethenyl group or It is a phenyl group. m1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1 is preferably an integer between 0 and 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0040] Examples of structural units (a1-0) are given by equations (a1-0-1) to (a1-0-18). A structural unit represented by one of the following and R in the structural unit (a1-0) a01 This corresponds to A structure in which the til group is replaced by a hydrogen atom, a halogen atom, a haloalkyl group, or another alkyl group. The manufacturing units are listed, as in equations (a1-0-1) to (a1-0-10) and (a1-0-13). A structural unit represented by any of the formulas (a1-0-14) is preferred. TIFF0007920396000033.tif89161

[0041] As for the structural unit (a1-1), for example, as described in Japanese Patent Publication No. 2010-204646 Examples of structural units derived from monomers include those from formula (a1-1-1) to formula (a1 -1-7) Structural units represented by any of the above and R in structural units (a1-1) a4 in relation to The corresponding methyl group is replaced by a hydrogen atom, halogen atom, haloalkyl group, or other alkyl group. A divided structural unit is preferred, and can be represented by any of the formulas (a1-1-1) to (a1-1-4). A structural unit that can be made into a structural unit is preferable. TIFF0007920396000034.tif38168

[0042] The structural unit (a1-2) is any of the formulas (a1-2-1) to (a1-2-14). The structural unit represented by and the R in the structural unit (a1-2) a5 The methyl group corresponding to water Examples of structural units that are replaced by elementary atoms, halogen atoms, haloalkyl groups, or other alkyl groups include Equations (a1-2-2), (a1-2-5), (a1-2-6), and (a1- 2-10) A structural unit represented by any of the formulas (a1-2-14) is preferred. TIFF0007920396000035.tif67163

[0043] If resin (A) contains structural unit (a1-0), its content is the total structural unit of resin (A). The amount is usually 5 mol% or more relative to the position, preferably 10 mol% or more. Also, usually 8 It is 0 mol% or less, preferably 75 mol% or less, and more preferably 70 mol% or less. It is also typically 5-80 mol%, preferably 5-75 mol%, and more preferably It is either 10-70 mol% or 10-70 mol%. If resin (A) contains structural unit (a1-1) and / or structural unit (a1-2), The total content of these is usually 10 mol% or more relative to the total structural units of resin (A), and is preferred. It is more than 15 mol%, and more preferably more than 20 mol. Also, usually 90 mol The mol% is less than or equal to 10%, preferably 85 mol% or less, and more preferably 80 mol% or less. More preferably 75 mol% or less, and even more preferably 70 mol% or less. Furthermore, it is usually 10-90 mol%, preferably 15-85 mol%, and more preferably More preferably 20-80 mol%, more preferably 20-75 mol%, and even more Preferably, it is 20 to 70 mol%.

[0044] A structural unit having a base (2) in structural unit (a1) is represented by formula (a1-4). Examples of structural units (hereinafter sometimes referred to as "structural units (a1-4)") include the following. TIFF0007920396000036.tif4564[In formula (a1-4), R a32 This is a hydrogen atom, a halogen atom, or a carbon-1 atom which may have a halogen atom. Represents alkyl groups up to 6. R a33This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxyalkyl group having 2 to 12 carbon atoms Lucoxy group, C2-C4 alkylcarbonyl group, C2-C4 alkylcarbonyl This represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a30 is a single bond or * -X a31 -(A a32 -X a32 ) nc - represents -R a32 they combine This represents the bonding site with the carbon atom. A a32 This represents an alkanediyl group with 1 to 6 carbon atoms. X a31 and X a32 These represent -O-, -CO-O-, or -O-CO- independently. nc represents 0 or 1. la represents an integer from 0 to 4. If la is an integer greater than or equal to 2, Number R a33 They may be the same or different from each other. R a34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R a36 R represents a hydrocarbon group with 1 to 20 carbon atoms. a35 and R a36 they combine with each other and Together with the -CO- to which they bond, they form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the carbonized water The -CH2- contained in the elementary group and the divalent hydrocarbon group is replaced by -O- or -S- That's good too.

[0045] R a32 and R a33 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. These are some examples. R a32 C1-C6 alkyl groups that may have a halogen atom include: Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pe fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, Tyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples include pentyl groups, pentyl groups, hexyl groups, and perfluorohexyl groups. R a32 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable. R a33 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Examples include the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and may have a methyl group or an ethyl group. More preferably, a methyl group is even more preferred. R a33 The alkoxy groups in this context include methoxy, ethoxy, propoxy, and iso Propoxy group, butoxy group, sec-butoxy group, tert-butoxy group, pentyl oxy Examples include the hydroxyl group and the hexyloxy group. Alkoxy groups are alkoxy groups with 1 to 4 carbon atoms. Preferably, a methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. R a33 The alkoxyalkyl groups in this context are methoxymethyl group and ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples include methyl groups and tert-butoxymethyl groups. Alkoxyalkyl groups have a number of carbon atoms. 2 to 8 alkoxyalkyl groups are preferred, and methoxymethyl or ethoxyethyl groups are preferred. A methoxymethyl group is more preferable, and a methoxymethyl group is even more preferable. R a33 Examples of alkoxyalkoxy groups in this context include methoxymethoxy groups and methoxyethyl groups. Xy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isoprop Xymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy A cymethoxy group is one example. Alkoxyalkoxy groups are alkoxyal groups with 2 to 8 carbon atoms. A coxy group is preferred, and a methoxyethoxy group or an ethoxyethoxy group is more preferred. R a33 The alkylcarbonyl groups in this context include acetyl, propionyl, and butyric groups. Examples include lyl groups. Alkyl carbonyl groups are alkyl carbonyl groups having 2 to 3 carbon atoms. A is preferred, and an acetyl group is more preferred. R a33 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups and propionyl groups. Examples include the oxy group and the butyryloxy group. The alkylcarbonyloxy group has a number of carbon atoms. Two to three alkylcarbonyloxy groups are preferred, and acetyloxy groups are more preferred. R a33 This includes halogen atoms, hydroxyl groups, C1-C4 alkyl groups, and C1-C4 An alkoxy group or an alkoxyalkoxy group having 2 to 8 carbon atoms is preferred, along with a fluorine atom and iodine. Elementary atom, hydroxyl group, methyl group, methoxy group, ethoxy group, ethoxyethoxy group or ethoxyethoxy group A toxicmethoxy group is more preferred, along with a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, A methoxy group or an ethoxyethoxy group is even more preferred.

[0046] *-X a31 -(A a32 -X a32 ) nc - for example, *-O-, *-CO-O-, *-OC O-, *-CO-OA a32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO-, These include *-CO-O- and *-CO-OA. a32 -CO-O- or *- OA a32 -CO-O- is preferred.

[0047] A a32 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1 ,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methyl Propane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples include 4-diyl groups and 2-methylbutane-1,4-diyl groups. A a32 It is preferable that this is a methylene group or an ethylene group.

[0048] A a30 These are single bonds, *-CO-O- or *-CO-OA a32 Being a CO-O Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. More preferably, the bond is a single bond or even more preferably *-CO-O-.

[0049] la is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. R a34 , R a35 and R a36 Examples of hydrocarbon groups in this context include alkyl groups and alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups and groups formed by combining these. Alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples include syl groups, heptyl groups, and octyl groups. The alicyclic hydrocarbon group may be monocyclic or polycyclic. Monocyclic alicyclic hydrocarbon group Examples include cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups. Examples of cycloalkyl groups include decahydrona. Phthyl groups, adamantyl groups, norbornyl groups, and the following groups (* indicates a bonding site), etc. It can be listed. TIFF0007920396000037.tif10151 Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. (For example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group) Cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbol Alkylcycloalkyl groups such as ylethyl groups or cycloalkylalkyl groups), benzyl Aralkyl groups such as p-methylphenyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl group, p -tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2, 6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc., alicyclic hydrocarbon group Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group) Examples include aryl-cycloalkyl groups such as phenylcyclohexyl groups, etc. , R a36 Examples include alkyl groups having 1 to 18 carbon atoms, and alicyclic hydrocarbon groups having 3 to 18 carbon atoms. Aromatic hydrocarbon groups having 6 to 18 carbon atoms, or groups formed by combining these. It can be listed.

[0050] R a34 Preferably, it is a hydrogen atom. R a35 Preferably, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a C3 to 12 carbon atom. It is an alicyclic hydrocarbon group, more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, or a C3 to 18 carbon atom Alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof The group formed is more preferably an alkyl group having 1 to 18 carbon atoms, or a group having 3 to 1 carbon atoms. It is an 8-cell alicyclic hydrocarbon group or an aralkyl group having 7 to 18 carbon atoms. a36 Alki in The rico group and alicyclic hydrocarbon group are preferably unsubstituted. a36 Aromatic carbonization in The hydrogen group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms. -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36 is an acid (for example) It is eliminated upon contact with p-toluenesulfonic acid, forming a hydroxyl group. -OC(R a34 )(R a35 )-OR a36 It bonds to the ortho- or para-position of the benzene ring. It is preferable that the bond is formed at the p-position, and more preferably that it is formed at the p-position.

[0051] As for structural units (a1-4), for example, see Japanese Patent Publication No. 2010-204646. Examples include monomer-derived structural units. Preferably, formulas (a1-4-1) to (a1 -4-24) The structural units and R in the structural unit (a1-4) a32 to A structure in which the corresponding hydrogen atom is replaced by a halogen atom, a haloalkyl group, or an alkyl group. The units are listed, more preferably formulas (a1-4-1) to (a1-4-5), formula (a1 The structural units represented by equations (a1-4-10), (a1-4-13), and (a1-4-14) respectively The rank can be listed. TIFF0007920396000038.tif129162

[0052] If resin (A) contains structural units (a1-4), the content of these units is the total structural content of resin (A). The percentage of the total units is preferably 3 to 80 mol%, and preferably 5 to 75 mol%. More preferably, 7 to 70 mol%, and even more preferably 7 to 65 mol%. It is even more preferable that the amount is 10 to 60 mol%, and is particularly preferable.

[0053] As structural units derived from (meth)acrylic monomers having group (2), formula (a1 Structural units represented by -5) (hereinafter sometimes referred to as "structural units (a1-5)") are also mentioned. It can be done. TIFF0007920396000039.tif4558 formula (a1-5), R a8 This may have a halogen atom, or it may have a C1-C6 alkyl group, a hydrogen atom, or a halogen atom. This represents a chlorogenic atom. Z a1 This is a single bond or *-(CH2)h3 -CO-L 54 - represents one of 1-4. Represents an integer of L, where * is L 51 This represents the connection point. L 51 , L 52 , L 53 and L 54 These represent either -O- or -S- independently. s1 represents an integer between 1 and 3. s1' represents an integer between 0 and 3.

[0054] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of C1-C6 alkyl groups that may have a halogen atom include methyl and ethyl groups. Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluorine Examples include methyl and trifluoromethyl groups. In equation (a1-5), R a8 This is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 A single bond or *-CH2-CO-O- is preferred.

[0055] Examples of structural units (a1-5) are described in Japanese Patent Publication No. 2010-61117. Examples of monomer-derived structural units include those from formula (a1-5-1) to formula (a1-5- 4) The structural units represented by formula (a1-5-1) or formula (a1-5-2 A structural unit represented by ) is more preferable. TIFF0007920396000040.tif33133

[0056] If resin (A) contains structural units (a1-5), the percentage of these units is the total structural content of resin (A). The amount is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and 5 to 40 mol% relative to the unit. A % of 10% is more preferable, and 5 to 30 mol% is even more preferable.

[0057] In addition, the following structural units (a1) can also be listed. TIFF0007920396000041.tif31162

[0058] When resin (A) contains structural units such as (a1-3-1) to (a1-3-7) above The content is preferably 10 to 95 mol% relative to the total structural units of resin (A), and 15 ~90 mol% is more preferred, 20~85 mol% is even more preferred, and 20~70 mol% is More preferably, 20 to 60 mol% is particularly preferred.

[0059] In addition, the following structural units (a1) can also be listed. TIFF0007920396000042.tif5195 When resin (A) contains structural units such as (a1-6-1) to (a1-6-3) above. The content is preferably 10 to 60 mol% relative to the total structural units of resin (A), and 15 ~55 mol% is more preferred, 20~50 mol% is even more preferred, and 20~45 mol% is More preferably, 20 to 40 mol% is particularly preferred.

[0060] <Structural unit (s)> A structural unit (s) is a monomer that does not have an acid-unstable group (hereinafter referred to as "monomer (s)"). It is derived from (there is a combination). The monomer that derives the structural unit (s) is an acid-resistant monomer known in the field of resists. Monomers without a stable group can be used. The structural unit (s) preferably has a hydroxyl group or a lactone ring. A structural unit having a xyl group and not having an acid-unstable group (hereinafter referred to as "structural unit (a2)") A structural unit having a lactone ring and / or not having an acid-unstable group (hereinafter referred to as "structural unit") If a resin containing a "production unit (a3)" is used in the resist composition of the present invention, This improves the resolution of the resist pattern and its adhesion to the substrate.

[0061] <Structural Unit (a2)> The hydroxyl group in structural unit (a2) can be an alcoholic hydroxyl group or a phenolic group. A hydroxyl group may also be used. When manufacturing a resist pattern from the resist composition of the present invention, KrF is used as the exposure light source. High-energy beams such as excimer lasers (248 nm), electron beams, or EUV (ultra-ultraviolet light) are used. If present, the structural unit (a2) is a structural unit having a phenolic hydroxyl group ( a2) is preferred, and it is even more preferable to use the structural unit (a2-A) described later. When using an ArF excimer laser (193 nm), the structural unit (a2) is A A structural unit (a2) having a hydroxyl group is preferred, and the structural unit (a2) described later -1) is more preferable. The structural unit (a2) contains one type alone. It is acceptable to include two or more types.

[0062] Structural units having a phenolic hydroxyl group in structural unit (a2) include those of formula (a Examples of structural units represented by 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") include It is possible. TIFF0007920396000043.tif4753[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents the alkyl group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxyalkyl group having 2 to 12 carbon atoms Lucoxy group, C2-C4 alkylcarbonyl group, C2-C4 alkylcarbonyl This represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 -(A a52 -X a52 ) nb - represents -R a50 they combine This represents the bonding site with the carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, Number R a51 They may be the same or different from each other.

[0063] R a50 and R a51 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. These are some examples. R a50 C1-C6 alkyl groups that may have a halogen atom include: Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pe fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, Tyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples include pentyl groups, pentyl groups, hexyl groups, and perfluorohexyl groups. R a50 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable. R a51 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Examples include the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and may have a methyl group or an ethyl group. More preferably, a methyl group is even more preferred. R a51 The alkoxy groups in this context include methoxy, ethoxy, propoxy, and iso Examples include propoxy groups, butoxy groups, sec-butoxy groups, and tert-butoxy groups. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and is either a methoxy group or an ethoxy group. More preferably, a methoxy group is even more preferred. R a51 The alkoxyalkyl groups in this context are methoxymethyl group and ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples include methyl groups and tert-butoxymethyl groups. Alkoxyalkyl groups have a number of carbon atoms. 2 to 8 alkoxyalkyl groups are preferred, and methoxymethyl or ethoxyethyl groups are preferred. A methoxymethyl group is more preferable, and a methoxymethyl group is even more preferable. R a51 Examples of alkoxyalkoxy groups in this context include methoxymethoxy groups and methoxyethyl groups. Xy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isoprop Xymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy A cymethoxy group is one example. Alkoxyalkoxy groups are alkoxyal groups with 2 to 8 carbon atoms. A coxy group is preferred, and a methoxyethoxy group or an ethoxyethoxy group is more preferred. R a51 The alkylcarbonyl groups in this context include acetyl, propionyl, and butyric groups. Examples include lyl groups. Alkyl carbonyl groups are alkyl carbonyl groups having 2 to 3 carbon atoms. A is preferred, and an acetyl group is more preferred. R a51 Examples of alkylcarbonyloxy groups in this context include acetyloxy groups and propionyl groups. Examples include the oxy group and the butyryloxy group. The alkylcarbonyloxy group has a number of carbon atoms. Two to three alkylcarbonyloxy groups are preferred, and acetyloxy groups are more preferred. R a51 This includes halogen atoms, hydroxyl groups, C1-C4 alkyl groups, and C1-C4 An alkoxy group or an alkoxyalkoxy group having 2 to 8 carbon atoms is preferred, along with a fluorine atom and iodine. Elementary atom, hydroxyl group, methyl group, methoxy group, ethoxy group, ethoxyethoxy group or ethoxyethoxy group A toxicmethoxy group is more preferred, along with a fluorine atom, an iodine atom, a hydroxyl group, a methyl group, A methoxy group or an ethoxyethoxy group is even more preferred.

[0064] *-X a51 -(A a52 -X a52 ) nb - for example, *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, These include *-CO-O- and *-CO-OA. a52 -CO-O- or *- OA a52 -CO-O- is preferred.

[0065] A a52 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1 ,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methyl Propane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples include 4-diyl groups and 2-methylbutane-1,4-diyl groups. A a52 It is preferable that this is a methylene group or an ethylene group.

[0066] A a50 These are single bonds, *-CO-O- or *-CO-OA a52 Being a CO-O Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. More preferably, the bond is a single bond or even more preferably *-CO-O-.

[0067] mb is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. The hydroxyl group is preferably bonded to the ortho- or para-position of the benzene ring, and at the para-position It is more preferable for them to combine.

[0068] As for the structural unit (a2-A), see Japanese Patent Publication No. 2010-204634, Japanese Patent Publication No. 2012- Examples include monomer-derived structural units described in Publication No. 12577.

[0069] The structural unit (a2-A) is represented by equations (a2-2-1) to (a2-2-24). In the structural units and structural units represented by formulas (a2-2-1) to (a2-2-24) R in structural unit (a2-A) a50 The methyl group corresponding to a hydrogen atom, halogen atom, Examples include structural units that are replaced by a γ-alkyl group or other alkyl groups. Structural unit (a2 -A) is a structural unit represented by formula (a2-2-1), and a structure represented by formula (a2-2-3). Units, structural units represented by formula (a2-2-6), structural units represented by formula (a2-2-8) and structural units represented by formulas (a2-2-12) to (a2-2-14), as well as formula (a2- 2-1) Structural units represented by formula (a2-2-3), Structural units represented by formula (a2-2- 6) Structural units represented by formula (a2-2-8) and formula (a2-2-1 2) In the structural unit represented by formula (a2-2-14), in the structural unit (a2-A) R a50 Preferably, the structural unit is one in which the corresponding methyl group is replaced by a hydrogen atom. Structural units represented by formula (a2-2-3), structural units represented by formula (a2-2-8), formula ( a2-2-12) ~ Structural units represented by formula (a2-2-14) and formula (a2-2-3) The structural units represented by or the structural units represented by formula (a2-2-8), formula (a2-2-12) ~ In the structural unit represented by formula (a2-2-14), R in structural unit (a2-A) a 50It is more preferable that the corresponding methyl group is replaced by a hydrogen atom in the structural unit. In the structural units represented by formula (a2-2-8) and the structural units represented by formula (a2-2-8) And, in the structural unit (a2-A) R a50 The corresponding methyl group is replaced by a hydrogen atom. It is even more preferable that the structural units are such that they are. TIFF0007920396000044.tif79168

[0070] Content of structural unit (a2-A) when structural unit (a2-A) is present in resin (A) The amount of this component is preferably 5 mol% or more, and more preferably 10 mol% or less, relative to the total structural units. It is above, more preferably 15 mol% or more, and even more preferably 20 mol% or less. The above. Furthermore, it is preferably 80 mol% or less, and more preferably 70 mol% or less. Furthermore, it is more preferably 65 mol% or less. Also, it is preferably 5 to 80 mol%, More preferably 10 to 70 mol%, and even more preferably 15 to 65 mol%, More preferably, the percentage is 20 to 65 mol%. Structural unit (a2-A) is polymerized, for example, using structural unit (a1-4), and then p-Tol It can be incorporated into resin (A) by treating it with an acid such as ene sulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0071] Structural units having an alcoholic hydroxyl group in structural unit (a2) include those with the formula ( The structural unit represented by a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") It can be listed. TIFF0007920396000045.tif4461 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 -CO-O- represents, k2 represents an integer between 1 and 7. * represents a connection site with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 Each of these independently represents a hydrogen atom, a methyl group, or a hydroxyl group. o1 represents an integer between 0 and 10.

[0072] In equation (a2-1), L a3 Preferably, -O-, -O-(CH2) f1 -CO-O- (where f1 represents any integer from 1 to 4), and more preferably -O-. R a14 The group is preferably a methyl group. R a15 Preferably, it is a hydrogen atom. R a16 This is preferably a hydrogen atom or a hydroxyl group. o1 is preferably an integer between 0 and 3, more preferably 0 or 1.

[0073] As for the structural unit (a2-1), for example, see Japanese Patent Publication No. 2010-204646. Examples of structural units derived from monomers are given by equations (a2-1-1) to (a2-1-6). A structural unit represented by any of the following formulas is preferred, from formula (a2-1-1) to formula (a2-1-4) A structural unit represented by either formula (a2-1-1) or formula (a2-1- The structural unit represented in 3) is even more preferable. TIFF0007920396000046.tif50139

[0074] If resin (A) contains structural units (a2-1), the content of these units is the total structural unit content of resin (A). It is usually 1 mol% or more relative to the position. Also, it is usually 45 mol% or less, and preferably 4 It is 0 mol% or less, more preferably 35 mol% or less, and even more preferably 20 mol It is less than or equal to % and more preferably less than or equal to 10 mol%. Also, typically 1 to 45 mol% The amount is preferably 1 to 40 mol%, more preferably 1 to 35 mol%, and further Preferably, the amount is 1 to 20 mol%, and more preferably 1 to 10 mol%.

[0075] <Structural unit (a3)> The lactone rings of structural unit (a3) ​​are a β-propiolactone ring and a γ-butyrolactone ring. It can be a monocyclic ring such as a δ-valerolactone ring, and the contraction of a monocyclic lactone ring with other rings. A ring compound is also acceptable. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or γ - A bridged ring containing a butyrolactone ring structure (e.g., a structural unit represented by the following formula (a3-2)) These are some examples.

[0076] The structural unit (a3) ​​is preferably formula (a3-1), formula (a3-2), formula (a3-3) Alternatively, it is a structural unit represented by formula (a3-4). These may be contained individually. It may contain two or more types. TIFF0007920396000047.tif48155[In formulas (a3-1), (a3-2), (a3-3), and (a3-4), L a4 , L a5 and L a6 These are, independently, -O- or *-O-(CH2) k3 -C This represents a base represented by OO-(where k3 is an integer from 1 to 7). L a7 is -O-, *-OLa8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- represents vinegar. L a8 and L a9 Each of these independently represents an alkanediyl group with 1 to 6 carbon atoms. * indicates a bond site with a carbonyl group. R a18 , R a19 and R a20 Each of these independently represents either a hydrogen atom or a methyl group. R a24 This is a hydrogen atom, a halogen atom, or a C1-C2 atom which may have a halogen atom. This represents an alkyl group of 6. X a3 represents -CH2- or an oxygen atom. R a21 This represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. R a22 , R a23 and R a25 Each of these independently comprises a carboxyl group, a cyano group, or a carbon Represents aliphatic hydrocarbon groups with prime numbers 1 through 4. p1 represents an integer between 0 and 5. q1 represents an integer between 0 and 3. r1 represents an integer between 0 and 3. w1 represents an integer between 0 and 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 They may be the same or different from each other.

[0077] R a21 , R a22 , R a23 and Ra25 As for aliphatic hydrocarbon groups in this context, methyl ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and ter Examples include alkyl groups such as t-butyl groups. R a24 The halogen atoms in this include fluorine, chlorine, bromine, and iodine. Atoms are one example. R a24 The alkyl groups in this context include methyl, ethyl, propyl, and isopropyl groups. butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Examples include alkyl groups having 1 to 4 carbon atoms, and more preferably methyl groups. Alternatively, an ethyl group may be used. R a24 Examples of alkyl groups having a halogen atom include the trifluoromethyl group. Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perf Perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Lufluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl Examples include the 14-3 group and the triiodomethyl group.

[0078] L a8 and L a9 Examples of alkanediyl groups in this context include methylene groups, ethylene groups, and pro groups. Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, tan-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen Examples include tan-1,4-diyl groups and 2-methylbutane-1,4-diyl groups.

[0079] In equations (a3-1) to (a3-3), L a4 ~L a6 Each is independently preferred Alternatively, -O- or *-O-(CH2) k3 In -CO-O-, k3 is one of 1 to 4. The base is an integer, more preferably -O- and *-O-CH2-CO-O-, even more preferably It is an oxygen atom. R a18 ~R a21 The group is preferably a methyl group. R a22 and R a23 Each of these is independently preferably a carboxyl group, a cyano group, or a melanin group. It is a chill group. p1, q1, and r1 are each independently, preferably integers between 0 and 2. More preferably, it is 0 or 1.

[0080] In equation (a3-4), R a24 Preferably, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is a group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a group of the same type. It is either a hydrogen atom or a methyl group. R a25 The group is preferably a carboxyl group, a cyano group, or a methyl group. L a7 Preferably -O- or *-OL a8 -CO-O- and, far It is -O-, -O-CH2-CO-O-, or -O-C2H4-CO-O-. w1 is preferably an integer between 0 and 2, and more preferably 0 or 1. In particular, formula (a3-4)' is preferred over formula (a3-4). TIFF0007920396000048.tif3848(in the formula, R a24 , L a7 (This expresses the same meaning as above.)

[0081] The structural unit (a3) ​​is the monomer described in Japanese Patent Publication No. 2010-204646. , monomers described in Japanese Patent Publication No. 2000-122294, Japanese Patent Publication No. 2012-41274 Examples of structural units derived from monomers described in the publication are listed below. Structural unit (a3) ​​is , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , equation (a3-3-1), equation (a3-3-2), and equation (a3-4-1) ~ equation (a3-4-1 2) A structural unit represented by any of the above, and in the said structural unit, formula (a3-1) to formula ( R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to water Structural units that are replaced by elementary atoms are preferred.

[0082] TIFF0007920396000049.tif116165

[0083] If resin (A) contains structural units (a3), the total content of these units is the total structural unit content of resin (A). The amount is usually 1 mol% or more, preferably 3 mol% or more, and more preferably 1 mol% or more relative to the position. It is 5 mol% or more. Also, it is usually 70 mol% or less, preferably 65 mol% or less. More preferably, it is 60 mol% or less. Also, it is usually 1 to 70 mol%, and preferably The concentration is 3-65 mol%, and more preferably 5-60 mol%. Also, structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structure The content of each unit (a3-4) is preferably, relative to the total structural units of resin (A). It is 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or less. The above. Furthermore, it is preferably 60 mol% or less, and more preferably 50 mol% or less. Furthermore, 1 to 60 mol% is preferred, 3 to 50 mol% is more preferred, and 5 to 50 mol% is preferred. That is even more preferable.

[0084] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF0007920396000050.tif2962[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 This represents a saturated hydrocarbon group having a halogen atom with 1 to 24 carbon atoms, and the saturated hydrocarbon water The -CH2- group in the element may be replaced by -O- or -CO-. R 42 The saturated hydrocarbon groups represented by these terms include chain-type saturated hydrocarbon groups and monocyclic or polycyclic alicyclic saturated hydrocarbon groups. Examples include hydrocarbon groups, and groups formed by combining these.

[0085] Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, and pentyl groups. Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, Examples include xadecyl groups, heptadecyl groups, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include cyclopentyl groups and cyclohexyl groups. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic lipids such as adamantyl groups, norbornyl groups, and the following groups (* indicates the binding site). Examples include cyclic saturated hydrocarbon groups. TIFF0007920396000051.tif10146 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic saturated hydrocarbon groups include -Alkanediyl group-alicyclic saturated hydrocarbon group, -Alkanediyl group-alkyl Examples include AL groups, -alkanediyl groups, -alicyclic saturated hydrocarbon groups, -alkyl groups, etc.

[0086] The structural unit (a4) is the structural unit represented by formula (a4-0) and the structural unit represented by formula (a4-1). Examples include structural units and structural units represented by formula (a4-4). TIFF0007920396000052.tif4551[In formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L 4a This represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3a This is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. This represents a luorocycloalkanediyl group. R 64 This represents a hydrogen atom or a fluorine atom.

[0087] L 4a The alkanediyl groups in this include methylene group, ethylene group, propane-1, Linear alkanediyl groups such as 3-diyl groups and butane-1,4-diyl groups, ethane-1,1 -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylprop Branched alkanes such as pan-1,3-diyl groups and 2-methylpropane-1,2-diyl groups A diyl group is one example.

[0088] L 3a In this context, perfluoroalkanediyl groups include difluoromethylene groups and per Fluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane- 1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane- 2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2, 2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5 -diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3 -diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2 -diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4 -diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8 -diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3 Examples include diyl groups and perfluorooctane-4,4-diyl groups. L 3a As for the perfluorocycloalkanediyl group in this context, perfluorocyclo xandiyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl Examples include yl groups and perfluoroadamantanediyl groups.

[0089] L 4a The is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond. The bond is a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably Alternatively, it is a perfluoroalkanediyl group with 1 to 3 carbon atoms.

[0090] The structural units (a4-0) include the structural units shown below and the structural units within the following structural units ( a4-0) R 54 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007920396000053.tif96166

[0091] TIFF0007920396000054.tif4866[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 This represents a saturated hydrocarbon group having 1 to 20 carbon atoms, which may have substituents. The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. A a41 This is an alkanediyl group having 1 to 6 carbon atoms, which may have substituents, or a compound of formula (ag 1) represents the base. However, A a41 and R a42 At least one of them is a substitution It has a halogen atom (preferably a fluorine atom) as a base. TIFF0007920396000055.tif1487 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44 Each of these is independently a divalent carbon atom having 1 to 5 carbon atoms, which may have substituents. This represents a saturated hydrocarbon group. A a43 This is a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, which may have single bonds or substituents. It represents. X a41 and X a42 These are, independently, -O-, -CO-, -CO-O-, or -O-CO - represents However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates a binding site, and the * on the right is -O-CO-R a42 This is the junction site.

[0092] R a42 The saturated hydrocarbon groups in this context include chain-type saturated hydrocarbon groups and monocyclic or polycyclic alicyclic groups. Examples include saturated hydrocarbon groups and groups formed by combining them. ru.

[0093] Examples of chain-type saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, and pentyl groups. Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, Examples include xadecyl groups, heptadecyl groups, and octadecyl groups. Examples of monocyclic or polycyclic alicyclic saturated hydrocarbon groups include cyclopentyl groups and cyclohexyl groups. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic lipids such as adamantyl groups, norbornyl groups, and the following groups (* indicates the binding site). Examples include cyclic saturated hydrocarbon groups. TIFF0007920396000056.tif10160 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic saturated hydrocarbon groups include -Alkanediyl group-alicyclic saturated hydrocarbon group, -Alkanediyl group-alkyl Examples include AL groups, -alkanediyl groups, -alicyclic saturated hydrocarbon groups, -alkyl groups, etc.

[0094] R a42 The substituents it possesses consist of halogen atoms and groups represented by formula (a-g3). At least one selected from the group is mentioned. Examples of halogen atoms include fluorine atoms and salts. Examples include elementary atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. TIFF0007920396000057.tif855[In formula (a-g3), X a43* represents an oxygen atom, a carbonyl group, *-O-CO-, or *-CO-O-. A a45 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. * is R a42 This represents the connection point with [the other element]. However, R a42 -X a43 -A a45 In R a42 If it does not have a halogen atom, then A a4 5 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms and containing at least one halogen atom.

[0095] A a45 The saturated hydrocarbon groups in this context include methyl, ethyl, propyl, and butyl groups. pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentade Alkyl groups such as syl, hexadecyl, heptadecyl, and octadecyl groups; Monocyclic groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups Alicyclic hydrocarbon groups; as well as decahydronaphthyl groups, adamantyl groups, norbornyl groups and Examples include polycyclic alicyclic hydrocarbon groups such as the following groups (* indicates a bonding site). TIFF0007920396000058.tif10160 The groups formed by the combination include one or more alkyl groups or one or more alkanes. Examples of groups formed by combining an yl group with one or more alicyclic hydrocarbon groups include -Alkanediyl group-alicyclic hydrocarbon group, -Alkanediyl group-alkyl group, -Al Examples include candiyl group-alicyclic hydrocarbon group-alkyl group, etc.

[0096] R a42 The halogen atom is preferably a saturated hydrocarbon group which may have a halogen atom. Alkyl groups having and / or saturated hydrocarbon groups having a group represented by formula (a-g3) are suitable. It is preferable. R a42 If it is a saturated hydrocarbon group having a halogen atom, it preferably has a fluorine atom. A saturated hydrocarbon group, more preferably a perfluoroalkyl group or perfluoroalkyl group. It is a chloroalkyl group, and more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. The perfluoromethyl group, perfluoroethyl group, and perfluoropropyl group are examples of perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples include oroheptyl groups and perfluorooctyl groups. Examples of the 'l' group include the perfluorocyclohexyl group. R a42 However, if it is a saturated hydrocarbon group having a group represented by formula (a-g3), then formula (a- Including the number of carbon atoms in the group represented by g3), R a42 The total number of carbon atoms should preferably be 15 or less. Furthermore, 12 or less is more preferable. When the group represented by formula (a-g3) is used as a substituent, The number should preferably be one.

[0097] R a42 If is a saturated hydrocarbon group having a group represented by formula (a-g3), then R a42 is, More preferably, the group is represented by the formula (a-g2). TIFF0007920396000059.tif871[In formula (a-g2), A a46 This comprises a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, which may have a halogen atom. represent. X a44This represents **-O-CO- or **-CO-O- (where ** is A a46 The connection site represent.). A a47 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a halogen atom. However, A a46 , A a47 and X a44 The total number of carbon atoms is 18 or less, A a46 and A a47 of Of these, at least one has at least one halogen atom. * indicates a bonding site with a carbonyl group.

[0098] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3. A a47 The number of carbon atoms in the saturated hydrocarbon group is preferably 4 to 15, more preferably 5 to 12, A a 47 A cyclohexyl group or an adamantyl group is more preferable.

[0099] The preferred structure of the group represented by formula (a-g2) is as follows (* represents a carbonyl group) (This is the junction site.) TIFF0007920396000060.tif14160

[0100] A a41 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 Linear alkanediyl groups such as ,6-diyl groups; propane-1,2-diyl groups, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- Examples include branched alkanediyl groups such as diyl groups and 2-methylbutane-1,4-diyl groups. ru. A a41 The substituents in the alkanediyl group represented by are a hydroxyl group and a carbon-1- Examples include 6 alkoxy groups. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a carbon number The group is an alkanediyl group of type 2 to 4, and more preferably an ethylene group.

[0101] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Divalent saturated carbonized water The elemental groups include linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated hydrocarbon groups. , and formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group. Examples include divalent saturated hydrocarbon groups. Specifically, methylene groups, ethylene groups, and p Ropan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2- Examples include methylpropane-1,2-diyl groups. A a42 , A a43 and A a44 The substituents of the divalent saturated hydrocarbon group represented by are hydroxyl groups. Examples include alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0102] In the group represented by formula (a-g1), X a42 -O-, -CO-, -CO-O- or The following are examples of groups that are -O-CO-. In the following examples, * and ** represents a bonding site, and ** is -O-CO-R a42 This is the junction site. TIFF0007920396000061.tif47140

[0103] The structural units represented by formula (a4-1) are the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to this is placed on a hydrogen atom. Examples of replaced structural units include: TIFF0007920396000062.tif99145

[0104] TIFF0007920396000063.tif132150

[0105] The structural units represented by formula (a4-1) are the structural units represented by formula (a4-2) and Examples of structural units are given by formula (a4-3). TIFF0007920396000064.tif4356[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 This represents an alkanediyl group having 1 to 6 carbon atoms, and the -C contained in the alkanediyl group H2- may be replaced by -O- or -CO-. R f6 This represents a saturated hydrocarbon group having 1 to 20 fluorine atoms. However, L 44 and R f6 The upper limit for the total number of carbon atoms is 21.

[0106] L 44 The alkanediyl group with 1 to 6 carbon atoms is A a41 Similar to the examples given above, It can be done. R f6 The saturated hydrocarbon group is R 42 Similar to the examples given earlier, the same types of bases can be cited. L 44 In this context, an alkanediyl group having 2 to 4 carbon atoms is preferred. An ethylene group is more preferable.

[0107] Examples of structural units represented by formula (a4-2) include formulas (a4-1-1) to (a4 The structural units represented in (a4-2) are as follows. R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It can be cited as a structural unit.

[0108] TIFF0007920396000065.tif5671[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 This represents an alkanediyl group with 1 to 6 carbon atoms. A f13 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, which may contain a fluorine atom. vinegar. X f12 This represents *-O-CO- or *-CO-O- (* is A f13 This represents the connection point. ). A f14 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a fluorine atom. However, A f13 and A f14 At least one of them has a fluorine atom, L 5 , A f13 and A f14 The upper limit for the total number of carbon atoms is 20.

[0109] L 5 The alkanediyl group in A is a41 The same as the example with the alkanediyl group. The basis for this can be cited.

[0110] A f13 A preferred divalent saturated hydrocarbon group which may have a fluorine atom is A divalent chain-type saturated hydrocarbon group which may have a fluorine atom and a fluorine atom A divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanedi It is a lu group. Examples of divalent chain-type saturated hydrocarbon groups that may contain a fluorine atom include methylene groups and ethyl acetate groups. Alkanediyl groups such as len group, propanediyl group, butanediyl group and pentanediyl group ; Difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, Perfluoroalkanes such as the fluorobutanediyl group and the perfluoropentanediyl group. Examples include diyl groups. Divalent alicyclic saturated hydrocarbon groups, which may contain a fluorine atom, are monocyclic and polycyclic. A slight misalignment is also acceptable. Examples of monocyclic groups include cyclohexanediyl groups and perfluorocyclodiyl groups. Examples include the xandiyl group. Polycyclic groups include the adamantanediyl group and norbol. Examples include the nandiyl group and the perfluoroadamantanediyl group.

[0111] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are R a42 in Similar groups to those exemplified can be cited. Among them, the trifluoromethyl group and the difluoromethyl group are particularly noteworthy. Tyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-Pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-Octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and per Fluoroctyl groups and other alkyl fluorides, cyclopropylmethyl groups, cyclopropyl groups Cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group Xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbol Nyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl A methyl group is preferred.

[0112] In equation (a4-3), L 5 An ethylene group is preferred. A f13 The divalent saturated hydrocarbon group is a divalent chain-type saturated hydrocarbon group having 1 to 6 carbon atoms and carbon A group containing a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms is preferred, and a divalent chain having 2 to 3 carbon atoms is preferred. A saturated hydrocarbon group is even more preferred. A f14 The saturated hydrocarbon group is a chain-type saturated hydrocarbon group having 3 to 12 carbon atoms and a group having 3 to 12 carbon atoms. Groups containing alicyclic saturated hydrocarbon groups are preferred, and chain-type saturated hydrocarbon groups having 3 to 10 carbon atoms and Groups containing alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms are even more preferred. Among them, A f14 teeth Preferably, the group contains an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably, Cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and It is a damantyl group.

[0113] Examples of structural units represented by equation (a4-3) include equation (a4-1'-1) ~ equation (a The structural units represented in 4-1'-11) are listed below. Keru R f7The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also shown in formula (a4-3). It can be cited as a structural unit.

[0114] Another example of a structural unit (a4) is the structural unit represented by formula (a4-4). TIFF0007920396000066.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is, -(CH2) j1 -,-(CH2) j2 -O-(CH2) j3 - or - (CH2) j4 - CO-O-(CH2) j5 - represents j1 through j5 each independently represent an integer from 1 to 6. R f22 This represents a saturated hydrocarbon group with 1 to 10 carbon atoms containing a fluorine atom.

[0115] R f22 The saturated hydrocarbon group is R a42 Examples include saturated hydrocarbon groups similar to those represented by the symbol. R f22 This refers to an alkyl group having 1 to 10 carbon atoms that contains a fluorine atom, or a carbon atom containing a fluorine atom. A cycloaliphatic saturated hydrocarbon group having 1 to 10 prime atoms is preferred, and a group having 1 to 10 carbon atoms and a fluorine atom is preferred. Alkyl alkyl groups are more preferred, and C1-C6 alkyl groups having a fluorine atom are even more preferred. It's nice.

[0116] In equation (a4-4), A f21 As for, -(CH2) j1 - is preferred, ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0117] Examples of structural units represented by formula (a4-4) include the following structural units and the following formula In the structural unit shown, R in structural unit (a4-4) f21 The methyl group corresponding to One example is a structural unit in which a hydrogen atom has been replaced. TIFF0007920396000067.tif86160

[0118] If resin (A) has structural units (a4), the content of these units is the total structural unit content of resin (A). A percentage of the position is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and 3 to 10 mol%. A percentage is even more preferable.

[0119] <Structural Unit (a5)> The non-leaved hydrocarbon groups possessed by structural unit (a5) include linear, branched, or cyclic hydrocarbons. Groups having a group are examples. In particular, structural unit (a5) has an alicyclic hydrocarbon group. The base is preferable. Examples of structural units (a5) include the structural unit represented by formula (a5-1). . TIFF0007920396000068.tif3351[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in this alicyclic hydrocarbon group The elementary atoms may be substituted with aliphatic hydrocarbon groups having 1 to 8 carbon atoms. L 55 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- group contained in may be replaced by -O- or -CO-.

[0120] R 52 The alicyclic hydrocarbon group in this can be either monocyclic or polycyclic. Examples of alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, and cyclopene. Examples include chill groups and cyclohexyl groups. Examples of polycyclic alicyclic hydrocarbon groups include, for example, Examples include adamantyl groups and norbornyl groups. Aliphatic hydrocarbon groups with 1 to 8 carbon atoms include, for example, methyl, ethyl, propyl, and iso groups. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl Examples include alkyl groups such as the octyl group and the 2-ethylhexyl group. Examples of alicyclic hydrocarbon groups with substituents include the 3-methyladamantyl group. ru. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably k is an adamantyl group, a norbornyl group, or a cyclohexyl group.

[0121] L 55 In this context, divalent saturated hydrocarbon groups include divalent chain saturated hydrocarbon groups and divalent lipids. Examples include cyclic saturated hydrocarbon groups, preferably divalent chain saturated hydrocarbon groups. Examples of divalent chain-type saturated hydrocarbon groups include methylene groups, ethylene groups, and propanedi groups. Examples include alkanediyl groups such as the yl group, butanediyl group, and pentanediyl group. The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl groups and cyclohexanediyl groups. Examples include the roalkanediyl group. Examples of polycyclic divalent alicyclic saturated hydrocarbon groups include ada Examples include mantanediyl groups and norbornanediyl groups.

[0122] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by can be replaced with -O- or -CO-. Examples of the replaced groups include those represented by formulas (L1-1) to (L1-4). In the following formula, * and ** represent bonding sites, respectively, with * representing the bonding site with the oxygen atom. TIFF0007920396000069.tif18164 formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is L x1 (This represents the connection point with [another element].) . L x1 This represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 Each of these independently involves single bonds or divalent aliphatic saturated carbons with 1 to 14 carbon atoms. It represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 This represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. However, L x8 , L x9and W x1 The total number of carbon atoms is 15 or less.

[0123] L x1 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x2 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a single bond. L x3 Preferably, it is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x6 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably The group is either a methylene group or an ethylene group. L x7 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. L x9 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. W x1 Preferably, a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably It is either a cyclohexanediyl group or an adamantanediyl group.

[0124] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF0007920396000070.tif53136

[0125] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF0007920396000071.tif23130

[0126] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF0007920396000072.tif15148

[0127] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF0007920396000073.tif26114

[0128] L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0129] Structural units (a5-1) include the structural units shown below and the structural units within the following structural units ( a5-1) R 51 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007920396000074.tif111150 If resin (A) has structural units (a5), the content of these units is the total structural unit content of resin (A). A value of 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 3 to 15 mol% is preferred. A percentage is even more preferable.

[0130] <Structural Unit (a6)> Structural unit (a6) is a structural unit having an -SO2- group, and has an -SO2- group in its side chain. It is preferable to do so. A structural unit having an -SO2- group may also have a linear structure having an -SO2- group. or it may have a branched structure having an -SO2- group, or a ring having an -SO2- group It may have a ring structure (monocyclic and polycyclic structures). Preferably, a ring having an -SO2- group. A structural unit having a cyclic structure, more preferably a cyclic structure containing -SO2-O- It is a structural unit that has a Ton ring.

[0131] As a sultone ring, the following equation (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula ( T 1 A ring represented by -4) is an example. The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. This refers to a bridging ring containing -SO2-O- as the atomic group that makes up the ring, and is given by equation (T 1 -1 ) and formula (T 1 A ring represented by equation (T) is an example. A Sultone ring is given by equation (T 1 (-2) is expressed as Like a ring, in addition to -SO2-O-, there are also heteroatoms as atomic groups that make up the ring. It may also contain heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, or nitrogen atoms. , preferably an oxygen atom. TIFF0007920396000075.tif3087

[0132] The sultone ring may have substituents, such as halogen atoms or hydroxyl groups. Alkyl groups with 1 to 12 carbon atoms, halogen atoms, hydroxyl groups, cyanoacrylate atoms may also be present. alkoxy groups with 1 to 12 carbon atoms, aryl groups with 6 to 12 carbon atoms, and aryl groups with 7 to 12 carbon atoms. Larkyl group, glycidyloxy group, alkoxycarbonyl group having 2 to 12 carbon atoms and carbon number Examples include 2-4 alkylcarbonyl groups.

[0133] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. . Alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Examples include syl groups, octyl groups, and decyl groups, preferably alkyl groups having 1 to 6 carbon atoms. More preferably, it is a methyl group. Examples of alkyl groups having a halogen atom include trifluoromethyl and perfluoroethyl groups. Perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, Perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl chloromethyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group and triyomethyl group Examples include methyl groups, preferably trifluoromethyl groups. Examples of alkyl groups having a hydroxyl group include hydroxymethyl and 2-hydroxymethyl groups. Examples include hydroxyalkyl groups with a chill group. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include the dodecyloxy group. Examples of aryl groups include phenyl, naphthyl, anthryl, and p-methylphenyl groups. p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl Examples include the 2-methyl-6-ethylphenyl group and the 2-methyl-6-ethylphenyl group. Examples of aralkyl groups include benzyl group, phenethyl group, phenylpropyl group, and naphthyl group. Examples include tyl groups and naphthyl ethyl groups. Examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups. Examples include groups in which an alkoxy group and a carbonyl group are bonded, preferably having 6 or fewer carbon atoms. Examples include the coxycarbonyl group, and more preferably the methoxycarbonyl group. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It can be done.

[0134] From the viewpoint of ease of manufacturing monomers that lead to structural unit (a6), substituents are not present. A sultone ring is preferred. As the sultone ring, the ring represented by the following formula (T1') is preferred. TIFF0007920396000076.tif3072[In formula (T1'), X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 This is an alkyl group having 1 to 12 carbon atoms, which may have a halogen atom or a hydroxyl group. C1-C12 alkoxy group, halogen atom, hydroxyl group, cyano group, C1-C12 alkoxy group, C1 6-12 aryl groups, 7-12 aralkyl groups, glycidyloxy groups, 2 carbon atoms This represents an alkoxycarbonyl group with up to 12 carbon atoms or an alkylcarbonyl group with 2 to 4 carbon atoms. ma represents an integer from 0 to 9. When ma is 2 or greater, multiple R 41 They are the same It's fine if it exists or not. The connection point can be any position. X 11 is preferably an oxygen atom or a methylene group, more preferably a methylene group. ru. R 41 Examples include substituents similar to those of a sultone ring, such as halogen atoms or hydrides C1 to C12 alkyl groups, which may have a roxy group, are preferred.

[0135] As a sultone ring, the ring represented by formula (T1) is more preferable. TIFF0007920396000077.tif3049[In formula (T1), R 8 This is an alkyl group having 1 to 12 carbon atoms, which may have a halogen atom or a hydroxyl group. Groups, halogen atoms, hydroxyl groups, cyano groups, alkoxy groups with 1 to 12 carbon atoms, and 6 carbon atoms. ~12 aryl groups, aralkyl groups with 7-12 carbon atoms, glycidyloxy groups, 2- carbon atoms This represents 12 alkoxycarbonyl groups or alkylcarbonyl groups with 2 to 4 carbon atoms. m represents an integer from 0 to 9. When m is 2 or greater, multiple R 8 They are the same. They can also be different. The connection point can be any position.

[0136] R 8 R 41 Similar examples include the above. In formula (T1'), ma and in formula (T1), m are preferably 0 or 1. More preferably, it is 0.

[0137] The following are examples of rings represented by equation (T1') and equation (T1): The connection point can be at any position. TIFF0007920396000078.tif47144

[0138] The structural unit having a sultone ring preferably has the following group: * in the following group The symbol represents the bonding site. TIFF0007920396000079.tif45144

[0139] The structural unit having the -SO2- group preferably also has a group derived from a polymerizable group. The polymerizable groups include vinyl group, acryloyl group, methacryloyl group, and acryloyl Oxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, Examples include acryloylthio groups and methacryloylthio groups. In particular, the monomer that leads to the structural unit (a6) preferably has an ethylenically unsaturated bond. It is a monomer, and more preferably a (meth)acrylic monomer.

[0140] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007920396000080.tif4956[In formula (Ix), R x This is an alkyl group having 1 to 6 carbon atoms, which may have a halogen atom, and water Represents an elementary atom or a halogen atom. A xx is an oxygen atom, -N(R c )- or represents a sulfur atom. A x This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group contains -CH2- is -O-, -CO- or -N(R d )- may be replaced with this. X 11 represents an oxygen atom, a sulfur atom, or a methylene group. R 41 This is an alkyl group having 1 to 12 carbon atoms, which may have a halogen atom or a hydroxyl group. C1-C12 alkoxy group, halogen atom, hydroxyl group, cyano group, C1-C12 alkoxy group, C1 6-12 aryl groups, 7-12 aralkyl groups, glycidyloxy groups, 2 carbon atoms This represents an alkoxycarbonyl group with up to 12 carbon atoms or an alkylcarbonyl group with 2 to 4 carbon atoms. ma represents an integer from 0 to 9. When ma is 2 or greater, multiple R 41 They are the same It's fine if it exists or not. R c and Rd Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0141] R x Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. It is possible. R x Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group. Pyr group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n - Examples include hexyl groups, preferably alkyl groups having 1 to 4 carbon atoms, and more preferably This is either a methyl group or an ethyl group. R x Examples of alkyl groups having a halogen atom include trifluoromethyl group, pe Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroethyl group Olobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, per Fluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl Examples include the triiodomethyl group and other similar groups. R x is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably water It is an elementary atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.

[0142] A x Examples of divalent saturated hydrocarbon groups include linear alkanediyl groups and branched alkanediyl groups. Examples include divalent alicyclic saturated hydrocarbon groups, monocyclic or polycyclic, and of these groups, 2 Combinations of more than one species are also acceptable. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, do Decane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,1 4-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group heptadecane-1,17-diyl group, ethane-1,1-diyl group, propane-1,1- Linear alkanediyl groups such as diyl groups and propane-2,2-diyl groups; Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylprop Pan-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group Branched alkanediyl groups such as yl groups; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as n-1,4-diyl group and cyclooctane-1,5-diyl group A monocyclic, divalent, alicyclic saturated hydrocarbon group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic saturated carbon such as 1,5-diyl group and adamantane-2,6-diyl group Examples include hydrogen groups.

[0143] R 41 , X 11 And ma can be the same as in equation (T1'). Examples of sultone rings include those mentioned above, and among them, those whose bonding positions have been identified are also noteworthy. It is preferable to do so.

[0144] The following are examples of structural units (a6): TIFF0007920396000081.tif93150

[0145] In particular, equations (a6-1), (a6-2), (a6-6), (a6-7), ( Structural units represented by formulas a6-8) and (a6-12) are preferred, and formulas (a6-1), ( a6-2), more preferably, structural units represented by formulas (a6-7) and (a6-8). If resin (A) has structural units (a6), the content of these units is the total structural unit content of resin (A). A percentage of the total volume is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and 3 to 30 mol%. A percentage is even more preferable.

[0146] <Structural Unit (II)> Resin (A) further decomposes upon exposure to generate acid, resulting in structural units (hereinafter referred to as "structural units") It may contain (II) (in some cases). Structural unit (II) may be specifically Examples include the structural unit described in Japanese Patent Publication No. 2016-79235, with a sulfonate side chain. A structural unit having a carboxylate group or a side chain with an organic cation, or a sulfonate group. It is preferable that the structural unit has an o group and an organic anion.

[0147] Structural units having a sulfonate group or carboxylate group and an organic cation in the side chain It is preferable that the structural unit is represented by formula (II-2-A'). TIFF0007920396000082.tif3089 [In formula (II-2-A'), X III3 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group contains The -CH2- that is present may be replaced by -O-, -S-, or -CO-, and the saturated coal The hydrogen atoms contained in the hydrogen group are halogen atoms, and the number of carbon atoms that may contain halogen atoms. It may be replaced by alkyl groups or hydroxyl groups numbered 1 to 6. Ax1 This represents an alkanediyl group having 1 to 8 carbon atoms, and the water contained in the alkanediyl group The elementary atoms may be substituted with fluorine atoms or perfluoroalkyl groups having 1 to 6 carbon atoms. stomach. RA - This represents a sulfonate group or a carboxylate group. R III3 This is a hydrogen atom, a halogen atom, or a C1 atom which may have a halogen atom. Represents alkyl groups up to 6. ZA + This represents an organic cation.

[0148] R III3 The halogen atoms represented include fluorine, chlorine, bromine, and yo Examples include porcini atoms. R III3 A C1-C6 alkyl group which may have a halogen atom represented by So, R a8 A C1-C6 alkyl group which may have a halogen atom represented by the same Some examples include the following. A x1 Examples of alkanediyl groups with 1 to 8 carbon atoms, represented by the methylene group and the ethylene group, are available. , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl Group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group yl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples include the 1,4-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. ru. A x1 Perfluoroalkyl groups having 1 to 6 carbon atoms that may be substituted include: , trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Roisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorote Examples include rt-butyl groups, perfluoropentyl groups, and perfluorohexyl groups.

[0149] X III3 Divalent saturated hydrocarbon groups having 1 to 18 carbon atoms, as represented by , can be linear or branched. Examples include alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these These can be combined in any way. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, do Linear alkanediyl groups such as decane-1,12-diyl groups; butane-1,3-diyl groups, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pen Branched alkanedi such as tan-1,4-diyl group and 2-methylbutane-1,4-diyl group Lu group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as n-1,4-diyl group and cyclooctane-1,5-diyl group Divalent monocyclic or alicyclic saturated hydrocarbon groups such as; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Divalent polycyclic alicyclic saturated carbonated water containing 1,5-diyl groups, adamantane-2,6-diyl groups, etc. Examples include elements and so on.

[0150] The -CH2- group in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. Examples include the divalent groups represented by equations (X1) to (X53). However, Furthermore, the -CH2- group contained in the saturated hydrocarbon group is replaced by -O-, -S-, or -CO-. The number of carbon atoms in each preceding element is 17 or less. In the following formula, * and ** represent bonding sites. * is A x1 This represents the connection point. TIFF0007920396000083.tif145161

[0151] X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6 This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 This represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0152] ZA + Examples of organic cations represented include organic onium cations and organic sulfonium cations. Thione, organic iodonium cation, organic ammonium cation, benzothiazolium cation Examples include thione and organic phosphonium cations. Among these, organic sulfonium Mucations and organiciodonium cations are preferred, and arylsulfonium cations are More preferable. Specifically, it can be expressed by any of the following equations (b2-1) to (b2-4). The cation (hereinafter, depending on the formula number, may be referred to as "cation (b2-1)," etc.) It can be listed.

[0153] The structural unit represented by formula (II-2-A') is the structural unit represented by formula (II-2-A) It is preferable that this be the case. JPEG0007920396000084.jpg37109 [In formula (II-2-A), R III3 , X III3 and ZA + This expresses the same meaning as above. z represents an integer between 0 and 6. R III2 and R III4 Each of these is independently a hydrogen atom, a fluorine atom, or a carbon atom with 1 carbon atom. Represents a perfluoroalkyl group of ~6, and when z is 2 or greater, multiple R III2 and R II I4 They may be the same or different from each other. Q a and Q b Each is independently a fluorine atom or a perfluoroal with 1 to 6 carbon atoms. [Represents the kill group.]

[0154] R III2 , R III4 Q a and Q b Perfluoroalkyl compounds with 1 to 6 carbon atoms, represented by As for the group, see Q, which will be discussed later. b1 This is the same as a perfluoroalkyl group with 1 to 6 carbon atoms, as represented by This is one example.

[0155] The structural unit represented by formula (II-2-A) is the same as the structural unit represented by formula (II-2-A-1). It is preferable that it be in that position. TIFF0007920396000085.tif5576 [In formula (II-2-A-1), R III2 , R III3 , R III4 Q a Q b , z and ZA+ This has the same meaning as above. represent. R III5 This represents a saturated hydrocarbon group with 1 to 12 carbon atoms. X I2 This represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and contains -CH2- may be replaced with -O-, -S-, or -CO- in the saturated carbonized water. The hydrogen atoms in the elementary group may be substituted with halogen atoms or hydroxyl groups.

[0156] R III5 Examples of saturated hydrocarbon groups having 1 to 12 carbon atoms include the methyl group and the ethyl group. propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pe Nthyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and Examples include linear or branched alkyl groups such as dodecyl groups. X I2 As a divalent saturated hydrocarbon group represented by , X III3 Divalent saturated carbon represented by Examples include those similar to hydrogenated groups.

[0157] The structural unit represented by formula (II-2-A-1) is represented by formula (II-2-A-2). A structural unit that can be made into a structure is preferable. TIFF0007920396000086.tif5287 [In formula (II-2-A-2), R III3 , R III5 and ZA + This expresses the same meaning as above. m and nA each independently represent either 1 or 2.

[0158] Examples of structural units represented by formula (II-2-A') include the following structural unit, R III3 The group equivalent to the methyl group is a hydrogen atom, a halogen atom (e.g., a fluorine atom), or a halogen A C1-C6 alkyl group that may have a C1 atom (for example, a trifluoromethyl group, etc.) Structural units that have been replaced by ) etc. and structural units described in International Publication No. 2012 / 050015 It can be listed. ZA + This represents an organic cation. TIFF0007920396000087.tif86163

[0159] A structural unit having a sulfonio group and an organic anion in its side chain is represented by formula (II-1-1). It is preferable that the structural unit is such that it can be formed. TIFF0007920396000088.tif3689 [In formula (II-1-1), A II1 This represents a single bond or a divalent linking group. R II1 This represents a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms. R II2 and R II3 Each of these independently represents a hydrocarbon group with 1 to 18 carbon atoms, and R II2 and R II3 They bond to each other, forming a ring with the sulfur atoms to which they are bonded. That's fine. R II4 This is a hydrogen atom, a halogen atom, or a C1-C2 atom which may have a halogen atom. This represents an alkyl group of 6. A - This represents an organic anion. R II1 As a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, the phenylene group is an example. Examples include naphthylene groups, etc. R II2 and R II3 Examples of hydrocarbon groups represented include alkyl groups and alicyclic hydrocarbon groups. Examples include aromatic hydrocarbon groups and groups formed by combining them. Examples of alkyl groups and alicyclic hydrocarbon groups are the same as those described above. Aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, biphenyl group, Examples include aryl groups such as phenanthryl groups. The combined groups include those that combine the alkyl group and alicyclic hydrocarbon group mentioned above. , aralkyl groups such as benzyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl Nyl group, p-tert-butylphenyl group, tolyl group, xylyl group, coumenyl group, mesityl (e.g., 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group), alicyclic carbon Aromatic hydrocarbon groups having a hydrogenated group (p-cyclohexylphenyl group, p-adamantyl group) Examples include phenyl groups, phenylcyclohexyl groups, and other aryl-cycloalkyl groups. It can be done. R II4 The halogen atoms represented include fluorine, chlorine, bromine, and iodine. Examples include elementary atoms. R II4 A C1-C6 alkyl group which may have a halogen atom represented by R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by Some examples can be listed. A II1 Examples of divalent linking groups represented by include divalent saturated carbons with 1 to 18 carbon atoms. A hydrogen group is one example, and the -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or It may be replaced with -CO-. Specifically, X III3 Represented by 1 to 1 carbon atoms Examples include the same divalent saturated hydrocarbon group as in 8.

[0160] The structural units containing cations in formula (II-1-1) are the structural units represented below, R II4The group corresponding to the methyl group is a hydrogen atom, a halogen atom (for example, a fluorine atom) or A C1-C6 alkyl group which may have a halogen atom (for example, trifluoromethyl Examples include structural units that have been replaced by groups such as the 'L' group. TIFF0007920396000089.tif85130

[0161] A - Organic anions represented by these include sulfonic acid anions and sulfonylimido anions. Examples include sulfonylmethide anions and carboxylic acid anions. - It is represented The organic anion is preferably a sulfonate anion, and the sulfonate anion is as follows: Examples include those similar to the anion represented by formula (B1).

[0162] A - Examples of sulfonylimid anions represented by the formula include the following: TIFF0007920396000090.tif36136

[0163] Examples of sulfonylmethide anions include the following: TIFF0007920396000091.tif29123

[0164] Examples of carboxylic acid anions include the following: TIFF0007920396000092.tif45152

[0165] Examples of structural units represented by formula (II-1-1) include the following: It is possible. TIFF0007920396000093.tif88149

[0166] When resin (A) contains structural unit (II), the content of structural unit (II) is: The amount is preferably 1 to 20 mol%, and more preferably 2 to 1 mol%, relative to the total structural units of fat (A). The percentage is 15 mol%, and more preferably 3 to 10 mol%.

[0167] Resin (A) may have structural units other than those described above, and such structural units In terms of rank, well-known structural units in this field can be cited.

[0168] The resin (A) is preferably a resin consisting of structural unit (I) and structural unit (a1), structure A resin consisting of unit (I) and structural unit (s), structural unit (I) and structural unit (a1) and structure A resin consisting of units (s), structural unit (I), structural unit (a1), structural unit (s), and structure A resin consisting of unit (a4) and / or structural unit (a5), or consisting only of structural unit (I). A resin, or a resin consisting only of structural unit (I) and structural unit (a4), more preferably Alternatively, a resin consisting of structural unit (I), structural unit (a1), and structural unit (s), structural unit A resin consisting of (I) and structural units (s), or structural units (I) and structural units (a4) A resin consisting only of structural unit (a5), and a resin consisting only of structural unit (I) and structural unit (a4) A resin consisting only of structural unit (I), structural unit (a4), and structural unit (a1). be.

[0169] The structural unit (a1) is preferably structural unit (a1-0), structural unit (a1-1) and structural unit (a1-0) Manufacturing unit (a1-2) (preferably having a cyclohexyl group or a cyclopentyl group) At least one selected from the group consisting of structural units (a1 -0), structural unit (a1-1) and structural unit (a1-2) (preferably a cyclohexyl group) At least two selected from the group consisting of (or structural units having a cyclopentyl group) be. The structural unit (s) is preferably from the group consisting of structural unit (a2) and structural unit (a3). At least one of the selected structural units (a2) is preferably structural unit (a2-A). Alternatively, it is a structural unit (a2-1). The structural unit (a3) ​​is preferably expressed by formula (a3-1). The structural units that are formed, the structural units represented by formula (a3-2) and the structural units represented by formula (a3-4) It is at least one of the units selected from the group.

[0170] Each structural unit constituting resin (A) may be used individually or in combination of two or more types. Using monomers that derive these structural units, known polymerization methods (e.g., radical polymerization) are used. It can be manufactured by the following: The content of each structural unit in resin (A) is determined by the amount of the material used in polymerization. It can be adjusted by the amount of Ma used. The weight-average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,500 0 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30, It is less than or equal to 000, and more preferably less than or equal to 15,000. In this specification, weight-average molecular weight is determined by gel permuration chromatography. This is the value obtained. Gel permuration chromatography is performed as described in the examples. It can be measured under specific analytical conditions.

[0171] [Resist composition] The resist composition of the present invention comprises a resin (A) and an acid generator known in the resist field (hereinafter referred to as "acid generator"). It is preferable to include a generating agent (sometimes referred to as "B"). The resist composition of the present invention may further contain resins other than resin (A). The resist composition of the present invention generates an acid that is less acidic than the acid generated by the acid generator. It may contain a quencher such as salt (hereinafter sometimes referred to as "quencher (C)"). Preferably, it contains a solvent (which may be referred to as "solvent (E)" below).

[0172] <Resins other than resin (A)> The resist composition of the present invention may also contain resins other than resin (A). A resin is a resin that does not contain structural unit (I), and examples of such resins include, A resin having a structural unit with an acid-unstable group and not containing structural unit (I) (hereinafter referred to as "resin( A2) In some cases, resins and structural units (a4) consist only of structural units (a4). A resin consisting of structural units (a5) (hereinafter, a resin consisting only of structural units (a4), and a structure In some cases, a resin consisting of a building block (a4) and a structural block (a5) is referred to as resin (X). Examples include ( ). In resin (X), the content of structural unit (a4) is equal to the sum of all structural units in resin (X). In contrast, it is preferable that the amount be 30 mol% or more, and more preferably 40 mol% or more. Furthermore, it is more preferable that the amount be 45 mol% or more. Each structural unit constituting the resin (X) may be used individually or in combination of two or more types. These monomers that induce structural units can be used in known polymerization methods (e.g., radical polymerization). Therefore, it can be manufactured. The content of each structural unit in resin (X) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weights of resin (A2) and resin (X) are preferably 6, independently of each other. 000 or more (more preferably 7,000 or more), 80,000 or less (more preferably 60 It is less than ,000). The means for measuring the weight-average molecular weight of resin (A2) and resin (X) is a tree The same applies as in the case of fat (A). If the resist composition of the present invention contains resin (A2), the content thereof is resin (A) 10 Typically, 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) per 0 parts by mass. That is the case. Furthermore, if the resist composition contains resin (X), its content is equal to 100 mass of resin (A). Preferably, the amount is 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, More preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, More preferably, the amount is 1 to 8 parts by mass.

[0173] The content of resin (A) in the resist composition is 8 in relation to the solid content of the resist composition. Preferably, it is 0% by mass or more and 99% by mass or less, and preferably 90% by mass or more and 99% by mass or less. It is preferable. Also, if it contains resins other than resin (A), then resin (A) and resins other than resin (A) The total content of the resin is 80% by mass or more and 99% by mass or less relative to the solid content of the resist composition. The resist composition is preferably as follows: The solid content of a substance and the resin content thereto are determined by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as fluoroscopy.

[0174] <Acid Generator (B)> The acid generator (B) may be either nonionic or ionic. As herbal preparations, sulfonate esters (e.g., 2-nitrobenzyl ester, aromatic sulfonate ester) are used. Sulfonate, oximesulfonate, N-sulfonyloxiimide, sulfonyloxyke Ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g., disulfone, keto Examples include sulfones, sulfonyl diazomethanes, etc. Ionic acid generators include onions. Onium salts containing um cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples include salts (iodonium salts). An anion of anium salts is aniodonium sulfonate. Examples include sulfonylimide anions, sulfonylmethide anions, and others. As for the acid generating agent (B), see Japanese Patent Publication No. 63-26653, Japanese Patent Publication No. 55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 Japanese Patent Publication No. 62-153853, Japanese Patent Publication No. 63-146029, U.S. Patent No. 3,779, Patent No. 778, U.S. Patent No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate acid when exposed to radiation, as described in publications No. 126, 712, etc., can be used. Compounds manufactured by known methods may also be used. The acid generator (B) may consist of two or more types. They may be used in combination.

[0175] The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a fluorine-containing acid generator of formula (B1). This is a salt represented by (hereinafter sometimes referred to as "acid generator (B1)"). TIFF0007920396000094.tif2958[In formula (B1), Q b1 and Q b2 Each of these independently comprises a fluorine atom or a perfluorinated atom having 1 to 6 carbon atoms. This represents a luquill group. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and this divalent saturated hydrocarbon group The -CH2- contained may be replaced by -O- or -CO-, and the divalent saturated carbon The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms or hydroxyl groups. Y is a methyl group which may have substituents or a C3-C2 group which may have substituents 4 represents an alicyclic hydrocarbon group, and the -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced with SO2- or -CO-. Z + This represents an organic cation.

[0176] Q b1 and Q b2 Examples of perfluoroalkyl groups include trifluoromethyl group, perfluoroalkyl group. Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroethyl group Olobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, per Examples include fluoropentyl groups and perfluorohexyl groups. Q b1 and Q b2 These are, independently, a fluorine atom or a trifluoromethyl group. It is preferable that both are fluorine atoms, and it is even more preferable that both are fluorine atoms.

[0177] L b1 In this context, divalent saturated hydrocarbon groups include linear alkanediyl groups and branched alkanediyl groups. Examples include candiyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these groups It may also be a group formed by combining two or more of the above. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- Linear alkanediyl groups such as diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, 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 Branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as n-1,4-diyl group and cyclooctane-1,5-diyl group A monocyclic, divalent, alicyclic saturated hydrocarbon group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane- Polycyclic divalent alicyclic saturated carbon such as 1,5-diyl group and adamantane-2,6-diyl group Examples include hydrogen groups.

[0178] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by is either -O- or -CO- The replaced base can be represented, for example, by any of the equations (b1-1) to (b1-3). The following are examples of the groups. Furthermore, the groups represented by formulas (b1-1) to (b1-3) and their components are also included. In the groups represented by formulas (b1-4) to (b1-11), which are examples, * and ** are bonds. The symbols indicate the location, and * represents the connection site with -Y.

[0179] TIFF0007920396000095.tif26118[In formula (b1-1), L b2This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b3 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxyl groups, and the saturated The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b5 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxyl groups, and the saturated The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms or hydroxyl groups. L b7 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxyl groups, and the saturated The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. However, L b6and L b7 The total number of carbon atoms is 23 or less.

[0180] In the groups represented by formulas (b1-1) to (b1-3), the saturated hydrocarbon group is included. If -CH2- is replaced by -O- or -CO-, the number of carbon atoms before replacement is... This is the number of carbon atoms in the hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups. It can be done.

[0181] L b2 The bond is preferably a single bond. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 The is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the divalent saturated carbon The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms. L b5 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 The saturated hydrocarbon group is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms. L b7 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. The -CH2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO-. That's fine.

[0182] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by is either -O- or -CO- The replaced group is preferably the group represented by formula (b1-1) or formula (b1-3). The base represented by equation (b1-1) is shown in equations (b1-4) to (b1-8), respectively. The basis for this is listed below. TIFF0007920396000096.tif48120[In formula (b1-4), L b8 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms or hydroxyl groups. In formula (b1-5), L b9 This represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and this divalent saturated hydrocarbon group The -CH2- group may be replaced by -O- or -CO-. L b10 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the divalent saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. . However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b12 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the divalent saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. . However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 This represents a divalent saturated hydrocarbon group with 1 to 19 carbon atoms. L b14 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the divalent saturated The -CH2- group in the hydrocarbon group may be replaced by -O- or -CO-. L b15 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the divalent saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. . However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the divalent saturated hydrocarbon group The -CH2- group contained in may be replaced by -O- or -CO-. L b17 This represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. L b18 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the divalent saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. . However, L b16 ~L b18 The total number of carbon atoms is 19 or less.

[0183] L b8 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 It is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 This is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 It is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 This is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 It is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0184] The base represented by equation (b1-3) is given by equations (b1-9) to (b1-11), respectively. The bases that can be represented are listed below. TIFF0007920396000097.tif23140[In formula (b1-9), L b19 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b20 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b22 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atoms in the group may be substituted with fluorine atoms. L b25 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b26 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the saturated hydrocarbon The hydrogen atom contained in the group is a fluorine atom, a hydroxyl group, or an alkylcarbonyloxy group. It may be substituted. The -CH2- contained in the alkylcarbonyloxy group is -O- Alternatively, it may be replaced with -CO-, and the hydrogen contained in the alkylcarbonyloxy group The atoms may be substituted with hydroxyl groups. However, L b24 , L b25 and Lb26 The total number of carbon atoms is 21 or less.

[0185] Furthermore, between the group represented by formula (b1-9) and the group represented by formula (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before replacement is defined as the number of carbon atoms in the saturated hydrocarbon group. Examples of alkylcarbonyloxy groups include acetyloxy group, propionyloxy group, and b thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group These are some examples.

[0186] The following are examples of bases represented by formula (b1-4): TIFF0007920396000098.tif16154

[0187] The following are examples of bases represented by formula (b1-5): TIFF0007920396000099.tif68152

[0188] The following are examples of bases represented by formula (b1-6): TIFF0007920396000100.tif29150

[0189] The following are examples of bases represented by formula (b1-7): TIFF0007920396000101.tif57146

[0190] The following are examples of bases represented by formula (b1-8): TIFF0007920396000102.tif23150

[0191] The following are examples of bases represented by formula (b1-2): TIFF0007920396000103.tif31161

[0192] The following are examples of bases represented by formula (b1-9): TIFF0007920396000104.tif44137

[0193] The following are examples of bases represented by formula (b1-10): TIFF0007920396000105.tif92165

[0194] The following are examples of bases represented by formula (b1-11): TIFF0007920396000106.tif84164

[0195] Examples of alicyclic hydrocarbon groups represented by Y include formulas (Y1) to (Y11), formula (Y36) to (Y36). Examples of groups represented by formula (Y38) include those shown. The -CH2- group in the alicyclic hydrocarbon group represented by Y is either -O-, -SO2-, or -CO When replaced by -, the number of replacements may be one or two or more. Such a base is Examples of groups represented by equations (Y12) to (Y35) and (Y39) to (Y43) include those represented by equations (Y12) to (Y35) and (Y39) to (Y43). . * is L b1 This represents the connection point.

[0196] The alicyclic hydrocarbon group represented by TIFF0007920396000107.tif83167Y is preferably formula (Y1) to formula (Y20), formula ( Y26), equation (Y27), equation (Y30), equation (Y31), equation (Y39) to equation (Y43) A group represented by any of the following, more preferably by formula (Y11), formula (Y15), or formula (Y16) ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39) A group represented by formula (Y40), formula (Y42), or formula (Y43), more preferably Alternatively, see equation (Y11), equation (Y15), equation (Y20), equation (Y26), equation (Y27), equation ( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43) It is a base represented by . The alicyclic hydrocarbon group represented by Y is given by formulas (Y28) to (Y35), (Y39), and (Y 40) In the case of a spiro ring having an oxygen atom, such as formula (Y42) or formula (Y43), 2 The alkanediyl group between the oxygen atoms preferably has one or more fluorine atoms. Furthermore, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom It is preferable that the fluorine atom is not substituted.

[0197] The substituents of the methyl group represented by Y include halogen atoms, hydroxyl groups, and groups with 3 to 1 carbon atoms. 6 alicyclic hydrocarbon groups, C6-C18 aromatic hydrocarbon groups, glycidyloxy groups, -( CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 These are alkyl groups with 1 to 16 carbon atoms, alicyclic hydrocarbon groups with 3 to 16 carbon atoms, and groups with 6 carbon atoms. ~18 represent aromatic hydrocarbon groups or combinations thereof, and the alkyl group and the alicyclic group. The -CH2- contained in the hydrocarbon group is replaced by -O-, -SO2-, or -CO-. The alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may contain hydrogen The atom may be replaced by a hydroxyl group or a fluorine atom. ja is any of 0 to 4. It represents any integer. Examples include: The substituents of the alicyclic hydrocarbon group represented by Y include halogen atoms, hydroxyl groups, and hydroxyl groups. A C1-C16 alkyl group which may be substituted with a roxy group (the alkyl group contains -CH2- may be replaced by -O- or -CO-. ), lipids with 3 to 16 carbon atoms. Cyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, aralkyl groups with 7 to 21 carbon atoms, Glycidyloxy group, -(CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO -R b1 group (in the formula, R b1 This refers to alkyl groups with 1 to 16 carbon atoms and alicyclic carbonized water with 3 to 16 carbon atoms. The alkyl group represents an elemental group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. The -CH2- contained in the alicyclic hydrocarbon group and the alicyclic hydrocarbon group is -O-, -SO2-, or -CO- The alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be replaced by the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group The hydrogen atoms contained in may be replaced by hydroxyl groups or fluorine atoms. Examples include: , representing an integer between 0 and 4.

[0198] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, and methyl cyclohexyl groups. Chlohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, no Examples include the rubornyl group and the adamantyl group. Alicyclic hydrocarbon groups are chain hydrocarbon groups. They may also contain, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 12, more preferably 3 to 10. be. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, and biphenyl groups. Examples include aryl groups such as nyl groups and phenanthryl groups. Aromatic hydrocarbon groups are chain carbon It may have a hydrogenated group or an alicyclic hydrocarbon group, and a chain hydrocarbon group having 1 to 18 carbon atoms. Aromatic hydrocarbon groups (tolyl group, xylyl group, cumenyl group, mesityl group, p-methyl) Phenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethyl (e.g., 2-methyl-6-ethylphenyl group, 2-methyl-6-ethylphenyl group), and alicyclic carbons having 3 to 18 carbon atoms. Aromatic hydrocarbon groups having a hydrogenated group (p-adamantylphenyl group, p-cyclohexyl Phenyl groups, etc., are preferred. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14. More preferably, 6 to 10. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, and b Tyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group Examples include the following. The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 It is ~6, and more preferably 1~4. Alkyl groups substituted with hydroxyl groups include hydroxymethyl groups and hydroxy Examples include hydroxyalkyl groups such as ethyl groups. Examples of aralkyl groups include benzyl group, phenethyl group, phenylpropyl group, and naphthyl group. Examples include tyl groups and naphthylethyl groups. The -CH2- group in the alkyl group is replaced by -O-, -SO2-, or -CO-, etc. The groups include alkoxy groups, alkylsulfonyl groups, alkoxycarbonyl groups, and alkyl groups. Examples include carbonyl groups, alkylcarbonyloxy groups, or combinations thereof. ru. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups. The number of carbon atoms in the alkoxy group is preferably 1 to 12. Yes, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkylsulfonyl groups include methylsulfonyl group, ethylsulfonyl group, and propyl group. Examples include sulfonyl groups. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 12. Yes, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups. Examples include alkoxycarbonyl groups and butoxycarbonyl groups. The number of carbon atoms in the alkoxycarbonyl group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples include the following. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably The value is between 2 and 6, and more preferably between 2 and 4. Examples of alkylcarbonyloxy groups include acetyloxy groups and propionyloxy groups. Examples include the cy group and the butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of combined groups include groups that combine an alkoxy group and an alkyl group, and A group combining a lucoxy group and an alkoxy group, or a group combining an alkoxy group and an alkylcarbonyl group. Groups combining these, groups combining an alkoxy group and an alkylcarbonyloxy group, etc. It can be listed. Examples of groups combining an alkoxy group and an alkyl group include the methoxymethyl group. Alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, and ethoxymethyl group For example, the number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, and more preferably k is 2 to 6, and more preferably 2 to 4. Groups that combine alkoxy groups include methoxymethoxy groups and metoxy groups. Alkoxyalkoxy groups such as xyethoxy group, ethoxymethoxy group, and ethoxyethoxy group Examples include the following. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, and more Preferably, it is 2 to 6, and more preferably 2 to 4. Examples of groups combining an alkoxy group and an alkylcarbonyl group include methoxyacetyl. Alco groups such as methoxypropionyl group, ethoxyacetyl group, and ethoxypropionyl group Examples include xyalkylcarbonyl groups. The number of carbon atoms in an alkoxyalkylcarbonyl group is... Preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. be. Groups that combine an alkoxy group and an alkylcarbonyloxy group include methoxya Cetyloxy group, Methoxypropionyloxy group, Ethoxyacetyloxy group, Ethoxy Examples include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the coxyalkylcarbonyloxy group is preferably 3 to 13, and more preferably The value of k is between 3 and 7, and more preferably between 3 and 5. The -CH2- group in the alicyclic hydrocarbon group is replaced by -O-, -SO2-, or -CO-, etc. The basis for the division is expressed by equations (Y12) to (Y35) and (Y39) to (Y43). The basis is as follows.

[0199] The following are examples of Y: TIFF0007920396000108.tif129165

[0200] TIFF0007920396000109.tif36150

[0201] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms, which may have substituents. More preferably, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, which may have substituents. More preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms, which may have substituents. More preferably, an adamantyl group which may have a substituent, and the alicyclic hydrocarbon The -CH2- group constituting the group or adamantyl group is replaced with -CO-, -SO2-, or -CO-. It may be replaced. Specifically, Y is preferably an adamantyl group, a hydroxyadamantine group. A group represented by a dol group, an oxoadamantyl group, or formulas (Y42), (Y100) to (Y114) It is a base.

[0202] The anions in the salt represented by formula (B1) are given by formula (B1-A-1) ~ formula (B1- Anions represented by A-59) (hereinafter referred to as "anion (B1-A-1)" etc. depending on the formula number) In some cases, this is preferable, and formulas (B1-A-1) to (B1-A-4), formula (B1 -A-9), Formula (B1-A-10), Formula (B1-A-24) ~ Formula (B1-A-33), Formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 An anion represented by any of 9) is more preferred. TIFF0007920396000110.tif232165

[0203] TIFF0007920396000111.tif238165

[0204] TIFF0007920396000112.tif168160 Here R i2 ~R i7 These are, independently of each other, for example, alkyl groups having 1 to 4 carbon atoms, preferably The group is either a methyl group or an ethyl group. i8 For example, a chain-like hydrocarbon group having 1 to 12 carbon atoms. Preferably, alkyl groups having 1 to 4 carbon atoms, alicyclic hydrocarbon groups having 5 to 12 carbon atoms, or these. A group formed by combining these, more preferably a methyl group, an ethyl group, or a cyclohex group. It is either an adamantyl group or an adamantyl group. A41 These are single bonds or alkanediyl compounds with 1 to 4 carbon atoms. It is the basis. Q b1 and Q b2 This expresses the same meaning as above. Specifically, the anion in the salt represented by formula (B1) is as shown in Japanese Patent Publication No. 2010-20. Anions listed in Public Gazette No. 4646 are examples.

[0205] Preferably, the anion in the salt represented by formula (B1) is formula (B1a-1) ~ formula ( The anions represented by B1a-38 are listed below. TIFF0007920396000113.tif238158

[0206] TIFF0007920396000114.tif129154

[0207] In particular, equations (B1a-1) to (B1a-3), and equations (B1a-7) to (B1a-1) 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a-3) An anion represented by any of 8) is preferred.

[0208] Z +Examples of organic cations include organic onium cations, organic sulfonium cations, and Organic iodonium cation, organic ammonium cation, benzothiazolium cation and Examples include organic phosphonium cations. Among these, organic sulfonium cations are particularly noteworthy. Organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) (hereinafter) Depending on the formula number, it may be referred to as "cation (b2-1)," etc. ) is one example.

[0209] In formulas (b2-1) to (b2-4) of TIFF0007920396000115.tif47166, R b4 ~R b6 These are, independently, chain hydrocarbon groups with 1 to 30 carbon atoms and groups with 3 to 36 carbon atoms. This term represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and is contained in the chain-like hydrocarbon group. The hydrogen atoms present are found in hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, and lipid groups with 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms and aliphatic hydrocarbon groups with 1 to 18 carbon atoms. They may also be substituted with an alkylcarbonyl group or glycidyloxy group having 2 to 4 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group are halogen atoms, hydroxyl groups, and C1- 18 aliphatic hydrocarbon groups, C1-C12 alkyl fluorides, or C1-C12 It may be substituted with a coxy group. R b4 and R b5 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. Even if the -CH2- contained in the ring is replaced by -O-, -S-, or -CO- good. R b7 and R b8 These are, independently, a halogen atom, a hydroxyl group, and a lipid with 1 to 12 carbon atoms. Alkaline hydrocarbon groups, C1-C12 alkyl fluorides, or C1-C12 alkoxy groups It represents. m2 and n2 each independently represent an integer between 0 and 5. When m2 is 2 or more, multiple R b7 They may be the same or different, and when n2 is 2 or more, multiple Number R b8 They may be the same or different. R b9 and R b10 Each of these is independently a chain-like hydrocarbon group having 1 to 36 carbon atoms or a group having 3 to 3 carbon atoms. It represents 36 alicyclic hydrocarbon groups. R b9 and R b10 This means that they bond with each other and, together with the sulfur atoms they bond to, form a ring. It may be done, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. That's good too. R b11 This consists of a hydrogen atom, a chain hydrocarbon group with 1 to 36 carbon atoms, and an alicyclic carbon group with 3 to 36 carbon atoms. This represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 This refers to a chain-type hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or This represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in this chain-like hydrocarbon group are carbon It may also be substituted with an aromatic hydrocarbon group with prime numbers 6 to 18, and said aromatic hydrocarbon group contains The hydrogen atom is a carbon-1 to carbon-12 alkoxy group or a carbon-1 to carbon-12 alkyl carbonyl group. It may be substituted with an oxy group. R b11 and R b12 These molecules bond to each other, forming a ring including the -CH-CO- groups to which they are joined. It is also possible that the -CH2- contained in the ring is replaced by -O-, -S-, or -CO-. That's fine. R b13 ~R b18 These are, independently, a halogen atom, a hydroxyl group, and a lipid with 1 to 12 carbon atoms. Alkaline hydrocarbon groups, C1-C12 alkyl fluorides, or C1-C12 alkoxy groups It represents. L b31 This represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer between 0 and 5. q2 and r2 each independently represent an integer between 0 and 4. u2 represents either 0 or 1. When o2 is 2 or more, multiple R b13 They are the same or different, and when p2 is 2 or more, multiple R b14 They are the same or different, and when q2 is 2 or more, multiple R b15 They are the same or different, r2 When there are 2 or more R b16 They are the same or different, and when s2 is 2 or more, multiple R b17 teeth If the same or different, and t2 is 2 or more, multiple R b18 They are either the same or different. Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, and butyl groups. Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and Examples include alkyl groups with a 2-ethylhexyl group. In particular, R b9 ~R b12 The chain-like hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and monocyclic alicyclic carbon Examples of hydrogen groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of cycloalkyl groups include cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include the decahydronaphthyl group and the adamantyl group. Examples include norbornyl groups and the following groups. TIFF0007920396000116.tif10158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably These have 4 to 12 carbon atoms. As an example of an alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, methylcyclohex xyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 2-ethyl Ruadamantan-2-yl group, 2-isopropyladamantan-2-yl group, methyl nor Examples include bornyl groups and isobornyl groups. Hydrogen atoms are substituted with aliphatic hydrocarbon groups. In alicyclic hydrocarbon groups, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferable. The number is 20 or less. A fluoride alkyl group refers to an alkyl group having 1 to 12 carbon atoms and containing a fluorine atom. Oromethyl group, difluoromethyl group, trifluoromethyl group, perfluorobutyl group, etc. Examples include: The number of carbon atoms in the alkyl fluoride is preferably 1 to 9, and more preferably 1 It is ~6, and more preferably 1~4. Aromatic hydrocarbon groups include phenyl, biphenyl, naphthyl, and phenanthryl groups. Examples include aryl groups such as the Aromatic hydrocarbon group, Chain hydrocarbon group, or Alicyclic hydrocarbon group. It may have an elementary group, and an aromatic hydrocarbon group having a chain-like hydrocarbon group with 1 to 18 carbon atoms ( Tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert -Butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group (etc.) and aromatic hydrocarbon groups having alicyclic hydrocarbon groups with 3 to 18 carbon atoms (p-cyclohex Examples include silphenyl groups, p-adamantylphenyl groups, etc. Furthermore, aromatic carbonized water... If the elementary group has a chain hydrocarbon group or an alicyclic hydrocarbon group, a chain hydrocarbon having 1 to 18 carbon atoms. Hydrogenated groups and alicyclic hydrocarbon groups having 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which a hydrogen atom is substituted with an alkoxy group include p-methoxyphenyl Examples include the 'L' group. Examples of chain hydrocarbon groups in which hydrogen atoms are substituted with aromatic hydrocarbon groups include the benzyl group and the ferrous hydrocarbon group. Netyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. An example is the aralkyl group. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. oxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group Examples include dodecyloxy groups, etc. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. It is possible. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkylcarbonyloxy groups include methylcarbonyloxy group and ethylcarbonyl Oxy group, propyl carbonyloxy group, isopropyl carbonyloxy group, butylcarbon Bonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy C group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include oxy groups and 2-ethylhexylcarbonyloxy groups. R b4 and R b5 The ring formed when these atoms bond to each other and together with the sulfur atom they bond to is The rings may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may have 3 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Furthermore, the ring containing the sulfur atom can be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. For example, the following ring can be cited. * indicates a bonding site. TIFF0007920396000117.tif23144R b9 and R b10 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothi Examples include the ophenium ring, thian-1-ium ring, and 1,4-oxatian-4-ium ring. It can be done. R b11 and R b12 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring Examples include oxonorbornane rings and oxoadamantane rings.

[0210] Among cations (b2-1) to (b2-4), preferably cation (b2 -1) The following cations can be considered as cations (b2-1): TIFF0007920396000118.tif117161

[0211] TIFF0007920396000119.tif70164 The following cations can be considered as cations (b2-2): TIFF0007920396000120.tif18150 The following cations can be considered as cations (b2-3): TIFF0007920396000121.tif26140 The following cations can be considered as cations (b2-4): TIFF0007920396000122.tif127165

[0212] The acid generator (B) is a combination of the anion and the organic cation described above, and these are They can be combined in any way. The acid generator (B) is preferably of formula (B1a-1)~ Formula (B1a-3), Formula (B1a-7) ~ Formula (B1a-16), Formula (B1a-18), Formula ( Anio expressed by any of the following equations (B1a-19), (B1a-22) to (B1a-38) A combination of cation (b2-1), cation (b2-3), or cation (b2-4) The voice can be raised.

[0213] The acid generator (B) is preferably represented by formulas (B1-1) to (B1-57), respectively. Examples include those that are used. Among them, those containing arylsulfonium cations are preferred. Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B 1-31) The form represented by formula (B1-57) is particularly preferred. JPEG0007920396000123.jpg191166

[0214] TIFF0007920396000124.tif250153

[0215] TIFF0007920396000125.tif205166

[0216] In the resist composition of the present invention, the content of the acid generator is as follows: per 100 parts by mass of resin (A) In contrast, 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 The resist composition of the present invention is less than or equal to 3 parts by mass, more preferably 3 parts by mass or more and 35 parts by mass or less. The acid generator (B) may contain one type alone or multiple types.

[0217] <Solvent (E)> The solvent (E) content is typically 90% by mass or more and 99.9% by mass or less in the resist composition. Yes, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of solvent (E) is 99% by mass or less. The content of solvent (E) is determined, for example, by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as chromatography. As solvent (E), ethyl cellosolve acetate, methyl cellosolve acetate and Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, vinegar Esters such as butyl acid, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl Ketones such as lucetone, 2-heptanone, and cyclohexanone; γ-butyrolactone, etc. Examples include cyclic esters; etc. One of the solvents (E) may be used alone. You may use two or more types.

[0218] <Quencher (C)> The quencher (C) is an acid that is less acidic than the acid generated by the acid generator (B). Generated salts, and basic nitrogen-containing organic compounds. Content of quencher (C) is preferably about 0.01 to 15% by mass based on the solid content of the resist composition , more preferably about 0.01 to 10% by mass, and still more preferably about 0.1 to 8% by mass , and even still more preferably about 0.1 to 7% by mass.

[0219] <Salts that generate an acid having weaker acidity than the acid generated from the acid generator> The acidity of a salt that generates an acid having weaker acidity than the acid generated from the acid generator (B) is represented by an acid dissociation constant (pKa). An acid having weaker acidity than the acid generated from the acid generator (B) that is generated from the salt is a salt wherein the acid dissociation constant of the acid generated from the salt usually satisfies -3 < pKa, preferably a salt satisfying -1 < pKa < 7, and more preferably a salt satisfying 0 < pKa < 5. Examples of salts that generate an acid having weaker acidity than the acid generated from the acid generator (B) include, represented by the following formula salts, and the salt represented by formula (D) described in JP-A-2015-147926 (hereinafter, " weak acid inner salt (D)" in some cases.), as well as JP-A-2012-229206 , JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and salts described in JP-A-2011-191745. Acid generator As the salt that generates an acid having weaker acidity than the acid generated from (B), preferably, the acid generator is a salt that generates a carboxylic acid having weaker acidity than the acid generated from (B) (carboxylic acid anion containing salt), more preferably a weak acid inner salt (D), still more preferably among weak acid inner salts (D), diphenyliodonium containing a phenyl group substituted with a carboxylic acid anion is a iodonium salt. TIFF0007920396000126.tif116167

[0220] As a weak acid intramolecular salt (D), there is an iodonium cation with two phenyl groups bonded to it, At least one of the two phenyl groups bonded to the iodonium cation It is preferable that the diphenyliodonium salt has a substituted carboxylic acid anion. More specifically, the following salts can be cited.

[0221] TIFF0007920396000127.tif2362[In formula (D), R D1 and R D2 These are, independently, hydrocarbon groups with 1 to 12 carbon atoms and aluminum groups with 1 to 6 carbon atoms. Coxy group, acyl group with 2-7 carbon atoms, acyloxy group with 2-7 carbon atoms, acyloxy group with 2-7 carbon atoms This represents a lucoxycarbonyl group, a nitro group, or a halogen atom. m' and n' each independently represent an integer from 0 to 4, and when m' is 2 or greater... In combination, multiple R D1 They may be the same or different, and if n' is 2 or more, multiple R D2 is the same It may be one or different. R D1 and R D2 Examples of hydrocarbon groups include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic carbon groups. Examples include hydrogen groups and groups formed by combining them. Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, and butyl groups. Alkyl groups such as isobutyl group, tert-butyl group, pentyl group, hexyl group, and nonyl group. One example is the 'L' group. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and can be saturated or unsaturated. Any misalignment is acceptable. Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Cycloalkyl groups such as cyclononyl groups and cyclododecyl groups, norbonyl groups, adamant Examples include chill groups. Examples of aromatic hydrocarbon groups include phenyl group, 1-naphthyl group, 2-naphthyl group, and 2-methyl group. 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, ant Lyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group , biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6- Examples include aryl groups such as ethylphenyl. The groups formed by combining these include alkyl-cycloalkyl groups. , cycloalkyl-alkyl groups, aralkyl groups (e.g., phenylmethyl group, 1-phenyl ethyl 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-propyl Phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group Examples include: Examples of alkoxy groups include methoxy groups and ethoxy groups. Examples of acyl groups include acetyl, propanoyl, benzoyl, and cyclohexanecal. Examples include the bonyl group. Examples of acyloxy groups include groups in which an oxy group (-O-) is bonded to the above-mentioned acyl group. It can be done. As an alkoxycarbonyl group, a carbonyl group (-CO-) is bonded to the above alkoxy group. Examples include combined bases, etc. Examples of halogen atoms include fluorine, chlorine, and bromine atoms. R D1 and R D2 These are, independently, alkyl groups with 1 to 8 carbon atoms and sicq groups with 3 to 10 carbon atoms. alkoxy groups with 1 to 6 carbon atoms, acyl groups with 2 to 4 carbon atoms, and groups with 2 to 4 carbon atoms. Acyloxy group, alkoxycarbonyl group with 2-4 carbon atoms, nitro group, or halogen atom preferable. m' and n' are each preferably independent integers between 0 and 2. It is more preferable that m' is 2 or more, D1 Even if they are the same, they are different Also, if n' is 2 or greater, multiple R D2 They may be the same or different.

[0222] More specifically, the following salts are examples: TIFF0007920396000128.tif72165

[0223] Basic nitrogen-containing organic compounds include amines and ammonium salts. Examples include aliphatic amines and aromatic amines. Aliphatic amines include primary amines. Examples include amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, and diisopropylamine. Ruaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine Octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine mine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, methyldinonylamine, methylddecylamine, ethyl dibuty Luamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine Ethyl dioctylamine, ethyl dinonylamine, ethyl didecylamine, dicyclo Xylmethylamine, Tris[2-(2-methoxyethoxy)ethyl]amine, Triiso Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine Mine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmeth , 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridazole 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl (Lu)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-Pyridyl)ketone, 4,4'-dipyridylsulfide, 4,4'-dipyridyldisulfide Examples include phyto, 2,2'-dipyridylamine, 2,2'-dipicolylamine, and bipyridine. Aromatic amines such as diisopropylaniline are preferred, and more preferably One example is 2,6-diisopropylaniline. Examples of ammonium salts include tetramethylammonium hydroxide and tetraisopropylammonium Ammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl Ammonium hydroxide, tetraoctylammonium hydroxide, phenyl trim Tylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium Examples include nium hydroxide, tetra-n-butylammonium salicylate, and choline. It is possible.

[0224] <Other ingredients> The resist composition of the present invention may optionally include components other than those described above (hereinafter referred to as "other components"). It may be referred to as "F (F)". It may contain other components (F) that are not particularly limited. There are no known additives in the resist field, such as sensitizers, dissolution inhibitors, surfactants, and stabilizers. Agents, dyes, etc. can be used.

[0225] <Preparation of resist composition> The resist composition of the present invention comprises the resin (A) and the acid generator (B) of the present invention, and, if necessary, Accordingly, resin (A2), resin (X), quencher (C), solvent (E), and other components. It can be prepared by mixing (F). The mixing order is arbitrary and not particularly limited. It is not a matter of mixing. The mixing temperature should be between 10 and 40°C, depending on the type of resin and the solvent used. The appropriate temperature can be selected depending on the solubility of (E), etc. The mixing time is the mixing temperature. Depending on the situation, you can choose an appropriate time from 0.5 to 24 hours. Also, mixed methods are available. There are no particular restrictions; stirring and mixing methods can be used. After mixing each component, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable to do so.

[0226] <Method for manufacturing resist patterns> The method for manufacturing a resist pattern of the present invention is: (1) A step of coating the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) Includes a step of developing the composition layer after heating.

[0227] To coat the resist composition onto the substrate, a commonly used device such as a spin coater is used. This can be done. The substrate can be an inorganic substrate such as a silicon wafer, with a resist on the surface. An example is an organic substrate on which a film has been formed. Before applying the resist composition, the substrate is cleaned. Alternatively, an anti-reflective coating or the like may be formed on the substrate. By drying the applied composition, the solvent is removed and a composition layer is formed. Drying is performed. For example, evaporating a solvent using a heating device such as a hot plate (so-called private heating) This is done by (k) or by using a vacuum device. The heating temperature is 50-200°C. It is preferable that the heating time be 10 to 180 seconds. Also, vacuum drying The pressure used during this process is 1 to 1.0 × 10 5 It is preferable that the pressure be around Pa. The resulting composition layer is typically exposed using an exposure machine. The exposure machine is an immersion exposure machine. This is also good. As exposure light sources, KrF excimer laser (wavelength 248nm), ArF excimer Ultraviolet lasers such as lasers (wavelength 193nm) and F2 excimer lasers (wavelength 157nm) Laser light is emitted from solid-state laser sources (such as YAG or semiconductor lasers). These devices emit high-harmonic laser light in the far-ultraviolet or vacuum-ultraviolet region by wavelength conversion, such as electron beams and ultra-high-frequency lasers. Various methods can be used, such as those that irradiate with ultraviolet light (EUV). In some cases, the act of irradiating with these radiations is collectively referred to as "exposure." Typically, exposure is performed through a mask corresponding to the desired pattern. The exposure light source is electron In the case of lines, exposure may be performed by direct drawing without using a mask. The composition layer after exposure is heat-treated to promote the deprotection reaction at the acid-unstable groups. Perform a loose post-exposure bake. The heating temperature is usually around 50-200°C, or as preferred. The temperature is approximately 70-150°C. The hydrophilicity or hydrophobicity of the resin on the surface of the composition after heating. Chemical treatments (silylation) may be performed to adjust the properties. Also, before developing, the post-exposure components may be combined. The process of coating, drying, exposure, and heating of the resist composition may be repeated on the resulting layer. The heated composition layer is typically developed using a developing device and a developing solution. Examples include the dipping method, paddle method, spray method, and dynamic dispensing method. The development temperature is preferably, for example, 5 to 60°C, and the development time is, for example, 5 It is preferable that the developing time is ~300 seconds. By selecting the type of developer as follows: Positive-type resist patterns or negative-type resist patterns can be manufactured. When producing a positive-type resist pattern from the resist composition of the present invention, the developer is used as follows: An alkaline developer is used. The alkaline developer is a type of alkaline water used in this field. Any solution will do. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). Alkaline developers may contain surfactants. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is washed away. It is preferable to remove it. When manufacturing a negative-type resist pattern from the resist composition of the present invention, the developer is used as A developer containing an organic solvent (hereinafter sometimes referred to as "organic developer") is used. Organic solvents contained in organic developers include ketosols such as 2-hexanone and 2-heptanone. Solvents; glycol ethers such as propylene glycol monomethyl ether acetate Sterling solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole Examples include aromatic hydrocarbon solvents such as the like. In organic developer solutions, the content of organic solvents is preferably 90% by mass or more and 100% by mass or less. It is more preferable that the concentration be 95% by mass or more and 100% by mass or less, and that it be substantially composed of only organic solvents. It is preferable. Among organic developers, those containing butyl acetate and / or 2-heptanone are Preferred. The total content of butyl acetate and 2-heptanone in the organic developer is 50% by mass. Preferably, the amount is 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the composition consists solely of butyl acetate and / or 2-heptanone. Organic developers may contain surfactants. Also, organic developers may contain trace amounts of surfactants. It may contain moisture. During development, by substituting a different type of solvent than the organic developer, development can be stopped. That's good too. It is preferable to wash the resist pattern with a rinsing solution after development. The rinsing solution can be: There are no particular restrictions as long as it does not dissolve the resist pattern, including general organic solvents. A liquid can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove any remaining rinse solution from the substrate and patterns.

[0228] <Application> The resist composition of the present invention is a resist composition for KrF excimer laser exposure, and ArF Resist compositions for Kishima laser exposure, resist compositions for electron beam (EB) exposure, or EU Resist compositions for V exposure, particularly resist compositions for ArF excimer laser exposure, electron beam It is suitable as a resist composition for (EB) exposure or EUV exposure, It is useful for the microfabrication of semiconductors. [Examples]

[0229] The present invention will be described in more detail with reference to examples. In the examples, the content or amount used is expressed Unless otherwise specified, "%" and "parts" refer to mass. The weight-average molecular weight was determined by gel permeation chromatography under the following conditions. It is a value. Equipment: HLC-8120GPC model (manufactured by Tosoh Corporation) Column: TSKgel Multipore H XL -M x 3 + guardcolumn (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation) Furthermore, the structure of the compound was determined by mass spectrometry (LC: Agilent 1100, MASS: A This was confirmed by measuring molecular ion peaks using a Gilent LC / MSD (LC / MSD) system. In the following examples, the value of this molecular ion peak is indicated by "MASS".

[0230] Example 1: Synthesis of the compound represented by formula (I-1) TIFF0007920396000129.tif3297 2.24 parts of compound represented by formula (I-1-a), 4 parts of compound represented by formula (I-1-b) 0.40 parts and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the mixture, add 1.76 parts of potassium carbonate, stir at 23°C for 30 minutes, and then further... The mixture was stirred at 90°C for 3 hours. After the resulting mixture was cooled to 23°C, 50 parts of chloroform were added. Then, add 20 parts of deionized water and stir at 23°C for 30 minutes, then separate and remove the organic layer. Then, 20 parts of deionized water were added to the resulting organic layer, and after stirring at 23°C for 30 minutes, The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was concentrated. The concentrated mixture was processed on a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd. By using a developing solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by [company name], 2.14 parts of the compound represented by formula (I-1-c) were obtained. Mix 0.65 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 1.34 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was given by formula (I-1-c). 2.35 parts of the compound were added and the mixture was stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C. After mixing, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate = 1 / 1 By fractionation using ), 2.24 parts of the compound represented by formula (I-1) were obtained. MASS:381.0[M+H] +

[0231] Example 2: Synthesis of the compound represented by formula (I-2) TIFF0007920396000131.tif4397 2.24 parts of compound represented by formula (I-1-a), 9 parts of compound represented by formula (I-2-b) 0.44 parts and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the mixture, add 1.76 parts of potassium carbonate, stir at 23°C for 30 minutes, and then further... The mixture was stirred at 90°C for 3 hours. After the resulting mixture was cooled to 23°C, 50 parts of chloroform were added. Then, add 20 parts of deionized water and stir at 23°C for 30 minutes, then separate and remove the organic layer. Then, 20 parts of deionized water were added to the resulting organic layer, and after stirring at 23°C for 30 minutes, The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was concentrated. The concentrated mixture was processed on a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd. By using a developing solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by [company name], 3.37 parts of the compound represented by formula (I-2-c) were obtained. Mix 0.65 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 1.34 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture contained the compound represented by formula (I-2-c). 4.25 parts of the compound were added and the mixture was stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C. After mixing, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate = 1 / 1 By fractionation using ), 4.03 parts of the compound represented by formula (I-2) were obtained. MASS: 632.8 [M+H] +

[0232] Example 3: Synthesis of the compound represented by formula (I-5) TIFF0007920396000133.tif40100 2.24 parts of compound represented by formula (I-1-a), 3 parts of compound represented by formula (I-5-b) 0.64 parts and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. To the mixture, add 1.76 parts of potassium carbonate, stir at 23°C for 30 minutes, and then further... The mixture was stirred at 90°C for 3 hours. After the resulting mixture was cooled to 23°C, 50 parts of chloroform were added. Then, add 20 parts of deionized water and stir at 23°C for 30 minutes, then separate and remove the organic layer. Then, 20 parts of deionized water were added to the resulting organic layer, and after stirring at 23°C for 30 minutes, The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was concentrated. The concentrated mixture was processed on a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd. By using a developing solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by [company name], 1.46 parts of the compound represented by formula (I-5-c) were obtained. Mix 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 0.94 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was given by formula (I-5-c). Add 1.45 parts of the compound and stir at 50°C for 2 hours. Cool the resulting mixture to 23°C. After mixing, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate = 1 / 1 By fractionation using ), 1.22 parts of the compound represented by formula (I-5) were obtained. MASS:343.1[M+H] +

[0233] Example 4: Synthesis of the compound represented by formula (I-13) TIFF0007920396000135.tif4399 2.24 parts of the compound represented by formula (I-1-a), and the compound represented by formula (I-13-b) Mix 7.24 parts and 20 parts of dimethylformamide and stir at 23°C for 30 minutes. Add 1.76 parts of potassium carbonate to the mixture, stir at 23°C for 30 minutes, and then The mixture was stirred at 90°C for 3 hours. After the resulting mixture was cooled to 23°C, chloroform 50 Add 20 parts of the mixture and 20 parts of deionized water, stir at 23°C for 30 minutes, then separate to obtain the organic layer. After removing it, 20 parts of deionized water were added to the resulting organic layer and stirred at 23°C for 30 minutes. The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was then concentrated. The concentrated mixture was then filtered through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd.) By using a solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Gaku Co., Ltd. Thus, 5.68 parts of the compound represented by formula (I-13-c) were obtained. Mix 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 0.94 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was treated with the formula (I-13-c). Add 2.40 parts of the compound and stir at 50°C for 2 hours. Allow the resulting mixture to cool to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). ) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / By fractionation using (1), 2.34 parts of the compound represented by formula (I-13) were obtained. MASS: 522.9 [M+H] +

[0234] Example 5: Synthesis of the compound represented by formula (I-14) TIFF0007920396000137.tif4190 2.24 parts of compound represented by formula (I-1-a), compound represented by formula (I-14-b) 5.32 parts and 20 parts of dimethylformamide were mixed and stirred at 23°C for 30 minutes. Add 1.76 parts of potassium carbonate to the mixture, stir at 23°C for 30 minutes, and then The mixture was stirred at 90°C for 3 hours. After the resulting mixture was cooled to 23°C, chloroform 50 Add 20 parts of the mixture and 20 parts of deionized water, stir at 23°C for 30 minutes, then separate to obtain the organic layer. After removing it, 20 parts of deionized water were added to the resulting organic layer and stirred at 23°C for 30 minutes. The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was then concentrated. The concentrated mixture was then filtered through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd.) By using a solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Gaku Co., Ltd. Thus, 4.91 parts of the compound represented by formula (I-14-c) were obtained. Mix 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 0.94 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was treated with the formula (I-14-c). Add 1.89 parts of the compound and stir at 50°C for 2 hours. Allow the resulting mixture to cool to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). ) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / By fractionation using (1), 1.78 parts of the compound represented by formula (I-14) were obtained. MASS: 427.0 [M+H] +

[0235] Example 6: Synthesis of the compound represented by formula (I-15) TIFF0007920396000139.tif4188 2.24 parts of the compound represented by formula (I-1-a), and the compound represented by formula (I-15-b) Mix 4.72 parts and 20 parts of dimethylformamide and stir at 23°C for 30 minutes. Add 1.76 parts of potassium carbonate to the mixture, stir at 23°C for 30 minutes, and then The mixture was stirred at 90°C for 3 hours. After the resulting mixture was cooled to 23°C, chloroform 50 Add 20 parts of the mixture and 20 parts of deionized water, stir at 23°C for 30 minutes, then separate to obtain the organic layer. After removing it, 20 parts of deionized water were added to the resulting organic layer and stirred at 23°C for 30 minutes. The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was then concentrated. The concentrated mixture was then filtered through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd.) By using a solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Gaku Co., Ltd. Thus, 3.92 parts of the compound represented by formula (I-15-c) were obtained. Mix 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 0.94 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was then treated with the formula (I-15-c). Add 1.73 parts of the compound and stir at 50°C for 2 hours. Allow the resulting mixture to cool to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). ) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / By fractionation using (1), 1.34 parts of the compound represented by formula (I-15) were obtained. MASS:397.0[M+H] +

[0236] Example 7: Synthesis of the compound represented by formula (I-7) Mix 1.22 parts of the compound represented by formula (I-7-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 1.34 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was treated with the formula (I-14-c). Add 2.70 parts of the compound and stir at 50°C for 2 hours. Allow the resulting mixture to cool to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). ) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / By fractionation using (1), 2.75 parts of the compound represented by formula (I-7) were obtained. MASS:503.0[M+H]+

[0237] Example 8: Synthesis of the compound represented by formula (I-8) Mix 1.55 parts of the compound represented by formula (I-8-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 1.34 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was treated with the formula (I-14-c). Add 2.70 parts of the compound and stir at 50°C for 2 hours. Allow the resulting mixture to cool to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). ) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / By fractionation using (1), 2.86 parts of the compound represented by formula (I-8) were obtained. MASS: 547.0 [M+H] +

[0238] Example 9: Synthesis of the compound represented by formula (I-26) Mix 2.00 parts of the compound represented by formula (I-26-d) and 20 parts of acetonitrile. After stirring at 23°C for 30 minutes, add 1.34 parts of the compound represented by formula (I-1-e). After raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was then labeled with formula (I-14-c). 2.70 parts of the compound were added and stirred at 50°C for 2 hours. The resulting mixture was then cooled to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. After mixing, the mixture was separated to obtain the organic layer. 20 parts of deionized water were added to the resulting organic layer. Then, after stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned to the column (silica gel 60N (spherical, medium). (Pattern) 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate = 1 By fractionation using (1), 2.98 parts of the compound represented by formula (I-26) were obtained. . MASS:607.0[M+H] +

[0239] Example 10: Synthesis of the salt represented by formula (I-18) TIFF0007920396000144.tif5595 3.92 parts of the compound represented by formula (I-18-a), and the compound represented by formula (I-18-b) Mix 5.32 parts of the substance and 20 parts of dimethylformamide and stir at 23°C for 30 minutes. To the mixture, add 1.76 parts of potassium carbonate, stir at 23°C for 30 minutes, and then further... The mixture was stirred at 90°C for 3 hours. After the resulting mixture was cooled to 23°C, chloroform 5 was added. Add 0 parts and 20 parts of deionized water, stir at 23°C for 30 minutes, then separate to obtain the organic layer. The resulting organic layer was mixed with 20 parts of deionized water and stirred at 23°C for 30 minutes. Next, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The obtained organic layer was concentrated. Shrink and concentrate the mixture and process it on a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto region) The solution was to be separated using a solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Chemical Co., Ltd. From this, 6.13 parts of the compound represented by formula (I-18) were obtained. MASS: 443.0 [M+H]+

[0240] Example 11: Synthesis of the compound represented by formula (I-42) TIFF0007920396000145.tif4399 2.24 parts of the compound represented by formula (I-1-a), and the compound represented by formula (I-42-b) Mix 7.24 parts and 20 parts of dimethylformamide and stir at 23°C for 30 minutes. Add 1.76 parts of potassium carbonate to the mixture, stir at 23°C for 30 minutes, and then The mixture was stirred at 90°C for 3 hours. After the resulting mixture was cooled to 23°C, chloroform 50 Add 20 parts of the mixture and 20 parts of deionized water, stir at 23°C for 30 minutes, then separate to obtain the organic layer. After removing it, 20 parts of deionized water were added to the resulting organic layer and stirred at 23°C for 30 minutes. The organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The resulting organic layer was then concentrated. The concentrated mixture was then filtered through a column (silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd.) By using a solvent (n-heptane / ethyl acetate = 1 / 1) manufactured by Gaku Co., Ltd. Thus, 2.81 parts of the compound represented by formula (I-42-c) were obtained. Mix 0.46 parts of the compound represented by formula (I-1-d) and 20 parts of acetonitrile, 2 After stirring at 3°C ​​for 30 minutes, add 0.94 parts of the compound represented by formula (I-1-e), and 5 After raising the temperature to 0°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was then treated with the formula (I-42-c). Add 2.40 parts of the compound and stir at 50°C for 2 hours. Allow the resulting mixture to cool to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). ) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / By fractionation using (1), 1.89 parts of the compound represented by formula (I-42) were obtained. MASS: 522.9 [M+H] +

[0241] Example 12: Synthesis of the compound represented by formula (I-47) Mix 2.00 parts of the compound represented by formula (I-26-d) and 20 parts of acetonitrile. After stirring at 23°C for 30 minutes, add 1.34 parts of the compound represented by formula (I-1-e). After raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was then labeled with formula (I-13-c). 3.42 parts of the compound were added and stirred at 50°C for 2 hours. The resulting mixture was then cooled to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. After mixing, the mixture was separated to obtain the organic layer. 20 parts of deionized water were added to the resulting organic layer. Then, after stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned to the column (silica gel 60N (spherical, medium). (Pattern) 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate = 1 By fractionation using (1), 4.38 parts of the compound represented by formula (I-47) were obtained. . MASS:702.9[M+H] +

[0242] Example 13: Synthesis of the compound represented by formula (I-48) Mix 2.00 parts of the compound represented by formula (I-26-d) and 20 parts of acetonitrile. After stirring at 23°C for 30 minutes, add 1.34 parts of the compound represented by formula (I-1-e). After raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was then labeled with formula (I-42-c). 3.42 parts of the compound were added and stirred at 50°C for 2 hours. The resulting mixture was then cooled to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. After mixing, the mixture was separated to obtain the organic layer. 20 parts of deionized water were added to the resulting organic layer. Then, after stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned to the column (silica gel 60N (spherical, medium). (Pattern) 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate = 1 By fractionation using (1), 2.89 parts of the compound represented by formula (I-48) were obtained. . MASS:702.9[M+H] +

[0243] Example 14: Synthesis of the compound represented by formula (I-50) Mix 2.00 parts of the compound represented by formula (I-26-d) and 20 parts of acetonitrile. After stirring at 23°C for 30 minutes, add 1.34 parts of the compound represented by formula (I-1-e). After raising the temperature to 50°C, the mixture was stirred at 50°C for 2 hours. The resulting mixture was then treated with the formula (I-1-c). Add 2.35 parts of the compound and stir at 50°C for 2 hours. Allow the resulting mixture to cool to 23°C. After cooling, add 50 parts chloroform and 20 parts deionized water and stir at 23°C for 30 minutes. Afterward, the organic layer was separated by liquid-liquid extraction. 20 parts of deionized water were added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated by liquid-liquid extraction. This washing procedure was repeated five times. The mixture was returned. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral)). ) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1 / By fractionation using (1), 3.67 parts of the compound represented by formula (I-50) were obtained. MASS: 561.0 [M+H] +

[0244] Resin synthesis The compounds (monomers) used in the synthesis of the resin are shown below. Hereinafter, these compounds will be referred to as "monomers (a1-2-6)" etc., according to their formula numbers. (TIFF0007920396000150.tif196163)

[0245] Example 15 [Synthesis of Resin A1] Monomers include acetoxystyrene, monomer (I-1), and monomer (a1-2-6 ), monomer (a2-1-3) and monomer (a3-4-2) are used, and their molar ratio [Ace Toxystyrene: Monomer (I-1): Monomer (a1-2-6): Monomer (a2-1 -3): The monomers (a3-4-2) are arranged in a ratio of 32:10:43:3:12. Mix them together, and further, add 1.5 mass of this monomer mixture relative to the total mass of all monomers. Twice the amount of methyl isobutyl ketone was mixed in. To the resulting mixture, azobisiso was added as an initiator. Butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total amount of monomers Then, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to extract the resin. By precipitating, filtering, and recovering, the weight-average molecular weight is approximately 5.5 × 10⁻⁶. 3 resin A A solution 1 was obtained with a yield of 78%. This resin A1 has the following structural units. TIFF0007920396000151.tif37161

[0246] Example 16 [Synthesis of Resin A2] Monomers include acetoxystyrene, monomer (I-2), and monomer (a1-2-6 ), monomer (a2-1-3) and monomer (a3-4-2) are used, and their molar ratio [Ace Toxystyrene: Monomer (I-2): Monomer (a1-2-6): Monomer (a2-1 -3): The monomers (a3-4-2) are arranged in a ratio of 32:10:43:3:12. Mix them together, and further, add 1.5 mass of this monomer mixture relative to the total mass of all monomers. Twice the amount of methyl isobutyl ketone was mixed in. To the resulting mixture, azobisiso was added as an initiator. Butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total amount of monomers Then, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to extract the resin. By precipitating, filtering, and recovering, the weight-average molecular weight is approximately 5.6 × 10⁻⁶. 3 resin A Compound 2 was obtained with a yield of 73%. This resin A2 has the following structural units. TIFF0007920396000152.tif37164

[0247] Example 17 [Synthesis of Resin A3] Monomers include acetoxystyrene, monomer (I-5), and monomer (a1-2-6). ), monomer (a2-1-3) and monomer (a3-4-2) are used, and their molar ratio [Ace Toxystyrene: Monomer (I-5): Monomer (a1-2-6): Monomer (a2-1 -3): The monomers (a3-4-2) are arranged in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 mass of this monomer mixture relative to the total mass of all monomers. Twice the amount of methyl isobutyl ketone was mixed in. To the resulting mixture, azobisiso was added as an initiator. Butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total amount of monomers Then, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to extract the resin. By precipitating, filtering, and recovering, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 resin A Resin A3 was obtained with a yield of 73%. This resin A3 has the following structural units. TIFF0007920396000153.tif38158

[0248] Example 18 [Synthesis of Resin A4] Monomers include acetoxystyrene, monomer (I-7), and monomer (a1-2-6). ), monomer (a2-1-3) and monomer (a3-4-2) are used, and their molar ratio [Ace Toxystyrene: Monomer (I-7): Monomer (a1-2-6): Monomer (a2-1 -3): The monomers (a3-4-2) are arranged in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 mass of this monomer mixture relative to the total mass of all monomers. Twice the amount of methyl isobutyl ketone was mixed in. To the resulting mixture, azobisiso was added as an initiator. Butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total amount of monomers Then, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to extract the resin. By precipitating, filtering, and recovering, the weight-average molecular weight is approximately 5.2 × 10⁻⁶. 3 resin A Resin A4 was obtained with a yield of 78%. This resin A4 has the following structural units. TIFF0007920396000154.tif57156

[0249] Example 19 [Synthesis of Resin A5] Monomers include acetoxystyrene, monomer (I-8), and monomer (a1-2-6). ), monomer (a2-1-3) and monomer (a3-4-2) are used, and their molar ratio [Ace Toxystyrene: Monomer (I-8): Monomer (a1-2-6): Monomer (a2-1 -3): The monomers (a3-4-2) are arranged in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 mass of this monomer mixture relative to the total mass of all monomers. Twice the amount of methyl isobutyl ketone was mixed in. To the resulting mixture, azobisiso was added as an initiator. Butyronitrile and azobis(2,4-dimethylvaleronitrile) relative to the total amount of monomers Then, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to extract the resin. By precipitating, filtering, and recovering, the weight-average molecular weight is approximately 5.5 × 10⁻⁶. 3 resin A Formulation 5 was obtained with a yield of 80%. This resin A5 has the following structural units. TIFF0007920396000155.tif65158

[0250] Example 20 [Synthesis of Resin A6] Monomers include acetoxystyrene, monomer (I-13), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-13): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 The tree Resin A6 was obtained in a yield of 68%. This resin A6 has the following structural units. TIFF0007920396000156.tif44160

[0251] Example 21 [Synthesis of Resin A7] Monomers include acetoxystyrene, monomer (I-14), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-14): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.4 × 10⁻⁶. 3 The tree Resin A7 was obtained in a yield of 83%. This resin A7 has the following structural units. TIFF0007920396000157.tif44160

[0252] Example 22 [Synthesis of Resin A8] Monomers include acetoxystyrene, monomer (I-15), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-15): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 The tree Resin A8 was obtained in a yield of 76%. This resin A8 has the following structural units. TIFF0007920396000158.tif43159

[0253] Example 23 [Synthesis of Resin A9] Monomers include acetoxystyrene, monomer (I-18), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-18): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.4 × 10⁻⁶.3 The tree Resin A9 was obtained in a yield of 79%. This resin A9 has the following structural units. TIFF0007920396000159.tif45159

[0254] Example 24 [Synthesis of Resin A10] Monomers include acetoxystyrene, monomer (I-26), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-26): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.7 × 10⁻⁶. 3 The tree Resin A10 was obtained in a yield of 85%. This resin A10 has the following structural units. TIFF0007920396000160.tif50164

[0255] Example 25 [Synthesis of Resin A11] Monomers include acetoxystyrene, monomer (I-42), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-42): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.1 × 10⁻⁶. 3 The tree Resin A11 was obtained in a yield of 63%. This resin A11 has the following structural units. TIFF0007920396000161.tif45162

[0256] Example 26 [Synthesis of Resin A12] Monomers include acetoxystyrene, monomer (I-47), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-47): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.5 × 10⁻⁶. 3 The tree Resin A12 was obtained in a yield of 78%. This resin A12 has the following structural units. TIFF0007920396000162.tif50163

[0257] Example 27 [Synthesis of Resin A13] Monomers include acetoxystyrene, monomer (I-48), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-48): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.2 × 10⁻⁶.3 The tree Resin A13 was obtained in a yield of 66%. This resin A13 has the following structural units. TIFF0007920396000163.tif50163

[0258] Example 28 [Synthesis of Resin A14] Monomers include acetoxystyrene, monomer (I-50), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (I-50): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.6 × 10⁻⁶. 3 The tree Resin A14 was obtained in a yield of 88%. This resin A14 has the following structural units. TIFF0007920396000164.tif50163

[0259] Synthesis Example 1 [Synthesis of Resin AX1] As monomers, acetoxystyrene, monomer (IX-1), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (IX-1): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 27:10:48:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.5 × 10⁻⁶. 3 The tree Resin AX1 was obtained in a yield of 77%. This resin AX1 has the following structural units. TIFF0007920396000165.tif38163

[0260] Synthesis Example 2 [Synthesis of Resin AX2] Monomers include acetoxystyrene, monomer (IX-2), monomer (a1-2- 6) Using monomers (a2-1-3) and monomers (a3-4-2), their molar ratio [A Cethoxystyrene: Monomer (IX-2): Monomer (a1-2-6): Monomer (a2 -1-3): The monomers (a3-4-2) are in a ratio of 32:10:43:3:12. Mix them together, and further, add 1.5 of the total mass of all monomers to this monomer mixture. A mass of methyl isobutyl ketone was mixed with the mixture. To the resulting mixture, azobis was added as an initiator. Isobutyronitrile and azobis(2,4-dimethylvaleronitrile) are added to the total amount of monomers. In contrast, 1.2 mol% and 3.6 mol% were added, respectively, and these were heated at 73°C for approximately 5 hours. Then, a 25% aqueous solution of tetramethylammonium hydroxide was added to the polymerization reaction solution. After stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the lipids and then filtering and recovering them, the weight-average molecular weight is approximately 5.8 × 10⁻⁶. 3 The tree Resin AX2 was obtained in a yield of 71%. This resin AX2 has the following structural units. TIFF0007920396000166.tif38163

[0261] <Preparation of the resist composition> The mixture obtained by mixing and dissolving each component shown in Table 1 was then processed using a pore size of 0.2 μm. The resist composition was prepared by filtering through an electropolymer filter. [Table 1]

[0262] <Resin> A1~A14, AX1, AX2: Resin A1~Resin A14, Resin AX1, Resin AX2 <Acid Generator (B)> B1-43: Salt represented by formula (B1-43) (Implementation of Japanese Patent Publication No. 2016-47815) (Synthesized according to the example) TIFF0007920396000168.tif4383<Quencher(C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 TIFF0007920396000169.tif4347D1: (Manufactured by Tokyo Chemical Industry Co., Ltd.) TIFF0007920396000170.tif1932<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0263] (Electron beam exposure evaluation of resist compositions) A 6-inch silicon wafer is subjected to hexamethyldisilaza on a direct hot plate. The silicon wafer was treated at 90°C for 60 seconds using a solvent. The resist composition was then applied to this silicon wafer. The layer was spin-coated to a thickness of 0.04 μm. Then, direct hot plated... On the grid, the composition layer was formed by pre-baking for 60 seconds at the temperature shown in the "PB" column of Table 1. A composition layer formed on the surface is subjected to electron beam lithography (ELS-F1 manufactured by Elionix Co., Ltd.). Using "25 125 keV", the exposure amount is changed in stages, and after development, line and shading is performed. The image was drawn directly to create a grid pattern (pitch 60nm / line width 30nm). After exposure, post-exposure is performed on a hot plate at the temperature shown in the "PEB" column of Table 1 for 60 seconds. Jar baking was performed. Next, the composition layer on this silicon wafer was treated with acetic acid as the developer. Using butyl (manufactured by Tokyo Chemical Industry Co., Ltd.), dynamic dispensing was performed at 23°C for 20 seconds. A resist pattern was obtained by developing the material according to the specified method. The obtained resist pattern (line and space pattern) is observed using a scanning electron microscope. I guess the line width and space width of the 60nm pitch line and space pattern are 1: The exposure level at which the value becomes 1 was defined as the effective sensitivity.

[0264] Line Edge Roughness Evaluation (LER): Sidewall of a resist pattern manufactured with effective sensitivity. The amplitude of surface irregularities was measured using a scanning electron microscope to determine the line edge roughness. The results are shown in Table 2. [Table 2] Compared with comparative compositions 1 and 2, the unevenness of the sidewall surface of the resist pattern in compositions 1 to 15 The amplitude of the vibration was small, and the line edge roughness evaluation was good. [Industrial applicability]

[0265] A resist composition containing the compound of the present invention and a resin containing structural units derived from the compound. It exhibits good line edge roughness (LER) and is useful for microfabrication of semiconductors.

Claims

1. A compound represented by formula (I). [In formula (I), R ０ This represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. X １ This represents a bonding species selected from the group consisting of ether bonds, ester bonds, and carbonate ester bonds, or a linking group formed by combining a single bond, an ether bond, an ester bond, and a carbonate ester bond with at least one or two bonding species selected from the group consisting of a single bond, an ether bond, an ester bond, and a carbonate ester bond, and an arylene group which may have a substituent. L １ This represents a hydrocarbon group having 1 to 28 carbon atoms, which may have single bonds or substituents, and the hydrocarbon group contains -CH 2 - is -O-, -S-, -SO ２ It may be replaced with - or -CO-. Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have substituents. X ２ This represents an oxygen atom or a sulfur atom. R １ This represents a fluorine atom, a bromine atom, an iodine atom, or a haloalkyl group having 1 to 12 carbon atoms. R ２ This represents an iodine atom, a fluorine atom, a hydroxyl group, a perfluoroalkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. m1 represents an integer from 1 to 6, and when m1 is 2 or greater, the bases within the parentheses may be the same or different. 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.]]

2. A compound represented by formula (I). [In formula (I), R0 represents an alkyl group having 1 to 6 carbon atoms, which may contain a halogen atom, a hydrogen atom, or a halogen atom. X1 represents a bonding species selected from the group consisting of ether bonds, ester bonds, and carbonate ester bonds, or a linking group formed by combining a single bond, an ether bond, an ester bond, and a carbonate ester bond with at least one or two bonding species selected from the group consisting of single bonds, ether bonds, ester bonds, and carbonate ester bonds, and an arylene group which may have a substituent. L1 represents a single bond or *-L2-CO-O-, L2 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 with an alkanediyl group having 1 to 4 carbon atoms. The cyclic hydrocarbon group may have substituents, and the -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO-, or -SO2-, and the -CH2- contained in the alkanediyl group may be replaced with -O- or -CO-. * represents the bonding site with X1. Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, which may have substituents. X² represents either an oxygen atom or a sulfur atom. R1 represents a fluorine atom, a bromine atom, an iodine atom, or a haloalkyl group having 1 to 12 carbon atoms. R2 represents a halogen atom, a hydroxyl group, a C1-C12 haloalkyl group, or a C1-C12 alkyl group, and the -CH2- contained in the haloalkyl group and the alkyl group may be replaced with -O- or -CO-. m1 represents an integer from 1 to 6, and when m1 is 2 or greater, the bases within the parentheses may be the same or different. m² represents an integer between 0 and 4, and when m² is 2 or greater, multiple R² values ​​may be the same or different from each other.

3. X １ However, equation (X １ -1) ~Formula (X １ The compound according to claim 1 or 2, wherein the group is represented by any of the following (-7). [Formula (X)] １ -1) ~ Equation (X) １ -7) Middle * and ** represent bonding sites, and ** is L 1 This represents the connection point with [the other element].

4. X １ However, equation (X １ -1), formula (X １ -3) or formula (X １ The compound according to claim 3, wherein the group is represented by -4).

5. L １ However, single bonds or *-L ２ -CO-O-(L ２ This 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 with an alkanediyl group having 1 to 4 carbon atoms, and the cyclic hydrocarbon group may have substituents, and the cyclic hydrocarbon group contains -CH 2 - stands for -O-, -S-, -CO-, or -SO ２ - may be replaced by -CH contained in the alkanediyl group. 2 - may be replaced with -O- or -CO-. * represents X １ The compound according to claim 1 or any of claims 3 and 4 that refer to claim 1, which represents the binding site with ).

6. The compound according to any one of claims 1 to 5, wherein Ar is an aromatic hydrocarbon group having 6 to 10 carbon atoms, which may have substituents.

7. X ２ The compound according to any one of claims 1 to 6, wherein the atom is an oxygen atom.

8. R １ The compound according to any one of claims 1 to 7, wherein the compound is an iodine atom, a fluorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms.

9. A resin comprising a structural unit derived from any one of the compounds described in claims 1 to 8.

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