Method for manufacturing resist compositions and resist patterns

Abstract

Provided is a resist composition capable of producing a resist pattern having good CD uniformity (CDU). 【Solution means】A resist composition containing a compound represented by formula (I), a resin having an acid-labile group, and an acid generator. JPEG2026123019000153.jpg4169 [In the formula, R 1 is *-O-CO-R 10 etc.; L 1 is a single bond or an alkanediyl group which may have a halogen atom; R 10 is a group represented by formula (1b); R 2 is *-L 1 -R 1 etc.; R 3 at least one of which is a halogen atom or a haloalkyl group; R ba1 and R ba2 are each a hydrogen atom, a fluorine atom or an alkyl group having a fluorine atom; R ba3 represents a fluorine atom or an alkyl group having a fluorine atom.]

Description

Technical Field

[0001] The present invention relates to a resist composition and a method for producing a resist pattern using the resist composition. and the like.

Background Art

[0002] Patent Document 1 describes a resist composition containing a compound represented by the following structural formula, a resin having an acid-labile group, and an acid generator. and a resist pattern formed from the resist composition. TIFF2026123019000001.tif2789

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] To provide a resist composition that forms a resist pattern with better CD uniformity (CDU) than a resist pattern formed from the above resist composition. This is the problem.

Means for Solving the Problems

[0005] The present invention includes the following inventions. 〔1〕A resist composition containing a compound represented by formula (I), a resin having an acid-labile group, and an acid generator. TIFF2026123019000002.tif4458[In formula (I), R , , , , , , , , , ,

[0004] , 10 , 10 , ,

[0005] , , , , , , , , 10 ,

[0003] , , 10 , , 1 is *-O-R 10 、*-O-CO-R 10 、*-O-CO-O-R 10 、*-C O-O-R 10 ​, *-O-L 2 -CO-O-R 10 or *-CO-O-L 2 -CO-O- R 10 represents, and * represents the bonding site with L 1 and L 1 represents a C1-C6 alkanediyl group which may have a single bond or a substituent L 2 represents a C1-C6 alkanediyl group R 10 represents a base-labile group R 2 is *-L 1 -OH, *-L 1 -CO-OH, *-L 1 -R​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​m2 represents an integer between 0 and 5, and when m2 is 1 or greater, multiple L 1 and multiple R 1 Each of them may be the same or different from each other, and when m2 is 2 or more, multiple R 2 They may be identical or different from one another. R 3 This includes halogen atoms, C1-C12 haloalkyl groups, or C1-C12 alkyl groups. The alkyl group is represented, and the -CH2- contained in the alkyl group is replaced with -O- or -CO-. It's okay to be there. m3 represents an integer between 0 and 5, and when m3 is 2 or greater, multiple R 3 They are the same It may be one or different, provided that 0 ≤ m² + m³ ≤ 5. [2] L 1 However, C1-C4 alkanediyls may have single bonds or halogen atoms. The resist composition described in [1] is the base. [3] R 10 The base-unstable group is the group represented by formula (1b) as indicated in [1] or [2]. The resist composition shown. TIFF2026123019000003.tif2056 [In formula (1b), R ba1 and R ba2 These are, independently, a hydrogen atom, a fluorine atom, or This represents an alkyl group with 1 to 6 carbon atoms that contains a fluorine atom. R ba3 This represents a fluorine atom or an alkyl group having 1 to 6 carbon atoms that contains a fluorine atom. * indicates a connection site. [4] R 2 However, *-L 1 -OH, *-L 1 -CO-OH, *-L 1 -R 1 , *-X 1 - Ph-L 1 -OH or *-X 1 -Ph-L 1-R 1 (* represents the bonding site with the benzene ring .) The resist composition according to any one of [1] to [3]. 〔5〕X 1 is a single bond, an alkanediyl group having 1 to 3 carbon atoms which may have a halogen atom , -O-, -S-, -CO-, -SO- or -SO2-. The resist composition according to any one of [1] to [4]. 〔6〕R 3 is a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 3 carbon atoms, a alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. The resist composition according to any one of [1] to [5]. 〔7〕The resin having an acid-labile group is at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1 ) and a structural unit represented by formula (a1-2). The resist composition according to any one of [1] to [6]. TIFF2026123019000004.tif44144[In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 each independently represents -O- or *-O-(CH2) k1 -CO-O-. k1 represents an integer of 1 to 7. * represents the bonding site with -CO- . R a01 , R a4 and R a5 each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, a Alicyclic hydrocarbon groups with 3 to 18 prime numbers, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof It represents the combined 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. [8] Resins having acid-unstable groups include structural units represented by formula (a2-A) [1]~ A resist composition as described in any of [7]. TIFF2026123019000005.tif3844[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 an 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 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 Xa52 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. [9] The acid generator contains a salt represented by formula (B1) as described in any of [1] to [8]. Resist composition. TIFF2026123019000006.tif2862[In formula (B1), Q b1 and Q b2 These are, independently, a hydrogen atom, a fluorine atom, and an alkyl group with 1 to 6 carbon atoms. This represents a perfluoroalkyl group or a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and 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 by S-, -SO2-, or -CO-. Z1 + This represents an organic cation.

[10] 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 [9].

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

[10] 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, (5) A method for manufacturing a resist pattern, comprising the step of developing the composition layer after heating. [Effects of the Invention]

[0006] By using the resist composition of the present invention, a resist with good CD uniformity (CDU) can be produced. Patterns can be manufactured. [Modes for carrying out the invention]

[0007] In this specification, "(meth)acrylic monomer" means "acrylic monomer and This means "at least one methacrylate monomer." "(meth)acrylate" and " The notation "(meth)acrylic acid," etc., also has the same meaning. In the groups described herein, For substances that can take both a linear and branched structure, either is acceptable. Hydrocarbon group The -CH2- contained in etc. is replaced by -O-, -S-, -CO-, -SO- or -SO2- In such cases, the same example shall apply to each group. “Combined groups” refers to examples. This refers to a group formed by bonding two or more of the aforementioned groups, and the valence of these groups is appropriately changed depending on the bonding configuration. It is also acceptable. "Derived from" or "induced from" means that polymerizable C=C bonds contained in the molecule. This refers to the process where a compound undergoes polymerization to form a -CC- group (single bond). If stereoisomers exist... , including all stereoisomers. In this specification, "solid content of the resist composition" means the amount of solids of the resist composition that is added to the total amount of solids of the resist composition. This refers to the sum of the components excluding the solvent (E) described above.

[0008] <Resist Composition> The resist composition of the present invention is a compound represented by formula (I) (hereinafter referred to as "compound (I)"). (In some cases) and a resin having an acid-unstable group (hereinafter sometimes referred to as "resin (A)"), It contains an acid generator (hereinafter sometimes referred to as "acid generator (B)"). A "stable group" has a leaving group, and upon contact with an acid, the leaving group is removed, resulting in a hydrophilic group (for example, a hydrophilic group). This refers to a group that converts into a constituent unit having a hydroxyl group or a carboxyl group. 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).

[0009] <Compound (I)> The resist composition of the present invention contains compound (I). TIFF2026123019000007.tif4458[In formula (I), all signs have the same meaning as defined above.]

[0010] L 1 and L 2 Examples of alkanediyl groups in this context include methylene group, ethylene group, and propane group. -1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexa Linear alkanediyl groups such as n-1,6-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 thealkanediyl group is preferably 1 to 4, more preferably 1 to 3. L 1 Examples of the substituent that thealkanediyl group of may have include a halogen atom, a hydroxy group , a cyano group, a carboxy group, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a group formed by combining two or more of these groups. are exemplified. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. etc. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 9, more preferably 1 to 6, still more preferably 1 to 4, and even more preferably 1 to 3 . Examples of the haloalkyl group having 1 to 6 carbon atoms represent an alkyl group having a halogen atom, and include a fluoroalkyl group, a chloroalkyl group, a bromoalkyl group, an iodoalkyl group, etc. Examples of the haloalkyl group include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group , a perfluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a perfluoro butyl group, a 1,1,2,2,3,3,4,4-octafluorobutyl group, a perfluoro pentyl group, a 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, a perfluoro hexyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, etc. The number of carbon atoms in the haloalkyl group is preferably 1 to 4, more preferably 1 to 3. 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 Examples include the following. The number of carbon atoms in the alkoxy group is preferably 1 to 9, and more preferably 1 It is ~6, more preferably 1~4, and even more preferably 1~3.

[0011] Groups combining two or more types include alkoxycarbonyl groups with 2 to 13 carbon atoms and carbon Alkylcarbonyl groups with 2 to 13 carbon atoms and alkylcarbonyloxy groups with 2 to 13 carbon atoms, etc. These are some examples. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and Alkylcarbonyloxy groups having 2 to 13 carbon atoms are the alkyl or alkoxy groups mentioned above. This represents a group in which a carbonyl group or a carbonyloxy group is bonded to a cy group. 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. L 1 This is an alkanediyl group having 1 to 4 carbon atoms, which may have single bonds or substituents. Preferably, a C1-C4 alkanediyl group which may have a single bond or a halogen atom. More preferably, an alkane having 1 to 4 carbon atoms, which may have single bonds or fluorine atoms. It is more preferable that it is a diyl group, and it may be a single bond or an alkanediyl group having 1 to 3 carbon atoms, and it is even more preferable that it is a single bond or -C(CF3)2-, and it is even more preferable that it is as described above. L 2 is preferably an alkanediyl group having 1 to 3 carbon atoms, and more preferably a methylene group.

[0012] R 1 The base-labile group contained in R 10 means that when it comes into contact with a base (for example, an aqueous solution of 2.38% tetramethylammonium hydroxide), a leaving group containing a group represented by R is eliminated, and when R 10 is a group represented by -O-R R 1 -O-CO-R 10 or -O-CO-O-R 10 a hydroxy group is formed in R 10 and when R is a group represented by -CO-O-R 1 -O-L 1 -CO-O-R 10 -CO-O-L 2 -CO-O-R 10 or -CO-O-L 2 ​​​​​​​​​​​​​​​​​​​​​​​​* indicates a connection site.

[0013] R ba1 , R ba2 and R ba3 Examples of alkyl groups having a fluorine atom include, Trifluoromethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 2 ,2,3,3,3-pentafluoropropyl group, 1-trifluoromethyl-2,2,2- Trifluoroethyl group, perfluoropropyl group, 2,2,3,3,4,4,4-hepta Fluorobutyl group, perfluorobutyl group, 2,2,3,3,4,4,5,5,5-nonano Examples include fluoropentyl groups, perfluoropentyl groups, and perfluorohexyl groups. The number of carbon atoms in the alkyl group having a fluorine atom is preferably 1 to 5, more preferably The range is 1 to 4, and more preferably 1 to 3. R ba1 It is preferable that this is a hydrogen atom or a fluorine atom. R ba2 It is preferable that this is a hydrogen atom, a fluorine atom, or a trifluoromethyl group. R ba3 This includes a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms, or a perfluoroalkyl group having 2 to 5 carbon atoms. It is preferably a perfluoroalkylmethyl group, and is a fluorine atom or a perfluoroalkylmethyl group having 1 to 4 carbon atoms. It is more preferable that the alkyl group be a fluoroalkyl group. -C(R ba1 )(R ba2 )(R ba3 ) are perfluorocarbons with 1 to 4 carbon atoms. Lukyl group, perfluoroalkylmethyl group having 1 to 4 carbon atoms, or 1-trifluoromethyl group Preferably a 2,2,2-trifluoroethyl group, and a perfluoro group having 1 to 4 carbon atoms. It is more preferable that the group be an alkyl group or a perfluoroalkylmethyl group having 1 to 4 carbon atoms. . R 1 is *-O-CO-R 10 *-CO-OR 10 or *-OL 2 -CO-O- R 10 It is preferable that it be *-O-CO-R 10 Or *-CO-OR 10 This is This is preferable. * is L 1 This represents the connection point.

[0014] X 1 The alkanediyl groups in this context include methylene, ethylene, and 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; and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl Examples include branched alkanediyl groups such as the 2-methylbutane-1,4-diyl group. The number of carbon atoms in the lucandiyl group is preferably 1 to 4, and more preferably 1 to 3. X 1 The -CH2- contained in the alkanediyl group in this case is -O-, -S-, -CO-, - It may be replaced with SO- or -SO2-. 1 The alkanediyl group in The -CH2- is replaced by -O-, -S-, -CO-, -SO-, or -SO2-. In this case, the number of carbon atoms before replacement shall be the number of carbon atoms in the alkanediyl group. The -CH2- contained in the alkanediyl group is -O-, -S-, -CO-, -SO- or The group that replaced -SO2- is the hydroxyl group (the -CH2- contained in the methyl group). However, the group replaced by -O-), carboxyl group (the -CH2-CH2- contained in the ethyl group) However, the group replaced by -O-CO-, the oxy group (the -CH2- contained in the methylene group) , a group replaced by -O-), carbonyl group (the -CH2- contained in the methylene group, - (a group replaced by CO-), a thio group (where the -CH2- contained in the methylene group is replaced by -S-) (The replaced group), sulfonyl group (the -CH2- contained in the methylene group is replaced by -SO2-) (Replaced group), alkanediyloxy group (any position contained within the alkanediyl group) (A group in which -CH2- is replaced by -O-), an alkanediyloxycarbonyl group (alka Any -CH2-CH2- group at any position in the nucleotide group is replaced by -O-CO-. (group), alkanediylcarbonyl group (-CH at any position contained within the alkanediyl group) 2- is a group in which -CO- is replaced, alkanediylcarbonyloxy group (alkanedi (A group in which any -CH2-CH2- at any position within the yl group is replaced by -CO-O-) , an alkanediylthio group (where -CH2- is located at any position within the alkanediyl group, - (S- replaced group), alkanediylsulfonyl group (contained within the alkanediyl group) Examples include groups in which -CH2- at any position is replaced by -SO2-. Examples of alkanediyloxy groups include those with 1 to 5 carbon atoms. For example, methyleneoxy group, ethyleneoxy group, propanediyloxy group, butanediyl Examples include the ruoxy group and the pentanediyloxy group. Alkanediyloxycarbonyl groups include those with 2 to 5 carbon atoms. Examples of carbonyl groups include methyleneoxycarbonyl group, ethyleneoxycarbonyl group, etc. Examples include the yl group, propanediyloxycarbonyl group, and butanediyloxycarbonyl group. Alkanediylcarbonyl groups include alkanediylcarbonyl groups with 2 to 6 carbon atoms. Examples of such groups include methylene carbonyl group, ethylene carbonyl group, and propanediyl group. Examples include carbonyl groups, butanediylcarbonyl groups, and pentanediylcarbonyl groups. As for the alkanediylcarbonyloxy group, alkanediylcarbonyl groups with 2 to 5 carbon atoms are Examples of oxy groups include methylene carbonyloxy groups and ethylene carbonyloxy groups. Examples include the cy group, propanediyl carbonyloxy group, and butanediyl carbonyloxy group. It can be done. Examples of alkanediylthio groups include alkanediylthio groups having 1 to 5 carbon atoms, for example Examples include methylenethio groups, ethylenethio groups, and propylenethio groups. Alkanediylsulfonyl groups include alkanediylsulfonyl groups with 1 to 5 carbon atoms. Examples include methylene sulfonyl group, ethylene sulfonyl group, and propylene sulfonyl group. Examples include the 'L' group. X 1 The alkanediyl group may have substituents such as halogen atoms and hydroxyl groups. cyano group, carboxyl group, C1-C12 alkyl group, C1-C6 haloalkyl group Examples include carbon atoms, alkoxy groups with 1 to 12 carbon atoms, and groups formed by combining two or more of these groups. Get, L 1 The alkanediyl group may have substituents similar to those listed above. It is possible. X 1 This includes single bonds, alkanediyl groups having 1 to 6 carbon atoms which may have substituents, -O-, - It is preferably S-, -CO-, -SO-, or -SO2-, and consists of a single bond and a halogen atom. A carbon-1 to carbon-3 alkanediyl group, -O-, -S-, -CO-, -SO- Or, more preferably, it is -SO2- and has a single bond, a fluorine atom or an iodine atom. A carbon-1 to carbon-3 alkanediyl group, -O-, -S-, -SO- or -SO2- It is even more preferable that this be the case.

[0015] R 2 The substituents that the pH may have include halogen atoms, hydroxyl groups, cyano groups, Carboxylic group, C1-C12 alkyl group, C1-C6 haloalkyl group, C1 Examples include ~12 alkoxy groups and groups formed by combining two or more of these groups. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. ru. Examples of alkyl groups with 1 to 12 carbon atoms include methyl, ethyl, propyl, and isopropyl groups. butyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl Examples include C13 groups and nonyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 9. Preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3 That is the case. A haloalkyl group having 1 to 6 carbon atoms represents an alkyl group having a halogen atom, and Examples include alkyl groups of iodides, alkyl groups of chlorides, alkyl groups of bromides, and alkyl groups of iodides. Examples of haloalkyl groups include trifluoromethyl groups, difluoromethyl groups, and perfluoromethyl groups. Tyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group , perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, perflu Olobutyl group, 1,1,2,2,3,3,4,4-Octafluorobutyl group, Perfluoro Lopentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, Perph Examples include the ruolohexyl group, chloromethyl group, bromomethyl group, and iodomethyl group. The number of carbon atoms in the haloalkyl group is preferably 1 to 4, and more preferably 1 to 3. 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 Examples include the following. The number of carbon atoms in the alkoxy group is preferably 1 to 9, and more preferably 1 It is ~6, more preferably 1~4, and even more preferably 1~3.

[0016] Groups combining two or more types include alkoxycarbonyl groups with 2 to 13 carbon atoms and carbon Alkylcarbonyl groups with 2 to 13 carbon atoms and alkylcarbonyloxy groups with 2 to 13 carbon atoms, etc. These are some examples. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and Alkylcarbonyloxy groups having 2 to 13 carbon atoms are the alkyl or alkoxy groups mentioned above. This represents a group in which a carbonyl group or a carbonyloxy group is bonded to a cy group. 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. Ph is a halogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. It is preferably a phenylene group which may have a haloalkyl group, and may contain a fluorine atom, iodine It is more preferable that the phenylene group may have an atom or a trifluoromethyl group. m2 is preferably an integer from 0 to 4, and more preferably an integer from 0 to 3. , more preferably an integer from 0 to 2, more preferably 1 or 2, and even more preferably 1 Even more preferable. R 2 is, *-L 1 -OH, *-L 1 -CO-OH, *-L 1 -R 1 , *-X 1 -Ph- L 1 -OH or *-X 1 -Ph-L 1 -R 1 It is preferable that * represents a benzene ring and This represents the joining site. R 2 R 2 In the benzene ring to which L is bonded, 1 For the binding position, ortho, meta They may be bonded at any position in the para or meta position, but at least one is bonded at the meta or para position. It is preferable that they match. In particular, when m2 is 1, R 2 L 1 at the joining position In contrast, it is preferable that the bond is at the meta or para position. When m2 is 2, R 2 teeth , L 1 With respect to the binding site, one atom is bonded at the ortho or meta position, and the other atom is bonded at the meta position or It is preferable that it is bonded in the para position. When m2 is 3, R 2 L 1 Bonding position In this case, two are bonded at the ortho or meta position, and one is bonded at the meta or para position. It is preferable that m2 is 4, 2 L 1 With respect to the bonding position, the two It is preferable that the two atoms are bonded at the ortho or meta position, and that they are bonded at the meta or para position. It's nice. Also, R 2 However, *-X 1 -Ph-L 1 -OH, *-X 1 -Ph-L 1 -CO-OH, * -X 1 -Ph-L 1 -R 1 , *-X 1 -Ph-L 1 -OR 1 or *-X 1 -Ph-L 1 -CO-OR 1 If this is the case, X will bind to Ph. 1 and L 1 This refers to Ph's ortho, meta, and pa They may be bonded at any position in the R position, but they are bonded so that they are in the para position relative to each other. This is preferable.

[0017] R 3 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. It can be done. R 3 A C1-C12 haloalkyl group is a C1-C12 group that has a halogen atom. This represents alkyl groups, specifically alkyl fluorides with 1 to 12 carbon atoms and alkyl chlorides with 1 to 12 carbon atoms. Examples include C1-C12 alkyl bromides and C1-C12 alkyl iodides. As for haloalkyl groups, perfluoroalkyl groups (trifluoro) having 1 to 12 carbon atoms are used. Methyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group (Perfluoropentyl group, perfluorohexyl group, etc.), fluoromethyl group, difluoro methyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group Pyr group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl 1,1,2,2,3,3,4,4-Octafluorobutyl group, 2,2,3,3,4 ,4,5,5,5-nonafluoropentyl group, chloromethyl group, bromomethyl group, iodine Examples include methyl groups. The number of carbon atoms in the haloalkyl group is preferably 1 to 9, and more preferably The number is 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. be. R 3 Examples 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.

[0018] R 3 In the alkyl group, the -CH2- is replaced by -O- or -CO-. In addition, the number of carbon atoms before replacement is defined as the total number of carbon atoms in the alkyl group. The replaced group is: Hydroxyl group (a group in which the -CH2- contained in a methyl group is replaced by -O-), Carbo Xy group (a group in which the -CH2-CH2- contained in the ethyl group is replaced with -O-CO-), Oxy group (a group in which the -CH2- contained in the methylene group is replaced by -O-), carbony Alkyl group (a group in which the -CH2- contained in the methylene group is replaced with -CO-), alkoxy A group (a group in which -CH2- at any position within an alkyl group is replaced by -O-), The lucoxycarbonyl group (where the -CH2-CH2- at any position within the alkyl group is -O A group replaced by -CO-), an alkylcarbonyl group (any position contained within the alkyl group) (A group in which the -CH2- is replaced by -CO-), alkylcarbonyloxy group (alkyl (A group in which any -CH2-CH2- at any position within the group is replaced by -CO-O-), Examples include groups that combine two or more of these groups. Examples of alkoxy groups include alkoxy groups having 1 to 11 carbon atoms, such as methoxy. Groups such as ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy groups Examples include: The number of carbon atoms in the alkoxy group is preferably 1 to 6, and more preferably 1 to 4. It is 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 basis. 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. 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 The number of carbon atoms in the alkylcarbonyl group is preferably 4, and more preferably 2 or 3. k is 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the lucylcarbonyloxy group is preferably 2 to 6, more preferably 2 to 4. It is more preferably 2 or 3.

[0019] R 3 Each of these is independently preferably a fluorine atom, an iodine atom, a hydroxyl group, and a carbon number 1-6 haloalkyl groups or alkyl groups having 1-6 carbon atoms (the alkyl group contains -CH 2- may be replaced by -O- or -CO-), and more preferably fluorine. Atoms, iodine atoms, hydroxyl groups, C1-C4 alkyl fluorides or C1-C4 Alkyl group (the -CH2- contained in the alkyl group is replaced by -O- or -CO-) (May also be present) and more preferably a fluorine atom, an iodine atom, and a perf atom having 1 to 3 carbon atoms. A ruoroalkyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. More preferably, it is a fluorine atom, an iodine atom, or a trifluoromethyl group. m3 is preferably an integer between 0 and 4, and is also an integer between 0 and 3. It is more preferable that it be an integer of any integer between 0 and 2, and even more preferably 1 or 2 It is even more preferable that it be so. R 3 R 3 In the benzene ring to which L is bonded, 1 For the binding position, ortho, meta , it may be coupled at any position in the para position, but if m2 is 0, at least one It is preferable that it is bonded at the meta or para position, specifically, when m3 is 1, It is preferable that the bond is in the ortho or para position, and if m3 is 2, one is in the ortho position or It is bonded at the meta position, and preferably one is bonded at the meta or para position, m3 If the number is 3, then two are bonded at the ortho or meta position, and one is bonded at the meta or para position. It is preferable that they are bonded, and if m3 is 4, the two are bonded at the ortho or meta position. It is preferable that the two are bonded at the meta or para position. Also, m2 is 1 or more. In some cases, it is preferable that at least one is bonded to the ortho or meta position, and specifically When m3 is 1, it is preferably bonded to the ortho or meta position, and when m3 is 2 In this case, it is preferable that the two are bonded at the ortho or meta position, and m3 is 3. In this case, two are bonded at the ortho or meta position, and one is bonded at the meta or para position. It is preferable that, when m3 is 4, three are bonded to the ortho or meta position, and 1 It is preferable that the two atoms are bonded at the meta or para position. Also, if m3 is 2 or more, Preferably, at least two of them are bonded to each other in either the meta or para position.

[0020] Compound (I) includes compounds represented by the following formula. TIFF2026123019000009.tif184132

[0021] TIFF2026123019000010.tif247146

[0022] TIFF2026123019000011.tif241135

[0023] TIFF2026123019000012.tif227149

[0024] TIFF2026123019000013.tif229160

[0025] The content of compound (I) is typically 0.001 to 20 based on the solid content of the resist composition. The amount is in mass%, preferably 0.005 to 15 mass%, more preferably 0.01 to 10 mass%. ru.

[0026] <Resin (A)> Resin (A) is a structural unit having an acid-unstable group (hereinafter referred to as "structural unit (a1)"). It is preferable that the resin (A) further contains structural units other than structural unit (a1). It is so. Structural units other than structural unit (a1) include structural units that do not have acid-unstable groups ( (Sometimes referred to as "structural unit (s)"), structural unit (a1), and other structural units (s) Structural units (for example, structural units having halogen atoms as described later (hereinafter referred to as "structural units (a4)") (There are cases where this occurs), structural units having non-eliminating hydrocarbon groups (hereinafter referred to as "structural units (a) 5) In some cases, this refers to structural units derived from monomers known in the field, etc. These are some examples.

[0027] <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. TIFF2026123019000014.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. TIFF2026123019000015.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.

[0028] 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. TIFF2026123019000016.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-. TIFF2026123019000017.tif31139

[0029] 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. TIFF2026123019000018.tif18130R a1’ and R a2’ Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0030] 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. TIFF2026123019000019.tif144153

[0031] The following are specific examples of group (2). * indicates a bonding site. TIFF2026123019000020.tif55153

[0032] 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.

[0033] 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.

[0034] 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 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. TIFF2026123019000021.tif46152[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 basis. 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.

[0035] 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 La2 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 , R a04 , R a6 and R a7 Alkyl groups, alkenyl groups, alicyclic groups in Hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these include R of group (1). a1 , R a2 and R a3 Similar groups to those listed above can be cited. R a02 , R a03 , and R a04 The alkyl group in 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 a6 and 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.

[0036] 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. TIFF2026123019000022.tif88160

[0037] 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 ni 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. TIFF2026123019000023.tif41168

[0038] 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. JPEG2026123019000024.jpg63162

[0039] If resin (A) contains structural unit (a1-0), its content is the total structural unit of resin (A). For each position, it is usually 5-80 mol%, preferably 5-75 mol%, and more preferably The percentage is between 10 and 70 mol%. If resin (A) contains structural unit (a1-1) and / or structural unit (a1-2), The total content of these is typically 10 to 90 mol% relative to the total structural units of resin (A), and is preferable. More preferably 15-85 mol%, more preferably 20-80 mol%, and even more preferably More preferably, it is 20-75 mol%, and more preferably 20-70 mol%.

[0040] 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. TIFF2026123019000025.tif4868[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 a33 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 a30 is a single bond or * -X a31 -(A a32 -X a32 ) nc - represents -Ra32 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 one another. 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.

[0041] 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.

[0042] *-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-Aa32 -O-CO-, These include *-CO-O- and *-CO-OA. a32 -CO-O- or *- OA a32 -CO-O- is preferred.

[0043] 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.

[0044] 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-.

[0045] 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. TIFF2026123019000026.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.

[0046] R a34Preferably, 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.

[0047] 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 -4-10), formula (a1-4-13), formula (a1-4-14), formula (a1-4-19), The structural units are represented by equation (a1-4-20). TIFF2026123019000027.tif127160

[0048] 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.

[0049] 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. TIFF2026123019000028.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 a value, and h3 is one of 1 to 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.

[0050] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of C1-C6 alkyl groups that may have halogen atoms include methyl group and ethyl group. propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, flu Examples include oromethyl groups and trifluoromethyl groups. In equation (a1-5), R a8 This is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 A single bond or *-CH2-CO-O- is preferred.

[0051] 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. TIFF2026123019000029.tif33133

[0052] 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.

[0053] In addition, the following structural units (a1) can also be listed. TIFF2026123019000030.tif31162

[0054] 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.

[0055] In addition, the following structural units (a1) can also be listed. TIFF2026123019000031.tif4994 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.

[0056] <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.

[0057] <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.

[0058] 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. TIFF2026123019000032.tif4855[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 an 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.

[0059] 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. Ra50 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.

[0060] *-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.

[0061] 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.

[0062] 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-.

[0063] mb is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. At least one hydroxyl group can be attached to the m- or p-position of the benzene ring. Preferably, the phenyl group is bonded at the m-position, and more preferably, at the m-position. If present, it is preferable that the two hydroxyl groups are bonded to the m- and p- positions, respectively. It seems so.

[0064] As for the structural unit (a2-A), see Japanese Patent Publication No. 2010-204634, Japanese Patent Publication No. 2012- Examples include monomer-derived structural units described in Publication No. 12577. The structural unit (a2-A) is represented by equations (a2-2-1) to (a2-2-24). 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 haloalkyl groups or other alkyl groups. Structural unit ( a2-A) is a structural unit represented by formulas (a2-2-1) to (a2-2-4), formula (a2 Structural units represented by formula (a2-2-8), formula (a2-2 -12)~Structural units represented by formula (a2-2-18) and formula (a2-2-1)~formula (a2 Structural units represented by formula (a2-2-4), structural units represented by formula (a2-2-6), formula (a2-2 -8) Structural units represented by formulas (a2-2-12) to (a2-2-18) In the structural unit, R in the structural unit (a2-A) a50 The methyl group corresponding to the hydrogen atom It is preferable that the structural unit is replaced by the structural unit represented by formula (a2-2-3). , structural units represented by formula (a2-2-4), structural units represented by formula (a2-2-8), formula (a2-2-12) ~ Structural units represented by equation (a2-2-14), equation (a2-2-18) Structural units represented by and structural units represented by formula (a2-2-3), and formula (a2-2-4) The structural units represented, the structural units represented by formula (a2-2-8), formula (a2-2-12) to formula The structural units represented by formula (a2-2-14) and formula (a2-2-18) And, in the structural unit (a2-A) R a50 The corresponding methyl group is replaced by a hydrogen atom. It is more preferable that the structural unit is a structural unit represented by formula (a2-2-3), formula ( Structural units represented by formula (a2-2-4), structural units represented by formula (a2-2-8), and formula (a Structural units represented by formula (a2-2-3), structural units represented by formula (a2-2-4), formula (a2- In the structural unit represented by 2-8), R in structural unit (a2-A) a50 This corresponds to It is even more preferable that the structural unit is one in which the methyl group is replaced by a hydrogen atom. TIFF2026123019000033.tif79169

[0065] Content of structural unit (a2-A) when structural unit (a2-A) is present in resin (A) This is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, relative to the total structural units. It is mol%, more preferably 15-65 mol%, and even more preferably 20- It is 65 mol%. Structural unit (a2-A) is polymerized using structural unit (a1-4), for example, and then p-Tol It can be incorporated into resin (A) by treating it with an acid such as ene sulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0066] 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. TIFF2026123019000034.tif4562 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 -CO-O- represents, k2 represents an integer between 1 and 7. * represents a connection site with -CO-. R a14 represents a hydrogen atom or a methyl group. Ra15 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.

[0067] 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.

[0068] 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. JPEG2026123019000035.jpg47132

[0069] If resin (A) contains structural units (a2-1), the content of these units is the total structural unit content of resin (A). For each position, it is usually 1 to 45 mol%, preferably 1 to 40 mol%, and more preferably The amount is 1 to 35 mol%, more preferably 1 to 20 mol%, and even more preferably The percentage is between 1 and 10 mol%.

[0070] <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.

[0071] 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. TIFF2026123019000036.tif52164[In formulas (a3-1), (a3-2), (a3-3), and (a3-4), L a4 , L a5 and L a6 These are, independently, -O- or *-O-(CH2) k3 -C This represents a base represented by OO-(where k3 is an integer from 1 to 7). L a7 is -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- represents vinegar. L a8 and L a9 Each of these independently represents an alkanediyl group with 1 to 6 carbon atoms. * indicates a bonding site with a carbonyl group. R a18 , R a19 and R a20 Each of these independently represents either a hydrogen atom or a methyl group. R a24 This is a hydrogen atom, a halogen atom, or a C1-C1 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.

[0072] R a21 , R a22 , R a23 and R a25 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.

[0073] 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.

[0074] 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 a23Each 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.

[0075] 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). TIFF2026123019000037.tif3849 (in the formula, R a24 , L a7 (This expresses the same meaning as above.)

[0076] 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.

[0077] JPEG2026123019000038.jpg116165

[0078] If resin (A) contains structural units (a3), the total content of these units is the total structural unit content of resin (A). The amount is usually 5-70 mol%, preferably 10-65 mol%, and more preferably It is either 10-60 mol% or 10-60 mol%. Also, structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structure The content of units (a3-4) is 5 to 60 units relative to the total structural units of resin (A), respectively. % is preferred, 5 to 50 mol% is more preferred, and 10 to 50 mol% is even more preferred.

[0079] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF2026123019000039.tif2862[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 This represents a saturated hydrocarbon group having a halogen atom with 1 to 24 carbon atoms, and the 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.

[0080] 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. TIFF2026123019000040.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.

[0081] 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). TIFF2026123019000041.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.

[0082] L 4aThe 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.

[0083] 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.

[0084] 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.

[0085] 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. JPEG2026123019000042.jpg95166

[0086] TIFF2026123019000043.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. TIFF2026123019000044.tif1488 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44Each 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.

[0087] 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.

[0088] 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. TIFF2026123019000045.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.

[0089] R a42 The substituents it possesses include halogen atoms and groups represented by formula (a-g3). At least one selected from the group is mentioned. Examples of halogen atoms include fluorine atoms, Examples include chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. TIFF2026123019000046.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.

[0090] 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). TIFF2026123019000047.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.

[0091] 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.

[0092] 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). TIFF2026123019000048.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 a44 This 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.

[0093] 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.

[0094] The preferred structure of the group represented by formula (a-g2) is as follows (* represents a carbonyl group) (This is the junction site.) TIFF2026123019000049.tif14160

[0095] A a41 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 Linear alkanediyl groups such as ,6-diyl groups; propane-1,2-diyl groups, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- Examples include branched alkanediyl groups such as diyl groups and 2-methylbutane-1,4-diyl groups. ru. A a41 The substituents on the alkanediyl group include a hydroxyl group and a carbon-1 to carbon-6 group. Examples include alkoxy groups. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a carbon number The group is an alkanediyl group of type 2 to 4, and more preferably an ethylene group.

[0096] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Divalent saturated carbonized water The elemental groups include linear or branched alkanediyl groups and monocyclic or polycyclic divalent alicyclic saturated carbon. By combining a hydrogenated group, as well as an alkanediyl group and a divalent alicyclic saturated hydrocarbon group... Examples include divalent saturated hydrocarbon groups formed from these groups. Specifically, methylene groups, ethylene groups, etc. n group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group Iyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl Examples include the 2-methylpropane-1,2-diyl group. 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.

[0097] In the group represented by formula (a-g1), X a42 -O-, -CO-, -CO-O- or The following are examples of groups that are -O-CO-. In the following examples, * and ** represents a binding site, and ** is -O-CO-R a42 This is the junction site. JPEG2026123019000050.jpg46140

[0098] 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: JPEG2026123019000051.jpg92135

[0099] TIFF2026123019000052.tif132150

[0100] 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). TIFF2026123019000053.tif4256[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 This represents an alkanediyl group having 1 to 6 carbon atoms, and the -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.

[0101] 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 a42 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.

[0102] 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.

[0103] TIFF2026123019000054.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. ). Af14 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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 with 3 to 12 carbon atoms and a group with 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.

[0108] Examples of structural units represented by equation (a4-3) include equation (a4-1'-1) ~ equation (a The structural units represented in 4-1'-11) are listed below. Keru R f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also shown in formula (a4-3). It can be cited as a structural unit.

[0109] As a structural unit (a4), the structural unit represented by formula (a4-4) can also be cited. TIFF2026123019000055.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.

[0110] R f22 The saturated hydrocarbon group is R a42 Examples include saturated hydrocarbon groups similar to those represented by the symbol. Rf22 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.

[0111] 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.

[0112] 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. JPEG2026123019000056.jpg87160

[0113] If resin (A) contains structural units (a4), the content of these units is equal to the total structural units of resin (A). For this, 1 to 20 mol% is preferred, 2 to 15 mol% is more preferred, and 3 to 10 mol% That is even more preferable.

[0114] <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). . TIFF2026123019000057.tif3555[In formula (a5-1), R 51represents 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-.

[0115] 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.

[0116] 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.

[0117] 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. TIFF2026123019000058.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 x5This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 Each of these independently consists of a single bond or a divalent aliphatic saturated carbon with 1 to 14 carbon atoms. It represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 This represents a divalent alicyclic saturated hydrocarbon group with 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0118] 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 x7Preferably, 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.

[0119] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF2026123019000059.tif53135

[0120] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF2026123019000060.tif23130

[0121] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF2026123019000061.tif15145

[0122] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF2026123019000062.tif26114

[0123] L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0124] Structural units (a5-1) include the structural units shown below and the structural units within the following structural units ( a5-1) R51 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF2026123019000063.tif111150 If resin (A) contains structural unit (a5), its content is the total structural unit of resin (A). For this, 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 3 to 15 mol% That is even more preferable.

[0125] <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.

[0126] 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 it is preferable that it be 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. TIFF2026123019000064.tif3087

[0127] 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.

[0128] 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.

[0129] 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. TIFF2026123019000065.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 at any location. 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.

[0130] As a sultone ring, the ring represented by formula (T1) is more preferable. TIFF2026123019000066.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 at any location.

[0131] 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.

[0132] The following are examples of rings represented by equation (T1') and equation (T1): The connection point can be at any position. TIFF2026123019000067.tif47144

[0133] The structural unit having a sultone ring preferably has the following group: * in the following group The symbol represents the bonding site. TIFF2026123019000068.tif45144

[0134] 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.

[0135] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF2026123019000069.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 R d Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] The following are examples of structural units (a6): TIFF2026123019000070.tif93150

[0140] 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.

[0141] <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.

[0142] 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'). TIFF2026123019000071.tif3189 [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. A x1 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.

[0143] 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 a8A 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.

[0144] 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 cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclo Cycloalkanes such as xane-1,4-diyl groups and cyclooctane-1,5-diyl groups Divalent monocyclic or alicyclic saturated hydrocarbon groups such as the 1,4-diyl group; norbornane-1,4-diyl group, Lunan-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6- Examples include divalent polycyclic and alicyclic saturated hydrocarbon groups such as diyl groups.

[0145] 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. TIFF2026123019000072.tif145161

[0146] X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 This represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0147] 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, it may be referred to as "cation (b2-1)," etc.) These are some examples.

[0148] 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. JPEG2026123019000073.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 bEach is independently a fluorine atom or a perfluoroal with 1 to 6 carbon atoms. [Represents the kill group.]

[0149] R III2 , R III4 Q a and Q b Perfluoroalkyl compounds with 1 to 6 carbon atoms, represented by As for the group Q, see the aforementioned Q b1 This is the same as a perfluoroalkyl group with 1 to 6 carbon atoms, as represented by This is one example.

[0150] 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. TIFF2026123019000074.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.

[0151] 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.

[0152] 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. TIFF2026123019000075.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.

[0153] 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. TIFF2026123019000076.tif86163

[0154] 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. JPEG2026123019000077.jpg3381 [In formula (II-1-1), A II1 This represents a single bond or a divalent linking group. R II1 This represents a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms. R II2 and R II3Each 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-C1 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.

[0155] The structural units containing cations in formula (II-1-1) are the structural units represented below, R II4 The 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. TIFF2026123019000078.tif85130

[0156] A - Examples of organic anions represented by this include sulfonic acid anions and sulfonylimido anions. Examples include sulfonylmethide anions and carboxylic acid anions. - It is represented The organic anion is preferably a sulfonate anion, and the sulfonate anions are described below. Examples include anions similar to those found in the salt represented by formula (B1).

[0157] A - Examples of sulfonylimid anions represented by the formula include the following: TIFF2026123019000079.tif36136

[0158] Examples of sulfonylmethide anions include the following: TIFF2026123019000080.tif29123

[0159] Examples of carboxylic acid anions include the following: TIFF2026123019000081.tif51152

[0160] Examples of structural units represented by formula (II-1-1) include the following structural units. It is possible. JPEG2026123019000082.jpg88149

[0161] 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%.

[0162] The resin (A) may contain 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.

[0163] The resin (A) is preferably a resin consisting of structural unit (a1) and structural unit (s), In other words, it is a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably structural unit (a1-0), structural unit (a1-1), and At least one selected from the group consisting of structural units (a1-2), more preferably, At least one selected from the group consisting of structural unit (a1-1) and structural unit (a1-2) More preferably, a group consisting of structural unit (a1-1) and structural unit (a1-2). It consists of at least two types selected from the following. The structural unit (s) is preferably from the group consisting of structural unit (a2) and structural unit (a3). It is at least one selected. The structural unit (a2) is preferably represented by formula (a2-1). It is a structural unit represented by formula (a2-A). The structural unit (a3) ​​is preferred Alternatively, structural units represented by formula (a3-1), structural units represented by formula (a3-2), and formula ( It is at least one selected from the group consisting of structural units represented in a3-4).

[0164] Each structural unit constituting resin (A) may be used individually or in combination of two or more types. Furthermore, using monomers that derive these structural units, known polymerization methods (e.g., radical polymerization) can be used. Therefore, it can be manufactured. The content of each structural unit in resin (A) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (A) is preferably 2,000 or more (more preferably 2,5 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 (less than 15,000, more preferably less than 15,000). In this specification, weight average fraction The amount of molecules was determined by gel permeation chromatography under the conditions described in the examples. That is the case.

[0165] <Resins other than resin (A)> The resist composition of the present invention may contain resins other than resin (A). Examples of resins other than resin (A) include structural unit (a4) or structural unit (a5). Examples include resins (hereinafter sometimes referred to as resin(X)).

[0166] Among the resins (X), resins containing structural units (a4) are preferred. In resin (X), the content of structural unit (a4) is equal to the sum of all structural units in resin (X). In contrast, it is preferable that the amount be 30 mol% or more, and more preferably 40 mol% or more. Furthermore, it is more preferable that the amount be 45 mol% or more. The structural units that resin (X) may further possess include structural unit (a2) and structural unit (a3) and other structural units derived from known monomers are examples. Among them, resin ( X) is preferably a resin consisting only of structural unit (a4) and / or structural unit (a5). It is more preferable that the resin consists solely of structural units (a4). Each structural unit constituting the resin (X) may be used individually or in combination of two or more types. These monomers that induce structural units can be used in known polymerization methods (e.g., radical polymerization). Therefore, it can be manufactured. The content of each structural unit in resin (X) is used in polymerization. This can be adjusted by controlling the amount of monomer used. The weight-average molecular weight of resin (X) is preferably 6,000 or more (more preferably 7,000). The value is 0 or greater, and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight-average molecular weight is the same as in the case of resin (A). If the resist composition contains resin (X), its content is as follows: per 100 parts by mass of resin (A) Preferably, it is 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, and further Preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 1 The layer is preferably 1 to 8 parts by mass.

[0167] 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.

[0168] <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.

[0169] 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.

[0170] The acid generator (B) is preferably a salt represented by formula (B1) (hereinafter referred to as "acid generator (B1)") (There are cases where this is true.) TIFF2026123019000083.tif2961[In formula (B1), Q b1 and Q b2 These are, independently, a hydrogen atom, a fluorine atom, and an alkyl group having 1 to 6 carbon atoms. Alternatively, it represents a perfluoroalkyl group having 1 to 6 carbon atoms. L b1 This represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and contains The -CH2- group 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 by S-, -SO2-, or -CO-. Z1 + This represents an organic cation.

[0171] Q b1 and Q b2 Examples of perfluoroalkyl groups include trifluoromethyl group, perfluoro ethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl Perfluoro group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include pentyl groups and perfluorohexyl groups. Q b1 and Q b2 Examples of alkyl groups include methyl group, ethyl group, propyl group, and isopropyl group. Pyr group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. These are some examples. Q b1 and Q b2 It contains at least one fluorine atom or a perfluoroalkyl group. Preferably, at least one of them is a fluorine atom or a perfluoroalkyl group. More preferably, each independently comprises a fluorine atom or a trifluoromethyl group. More preferably, both are fluorine atoms.

[0172] L b1 Examples of divalent saturated hydrocarbon groups in this context include linear alkanediyl groups and branched alkanediyl groups. Examples include dipropyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these groups It may also be a group formed by combining two or more of these types. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- Linear alkanediyl groups such as diyl groups; 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.

[0173] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The substituted base can be represented, for example, by any of the following equations: (b1-1) to (b1-3). The bases are listed. Furthermore, the bases represented by formulas (b1-1) to (b1-3) and their specific examples are In the example bases represented by formulas (b1-4) to (b1-11), * and ** are bonding parts. The position is indicated, and * represents the connection site with -Y.

[0174] TIFF2026123019000084.tif26117[In formula (b1-1), L b2 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in 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 group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms. L b5 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. L b7 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the saturated hydrocarbon group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups, and the saturated carbon The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0175] In the groups represented by formulas (b1-1) to (b1-3), the saturated hydrocarbon group is included. If -CH2- is replaced by -O- or -CO-, the number of carbon atoms before replacement is... This is the number of carbon atoms in the hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups. ru. L b2 Preferably, the bond consists of a single bond, a methylene group, -CH(CF3)-, and -C(CF3)2-. be. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 Preferably, the divalent saturated hydrocarbon group has 1 to 8 carbon atoms, and the divalent saturated hydrocarbon water The hydrogen atoms in the elementary group may be substituted with fluorine atoms. L b5 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 The saturated hydrocarbon group is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. The hydrogen atoms in the hydrogen group may be substituted with fluorine atoms. L b7 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated The hydrogen atoms in the hydrocarbon group may be substituted with fluorine atoms or hydroxyl groups. The -CH2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO-. That's good too.

[0176] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by -O- or -CO- The replaced group is preferably the group represented by formula (b1-1) or formula (b1-3). The base represented by equation (b1-1) is shown in equations (b1-4) to (b1-8), respectively. The basis for this is listed below. TIFF2026123019000085.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 group The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxyl groups. In formula (b1-5), L b9 This represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and contains The -CH2- group may be replaced by -O- or -CO-. L b10 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 This represents a divalent saturated hydrocarbon group with 1 to 21 carbon atoms. L b12 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 This represents a divalent saturated hydrocarbon group with 1 to 19 carbon atoms. L b14 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The -CH2- group contained in the hydrogenated group may be replaced by -O- or -CO-. L b15 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b13 ~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 this divalent saturated hydrocarbon group The -CH2- group may be replaced by -O- or -CO-. L b17 This represents a divalent saturated hydrocarbon group with 1 to 18 carbon atoms. L b18 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms. The hydrogen atoms in the hydrogenated group may be substituted with fluorine atoms or hydroxyl groups. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. L b8 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b11 Preferably, it is a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 This is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b16 This is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 This is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0177] 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. TIFF2026123019000086.tif22140[In formula (b1-9), L b19 This represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the 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 L b26 The total number of carbon atoms is 21 or less.

[0178] 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.

[0179] The following are examples of bases represented by formula (b1-4): TIFF2026123019000087.tif17150

[0180] The following are examples of bases represented by formula (b1-5): TIFF2026123019000088.tif72149

[0181] The following are examples of bases represented by formula (b1-6): TIFF2026123019000089.tif30150

[0182] The following are examples of bases represented by formula (b1-7): TIFF2026123019000090.tif64150

[0183] The following are examples of bases represented by formula (b1-8): TIFF2026123019000091.tif23150

[0184] The following are examples of bases represented by formula (b1-2): JPEG2026123019000092.jpg31161

[0185] The following are examples of bases represented by formula (b1-9): TIFF2026123019000093.tif44137

[0186] The following are examples of bases represented by formula (b1-10): JPEG2026123019000094.jpg89157

[0187] The following are examples of bases represented by formula (b1-11): TIFF2026123019000095.tif82158

[0188] The -CH2- contained in the alicyclic hydrocarbon group represented by Y is -O-, -S-, -SO2- or Examples of alicyclic hydrocarbon groups that have not been replaced by -CO- include formulas (Y1) to ( Examples of bases include those represented by equations (Y11), (Y36) to (Y38). The -CH2- contained in the alicyclic hydrocarbon group represented by Y is -O-, -S-, -SO2- or When -CO- is replaced, the number of replacements may be one or two or more. Examples include the bases expressed by equations (Y12) to (Y35) and (Y39) to (Y43). It can be expressed by the base represented by equations (Y12) to (Y35) and (Y39) to (Y43). O- or -CO- may be replaced by -S- or -SO2-. * is L b1 The conclusion This indicates the joining point. The alicyclic hydrocarbon group represented by TIFF2026123019000096.tif84165Y is preferably formula (Y1) to formula (Y20), formula ( Y26), equation (Y27), equation (Y30), equation (Y31), equation (Y39) to equation (Y43) A group represented by any of the following, more preferably by formula (Y11), formula (Y15), or formula (Y16) ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39) A group represented by formula (Y40), formula (Y42), or formula (Y43), more preferably Alternatively, see equation (Y11), equation (Y15), equation (Y20), equation (Y26), equation (Y27), equation ( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42), or formula (Y43) It is a base represented by . The alicyclic hydrocarbon group represented by Y is given by formulas (Y28) to (Y35), (Y39), and (Y 40) If it is a spiro ring containing an oxygen atom, such as formula (Y42) or formula (Y43), 2 The alkanediyl group between the oxygen atoms preferably has one or more fluorine atoms. Furthermore, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom It is preferable that the fluorine atom is not substituted.

[0189] The substituents of the methyl group represented by Y include halogen atoms, hydroxyl groups, and groups with 3 to 1 carbon atoms. 6 alicyclic hydrocarbon groups, C6-C18 aromatic hydrocarbon groups, glycidyloxy groups, -( CH2) ja -CO-OR b1 Base or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 teeth, Alkyl groups with 1 to 16 carbon atoms, alicyclic hydrocarbon groups with 3 to 16 carbon atoms, and aromatic groups with 6 to 18 carbon atoms. This represents a fragrant hydrocarbon group or a group formed by combining these groups, and the alkyl group and the alicyclic hydrocarbon. The -CH2- group may be replaced by -O-, -SO2-, or -CO-. The hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are It may be replaced by a droxy group or a fluorine atom. ja is an integer from 0 to 4. Examples include: ) which represent... 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.

[0190] 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 Examples include phenyl groups, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 14. Furthermore, it is 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 groups and ethylsulfonyl groups. Examples include propyl sulfonyl groups. The number of carbon atoms in the alkyl sulfonyl group is preferably 1. It is ~12, more preferably 1~6, and even more preferably 1~4. 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.

[0191] The following are examples of Y: TIFF2026123019000097.tif171163

[0192] 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 carbonized water The -CH2- group constituting the elementary group or adamantyl group is replaced with -O-, -SO2-, or -CO-. It may be replaced. Specifically, Y is preferably an adamantyl group, a hydroxyadamantine group. A group of oxycodyl group, an oxoadamantyl group, or formula (Y42), formula (Y100) to formula (Y114), formula ( Y134) is the base represented by equation (Y139).

[0193] The anions in the salt represented by formula (B1) are given by formula (B1-A-1) ~ formula (B1- Anions represented by A-62) (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-6 An anion represented by either of the two in (2) is more preferable.

[0194] TIFF2026123019000098.tif231164

[0195] TIFF2026123019000099.tif238165

[0196] TIFF2026123019000100.tif201159

[0197] 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.

[0198] Preferably, the anion in the salt represented by formula (B1) is formula (B1a-1) ~ formula ( The anions represented by B1a-40 are listed below. TIFF2026123019000101.tif125153

[0199] TIFF2026123019000102.tif92138

[0200] TIFF2026123019000103.tif197154

[0201] 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-4 An anion represented by any of the following is preferred.

[0202] Z1 + Examples of organic cations include organic onium cations and organic sulfonium cations. Organic iodium cation, organic ammonium cation, benzothiazolium cation and Examples include organic phosphonium cations. Among these, organic sulfonium cationic cations are particularly noteworthy. N and organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) ( Below, depending on the formula number, it may be referred to as "cation (b2-1)," etc. ) is an example. In formulas (b2-1) to (b2-4) of TIFF2026123019000104.tif46167, 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 Rb8 They may be the same or different. R b9 and R b10 Each of these is independently a chain-like hydrocarbon group having 1 to 36 carbon atoms or a group having 3 to 3 carbon atoms. It represents 36 alicyclic hydrocarbon groups. R b9 and R b10 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. It may be done, and the -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. That's good too. R b11 This consists of a hydrogen atom, a chain hydrocarbon group with 1 to 36 carbon atoms, and an alicyclic carbon group with 3 to 36 carbon atoms. This represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 This refers to a chain-type hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or This represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in this chain-like hydrocarbon group are carbon It may be substituted with an aromatic hydrocarbon group having prime numbers 6 to 18, and the aromatic hydrocarbon group contains The hydrogen atom is a carbon-1 to carbon-12 alkoxy group or a carbon-1 to carbon-12 alkyl carbonyl group. It may be substituted with an oxy group. 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. R b13 and R b14 This refers to the fact that they bond with each other and together with the benzene ring to which they bond, they form sulfurous compounds. A ring containing a child may be formed, and the -CH2- contained in the ring may be -O-, -S-, or -CO - may be used instead. 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.

[0203] 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. TIFF2026123019000105.tif11158 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.

[0204] 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.

[0205] Aromatic hydrocarbon groups include phenyl, biphenyl, naphthyl, and phenanthryl groups. Examples include aryl groups. Aromatic hydrocarbon groups include chain hydrocarbon groups or alicyclic hydrocarbon groups. It may have an elementary group, and an aromatic hydrocarbon group having a chain-like hydrocarbon group (tolyl group, xyl t-butylphenyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl (e.g., 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group) and alicyclic carbon Aromatic hydrocarbon groups having a hydrogenated group (p-cyclohexylphenyl group, p-adamantyl group) Examples include phenyl groups, etc. Furthermore, if the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, Chain-type hydrocarbon groups with 1 to 18 prime numbers and alicyclic hydrocarbon groups with 3 to 18 carbon atoms are preferred. As an aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group, p-methoxyphenyl Examples include the 'L' group. Examples of chain hydrocarbon groups in which hydrogen atoms are substituted with aromatic hydrocarbon groups include the benzyl group and the ferrous hydrocarbon group. Netyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. An example is the aralkyl group.

[0206] 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.

[0207] R b4 and Rb5 The ring formed when these atoms bond to each other and together with the sulfur atom to which they bond 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. TIFF2026123019000106.tif23143

[0208] R b9 and R b10 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothi Examples include the ophenium ring, thian-1-ium ring, and 1,4-oxatian-4-ium ring. It can be done. R b11 and R b12 The rings formed by these elements together can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. Examples of rings include 3-membered to 12-membered rings. Preferably a 3-membered to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring Examples include oxonorbornane rings and oxoadamantane rings.

[0209] Among cations (b2-1) to (b2-4), preferably cation (b2 -1) The following cations can be considered as cations (b2-1): TIFF2026123019000107.tif80158

[0210] TIFF2026123019000108.tif110165

[0211] The following cations can be considered as cations (b2-2): TIFF2026123019000109.tif18150

[0212] The following cations can be considered as cations (b2-3): TIFF2026123019000110.tif26140

[0213] The following cations can be considered as cations (b2-4): TIFF2026123019000111.tif153161

[0214] 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 represented by any of the following equations (B1a-19), (B1a-22) to (B1a-40) N and cation (b2-1), cation (b2-2), cation (b2-3) or catio One example is the combination with n(b2-4).

[0215] The acid generator (B) is preferably represented by formulas (B1-1) to (B1-60), 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) Those represented by formula (B1-60) are particularly preferred. TIFF2026123019000112.tif190167

[0216] TIFF2026123019000113.tif250153

[0217] TIFF2026123019000114.tif238165

[0218] In the resist composition of the present invention, the content of the acid generator is as follows: Preferably 1 to 45 parts by mass, more preferably 3 to 4 parts by mass, relative to the volume. The amount is 0 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less.

[0219] <Solvent (E)> The solvent (E) content is typically 90% by mass or more and 99.9% by mass or less in the resist composition. Yes, preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of solvent (E) is 99% by mass or less. The content of solvent (E) is determined, for example, by liquid chromatography or gas chromatography. It can be measured using known analytical methods such as chromatography. The solvent (E) includes ethyl cellosolve acetate, methyl cellosolve acetate, and Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, vinegar Esters such as butyl acid, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl Ketones such as lucetone, 2-heptanone, and cyclohexanone; γ-butyrolactone, etc. Examples include cyclic esters; etc. One of the solvents (E) may be used alone. You may use two or more types.

[0220] <Quencher (C)> Quencher (C) is generated from a basic nitrogen-containing organic compound and an acid generator (B). Examples include salts that produce acids with weaker acidity than the acid that produces the quencher. If (C) is included, the amount of quencher (C) is based on the solid content of the resist composition. Preferably, it is about 0.01 to 15% by mass, and about 0.01 to 10% by mass. It is more preferable that it be about 0.1 to 8% by mass, and even more preferable that it be about 0.1 to 7% by mass. It is even more preferable that the amount be approximately mass percent. Basic nitrogen-containing organic compounds include amines and ammonium salts. Examples include aliphatic amines and aromatic amines. Aliphatic amines include primary amines. Examples include amines, secondary amines, and tertiary amines. Examples of amines include 1-naphthylamine, 2-naphthylamine, aniline, and diisopropylamine. Ruaniline, 2-,3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine Octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine mine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, methyldinonylamine, methylddecylamine, ethyl dibuty Luamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine Ethyl dioctylamine, ethyl dinonylamine, ethyl didecylamine, dicyclo Xylmethylamine, Tris[2-(2-methoxyethoxy)ethyl]amine, Triiso Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine Mine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmeth , 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridazole 4-methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl (Lu)ethane, 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-di(4-pyridyl)propane, 1,2-di(4-pyridyloxy)ethane, di( 2-Pyridyl)ketone, 4,4'-dipyridylsulfide, 4,4'-dipyridyldisulfide Examples include phyto, 2,2'-dipyridylamine, 2,2'-dipicolylamine, and bipyridine. Preferably, diisopropylaniline is cited, and more preferably 2,6-diiso Propylaniline is one example. 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.

[0221] The acidity of a salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). An acid with a lower acidity than the acid generated from the acid generator (B) The salt that generates is a salt with an acid dissociation constant of the acid generated from the salt usually -3 < pKa, preferably or a salt of -1 < pKa < 7, more preferably a salt of 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter, may be referred to as " weak acid intramolecular salt (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. Preferably is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), more preferably a weak acid intramolecular salt (D), and still more preferably, among the weak acid intramolecular salts (D), a diphenyliodonium salt containing a phenyl group substituted with a carboxylic acid anion. As the weak acid intramolecular salt (D), a diphenyliodonium salt having an iodonium cation to which two phenyl groups are bonded and a carboxylic acid anion substituted on at least one of the two phenyl groups bonded to the iodonium cation is preferably JPEG2026123019000115.jpg121167

[0222] Specifically, salts represented by the following formula are preferably included. Among the two phenyl groups bonded to the iodonium cation, at least one of the phenyl groups is substituted with a carboxylic acid anion, and is a diphenyliodonium salt having Specifically, salts represented by the following formula are included.

[0223] JPEG2026123019000116.jpg2362 [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, there may be 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 groups. 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.

[0224] More specifically, the following salts are examples: TIFF2026123019000117.tif72165

[0225] <Other ingredients> The resist composition of the present invention may optionally include components other than those described above (hereinafter referred to as "other components"). It may be referred to as "F (F)". It may contain other components (F) in particular. There are no known additives in the resist field, such as sensitizers, dissolution inhibitors, surfactants, and stabilizers. Agents, dyes, etc. can be used.

[0226] <Preparation of resist composition> The resist composition of the present invention comprises a compound (I), a resin (A), and an acid generator (B), If necessary, resins other than resin (A), solvent (E), quencher (C), and other components may be used. It can be prepared by mixing (F). The mixing order is arbitrary and not particularly limited. It is not something that can be mixed. The mixing temperature should be between 10 and 40°C, depending on the type of resin and the solvent of the resin. The appropriate temperature can be selected depending on the solubility of agent (E), etc. The mixing time is determined by the mixing temperature. Depending on the degree, an appropriate time can be selected from 0.5 to 24 hours. There are no particular restrictions, and stirring and mixing can be used. After mixing each component, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable to do so.

[0227] <Method for manufacturing resist patterns> The method for manufacturing a resist pattern of the present invention is: (1) A step of applying the resist composition of the present invention onto a substrate, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) Includes a step of developing the composition layer after heating. To coat the resist composition onto the substrate, a commonly used device such as a spin coater is used. 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 electron beam (EB) exposure or EUV exposure It is suitable as a resist composition for use and is useful for semiconductor microfabrication. [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)

[0230] 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".

[0231] Synthesis Example 1: Synthesis of the compound represented by formula (I-1) TIFF2026123019000118.tif31131 5 parts of the compound represented by formula (I-1-a), 230 parts of ethyl acetate and the compound represented by formula (I-1-b) 18.05 parts of the compound shown were mixed, stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, add 23.48 parts of diisopropylethylamine dropwise, then heat up to 70°C. The mixture was heated to 70°C and stirred for 2 hours, then cooled to 23°C. The resulting mixture was then subjected to ion exchange. Add 120 parts of replacement water, stir at 23°C for 30 minutes, and separate the liquid to obtain the organic layer. Add 120 parts of a 5% oxalic acid aqueous solution to the prepared organic layer, stir at 23°C for 30 minutes, and then separate the liquids. This yielded an organic layer. To the obtained organic layer, 120 parts of deionized water were added and incubated at 23°C for 3 minutes. The organic layer was obtained by stirring for 0 minutes and then separating the liquid. This washing procedure was repeated 5 times. The organic layer is concentrated, and the concentrated mass is stored in a column (silica gel 60N (spherical, neutral) 100-210). μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) take a portion. This yielded 8.12 parts of the compound represented by formula (I-1). MASS (mass spectrometry):303.0[M+H] +

[0232] Synthesis Example 2: Synthesis of the compound represented by formula (I-5) TIFF2026123019000119.tif35130 8 parts of the compound represented by formula (I-5-a), 100 parts of ethyl acetate and the compound represented by formula (I-1-b) 22.03 parts of the compound shown were mixed, stirred at 23°C for 30 minutes, and then cooled to 5°C. To the resulting mixture, add 10.59 parts of diisopropylethylamine dropwise, then heat up to 70°C. The mixture was heated, stirred at 70°C for 4 hours, and then cooled to 23°C. The resulting mixture was then subjected to ion exchange. Add 100 parts of replacement water, stir at 23°C for 30 minutes, and separate the liquid to obtain the organic layer. Add 50 parts of a 5% oxalic acid aqueous solution to the prepared organic layer, stir at 23°C for 30 minutes, and then separate the liquid and liquid layers. An organic layer was obtained by this process. 50 parts of deionized water were added to the obtained organic layer and incubated at 23°C for 30 minutes. The organic layer was obtained by stirring and then separating the liquid. This washing procedure was repeated five times. The cell layer is concentrated, and the concentrated mass is placed in a column (silica gel 60N (spherical, neutral) 100-210 μm). (Manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to be taken separately. From this, 5.91 parts of the compound represented by formula (I-5) were obtained. MASS (mass spectrometry):603.0[M+H] +

[0233] Synthesis Example 3: Synthesis of the compound represented by formula (I-9) TIFF2026123019000120.tif29147 6.50 parts of the compound represented by formula (I-9-a), 160 parts of ethyl acetate and formula (I-1- Mix 21.28 parts of the compound represented in (b), stir at 23°C for 30 minutes, and then cool to 5°C. Then, 18.05 parts of diisopropylethylamine were added dropwise to the resulting mixture, and then 70 The mixture was heated to 70°C, stirred for 4 hours, and then cooled to 23°C. Add 160 parts of decontaminated water, stir at 23°C for 30 minutes, and separate to obtain an organic layer. Add 80 parts of a 5% oxalic acid aqueous solution to the obtained organic layer, stir at 23°C for 30 minutes, and separate the liquid-liquid. An organic layer was obtained by this process. 80 parts of deionized water were added to the obtained organic layer and heated at 23°C. The organic layer was obtained by stirring for 30 minutes and then separating the liquid. This washing procedure was repeated five times. The prepared organic layer was concentrated, and the concentrated mass was stored in a column (silica gel 60N (spherical, neutral) 100-21 0 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) take a portion. This yielded 5.19 parts of the compound represented by formula (I-9). MASS (mass spectrometry):395.0[M+H] +

[0234] Synthesis Example 4: Synthesis of the compound represented by formula (I-4) TIFF2026123019000121.tif30123 5 parts of the compound represented by formula (I-1-a), 230 parts of ethyl acetate, and formula (I-1-b) Mix 6.01 parts of the compound shown, stir at 23°C for 30 minutes, and then cool to 5°C. After adding 5.86 parts of diisopropylethylamine dropwise to the mixture, the temperature was raised to 70°C. The mixture was stirred at 70°C for 2 hours, then cooled to 23°C. Deionized water was added to the resulting mixture. 120 parts were added, stirred at 23°C for 30 minutes, and the organic layer was obtained by liquid-liquid separation. Add 120 parts of a 5% oxalic acid aqueous solution to the organic layer, stir at 23°C for 30 minutes, and then separate the liquids. An organic layer was obtained by this process. 120 parts of deionized water were added to the obtained organic layer and incubated at 23°C for 30 minutes. The organic layer was obtained by stirring and then separating the liquid. This washing procedure was repeated five times. The cell layer is concentrated, and the concentrated mass is placed in a column (silica gel 60N (spherical, neutral) 100-210 μm). (Manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 10 / 1) to be taken separately. From this, 3.12 parts of the compound represented by formula (I-4) were obtained. MASS (mass spectrometry):207.0[M+H] +

[0235] Synthesis Example 5: Synthesis of the compound represented by formula (I-41) TIFF2026123019000122.tif31131 5 parts of the compound represented by formula (I-41-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 5.49 parts of the compound represented by formula (I-1-b) to the mixture, it was incubated at 23°C for 18 hours. Stirring was continued. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. An organic layer was obtained by liquid-liquid separation. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. The washing operation was performed five times. The resulting organic layer was concentrated, and the concentrated mass was placed in a column (silica gel 6 0N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / By separating ethyl acetate (10 / 1), compound 4.08, represented by formula (I-41), is obtained. I got a part. MASS (mass spectrometry):554.8[M+H] +

[0236] Synthesis Example 6: Synthesis of the compound represented by formula (I-45) TIFF2026123019000123.tif36120 5 parts of the compound represented by formula (I-45-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 12.32 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. To the mixture, 8.42 parts of the compound represented by formula (I-1-b) were added, and then the mixture was heated at 23°C for 18 minutes. The mixture was stirred for a certain amount of time. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. The organic layer was then separated to obtain an organic layer. To the obtained organic layer, 16 parts of a 5% oxalic acid aqueous solution were added. The organic layer was then stirred at 23°C for 30 minutes and separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. This washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was placed on a column (silica gel). 60N (spherical, neutral), 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane By fractionating ethyl acetate (10 / 1), compound 3.9 represented by formula (I-45) is obtained. I got two parts. MASS (mass spectrometry):428.9[M+H] +

[0237] Synthesis Example 7: Synthesis of the compound represented by formula (I-65) TIFF2026123019000124.tif35130 5 parts of the compound represented by formula (I-65-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 5.49 parts of the compound represented by formula (I-1-b) to the mixture, it was incubated at 23°C for 18 hours. Stirring was continued. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. An organic layer was obtained by liquid-liquid separation. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. The washing operation was performed five times. The resulting organic layer was concentrated, and the concentrated mass was placed in a column (silica gel 6 0N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / By fractionating ethyl acetate (10 / 1), compound 2.12, represented by formula (I-65), is obtained. I got a part. MASS (mass spectrometry):554.8[M+H] +

[0238] Synthesis Example 8: Synthesis of the compound represented by formula (I-71) TIFF2026123019000125.tif34122 5 parts of the compound represented by formula (I-65-a), 20 parts of ethyl acetate and diisopropyl ethyl acetate 7.14 parts of luamine were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. After adding 2.61 parts of the compound represented by formula (I-1-b) to the mixture, ferment at 23°C for 18 hours. Stirring was continued. To the resulting mixture, 20 parts of deionized water were added and stirred at 23°C for 30 minutes. An organic layer was obtained by liquid-liquid separation. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. The organic layer was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. Ten parts of decontaminated water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated to obtain the organic layer. The washing operation was performed five times. The resulting organic layer was concentrated, and the concentrated mass was placed in a column (silica gel 6 0N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / By separating ethyl acetate (10 / 1), compound 3.19, represented by formula (I-71), is obtained. I got a part. MASS (mass spectrometry):458.8[M+H] +

[0239] Synthesis Example 9: Synthesis of the compound represented by formula (I-81) TIFF2026123019000126.tif30120 3.04 parts of the compound represented by formula (I-81-a), 20 parts of ethyl acetate and diisopropyl Mix 3.57 parts of ethylamine, stir at 23°C for 30 minutes, and then cool to 5°C. To the mixture, 2.75 parts of the compound represented by formula (I-1-b) were added, and then at 23°C... The mixture was stirred for 18 hours. 20 parts of deionized water were added to the resulting mixture, and it was stirred at 23°C for 30 minutes. The organic layer was obtained by mixing and liquid-liquid separation. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. Adding [the substance], the mixture was stirred at 23°C for 30 minutes, and the organic layer was obtained by liquid-liquid separation. Add 10 parts of deionized water, stir at 23°C for 30 minutes, and separate to obtain the organic layer. This washing operation was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was subjected to a column (silica). Gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-Hept By fractionating the tan / ethyl acetate (10 / 1), compound 3, represented by formula (I-81), is obtained. I obtained 0.24 copies. MASS (mass spectrometry):316.9[M+H] +

[0240] Synthesis Example 10: Synthesis of the compound represented by formula (I-83) Mix 4.96 parts of the compound represented by formula (I-83-a) and 40 parts of chloroform, 2 The mixture was stirred at 3°C ​​for 30 minutes. Compound 3, represented by formula (I-83-b), was added to the resulting mixed solution. 0.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I-8) was added to the resulting mixed solution. Add 2.00 parts of the compound represented in 3-c), then stir at 50°C for 3 hours, and then 2 The mixture was cooled to 3°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 30 minutes. After stirring for several minutes, the mixture was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. In addition, the mixture was stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing process was repeated five times. The process was repeated. The resulting 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 = By fractionation using 10 / 1), 5.92 parts of the compound represented by formula (I-83) are obtained. I got it. MASS (mass spectrometry):330.9[M+H] +

[0241] Synthesis Example 11: Synthesis of the compound represented by formula (I-87) Mix 2.44 parts of the compound represented by formula (I-87-a) and 40 parts of chloroform, 2 The mixture was stirred at 3°C ​​for 30 minutes. Compound 3, represented by formula (I-83-b), was added to the resulting mixed solution. 0.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I-8) was added to the resulting mixed solution. Add 2.00 parts of the compound represented in 3-c), then stir at 50°C for 3 hours, and then 2 The mixture was cooled to 3°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 30 minutes. After stirring for several minutes, the mixture was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. In addition, the mixture was stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing process was repeated five times. The process was repeated. The resulting 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 = By fractionation using 10 / 1), 3.62 parts of the compound represented by formula (I-87) are obtained. I got it. MASS (mass spectrometry):205.0[M+H] +

[0242] Synthesis Example 12: Synthesis of the compound represented by formula (I-33) TIFF2026123019000129.tif29116 1.30 parts of the compound represented by formula (I-33-a), 20 parts of ethyl acetate and diisopropyl Mix 3.57 parts of ethylamine, stir at 23°C for 30 minutes, and then cool to 5°C. To the mixture, 2.75 parts of the compound represented by formula (I-1-b) were added, and then at 23°C... The mixture was stirred for 18 hours. 20 parts of deionized water were added to the resulting mixture, and it was stirred at 23°C for 30 minutes. The organic layer was obtained by mixing and liquid-liquid separation. To the obtained organic layer, 10 parts of a 5% oxalic acid aqueous solution were added. Adding [the substance], the mixture was stirred at 23°C for 30 minutes, and the organic layer was obtained by liquid-liquid separation. Add 10 parts of deionized water, stir at 23°C for 30 minutes, and separate to obtain the organic layer. This washing operation was repeated five times. The resulting organic layer was concentrated, and the concentrated mass was subjected to a column (silica). Gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-Hept By fractionating the tan / ethyl acetate (10 / 1), compound 1 represented by formula (I-33) is obtained. I obtained 0.02 copies. MASS (mass spectrometry):191.0[M+H] +

[0243] Synthesis Example 13: Synthesis of the compound represented by formula (I-23) Mix 1.66 parts of the compound represented by formula (I-23-a) and 40 parts of chloroform, 2 The mixture was stirred at 3°C ​​for 30 minutes. Compound 3, represented by formula (I-83-b), was added to the resulting mixed solution. 0.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I-8) was added to the resulting mixed solution. Add 2.00 parts of the compound represented in 3-c), then stir at 50°C for 3 hours, and then 2 The mixture was cooled to 3°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 30 minutes. After stirring for several minutes, the mixture was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. In addition, the mixture was stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing process was repeated five times. The process was repeated. The resulting 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 = By fractionation using 10 / 1), 2.92 parts of the compound represented by formula (I-23) are obtained. I got it. MASS (mass spectrometry):331.0[M+H] +

[0244] Synthesis Example 14: Synthesis of the compound represented by formula (I-73) Mix 4.18 parts of the compound represented by formula (I-73-a) and 40 parts of chloroform, 2 The mixture was stirred at 3°C ​​for 30 minutes. Compound 3, represented by formula (I-83-b), was added to the resulting mixed solution. 0.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I-8) was added to the resulting mixed solution. Add 2.00 parts of the compound represented in 3-c), then stir at 50°C for 3 hours, and then 2 The mixture was cooled to 3°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 30 minutes. After stirring for several minutes, the mixture was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. In addition, the mixture was stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing process was repeated five times. The process was repeated. The resulting 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 = By fractionation using 10 / 1), 4.32 parts of the compound represented by formula (I-73) are obtained. I got it. MASS (mass spectrometry):582.8[M+H] +

[0245] Synthesis Example 15: Synthesis of the compound represented by formula (I-91) Mix 2.92 parts of the compound represented by formula (I-91-a) and 40 parts of chloroform, 2 The mixture was stirred at 3°C ​​for 30 minutes. Compound 3, represented by formula (I-83-b), was added to the resulting mixed solution. 0.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I-8) was added to the resulting mixed solution. Add 2.00 parts of the compound represented in 3-c), then stir at 50°C for 3 hours, and then 2 The mixture was cooled to 3°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 30 minutes. After stirring for several minutes, the mixture was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. In addition, the mixture was stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing process was repeated five times. The process was repeated. The resulting 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 = By fractionation using 10 / 1), 3.88 parts of the compound represented by formula (I-91) are obtained. I got it. MASS (mass spectrometry):456.9[M+H] +

[0246] Synthesis Example 16: Synthesis of the compound represented by formula (I-94) Mix 3.02 parts of the compound represented by formula (I-94-a) and 40 parts of chloroform, 2 The mixture was stirred at 3°C ​​for 30 minutes. Compound 3, represented by formula (I-83-b), was added to the resulting mixed solution. 0.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I-8) was added to the resulting mixed solution. Add 2.00 parts of the compound represented in 3-c), then stir at 50°C for 3 hours, and then 2 The mixture was cooled to 3°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 30 minutes. After stirring for several minutes, the mixture was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. In addition, the mixture was stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing process was repeated five times. The process was repeated. The resulting 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 = By fractionation using 10 / 1), 2.98 parts of the compound represented by formula (I-94) are obtained. I got it. MASS (mass spectrometry):467.0[M+H] +

[0247] Synthesis Example 17: Synthesis of the compound represented by formula (I-95) Mix 2.02 parts of the compound represented by formula (I-95-a) and 40 parts of chloroform, 2 The mixture was stirred at 3°C ​​for 30 minutes. Compound 3, represented by formula (I-83-b), was added to the resulting mixed solution. 0.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I-8) was added to the resulting mixed solution. Add 2.00 parts of the compound represented in 3-c), then stir at 50°C for 3 hours, and then 2 The mixture was cooled to 3°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 30 minutes. After stirring for several minutes, the mixture was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. In addition, the mixture was stirred at 23°C for 30 minutes, then separated to remove the organic layer. This washing process was repeated five times. The process was repeated. The resulting 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 = By fractionation using 10 / 1), 2.59 parts of the compound represented by formula (I-95) are obtained. I got it. MASS (mass spectrometry):367.0[M+H] +

[0248] Synthesis Example 18: Synthesis of the compound represented by formula (I-101) Mix 3.92 parts of the compound represented by formula (I-101-a) and 40 parts of chloroform. The mixture was stirred at 23°C for 30 minutes. The resulting mixed solution was then mixed with the compound represented by formula (I-83-b). 3.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I- Add 2.00 parts of the compound represented by 83-c), and then stir at 50°C for 3 hours. The mixture was cooled to 23°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 3 minutes. After stirring for 0 minutes, the organic layer was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. After adding and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was repeated 5 times. The process was repeated several times. The resulting organic layer was concentrated, and the concentrated mixture was placed on a column (silica gel 60N (spherical)). (Neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate By separating the compound using (=10 / 1), compound 3.22, represented by formula (I-101), is obtained. I got a part. MASS (mass spectrometry):557.1[M+H] +

[0249] Synthesis Example 19: Synthesis of the compound represented by formula (I-104) Mix 1.96 parts of the compound represented by formula (I-104-a) and 40 parts of chloroform. The mixture was stirred at 23°C for 30 minutes. The resulting mixed solution was then mixed with the compound represented by formula (I-83-b). 3.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I- Add 2.00 parts of the compound represented by 83-c), and then stir at 50°C for 3 hours. The mixture was cooled to 23°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 3 minutes. After stirring for 0 minutes, the organic layer was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. After adding and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was repeated 5 times. The process was repeated several times. The resulting organic layer was concentrated, and the concentrated mixture was placed on a column (silica gel 60N (spherical)). (Neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate By separating the compound using (=10 / 1), compound 2.14, represented by formula (I-104), is obtained. I got a part. MASS (mass spectrometry):719.0[M+H] +

[0250] Synthesis Example 20: Synthesis of the compound represented by formula (I-105) Mix 1.46 parts of the compound represented by formula (I-105-a) and 40 parts of chloroform. The mixture was stirred at 23°C for 30 minutes. The resulting mixed solution was then mixed with the compound represented by formula (I-83-b). 3.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I- Add 2.00 parts of the compound represented by 83-c), and then stir at 50°C for 3 hours. The mixture was cooled to 23°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 3 minutes. After stirring for 0 minutes, the organic layer was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. After adding and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was repeated 5 times. The process was repeated several times. The resulting organic layer was concentrated, and the concentrated mixture was placed on a column (silica gel 60N (spherical)). (Neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate By separating the compound 2.02 represented by formula (I-105) using (=10 / 1), the compound 2.02 I got a part. MASS (mass spectrometry):619.0[M+H]+

[0251] Synthesis Example 21: Synthesis of the compound represented by formula (I-106) Mix 2.54 parts of the compound represented by formula (I-106-a) and 40 parts of chloroform. The mixture was stirred at 23°C for 30 minutes. The resulting mixed solution was then mixed with the compound represented by formula (I-83-b). 3.24 parts were added, and the mixture was stirred at 50°C for 2 hours. Formula (I- Add 2.00 parts of the compound represented by 83-c), and then stir at 50°C for 3 hours. The mixture was cooled to 23°C. 20 parts of a 5% oxalic acid aqueous solution were added to the resulting mixture and incubated at 23°C for 3 minutes. After stirring for 0 minutes, the organic layer was separated and the organic layer was removed. 20 parts of deionized water were added to the resulting organic layer. After adding and stirring at 23°C for 30 minutes, the organic layer was separated. This washing procedure was repeated 5 times. The process was repeated several times. The resulting organic layer was concentrated, and the concentrated mixture was placed on a column (silica gel 60N (spherical)). (Neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd.; developing solvent: n-heptane / ethyl acetate By separating the compound using (=10 / 1), compound 3.39, represented by formula (I-106), is obtained. I got a part. MASS (mass spectrometry):834.8[M+H] +

[0252] Synthesis Example 22: Synthesis of the compound represented by formula (IX-1) TIFF2026123019000139.tif23116 25.7 parts of the compound represented by formula (IX-1-a), 120 parts of acetone and triethyl 48.58 parts of min were mixed and stirred at 23°C for 30 minutes, then cooled to 5°C. The resulting mixture After adding 36.91 parts of the compound represented by formula (IX-1-b) to the mixture, the temperature is raised to 23°C. The mixture was heated and stirred at 23°C for 6 hours. To the resulting mixture, tert-butyl methyl ether 1 Add 20 parts and 80 parts of deionized water, stir at 23°C for 30 minutes, and separate the liquids to obtain An organic layer was obtained. 60 parts of saturated ammonium chloride aqueous solution were added to the obtained organic layer, and it was incubated at 23°C for 3 minutes. The organic layer was stirred for 0 minutes and then separated to obtain an organic layer. 60% deionized water was added to the obtained organic layer. The mixture was added, stirred at 23°C for 30 minutes, and then separated to obtain an organic layer. This was followed by the washing procedure. This was repeated 5 times. The resulting organic layer was concentrated, and the concentrated mass was placed on a column (silica gel 60N (spherical, (Neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 5 / 1) By fractionation, 27.18 parts of the compound represented by formula (IX-1) were obtained. MASS (mass spectrometry):207.1[M+H] +

[0253] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. These are referred to as "monomers (a1-1-3)" etc., according to their formula numbers. TIFF2026123019000140.tif4075

[0254] Synthesis Example 23 [Synthesis of Resin A1] As monomers, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) is used, and its molar ratio [monomer (a1-4-2):monomer (a1-1 -3): Mix the monomers (a1-2-6) in a ratio of 38:24:38. Furthermore, this monomer mixture contains methyl methyl in an amount equal to 1.5 times the total mass of all monomers. Isobutyl ketone was mixed. To the resulting mixture, azobisisobutyronite was added as an initiator. Add lyl to a concentration of 7 mol% relative to the total number of moles of all monomers, and then heat at 85°C. Polymerization was carried out by heating for approximately 5 hours. After that, the total mass of all monomers was added to the polymerization reaction solution. To this, add 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5 wt%) and 6 hours After stirring, the mixture was separated. The resulting organic layer was poured into a large amount of n-heptane to precipitate the resin. By filtering and recovering the material, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 The resin A1 (co-weight) The composite was obtained with a yield of 78%. This resin A1 has the following structural units. TIFF2026123019000141.tif29126

[0255] Synthesis Example 24 [Synthesis of Resin A2] As monomers, monomer (a1-4-2) and monomer (a1-2-6) are used, The molar ratio [monomer(a1-4-2):monomer(a1-2-6)] is 38:62. Mix them together, and then add to this monomer mixture, relative to the total mass of all monomers. Then, 1.5 times the mass of methyl isobutyl ketone was mixed in. To the resulting mixture, as an initiator, Azobisisobutyronitrile is added in a quantity of 7 mol% relative to the total number of moles of all monomers. Polymerization was carried out by adding it to and heating it at 85°C for about 5 hours. After that, the polymerization reaction solution was added to , 2.0 times the mass of p-toluenesulfonic acid aqueous solution relative to the total mass of all monomers (2. 5% by weight was added, stirred for 6 hours, and then separated. The resulting organic layer was collected in large quantities of n-hepta By pouring it into a container and allowing the resin to precipitate, then filtering and recovering it, the weight-average molecular weight is approximately 5.4 × 10 3 Resin A2 (polymer) was obtained in a yield of 89%. This resin A2 has the following structural units It is something that one possesses. TIFF2026123019000142.tif2886

[0256] Synthesis Example 25 [Synthesis of Resin AX1] 100 parts of polyvinylphenol (VP-15000; manufactured by Nippon Soda Co., Ltd.), methyliso 400 parts of butyl ketone and 0.004 parts of p-toluenesulfonic acid dihydrate were added, The mixed solution was concentrated until the total volume was 273 parts. Ethyl vinyl ether was added to the concentrated resin solution. Add 8.01 parts dropwise and stir for 2.5 hours to allow the reaction to proceed. Then, add ions to this reaction solution. 58.2 parts of replacement water and 0.005 parts of triethylamine were added and the mixture was stirred and separated. Then, 60 parts of deionized water were added to the organic layer and the separation process was repeated four times. The organic layer after washing. By concentrating it, the weight-average molecular weight becomes approximately 1.6 × 10⁻⁶. 4 The resin AX1 yielded 8 The result was obtained at 8%. The introduction rate of ethoxyethyl groups to the total structural units of resin AX1 was 30.1 moles. It was %. Resin AX1 has the following structural units. TIFF2026123019000143.tif37107

[0257] <Preparation of the resist composition> As shown in Table 1, the following components were mixed, and the resulting mixture was subjected to a pore size of 0.001 μm. The resist composition was prepared by filtering through a polyethylene resin filter. [Table 1]

[0258] <Resin> A1, A2, AX1: Resin A1, Resin A2, Resin AX1 <Acid Generator> B1-43: Salt represented by formula (B1-43) (Implementation of Japanese Patent Publication No. 2016-47815) (Synthesized according to the example) TIFF2026123019000145.tif4381<Compound (I)> I-1: Compound represented by formula (I-1) I-4: Compound represented by formula (I-4) I-5: Compound represented by formula (I-5) I-9: Compound represented by formula (I-9) I-23: Compound represented by formula (I-23) I-33: Compound represented by formula (I-33) I-41: Compound represented by formula (I-41) I-45: Compound represented by formula (I-45) I-65: Compound represented by formula (I-65) I-71: Compound represented by formula (I-71) I-73: Compound represented by formula (I-73) I-81: Compound represented by formula (I-81) I-83: ​​Compound represented by formula (I-83) I-87: Compound represented by formula (I-87) I-91: Compound represented by formula (I-91) I-94: Compound represented by formula (I-94) I-95: Compound represented by formula (I-95) I-101: Compound represented by formula (I-101) I-104: Compound represented by formula (I-104) I-105: Compound represented by formula (I-105) I-106: Compound represented by formula (I-106) <Compound (IX)> IX-1: Compound represented by formula (IX-1) <Quencher (C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 TIFF2026123019000146.tif4347<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0259] (Electron Beam Exposure Evaluation of Resist Composition: Alkaline Development) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 °C for 60 seconds. The resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer was 0.04 μm. After that, it was pre-baked on a direct hot plate for 60 seconds at the temperature shown in the "PB" column of Table 1 to form a composition layer. On the composition layer formed on the wafer, a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn using an electron beam lithography machine ["ELS-F1 25 125 keV" manufactured by Elionix Co., Ltd.] with the exposure dose changed stepwise. After exposure, post-exposure baking was performed on a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 1, and further paddle development was carried out for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern. In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was defined as the effective sensitivity.

[0260]

[0261] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times for one hole, and the average value was taken as the average hole diameter of one hole. The average hole diameter of the patterns formed with a hole diameter of 17 nm within the same wafer was measured at 400 locations and used as the population to calculate the standard deviation. [[ID=3d]] The results are shown in Table 2. The numerical values in the table represent the standard deviation (nm).

Table 2

[0262] The resist composition of the present invention exhibits excellent CD uniformity (CDU) of the resulting resist pattern. Therefore, it is suitable for the microfabrication of semiconductors and is extremely useful in industry.

Claims

1. A resist composition comprising a compound represented by formula (I), a resin having an acid-unstable group, and an acid generator. [In formula (I), R １ is *-O-CO-R １０ , *-O-CO-OR １０ , *-CO-O-R １０ Or *-O-L ２ -CO-O-R １０ This represents, and * is L １ This represents the connection point. L １ This represents an alkanediyl group having 1 to 6 carbon atoms, which may have a single bond or a halogen atom. L ２ represents an alkanediyl group having 1 to 6 carbon atoms. R １０ This represents a base-unstable group represented by formula (1b). R ２ is, *-L １ -R １ , *-X １ -Ph-L １ -OH, *-X １ -Ph-L １ -CO-OH or *-X １ -Ph-L １ -R １ This represents the bond site with the benzene ring, and * indicates the bond site with the benzene ring. X 1 This represents a single bond, a C1-C6 alkanediyl group which may have a halogen atom, -O- or -CO-. Ph represents a phenylene group which may have a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a C1-C12 alkyl group, a C1-C6 haloalkyl group, or a C1-C12 alkoxy group. m2 represents an integer from 0 to 5, and when m2 is 1 or greater, multiple L １ and multiple R １ Each of them may be the same or different from each other, and when m2 is 2 or more, multiple R ２ They may be identical or different from one another. R ３ -CH is contained in halogen atoms, C1-C6 haloalkyl groups, C1-C6 alkyl groups, or C1-C6 alkyl groups. 2 This represents a group in which - is replaced by -O- or -CO-. However, R ３ At least one of them is a halogen atom or a haloalkyl group having 1 to 6 carbon atoms. m3 represents an integer from 1 to 5, and when m3 is 2 or greater, multiple R ３ They may be identical or different from each other, provided that 1 ≤ m² + m³ ≤ 5. [In formula (1b), R ｂａ１ and R ｂａ２ Each of these independently represents a hydrogen atom, a fluorine atom, or a C1-C6 alkyl group having a fluorine atom. R ｂａ３ This represents a fluorine atom or an alkyl group having 1 to 6 carbon atoms that contains a fluorine atom. * indicates a connection site.

2. R ３ The resist composition according to claim 1, wherein the resist is a fluorine atom, an iodine atom, a perfluoroalkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.

3. The resist composition according to claim 1 or 2, wherein the resin having an acid-unstable group comprises at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2). [In formulas (a1-0), (a1-1), and (a1-2), L ａ０１ , L ａ１ and L ａ２ These are, independently, -O- or *-O- (CH ２ ) ｋ１ This represents -CO-O-, where k1 is an integer from 1 to 7, and * represents the bonding site with -CO-. R ａ０１ , R ａ４ and R ａ５ Each of these independently represents a hydrogen atom, a halogen atom, or a C1-C6 alkyl group which may have a halogen atom. R ａ０２ , R ａ０３ and R ａ０４ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group combining these. R ａ６ and R ａ７ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by a combination of these. m1 represents an integer between 0 and 14. n1 represents an integer between 0 and 10. n1' represents an integer between 0 and 3.

4. The resist composition according to any one of claims 1 to 3, wherein the resin having an acid-unstable group comprises a structural unit represented by formula (a2-A). [In formula (a2-A), R a50 This represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may contain a halogen atom. R a51 This represents a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C12 alkoxyalkyl group, a C2-C12 alkoxyalkoxy group, a C2-C4 alkylcarbonyl group, a C2-C4 alkylcarbonyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 - (A a52 -X a52 ) nｂ - represents -R a50 This represents the bonding site with the carbon atom to which it is bonded. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent, independently, -O-, -CO-O-, or -O-CO-. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, then multiple R a51 They may be the same or different from each other.

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

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

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

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