Method for manufacturing resist compositions and resist patterns

Abstract

To provide a resist composition capable of producing a resist pattern having good line edge roughness.SOLUTION: The resist composition contains a compound represented by formula (I), a resin having an acid-labile group, and an acid generator. [In the formula, R2 represents * -X1-Ph - L1 - OH. Ph represents a substituted or unsubstituted phenylene; R3 represents a halogen atom, a hydroxy group, a haloalkyl group or an alkyl group, and - CH2 - included in the alkyl group may be replaced by - O - or - CO -. m2 is an integer of 1 to 4, m3 is an integer of 0 to 3, provided that 1 ≤ m2 + m3 ≤ 4, and one or more of L1, R1, R2, and R3 have a halogen atom. ] SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention provides a resist composition and a method for manufacturing a resist pattern using the resist composition. Regarding etc. [Background technology]

[0002] Patent Document 1 contains a compound with the following structural formula, a resin with the following structural formula, and an acid generator. A resist composition is described. TIFF0007912654000001.tif30121 [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. WO2018 / 180049 [Overview of the project] [Problems that the invention aims to solve]

[0004] The resist pattern formed from the above resist composition has a higher line edge roughness ( The objective is to provide a resist composition in which LER forms a good resist pattern. ru. [Means for solving the problem]

[0005] This invention includes the following inventions. [1] A compound represented by formula (I), a resin having an acid-unstable group, and an acid generator are included. A resist composition. TIFF0007912654000002.tif4267 [In formula (I), L 1 This represents an alkanediyl group having 1 to 6 carbon atoms, which may have a single bond or substituents. R 1represents a hydrogen atom, a halogen atom, or a haloalkyl group having 1 to 12 carbon atoms. R 2 is *-L 1 -OH or *-X 1 -Ph-L 1 -OH, and * represents the binding site to a benzene ring. X 1 represents a single bond, alkanediyl group having 1 to 6 carbon atoms, -O-, -S-, -CO-, -S O- or -SO2-. One -CH2- contained in said alkanediyl group having 1 to 6 carbon atoms may be replaced by -O-, -S-, -CO-, -SO- or -SO2-. Ph represents a phenylene group which may have a substituent(s). m2 represents an integer of any of 1 to 4, and when m2 is 2 or more, a plurality of R 2 may be the same as one another or different from one another. R 3 represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms, and one -CH2- contained in said alkyl group may be replaced by -O- or -CO- . m3 represents an integer of any of 0 to 3, and when m3 is 2 or more, a plurality of R 3 may be the same as one another or different from one another. Provided that 1≤m2+m3≤4. Provided that in formula (I), any one of L 1 , R 1 , R 2 and R 3 has at least one halogen atom.] [2] The resist composition according to [1], wherein L 1 is a single bond or an alkanediyl group having 1 to 4 carbon atoms that may have a halogen atom . [3] The resist composition according to [1] or [2], wherein in formula (I), m2 is 1, and R 2 is on the benzene ring relative to L 1With respect to the binding site, the meta or para bonded The resist composition according to [1] or [2]. [4] In formula (I), R 2 is, *-L 1 - Represents OH and is indicated by one of the following [1] to [3]. Dyst composition. [5] In formula (I), R 2 is, *-X 1 -Ph-L 1 - Represents OH, The Ph is the X 1 - and -L 1 Having one or two substituents other than -OH, These substituents are, independently of each other, a halogen atom or an alkyl fluoride having 1 to 6 carbon atoms. A resist composition according to any one of [1] to [3], which is the base. [6] X 1 However, an alkanediyl group having 1 to 4 carbon atoms (the alkanediyl group contains -C H2- may be replaced by -O-, -S-, -CO-, -SO-, or -SO2-. a) any of the following [1] to [5] which are -O-, -S-, -CO-, -SO- or -SO2- A resist composition as described below. [7] R 3 However, fluorine atoms, iodine atoms, hydroxyl groups, and alkyl fluorides with 1 to 3 carbon atoms A C1-C3 alkyl group (the -CH2- contained in the alkyl group is -O- or (May be replaced with -CO-) one of the resist sets described in any of [1] to [6] A finished product. [8] Resins having acid-unstable groups are structural units represented by formula (a1-0) and formula (a1-1 A small number of structural units selected from the group consisting of structural units represented by formula (a1-2) and structural units represented by formula (a1-2) A resist composition according to any one of [1] to [7], comprising at least one of the following: TIFF0007912654000003.tif46153[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 a 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. [9] Resins having acid-unstable groups include structural units represented by formula (a2-A) [1]~ A resist composition according to any of [8]. TIFF0007912654000004.tif4652[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents the alkyl group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. an alkoxy group, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalk oxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms oxy group, an acryloyloxy group or a methacryloyloxy group. A a50 represents a single bond or * -X a51 -(A a52 -X a52 ) nb -, and * represents a binding site to the carbon atom to which -R a50 binds . A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represent -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, a plura lity of R a51 may be the same or different from each other.]]

[10] The resist composition according to [9], wherein in formula (a2-A), at least one hydroxy group is bonded a50 at a meta position relative to the bonding position of A in the benzene ring.

[11] The resist composition according to any one of [1] to

[10] , wherein the acid generator comprises a salt represented by formula (B1) . TIFF0007912654000005.tif2859[In formula (B1), Q b1 and Q b2 each independently represent a hydrogen atom, a fluorine atom, a perflu oroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and in the 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-. Z + This represents an organic cation.

[12] 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

[11] .

[13] (1) Apply any of the resist compositions described in [1] to

[12] onto the substrate. process, (2) A step of drying the applied composition to form a composition layer, (3) A step of exposing the composition layer, (4) A step of heating the composition layer after exposure, (5) A 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, good line edge roughness (LER) can be achieved. It is possible to manufacture resist patterns. [Modes for carrying out the invention]

[0007] In this specification, "(meth)acrylic monomer" means "acrylic monomer and This means "at least one methacrylate monomer." "(meth)acrylate" and " The notation "(meth)acrylic acid," etc., also has the same meaning. For hydrocarbons that can take both a linear and branched structure, either is acceptable. When the -CH2- contained in the group is replaced by -O-, -S-, -CO-, or -SO2- The same example shall apply to each group. "Combined groups" refers to the groups exemplified. This refers to a group formed by the bonding of two or more types of groups, and the valencies of these groups may be appropriately changed depending on the bonding configuration. "Derived from" or "induced from" means that the polymerizable C=C bonds contained in the molecule polymerize. This refers to the formation of a single bond (-CC- group). If stereoisomers exist, all Includes stereoisomers. 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)"). An "unstable group" has a leaving group, and upon contact with an acid, the leaving group is removed, resulting in a hydrophilic group (for example, 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 further contains a quencher such as salt (hereinafter sometimes referred to as "quencher (C)"). It is preferable that the product contains a solvent (hereinafter sometimes referred to as "solvent (E)"), and it is even preferable that it contains a solvent. It seems so.

[0009] <Compound (I)> The resist composition of the present invention contains compound (I). TIFF0007912654000006.tif4267[In formula (I), all symbols each have the same meanings as defined above.]

[0010] L 1 Examples of the alkanediyl group in include a methylene group, an ethylene group, propane-1,3 -diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1, 6-diyl group and other linear alkanediyl 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 group, 2-methylbutane-1,4-diyl group and other branched alkanediyl groups. The alkan ediyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. L 1 Examples of the substituent which the alkanediyl 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 groups formed by combining two or more of these groups are mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like . Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group and the like. The alkyl group preferably has 1 to 9 carbon atoms, more Preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3 That is the case. A haloalkyl group with 1 to 6 carbon atoms refers to an alkyl group that has a halogen atom, and fluoride Examples include alkyl groups, alkyl chlorides, alkyl bromides, alkyl iodides, etc. Examples of alkyl groups include trifluoromethyl, difluoromethyl, and perfluoroethyl groups. group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, Perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, perfluoro Butyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluoro phthal group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, perfluor Examples include the hexyl group, chloromethyl group, bromomethyl group, and iodomethyl group. The number of carbon atoms in the alkyl 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. 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 preferably a diyl group, and is a single bond, -C(CH3)2- or -C(CF3) It is even more preferable that it be 2.

[0011] R 1 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. It can be done. R 1 In this context, a C1-C12 haloalkyl group refers to a C1-C12 group that has a halogen atom. This represents an alkyl group with 1 to 12 carbon atoms, including alkyl fluorides and alkyl chlorides with 1 to 12 carbon atoms. Examples include lucyl groups, alkyl bromides with 1 to 12 carbon atoms, and alkyl iodides with 1 to 12 carbon atoms. It can be given. As a haloalkyl group, a perfluoroalkyl group (trif) having 1 to 12 carbon atoms is used. Luoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluoropropyl group (e.g., tyl group), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group , 4,4,4-trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl Examples include groups such as chloromethyl, bromomethyl, and iodomethyl groups. The number of carbon atoms is preferably 1 to 9, more preferably 1 to 6, and even more preferably The range is 1 to 4, and more preferably 1 to 3. R 1 This includes hydrogen atoms, iodine atoms, fluorine atoms, bromine atoms, or haloalkyl groups having 1 to 6 carbon atoms. A perfluorinated group is preferred, and a hydrogen atom, iodine atom, fluorine atom, or a perfluorinated group having 1 to 3 carbon atoms is preferred. A lukyl group is more preferred, along with a hydrogen atom, iodine atom, fluorine atom, or trifluoromethyl group. This is even more preferable, and an iodine atom is even more preferable. R 1 L is bonded to the benzene ring. 1 This refers to the binding position at the ortho, meta, or para position. This is also acceptable, but bonding to the ortho or meta position is preferred.

[0012] 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. The -CH2- contained in the alkanediyl group is -O-, -S-, -CO-, -SO- or It may be replaced by -SO2-. The -CH2- contained in the alkanediyl group is -O- If it is replaced by -S-, -CO-, -SO-, or -SO2-, the original The number of carbon atoms is defined as 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 carbonyloxy group (which is contained in the ethylene group). (A group in which CH2-CH2- is replaced by -O-CO-), an alkanediyloxy group (alka (A group in which any -CH2- at any position in the nucleotide group is replaced by -O-), Alkanediyloxycarbonyl group (-CH2-C at any position within the alkanediyl group) (A group in which H2- is replaced by -O-CO-), an alkanediylcarbonyl group (alkanedi Alkanes (groups in which any -CH2- at any position within the yl group is replaced by -CO-) Diylcarbonyloxy group (a -CH2-CH2 group at any position within an alkanediyl group) - is a group that has been replaced by -CO-O-), an alkanediylthio group (with an alkanediyl group) (A group in which any -CH2- at any position is replaced by -S-), alkanediylsulfo The -CH2- at any position within the alkanediyl group is replaced by -SO2- Examples include (and other similar terms). Examples of alkanediyloxy groups include methyleneoxy group, ethyleneoxy group, and propylene Examples include oxy groups and butylene oxy groups. Alkanediyloxycarbonyl group, alkanediylcarbonyl group and alkanediyl The carbonyloxy group is the alkanediyl group or alkanediyloxy group mentioned above. This represents a group to which a nyl group or a carbonyloxy group is attached. Examples of alkanediyloxycarbonyl groups include methyleneoxycarbonyl groups and ethylene Examples include oxycarbonyl groups and butyleneoxycarbonyl groups, and alkanediylcarbonyl groups. Examples of nyl groups include ethylene carbonyl group, propylene carbonyl group, and butylene carbonyl group. Examples include the yl group, and as an alkanediylcarbonyloxy group, ethylenecarbonyloxy Examples include xyl groups, propylene carbonyloxy groups, butylene carbonyloxy groups, and a Examples of lucandiylthio groups include methylenethio groups, ethylenethio groups, and propylenethio groups. Examples of alkanediylsulfonyl groups include methylenesulfonyl groups and ethylenesulfonyl groups. Examples include honyl groups and propylenesulfonyl groups. X 1 This is an alkanediyl group having 1 to 6 carbon atoms which may have substituents (the alkanediyl group The -CH2- contained in is replaced by -O-, -S-, -CO-, -SO-, or -SO2- (It may be known that) it is -O-, -S-, -CO-, -SO- or -SO2- Preferably, an alkanediyl group having 1 to 4 carbon atoms (the alkanediyl group contains -CH2- (This may be replaced by -O-, -S-, -CO-, -SO-, or -SO2-), It is more preferable to have -O-, -S-, -CO-, -SO- or -SO2-, and has 2 carbon atoms. It is even more preferable that the group is a branched alkanediyl group of ~4 or -O-.

[0013] R 2 The substituents that the pH may have include halogen atoms, hydroxyl groups, cyano groups, Carboxy group, C1-C12 alkyl group, C1-C12 haloalkyl group, C1 Examples include 1 to 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 C1-C12 haloalkyl group is an alkyl group having a halogen atom. The term represents a fluoride alkyl group with 1 to 12 carbon atoms, a chloride alkyl group with 1 to 12 carbon atoms, and a carbon group. Examples include alkyl bromides with 1 to 12 prime numbers and alkyl iodides with 1 to 12 carbon atoms. Examples of perfluoroalkyl groups include those with 1 to 12 carbon atoms (trifluoromethyl (e.g., pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4 -Trifluorobutyl group, and 3,3,4,4,4-pentafluorobutyl group, chloromethyl Examples include tyl groups, bromomethyl groups, and iodomethyl groups. The number of carbon atoms in a haloalkyl group is: Preferably 1 to 9, more preferably 1 to 6, and even more 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 6, and more preferably 1 It is ~4, and more preferably 1~3. 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. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more. It is 6, more preferably 2 to 4, and even more preferably 2 or 3. The number of carbon atoms in the rubonyl group is preferably 2 to 6, more preferably 2 to 4, and further Preferably, it is 2 or 3. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 6. The ratio is, more preferably 2 to 4, and even more preferably 2 or 3. R 2 The substituents that the pH may have include halogen atoms, hydroxyl groups, and C1- It is a 6-C1 alkyl group, a C1-C6 haloalkyl group, or a C1-C6 alkoxy group. It is preferable that the element be a halogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms, and more preferably a halogen atom or a C1-C6 alkyl group. It must be a fluorine atom, an iodine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms. It is even more preferable that it be a fluorine atom, an iodine atom, or a trifluoromethyl group. This is preferable. R 2 is, *-L 1 -OH(here, L 1 This may have a single bond or substituent, and has 1 carbon atom. It is preferably an alkanediyl group of ~4, and may have a single bond or a halogen atom. It is more preferably an alkanediyl group having 1 to 4 carbon atoms, and having a single bond or a fluorine atom. It is more preferably an alkanediyl group having 1 to 4 carbon atoms, and may have a single bond, -C It is even more preferable that it be (CH3)2- or -C(CF3)2-. ) or *-X 1 -Ph-L 1 -OH(Here, X 1 This is an alkanediyl group having 1 to 4 carbon atoms (the alkanediyl group The yl group may be replaced with -O-, -S-, -CO-, -SO-, or -SO2-. i) Preferably, it is -O-, -S-, -CO-, -SO- or -SO2-, and carbon It is more preferable that the group is a branched alkanediyl group with 2 to 4 segments or -O- segments. 1 is single-unit Preferably, it is an alkanediyl group having 1 to 4 carbon atoms, which may have a compound or substituent. It is more likely to be an alkanediyl group having 1 to 4 carbon atoms, which may have bonds or halogen atoms. Preferably, it is an alkanediyl group having 1 to 4 carbon atoms, which may have a single bond or a fluorine atom. It is even more preferable that the bond be a single bond, -C(CH3)2- or -C(CF3)2-. This is even more preferable. Ph is X 1 - and -L1 - One or two substituents other than OH It is preferable that it has a substituent. The substituent of Ph is a halogen atom or a fluoride with 1 to 6 carbon atoms. It is preferably a lukyl group, and is an iodine atom, a fluorine atom, or a perfluorine atom having 1 to 3 carbon atoms. More preferably a chloroalkyl group, containing an iodine atom, a fluorine atom, or trifluoromethyl It is more preferably a ru group, and even more preferably an iodine atom. It is preferable to do so. Note, R 2 L is bonded to the benzene ring. 1 This refers to the position of the ortho, meta, or para position. They may be bonded, but it is preferable that at least one is bonded at the meta or para position. It's nice. Also, R 2 *-X 1 -Ph-L 1 -OH, if it is an OH group, X bond to Ph 1 and L 1 This means that it can be bonded at any of the ortho, meta, or para positions, but it can be bonded at the para position. It is preferable that they be present.

[0014] R 3 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. It can be done. R 3 As for C1-C12 haloalkyl groups, C1-C12 groups having a halogen atom This represents an alkyl group with 2 atoms, including fluorinated alkyl groups with 1 to 12 carbon atoms and alkyl chlorides with 1 to 12 carbon atoms. Examples include chyl groups, alkyl bromides with 1 to 12 carbon atoms, and alkyl iodides with 1 to 12 carbon atoms. As a haloalkyl group, a perfluoroalkyl group (trifluoroalkyl group) having 1 to 12 carbon atoms is used. Oromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl (e.g., trifluoropropyl group), 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group and 3,3,4,4,4-pentafluorobutyl group Examples include chloromethyl group, bromomethyl group, iodomethyl group, etc. The number of carbon atoms is preferably 1 to 9, more preferably 1 to 6, and even more preferably 1 It is ~4, and more preferably 1~3. 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. 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-), An alkoxy group (where any -CH2- in an alkyl group is replaced by -O-) (a group), alkoxycarbonyl group (a -CH2-CH2 group at any position within an alkyl group) -A group that has been replaced by -O-CO-), an alkylcarbonyl group (contained within the alkyl group) (A group in which -CH2- at any position is replaced by -CO-), alkylcarbonyloxy The group (where any -CH2-CH2- in the alkyl group is replaced by -CO-O-) Examples include groups that are composed of 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. R 3 Each of these is independently preferably a halogen atom, a hydroxyl group, and a C1-C6 halogen atom. A C1-C6 alkyl group or an alkyl group (the -CH2- contained in the alkyl group is - (may be replaced by O- or -CO-), more preferably a fluorine atom, iodine Elementary atoms, hydroxyl groups, C1-C3 alkyl fluorides, or C1-C3 alkyl groups (The -CH2- contained in the alkyl group may be replaced with -O- or -CO-.) ) and more preferably a fluorine atom, an iodine atom, or a trifluoromethyl group, More preferably, it is a fluorine atom or an iodine atom. m2 is preferably an integer from 1 to 3, more preferably 1 or 2, and even more preferably 1. It seems so. m3 is preferably 0, 1, or 3.

[0015] Compound (I) includes compounds represented by the following formula. TIFF0007912654000007.tif155166

[0016] TIFF0007912654000008.tif200169

[0017] TIFF0007912654000009.tif199170

[0018] TIFF0007912654000010.tif116163

[0019] 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.

[0020] <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). Preferred. As structural units other than the structural unit (a1), structural units having no acid-labile group (hereinafter may sometimes be referred to as "structural unit (s)"), and structural units other than the structural unit (a1) and the structural unit (s) structural units (for example, a structural unit having a halogen atom described later (hereinafter "structural unit (a4)" may sometimes be referred to), a structural unit having a non-leaving hydrocarbon group described later (hereinafter "structural unit (a 5)" may sometimes be referred to) and other structural units derived from monomers known in the art, etc. may be mentioned.

[0021] <Structural Unit (a1)> The structural unit (a1) is derived from a monomer having an acid-labile group (hereinafter referred to as "monomer (a1)" may sometimes be the case). The acid-labile group contained in the resin (A) is a group represented by formula (1) (hereinafter, also referred to as group (1) ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferable. TIFF0007912654000011.tif1988[In formula (1), R a1 , R a2 and R a3 each independently represent an alkyl group having 1 to 8 carbon atoms , an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a 6 to 1 carbon atoms represents an aromatic hydrocarbon group of 8 or a group obtained by combining these, or R a1 and R a2 are bonded to each other together with the carbon atom to which they are bonded form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms . ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a binding site.]] TIFF0007912654000012.tif2171[In formula (2), R a1’ and R a2’are each independently a hydrogen atom or a 1 to 1 2 carbon hydrocarbon group, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and and R a3’ are bonded to each other to form a 3 to 20 carbon heterocyclic ring together with the carbon atom to which they are bonded and X, and -CH₂- contained in said hydrocarbon group and said heterocyclic ring may be replaced by -O- or -S- . X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a binding site.]

[0022] R a1 , R a2 and R a3 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 Examples of the alkenyl group in include an ethenyl group, a propenyl group , an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, an isooctenyl group, and a nonenyl group . R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic . Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclo heptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a binding site). R a1 , R a2 and Ra3 Alicyclic carbonization The number of carbon atoms in the hydrogen group is preferably 3 to 16. TIFF0007912654000013.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-. TIFF0007912654000014.tif31139

[0023] 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. TIFF0007912654000015.tif18130R a1’ and R a2’ Preferably, at least one of them is a hydrogen atom. na' is preferably 0.

[0024] 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. TIFF0007912654000016.tif154163

[0025] The following are specific examples of group (2). * indicates a bonding site. TIFF0007912654000017.tif55153

[0026] 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.

[0027] 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.

[0028] 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. Resin (A) is preferably composed of structural unit (a1-0), structural unit (a1-1), and It is at least one structural unit selected from the group consisting of structural units (a1-2), and more Preferably, a small number selected from the group consisting of structural unit (a1-1) and structural unit (a1-2) They consist of at least one or two structural units. These may be used individually or in combination of two or more types. It may be used. TIFF0007912654000018.tif46150[In formulas (a1-0), (a1-1), and (a1-2), L a01 , L a1 and L a2 These are, independently, -O- or *-O-(CH2) k1 - CO-O- represents 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 a 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.

[0029] R a01 , R a4 and R a5 This is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. It is a chill group. L a01 , L a1 and L a2 Preferably, an oxygen atom or *-O-(CH2) k01 -C OO- (where k01 is preferably an integer from 1 to 4, more preferably It is 1, more preferably an oxygen atom. R a02 , R a03 and R a04 Alkyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and And as a group formed by combining these, the R of group (1) a1 , R a2 and R a3 Similar to the bases mentioned above. The basis is cited. R a6 and R a7alkyl groups, alkenyl groups, alicyclic hydrocarbon groups, aromatic carbon groups As for hydrogen groups and groups formed by combining them, R in formula (1) a1 , R a2 and R a3 The basis mentioned above and Similar groups can be cited. R a02 , R a03 , and R a04 The alkyl group in is preferably It is an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and further Preferably, it is a methyl group. R a6 and R a7 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, a methyl group, an ethyl group, an isopropyl group, or a t-butyl group, and further Preferably, it is an ethyl group or an isopropyl 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 specifically, 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.

[0030] 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 Equivalent 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. TIFF0007912654000019.tif98165

[0031] As for the structural unit (a1-1), for example, see Japanese Patent Publication No. 2010-204646. Examples of structural units derived from monomers include those from formula (a1-1-1) to formula (a1 -1-7) Structural units represented by any of the above and R in structural units (a1-1) a4 in relation to The corresponding methyl group is replaced by a hydrogen atom, halogen atom, haloalkyl group, or other alkyl group. A divided structural unit is preferred, and can be represented by any of the formulas (a1-1-1) to (a1-1-4). A structural unit that can be made is more preferable. TIFF0007912654000020.tif41168

[0032] 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. TIFF0007912654000021.tif71168

[0033] 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%.

[0034] 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. TIFF0007912654000022.tif4461[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 -R a32 they combine This represents the bonding site with the carbon atom. A a32 This represents an alkanediyl group with 1 to 6 carbon atoms. X a31 and X a32 These represent -O-, -CO-O-, or -O-CO- independently. nc represents 0 or 1. la represents an integer from 0 to 4. If la is an integer greater than or equal to 2, Number R a33 They may be the same or different from each other. R a34 and R a35 Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R a36 R represents a hydrocarbon group with 1 to 20 carbon atoms. a35 and R a36 they combine with each other and Together with the -CO- to which they bond, they form a divalent hydrocarbon group having 2 to 20 carbon atoms, and the carbonized water The -CH2- contained in the elementary group and the divalent hydrocarbon group is replaced by -O- or -S- That's good too.

[0035] 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. Ra33 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.

[0036] *-X a31 -(A a32 -X a32 ) nc - for example, *-O-, *-CO-O-, *-OC O-, *-CO-OA a32 -CO-O-, *-O-CO-A a32 -O-, *-OA a32 -CO-O-, *-CO-OA a32 -O-CO-, *-O-CO-A a32 -O-CO-, These include *-CO-O- and *-CO-OA. a32 -CO-O- or *- OA a32 -CO-O- is preferred.

[0037] Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, Propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and Examples include 2-methylbutane-1,4-diyl groups. A a32 It is preferable that this is a methylene group or an ethylene group.

[0038] 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-.

[0039] 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. TIFF0007912654000023.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.

[0040] R a34 Preferably, it is a hydrogen atom. R a35 Preferably, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a C3 to 12 carbon atom. It is an alicyclic hydrocarbon group, more preferably a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, or a C3 to 18 carbon atom Alicyclic hydrocarbon groups, aromatic hydrocarbon groups with 6 to 18 carbon atoms, or combinations thereof The group formed is more preferably an alkyl group having 1 to 18 carbon atoms, or a group having 3 to 1 carbon atoms. It is an 8-cell alicyclic hydrocarbon group or an aralkyl group having 7 to 18 carbon atoms. a36 Alki in The rico group and alicyclic hydrocarbon group are preferably unsubstituted. a36 Aromatic carbonization in The hydrogen group is preferably an aromatic ring having an aryloxy group with 6 to 10 carbon atoms. -OC(R) in structural units (a1-4) a34 )(R a35 )-OR a36 is an acid (for example) It is eliminated upon contact with p-toluenesulfonic acid, forming a hydroxyl group. -OC(R a34 )(R a35 )-OR a36 It bonds to the ortho- or para-position of the benzene ring. It is preferable that the bond is formed at the p-position, and more preferably that it is formed at the p-position.

[0041] 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 structural unit in which the corresponding hydrogen atom is replaced by a halogen atom, haloalkyl group, or alkyl group. The positions are listed, more preferably equations (a1-4-1) to (a1-4-5), and equation (a1- 4-10), formula (a1-4-13), formula (a1-4-14), formula (a1-4-19), formula The structural units represented by (a1-4-20) are listed below. TIFF0007912654000024.tif131165

[0042] 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.

[0043] 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. TIFF0007912654000025.tif4558 formula (a1-5), R a8 This may have a halogen atom, or it may have a C1-C6 alkyl group, a hydrogen atom, or a halogen atom. This represents a chlorogenic atom. Z a1 This is a single bond or *-(CH2) h3 -CO-L 54 - represents one of 1-4. Represents an integer of L, where * is L 51 This represents the connection point. L 51 , L 52 , L 53 and L 54 These represent either -O- or -S- independently. s1 represents an integer between 1 and 3. s1' represents an integer between 0 and 3.

[0044] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms being preferred. Examples of C1-C6 alkyl groups that may have a halogen atom include methyl and ethyl groups. Group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluorine Examples include methyl and trifluoromethyl groups. In equation (a1-5), R a8 This is a hydrogen atom, a methyl group, or a trifluoromethyl group preferable. L 51 An oxygen atom is preferred. L 52 and L 53 Preferably, one of them is -O- and the other is -S-. s1 is preferably 1. s1' is preferably an integer between 0 and 2. Z a1 A single bond or *-CH2-CO-O- is preferred.

[0045] 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. TIFF0007912654000026.tif33133

[0046] 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.

[0047] In addition, the following structural units (a1) can also be listed. TIFF0007912654000027.tif31162

[0048] 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.

[0049] In addition, the following structural units (a1) can also be listed. TIFF0007912654000028.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.

[0050] <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.

[0051] <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.

[0052] 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. TIFF0007912654000029.tif4854[In formula (a2-A), R a50 This is a hydrogen atom, a halogen atom, or a C1-C6 element which may have a halogen atom. It represents the alkyl group. R a51 This includes halogen atoms, hydroxyl groups, alkyl groups with 1 to 6 carbon atoms, and C1 to 6 atoms. Alkoxy group, alkoxyalkyl group having 2 to 12 carbon atoms, alkoxyalkyl group having 2 to 12 carbon atoms Lucoxy group, C2-C4 alkylcarbonyl group, C2-C4 alkylcarbonyl This represents an oxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 This is a single bond or *-X a51 -(A a52 -X a52 ) nb - represents -R a50 they combine This represents the bonding site with the carbon atom. A a52 This represents an alkanediyl group with 1 to 6 carbon atoms. X a51 and X a52 These represent -O-, -CO-O-, or -O-CO- independently. nb represents either 0 or 1. mb represents an integer between 0 and 4. If mb is an integer greater than or equal to 2, Number R a51 They may be the same or different from each other.

[0053] R a50 and R a51 Examples of halogen atoms in this context include fluorine, chlorine, and bromine atoms. These are some examples. R a50 C1-C6 alkyl groups that may have a halogen atom include: Trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2 ,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, pe fluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, Perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, Tyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoro Examples include pentyl groups, pentyl groups, hexyl groups, and perfluorohexyl groups. R a50 The hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and the hydrogen atom, methyl group or An ethyl group is more preferable, and a hydrogen atom or a methyl group is even more preferable. R a51 The alkyl groups in this context are methyl, ethyl, propyl, and isopropyl groups. Examples include the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and may have a methyl group or an ethyl group. More preferably, a methyl group is even more preferred. R a51 The alkoxy groups in this context include methoxy, ethoxy, propoxy, and iso Examples include propoxy groups, butoxy groups, sec-butoxy groups, and tert-butoxy groups. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and is either a methoxy group or an ethoxy group. More preferably, a methoxy group is even more preferred. R a51 The alkoxyalkyl groups in this context are methoxymethyl group and ethoxyethyl group. , propoxymethyl group, isopropoxymethyl group, butoxymethyl group, sec-butoxy Examples include methyl groups and tert-butoxymethyl groups. Alkoxyalkyl groups have a number of carbon atoms. 2 to 8 alkoxyalkyl groups are preferred, and methoxymethyl or ethoxyethyl groups are preferred. A methoxymethyl group is more preferable, and a methoxymethyl group is even more preferable. R a51 Examples of alkoxyalkoxy groups in this context include methoxymethoxy groups and methoxyethyl groups. Xy group, ethoxymethoxy group, ethoxyethoxy group, propoxymethoxy group, isoprop Xymethoxy group, butoxymethoxy group, sec-butoxymethoxy group, tert-butoxy A cymethoxy group is one example. Alkoxyalkoxy groups are alkoxyal groups with 2 to 8 carbon atoms. A coxy group is preferred, and a methoxyethoxy group or an ethoxyethoxy group is more preferred. R a51 The alkylcarbonyl groups in this context include acetyl, propionyl, and butyric groups. Examples include lyl groups. Alkyl carbonyl groups are alkyl carbonyl groups having 2 to 3 carbon atoms. A is preferred, and an acetyl group is more preferred. R a51Examples 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.

[0054] *-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.

[0055] 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.

[0056] 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-.

[0057] mb is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0. The hydroxyl group is preferably bonded to the m- or p-position of the benzene ring, and at the m-position It is more preferable for them to bond. If the phenyl group has two or more hydroxyl groups, then two Preferably, the hydroxyl groups are bonded to the m-position and the p-position, respectively.

[0058] 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 the 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. TIFF0007912654000030.tif79169

[0059] 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.

[0060] 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. TIFF0007912654000031.tif4562 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 -CO-O- represents, k2 represents an integer between 1 and 7. * represents a connection site with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 Each of these independently represents a hydrogen atom, a methyl group, or a hydroxyl group. o1 represents an integer between 0 and 10.

[0061] 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.

[0062] 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. TIFF0007912654000032.tif49135

[0063] 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%.

[0064] <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 formula (a3-2) below) These are some examples.

[0065] 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. TIFF0007912654000033.tif50160[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 bond site with a carbonyl group. R a18 , R a19 and R a20 Each of these independently represents either a hydrogen atom or a methyl group. R a24 This is a hydrogen atom, a halogen atom, or a C1-C2 atom which may have a halogen atom. This represents an alkyl group of 6. X a3 represents -CH2- or an oxygen atom. R a21 This represents an aliphatic hydrocarbon group with 1 to 4 carbon atoms. R a22 , R a23 and R a25 Each of these independently comprises a carboxyl group, a cyano group, or a carbon Represents aliphatic hydrocarbon groups with prime numbers 1 through 4. p1 represents an integer between 0 and 5. q1 represents an integer between 0 and 3. r1 represents an integer between 0 and 3. w1 represents an integer between 0 and 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 They may be the same or different from each other.

[0066] 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.

[0067] 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.

[0068] In equations (a3-1) to (a3-3), L a4 ~L a6 Each is independently preferred Alternatively, -O- or *-O-(CH2) k3 In -CO-O-, k3 is one of 1 to 4. The base is an integer, more preferably -O- and *-O-CH2-CO-O-, even more preferably It is an oxygen atom. R a18 ~R a21 The group is preferably a methyl group. R a22 and R a23 Each of these is independently preferably a carboxyl group, a cyano group, or a melanin group. It is a chill group. p1, q1, and r1 are each independently, preferably integers between 0 and 2. More preferably, it is 0 or 1.

[0069] 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). TIFF0007912654000034.tif3849(in the formula, R a24 , L a7 (This expresses the same meaning as above.)

[0070] 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.

[0071] TIFF0007912654000035.tif116165

[0072] If resin (A) contains structural units (a3), the total content of these units is the total structural unit content of resin (A). The amount is usually 5-70 mol%, preferably 10-65 mol%, and more preferably More specifically, it is between 10 and 60 mol%. Also, structural unit (a3-1), structural unit (a3-2), structural unit (a3-3) or structure The content of units (a3-4) is 5 to 60 units relative to the total structural units of resin (A), respectively. % is preferred, 5 to 50 mol% is more preferred, and 10 to 50 mol% is even more preferred.

[0073] <Structural Unit (a4)> The following are examples of structural units (a4): TIFF0007912654000036.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.

[0074] 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. TIFF0007912654000037.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.

[0075] 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). TIFF0007912654000038.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.

[0076] L 4a The alkanediyl groups in this include methylene group, ethylene group, propane-1, Linear alkanediyl groups such as 3-diyl groups and butane-1,4-diyl groups, ethane-1,1 -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylprop Branched alkanes such as pan-1,3-diyl groups and 2-methylpropane-1,2-diyl groups A diyl group is one example.

[0077] 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.

[0078] 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.

[0079] 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. JPEG0007912654000039.jpg95166

[0080] TIFF0007912654000040.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. TIFF0007912654000041.tif1488 [In formula (a-g1), s represents either 0 or 1. A a42 and A a44 Each of these is independently a divalent carbon atom having 1 to 5 carbon atoms, which may have substituents. This represents a saturated hydrocarbon group. A a43 This is a divalent saturated hydrocarbon group having 1 to 5 carbon atoms, which may have single bonds or substituents. It represents. X a41 and X a42 These are, independently, -O-, -CO-, -CO-O-, or -O-CO - represents However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * indicates a binding site, and the * on the right is -O-CO-R a42 This is the junction site.

[0081] 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.

[0082] 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. TIFF0007912654000042.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.

[0083] R a42 The substituents it possesses are 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. TIFF0007912654000043.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.

[0084] 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). TIFF0007912654000044.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.

[0085] 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. In particular, a perfluoroalkyl group having 1 to 3 carbon atoms is preferred. 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.

[0086] 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). TIFF0007912654000045.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 At least one of them has at least one halogen atom. * indicates a bonding site with a carbonyl group.

[0087] 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.

[0088] The preferred structure of the group represented by formula (a-g2) is as follows (* represents a carbonyl group) (This is the junction site.) TIFF0007912654000046.tif14160

[0089] A a41 The alkanediyl groups in this include methylene group, ethylene group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 Linear alkanediyl groups such as ,6-diyl groups; propane-1,2-diyl groups, butane-1 ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- Examples include branched alkanediyl groups such as diyl groups and 2-methylbutane-1,4-diyl groups. ru. A a41 The substituents in the alkanediyl group represented by are a hydroxyl group and a carbon 1- Examples include 6 alkoxy groups. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a carbon number The group is an alkanediyl group of type 2 to 4, and more preferably an ethylene group.

[0090] A in the group represented by formula (a-g1) a42 , A a43 and A a44 Divalent saturated carbonized water The elemental groups include linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated hydrocarbon groups. , and formed by combining an alkanediyl group and a divalent alicyclic saturated hydrocarbon group. Examples include divalent saturated hydrocarbon groups. Specifically, methylene groups, ethylene groups, and p Ropan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2- Examples include methylpropane-1,2-diyl groups. A a42 , A a43 and A a44 The substituents of the divalent saturated hydrocarbon group represented by are hydroxyl groups. Examples include alkoxy groups having 1 to 6 carbon atoms. s is preferably 0.

[0091] In the group represented by formula (a-g1), Xa42 -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. TIFF0007912654000047.tif46140

[0092] 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: TIFF0007912654000048.tif92135

[0093] TIFF0007912654000049.tif132150

[0094] 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). TIFF0007912654000050.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.

[0095] L 44 The alkanediyl group with 1 to 6 carbon atoms is A a41Similar to the examples given above, It can be done. R f6 The saturated hydrocarbon group is R 42 Similar to the examples given earlier, the same types of bases can be cited. L 44 In this context, an alkanediyl group having 2 to 4 carbon atoms is preferred. An ethylene group is more preferable.

[0096] 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.

[0097] TIFF0007912654000051.tif5671[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 This represents an alkanediyl group with 1 to 6 carbon atoms. A f13 This represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, which may contain a fluorine atom. vinegar. X f12 This represents *-O-CO- or *-CO-O- (* is A f13 This represents the connection point. ). A f14 This represents a saturated hydrocarbon group having 1 to 17 carbon atoms, which may contain a fluorine atom. However, A f13 and A f14 At least one of them has a fluorine atom, L 5 , A f13 and A f14 The upper limit for the total number of carbon atoms is 20.

[0098] L5 The alkanediyl group in A is a41 The same as the example with the alkanediyl group. The basis for this can be cited.

[0099] 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.

[0100] 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.

[0101] In equation (a4-3), L 5 An ethylene group is preferred. A f13 The divalent saturated hydrocarbon group is a divalent chain-type saturated hydrocarbon group having 1 to 6 carbon atoms and carbon A group containing a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms is preferred, and a divalent chain having 2 to 3 carbon atoms is preferred. A saturated hydrocarbon group is even more preferred. A f14 The saturated hydrocarbon group is a chain-type saturated hydrocarbon group having 3 to 12 carbon atoms and a group having 3 to 12 carbon atoms. Groups containing alicyclic saturated hydrocarbon groups are preferred, and chain-type saturated hydrocarbon groups having 3 to 10 carbon atoms and Groups containing alicyclic saturated hydrocarbon groups having 3 to 10 carbon atoms are even more preferred. Among them, A f14 teeth Preferably, the group contains an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably, Cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and It is a damantyl group.

[0102] 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.

[0103] As a structural unit (a4), the structural unit represented by formula (a4-4) can also be cited. TIFF0007912654000052.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.

[0104] R f22 The saturated hydrocarbon group is R a42 Examples include saturated hydrocarbon groups similar to those represented by the symbol. R f22 This refers to an alkyl group having 1 to 10 carbon atoms that contains a fluorine atom, or a carbon atom containing a fluorine atom. A cycloaliphatic saturated hydrocarbon group having 1 to 10 prime atoms is preferred, and a group having 1 to 10 carbon atoms and a fluorine atom is preferred. Alkyl alkyl groups are more preferred, and C1-C6 alkyl groups having a fluorine atom are even more preferred. It's nice.

[0105] 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.

[0106] 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. JPEG0007912654000053.jpg87160

[0107] If resin (A) has structural units (a4), the content of these units is the total structural unit content of resin (A). For each position, 1 to 20 mol% is preferred, 2 to 15 mol% is more preferred, and 3 to 10 mol% is preferred. A percentage is even more preferable.

[0108] <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). . TIFF0007912654000054.tif3555[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 This represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the 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-.

[0109] 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 substituted alicyclic hydrocarbon groups 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.

[0110] 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.

[0111] 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. TIFF0007912654000055.tif18164 formula (L1-1), X x1 This represents *-O-CO- or *-CO-O- (* is L x1 (This represents the connection point with [another element].) . L x1 This represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 17 carbon atoms. L x4 This represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 This represents a divalent aliphatic saturated hydrocarbon group with 1 to 15 carbon atoms. L x6 and L x7 Each of these independently 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), Lx8 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.

[0112] L x1 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x2 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a single bond. L x3 Preferably, it is a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 Preferably, a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably, It is a methylene group or an ethylene group. L x6 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably The group is either a methylene group or an ethylene group. L x7 Preferably, it is a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. L x9 Preferably, a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A single bond or a methylene group is a single bond or a methylene group. W x1Preferably, a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably It is either a cyclohexanediyl group or an adamantanediyl group.

[0113] Examples of groups represented by formula (L1-1) include the divalent groups shown below. TIFF0007912654000056.tif53135

[0114] Examples of groups represented by formula (L1-2) include the divalent groups shown below. TIFF0007912654000057.tif23130

[0115] Examples of groups represented by formula (L1-3) include the divalent groups shown below. TIFF0007912654000058.tif15145

[0116] Examples of groups represented by formula (L1-4) include the divalent groups shown below. TIFF0007912654000059.tif26114

[0117] L 55 Preferably, it is a single bond or a group represented by formula (L1-1).

[0118] Structural units (a5-1) include the structural units shown below and the structural units within the following structural units ( a5-1) R 51 Examples of structural units in which the corresponding methyl group is replaced by a hydrogen atom include It can be done. TIFF0007912654000060.tif111150 If resin (A) has structural units (a5), the content of these units is the total structural unit content of resin (A). For each position, 1 to 30 mol% is preferred, 2 to 20 mol% is more preferred, and 3 to 15 mol% is preferred. A percentage is even more preferable.

[0119] <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.

[0120] As a sultone ring, the following equation (T 1 -1), formula (T 1 -2), formula (T 1 -3) and formula ( T 1 A ring represented by -4) is an example. The bonding site can be at any position. The sultone ring may be monocyclic, but is preferably polycyclic. This refers to a bridging ring containing -SO2-O- as the atomic group that makes up the ring, and is given by equation (T 1 -1 ) and formula (T 1 A ring represented by equation (T) is an example. A Sultone ring is given by equation (T 1 (-2) is expressed as Like a ring, in addition to -SO2-O-, there are also heteroatoms as atomic groups that make up the ring. It may also contain heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, or nitrogen atoms. , preferably an oxygen atom. TIFF0007912654000061.tif3186

[0121] 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.

[0122] 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.

[0123] 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. TIFF0007912654000062.tif3172[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. X11 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.

[0124] As a sultone ring, the ring represented by formula (T1) is more preferable. TIFF0007912654000063.tif3149[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.

[0125] 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.

[0126] The following are examples of rings represented by equation (T1') and equation (T1): The connection point can be at any position. TIFF0007912654000064.tif47144

[0127] The structural unit having a sultone ring preferably has the following group: * in the following group The symbol represents the bonding site. TIFF0007912654000065.tif45144

[0128] 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.

[0129] The structural unit (a6) is preferably a structural unit represented by formula (Ix). TIFF0007912654000066.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.

[0130] 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.

[0131] A xExamples 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.

[0132] R 41 , X11 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.

[0133] The following are examples of structural units (a6): TIFF0007912654000067.tif92151

[0134] 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.

[0135] <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.

[0136] 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'). TIFF0007912654000068.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.

[0137] R III3 The halogen atoms represented include fluorine, chlorine, bromine, and yo Examples include porcini atoms. R III3 A C1-C6 alkyl group which may have a halogen atom represented by So, R a8 A C1-C6 alkyl group which may have a halogen atom represented by the same Some examples include the following. A x1 Examples of alkanediyl groups with 1 to 8 carbon atoms, represented by the methylene group and the ethylene group, are available. , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl Group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group yl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl Examples include the 1,4-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group. ru. A x1 Perfluoroalkyl groups having 1 to 6 carbon atoms that may be substituted include: , trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Roisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorote Examples include rt-butyl groups, perfluoropentyl groups, and perfluorohexyl groups.

[0138] 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.

[0139] 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. TIFF0007912654000069.tif145161

[0140] X 3 This represents a divalent saturated hydrocarbon group with 1 to 16 carbon atoms. X 4 This represents a divalent saturated hydrocarbon group with 1 to 15 carbon atoms. X 5 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms. X 6 This represents a divalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 7 This represents a trivalent saturated hydrocarbon group with 1 to 14 carbon atoms. X 8 This represents a divalent saturated hydrocarbon group with 1 to 13 carbon atoms.

[0141] 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.

[0142] 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. JPEG0007912654000070.jpg37109 [In formula (II-2-A), R III3 , X III3 and ZA + This expresses the same meaning as above. z represents an integer between 0 and 6. R III2 and R III4 Each of these is independently a hydrogen atom, a fluorine atom, or a carbon atom with 1 carbon atom. Represents a perfluoroalkyl group of ~6, and when z is 2 or greater, multiple R III2 and R II I4 They may be the same or different from each other. Q a and Q b Each is independently a fluorine atom or a perfluoroal with 1 to 6 carbon atoms. [Represents the kill group.]

[0143] 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 below. b1 This is the same as a perfluoroalkyl group with 1 to 6 carbon atoms, as represented by This is one example.

[0144] 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. TIFF0007912654000071.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.

[0145] 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.

[0146] 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. TIFF0007912654000072.tif5287 [In formula (II-2-A-2), R III3 , RIII5 and ZA + This expresses the same meaning as above. m and nA each independently represent either 1 or 2.

[0147] 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. TIFF0007912654000073.tif86163

[0148] 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. JPEG0007912654000074.jpg3381 [In formula (II-1-1), A II1 This represents a single bond or a divalent linking group. R II1 This represents a divalent aromatic hydrocarbon group with 6 to 18 carbon atoms. R II2 and R II3 Each of these independently represents a hydrocarbon group with 1 to 18 carbon atoms, and R II2 and R II3 They bond to each other, forming a ring with the sulfur atoms to which they are bonded. That's fine. R II4 This is a hydrogen atom, a halogen atom, or a C1-C2 atom which may have a halogen atom. This represents an alkyl group of 6. A - This represents an organic anion. R II1As 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.

[0149] 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. TIFF0007912654000075.tif85130

[0150] 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 anion is as follows: Examples include those similar to the anion represented by formula (B1).

[0151] A - Examples of sulfonylimid anions represented by the formula include the following: TIFF0007912654000076.tif36136

[0152] Examples of sulfonylmethide anions include the following: TIFF0007912654000077.tif29123

[0153] Examples of carboxylic acid anions include the following: TIFF0007912654000078.tif43156

[0154] Examples of structural units represented by formula (II-1-1) include the following structural units. It is possible. TIFF0007912654000079.tif88149

[0155] 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%.

[0156] Resin (A) may have structural units other than those described above, and such structural units In terms of rank, well-known structural units in this field can be cited.

[0157] 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 or two selected from the group consisting of structural units (a1-2), more preferably Alternatively, at least one selected from the group consisting of structural unit (a1-1) and structural unit (a1-2) Both are of type 1 or type 2. 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).

[0158] 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.

[0159] <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)).

[0160] 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 particularly preferred The amount is 1 to 8 parts by mass.

[0161] 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.

[0162] <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.

[0163] 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.

[0164] 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.) TIFF0007912654000080.tif2859 [In formula (B1), Q b1and Q b2 These are, independently, a hydrogen atom, a fluorine atom, and a perfluorine atom with 1 to 6 carbon atoms. This represents a chloroalkyl group or an alkyl 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-. Z + This represents an organic cation.

[0165] 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 The alkyl groups include methyl, ethyl, propyl, and isopropyl groups. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. It can be listed. The acid generator (B) is preferably a fluorine-containing acid generator, Q b1 and Q b2 Ha, izu Preferably, one of them is a fluorine atom or a perfluoroalkyl group, and each is unique It is more preferably a fluorine atom or a trifluoromethyl group, both of which are fluorine atoms. Being a child is even more preferable.

[0166] 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.

[0167] 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 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.

[0168] TIFF0007912654000081.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.

[0169] In the groups represented by formulas (b1-1) to (b1-3), the saturated hydrocarbon group is included. If -CH2- is replaced by -O- or -CO-, the number of carbon atoms before replacement is... This is the number of carbon atoms in the hydrocarbon group. As for divalent saturated hydrocarbon groups, L b1 Examples include divalent saturated hydrocarbon groups. ru. L b2 The bond is preferably a single bond. L b3 This is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 Preferably, the divalent saturated hydrocarbon group has 1 to 8 carbon atoms, and the divalent saturated hydrocarbon water The hydrogen atoms in the elementary group may be substituted with fluorine atoms. L b5Preferably, 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.

[0170] 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. TIFF0007912654000082.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 Lb10 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.

[0171] 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. TIFF0007912654000083.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.

[0172] 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.

[0173] The following are examples of bases represented by formula (b1-4): TIFF0007912654000084.tif17150

[0174] The following are examples of bases represented by formula (b1-5): TIFF0007912654000085.tif72149

[0175] The following are examples of bases represented by formula (b1-6): TIFF0007912654000086.tif30150

[0176] The following are examples of bases represented by formula (b1-7): TIFF0007912654000087.tif64150

[0177] The following are examples of bases represented by formula (b1-8): TIFF0007912654000088.tif23150

[0178] The following are examples of bases represented by formula (b1-2): TIFF0007912654000089.tif31161

[0179] The following are examples of bases represented by formula (b1-9): TIFF0007912654000090.tif44137

[0180] The following are examples of bases represented by formula (b1-10): TIFF0007912654000091.tif89157

[0181] The following are examples of bases represented by formula (b1-11): TIFF0007912654000092.tif82158

[0182] Examples of alicyclic hydrocarbon groups represented by Y include formulas (Y1) to (Y11), formula (Y36) to (Y36). Examples of groups represented by formula (Y38) include those shown. The -CH2- contained in the alicyclic hydrocarbon group represented by Y is -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 done. * is L b1This represents the bonding site with the group. The -O- or -CO- in the groups shown below means - It may be replaced with S- or -SO2-. The alicyclic hydrocarbon group represented by TIFF0007912654000093.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.

[0183] 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.

[0184] 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 group, ethylsulfonyl group, and propyl group. Examples include sulfonyl groups. The number of carbon atoms in the alkylsulfonyl group is preferably 1 to 12. Yes, more preferably 1 to 6, and even more preferably 1 to 4. Examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups. Examples include alkoxycarbonyl groups and butoxycarbonyl groups. The number of carbon atoms in the alkoxycarbonyl group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of alkylcarbonyl groups include acetyl, propionyl, and butyryl groups. Examples include the following. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably The value is between 2 and 6, and more preferably between 2 and 4. Examples of alkylcarbonyloxy groups include acetyloxy groups and propionyloxy groups. Examples include the cy group and the butyryloxy group. The number of carbon atoms in the alkylcarbonyloxy group is preferred. More preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. Examples of combined groups include groups that combine an alkoxy group and an alkyl group, and A group combining a lucoxy group and an alkoxy group, or a group combining an alkoxy group and an alkylcarbonyl group. Groups combining these, groups combining an alkoxy group and an alkylcarbonyloxy group, etc. It can be listed. Examples of groups combining an alkoxy group and an alkyl group include the methoxymethyl group. Alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, and ethoxymethyl group For example, the number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, and more preferably k is 2 to 6, and more preferably 2 to 4. Groups that combine alkoxy groups include methoxymethoxy groups and metoxy groups. Alkoxyalkoxy groups such as xyethoxy group, ethoxymethoxy group, and ethoxyethoxy group Examples include the following. The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, and more Preferably, it is 2 to 6, and more preferably 2 to 4. Examples of groups combining an alkoxy group and an alkylcarbonyl group include methoxyacetyl. Alco groups such as methoxypropionyl group, ethoxyacetyl group, and ethoxypropionyl group Examples include xyalkylcarbonyl groups. The number of carbon atoms in an alkoxyalkylcarbonyl group is... Preferably 3 to 13, more preferably 3 to 7, and even more preferably 3 to 5. be. Groups that combine an alkoxy group and an alkylcarbonyloxy group include methoxya Cetyloxy group, Methoxypropionyloxy group, Ethoxyacetyloxy group, Ethoxy Examples include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the coxyalkylcarbonyloxy group is preferably 3 to 13, and more preferably The value of k is between 3 and 7, and more preferably between 3 and 5.

[0185] The following are examples of Y: TIFF0007912654000094.tif160165

[0186] 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 represented by a dol group, an oxoadamantyl group, or formulas (Y42), (Y100) to (Y114) It is a base.

[0187] The anions in the salt represented by formula (B1) are given by formula (B1-A-1) ~ formula (B1- Anions represented by A-59) (hereinafter referred to as "anion (B1-A-1)" etc. depending on the formula number) In some cases, this is preferable, and formulas (B1-A-1) to (B1-A-4), formula (B1 -A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 An anion represented by any of 9) is more preferred. TIFF0007912654000095.tif231164

[0188] TIFF0007912654000096.tif238165

[0189] TIFF0007912654000097.tif168160

[0190] 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.

[0191] Preferably, the anion in the salt represented by formula (B1) is formula (B1a-1) ~ formula ( The anions represented by B1a-38 are listed below. TIFF0007912654000098.tif238158

[0192] TIFF0007912654000099.tif129154

[0193] In particular, equations (B1a-1) to (B1a-3), and equations (B1a-7) to (B1a-1) 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a-3 An anion represented by any of 8) is preferred.

[0194] Z + Examples of organic cations include organic onium cations, organic sulfonium cations, and Organic iodonium cation, organic ammonium cation, benzothiazolium cation and Examples include organic phosphonium cations. Among these, organic sulfonium cations are particularly noteworthy. Organic iodonium cations are preferred, and aryl sulfonium cations are more preferred. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) (hereinafter) Depending on the formula number, it may be referred to as "cation (b2-1)," etc. ) is one example. In formulas (b2-1) to (b2-4) of TIFF0007912654000100.tif47170, R b4 ~R b6 These are, independently, chain hydrocarbon groups with 1 to 30 carbon atoms and groups with 3 to 36 carbon atoms. This term represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and is contained in the chain-like hydrocarbon group. The hydrogen atoms present are found in hydroxyl groups, alkoxy groups with 1 to 12 carbon atoms, and lipid groups with 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms and aliphatic hydrocarbon groups with 1 to 18 carbon atoms. They may also be substituted with an alkylcarbonyl group or glycidyloxy group having 2 to 4 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group are halogen atoms, hydroxyl groups, and C1- 18 aliphatic hydrocarbon groups, C1-C12 alkyl fluorides, or C1-C12 It may be substituted with a coxy group. R b4 and R b5 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. Even if the -CH2- contained in the ring is replaced by -O-, -S-, or -CO- good. R b7 and R b8 These are, independently, a halogen atom, a hydroxyl group, and a lipid with 1 to 12 carbon atoms. Alkaline hydrocarbon groups, C1-C12 alkyl fluorides, or C1-C12 alkoxy groups It represents. m2 and n2 each independently represent an integer between 0 and 5. When m2 is 2 or more, multiple R b7 They may be the same or different, and when n2 is 2 or more, multiple Number R b8 They may be the same or different. R b9 and R b10 Each of these is independently a chain-like hydrocarbon group having 1 to 36 carbon atoms or a group having 3 to 3 carbon atoms. It represents 36 alicyclic hydrocarbon groups. R b9 and R b10 These atoms bond with each other and, together with the sulfur atoms they bond to, form a ring. It is also possible to replace the -CH2- contained in the ring with -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 with 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. When u2 is 0, then at least one of o2, p2, q2, and r2 is 1 or greater, and Rb1 3 ~R b16 Preferably, at least one of them is a halogen atom, when u2 is 1. , one of o2, p2, s2, t2, q2 and r2 is 1 or more, R b13 ~ R b18 Preferably, at least one of them is a halogen atom. Furthermore, when u2 is 0, it is preferable that r2 is 1 or greater, and even more preferable that it is 1. This is preferable. Also, when u2 is 0 and r2 is 1 or greater, R b16 is a halogen atom It is preferable.

[0195] Aliphatic hydrocarbon groups refer to both chain-type hydrocarbon groups and alicyclic hydrocarbon groups. Examples of chain-type 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. TIFF0007912654000101.tif11157 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] R b4 and R b5 The ring formed when these atoms bond to each other and together with the sulfur atom they bond to is The rings may be monocyclic, polycyclic, aromatic, non-aromatic, saturated, or unsaturated. This ring may have 3 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Furthermore, the ring containing the sulfur atom can be a 3-membered to 12-membered ring, preferably a 3-membered to 7-membered ring. For example, the following ring can be cited. * indicates a bonding site. TIFF0007912654000102.tif24142

[0201] 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.

[0202] Among cations (b2-1) to (b2-4), preferably cation (b2 -1) The following cations can be considered as cations (b2-1): TIFF0007912654000103.tif80158

[0203] TIFF0007912654000104.tif102165

[0204] The following cations can be considered as cations (b2-2): TIFF0007912654000105.tif19150

[0205] The following cations can be considered as cations (b2-3): TIFF0007912654000106.tif26140

[0206] The following cations can be considered as cations (b2-4): TIFF0007912654000107.tif153161

[0207] Salt (I) is a combination of the above-mentioned anion and the above-mentioned organic cation, which can be any combination. They can be combined. Preferably, the salt (I) is formula (B1a-1) to formula (B1a -3), formula (B1a-7) ~ formula (B1a-16), formula (B1a-18), formula (B1a-1 9) Anions represented by any of the formulas (B1a-22) to (B1a-38), and cati On (b2-1), cation (b2-2), cation (b2-3), or cation (b2- 4) is a possible combination.

[0208] 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) The one represented by formula (B1-60) is particularly preferred. TIFF0007912654000108.tif190167

[0209] TIFF0007912654000109.tif250153

[0210] TIFF0007912654000110.tif238165

[0211] 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 10 parts by mass or more and 40 parts by mass or less.

[0212] <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.

[0213] <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.

[0214] The acidity of a salt that produces an acid weaker than the acid produced by the acid generator (B) is: It is represented by the acid dissociation constant (pKa). An acid having a lower acidity than the acid generated from the acid generator (B) A salt that generates the acid as described above is a salt wherein the acid dissociation constant of the acid generated from the salt usually satisfies -3 < pKa, and preferably it is a salt satisfying -1 < pKa < 7, more preferably a salt satisfying 0 < pKa < 5. Examples of the salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula , a salt represented by formula (D) described in Japanese Patent Application Laid-Open No. 2015-147926 (hereinafter referred to as " weak acid intramolecular salt (D) in some cases.") and salts described in Japanese Patent Application Laid-Open No. 2012-229206 , Japanese Patent Application Laid-Open No. 2012-6908, Japanese Patent Application Laid-Open No. 2012-72109, Japanese Patent Application Laid-Open No. 2011-3 9502 and Japanese Patent Application Laid-Open No. 2011-191745. Preferable is a salt that generates a carboxylic acid having a lower acidity than the acid generated from the acid generator (B) (carboxy lic salt having a acid anion), more preferably the weak acid intramolecular salt (D), and further preferably, among the weak acid intramolecular salts (D), a diphenyliodonium salt containing a phenyl group substituted with a carboxylate anion. JPEG0007912654000111.jpg116167

[0215] The weak acid intramolecular salt (D) is preferably an iodonium cation having two phenyl groups bonded thereto, and a carboxylate anion substituted on at least one phenyl group among the two phenyl groups bonded to the iodonium cation , and it is preferably a diphenyliodonium salt having the above structure, and examples thereof include salts represented by the following formula. TIFF0007912654000112.tif1493[In formula (D), R D1 and R D2 each independently represent a hydrocarbon group having 1 to 12 carbon atoms, an alky group having 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-type hydrocarbon groups include methyl, ethyl, propyl, isopropyl, and butyl groups. Alkyl groups such as isobutyl group, tert-butyl group, pentyl group, hexyl group, and nonyl group. One example is the 'L' group. The alicyclic hydrocarbon group may be monocyclic or polycyclic, and can be saturated or unsaturated. Any misalignment is acceptable. Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Cycloalkyl groups such as cyclononyl groups and cyclododecyl groups, norbonyl groups, adamant Examples include chill groups. Examples of aromatic hydrocarbon groups include phenyl group, 1-naphthyl group, 2-naphthyl group, and 2-methyl group. methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-t -Butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, ant Lyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group , biphenyl group, phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6- Examples include aryl groups such as ethylphenyl. The groups formed by combining these include alkyl-cycloalkyl groups. , cycloalkyl-alkyl groups, aralkyl groups (e.g., phenylmethyl group, 1-phenyl ethyl group, 2-phenylethyl group, 1-phenyl-1-propyl group, 1-phenyl-2 -propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-propyl Phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group Examples include: Examples of alkoxy groups include methoxy groups and ethoxy groups. Examples of acyl groups include acetyl, propanoyl, benzoyl, and cyclohexanecal. Examples include the bonyl group. Examples of acyloxy groups include groups in which an oxy group (-O-) is bonded to the above-mentioned acyl group. It can be done. As an alkoxycarbonyl group, a carbonyl group (-CO-) is bonded to the above alkoxy group. Examples include combined bases, etc. Examples of halogen atoms include fluorine, chlorine, and bromine atoms. R D1 and R D2 These are, independently, alkyl groups with 1 to 8 carbon atoms and sicq groups with 3 to 10 carbon atoms. alkoxy groups with 1 to 6 carbon atoms, acyl groups with 2 to 4 carbon atoms, and groups with 2 to 4 carbon atoms. Acyloxy group, alkoxycarbonyl group with 2-4 carbon atoms, nitro group, or halogen atom preferable. m' and n' are each preferably independent integers between 0 and 2. It is more preferable that m' is 2 or more, D1 Even if they are the same, they are different Also, if n' is 2 or greater, multiple R D2 They may be the same or different. More specifically, the following salts are examples: TIFF0007912654000113.tif72165

[0216] <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.

[0217] <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 the resin (A) used, solvent (E), quencher (C), and It can be prepared by mixing other components (F). The mixing order is arbitrary. There are no particular limitations. The mixing temperature can range from 10 to 40°C, depending on the type of resin, etc. The appropriate temperature can be selected according to the solubility of the resin or other solvent (E). Mixing time Depending on the mixing temperature, the appropriate time can be selected from 0.5 to 24 hours. There are no particular restrictions on the mixing method, and stirring and mixing can be used. After mixing each component, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable to do so.

[0218] <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 formed 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.

[0219] <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]

[0220] 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)

[0221] 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".

[0222] 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. TIFF0007912654000114.tif90157

[0223] Synthesis Example 1 [Synthesis of Resin A1] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( Using a2-1-3), monomer (a3-4-2) and monomer (a1-4-2), Molar ratio [Monomer (a1-1-3):Monomer (a1-2-6):Monomer (a2-1- 3): Monomer (a3-4-2): Monomer (a1-4-2) is in a ratio of 20:35:3:1 Mix in a ratio of 5:27, and further, add the total amount of all monomers to this monomer mixture. Methyl isobutyl ketone was mixed in an amount 1.5 times its mass relative to the mass. As initiators, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) Add 1.2 mol% and 3.6 mol% of the total monomer amount, respectively, and then It was heated at 73°C for approximately 5 hours. After that, the polymerization reaction solution was mixed with a certain amount of monomer relative to the total mass of the monomers. Add 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5% by weight) and stir for 12 hours. Afterward, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane to precipitate the resin, and then filtered. By recovering the material, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 Resin A1 is produced with a yield of 63% It was obtained as follows. This resin A1 has the following structural units. TIFF0007912654000115.tif37154

[0224] Synthesis Example 2 [Synthesis of Resin A2] As monomers, monomer (a1-1-3), monomer (a1-2-6), monomer ( Using monomers (a2-1-3), (a3-4-2), and (a1-4-13), Molar ratio [monomer(a1-1-3):monomer(a1-2-6):monomer(a2-1 -3): Monomer (a3-4-2): Monomer (a1-4-13)] is 20:35:3 Mix them in a ratio of 15:27, and then add all the monomers to this monomer mixture. Methyl isobutyl ketone was mixed in an amount equal to 1.5 times the total mass. The resulting mixture In addition, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) are used as initiators. Tolyl was added at concentrations of 1.2 mol% and 3.6 mol% relative to the total amount of monomer, and The mixture was heated at 73°C for approximately 5 hours. After that, the polymerization reaction solution was mixed with a total amount of monomers relative to the total mass. Then, add 2.0 times the mass of p-toluenesulfonic acid aqueous solution (2.5% by weight) and stir for 12 hours. After mixing, the mixture was separated. The recovered 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 5.1 × 10⁻⁶. 3 The resin A2 is produced in a yield of 6 It was obtained at a concentration of 1%. This resin A2 has the following structural units. TIFF0007912654000116.tif38154

[0225] Synthesis Example 3 [Synthesis of Resin A3] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer ( Using a3-4-2) and monomer (a1-4-2), the molar ratio [monomer (a1-2 -6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (a1-4- 2) Mix the monomers in a ratio of 53:3:12:32, and further mix this monomer mixture The substance is mixed with methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all monomers. The resulting mixture was then mixed with azobisisobutyronitrile and azobis(2,4) as initiators. (dimethylvaleronitrile) is added at 1.2 mol% and 3.6 mol% respectively relative to the total amount of monomer. The mixture was added in ol% and heated at 73°C for approximately 5 hours. Afterward, the polymerization reaction solution was mixed with the total monomer. A p-toluenesulfonic acid aqueous solution (2.5% by weight) in an amount equal to 2.0 times the total mass of the total amount. After adding the mixture and stirring for 12 hours, the mixture was separated. The recovered organic layer was poured into a large amount of n-heptane. By precipitating the resin and then filtering and recovering it, the weight-average molecular weight is approximately 5.3 × 10⁻⁶. 3 dea Resin A3 was obtained with a yield of 88%. This resin A3 has the following structural units. TIFF0007912654000117.tif37129

[0226] Synthesis Example 4 [Synthesis of Resin A4] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer ( Using a3-4-2) and monomer (a1-4-13), the molar ratio [monomer (a1- 2-6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (a1-4 -13) Mix the monomers in a ratio of 53:3:12:32, and further, this monomer To the mixture, add methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all monomers. Combined. To the resulting mixture, azobisisobutyronitrile and azobis(2) were added as initiators. ,4-dimethylvaleronitrile) is added at 1.2 mol% and 3 mol% respectively relative to the total amount of monomer. 6 mol% was added, and these were heated at 73°C for approximately 5 hours. After that, the entire monopolymer was added to the polymerization reaction solution. A p-toluenesulfonic acid aqueous solution (2.5 by weight) is added in an amount equal to 2.0 times the total mass of the amount of Mer. %) was added, stirred for 12 hours, and then separated. The recovered organic layer contained a large amount of n-heptane. By pouring it into the solution and allowing the resin to precipitate, then filtering and recovering it, the weight-average molecular weight is approximately 5.1 × 10⁻⁶. 3 Resin A4 was obtained in a yield of 79%. This resin A4 has the following structural units: ru. TIFF0007912654000118.tif38129

[0227] Synthesis Example 5 [Synthesis of Resin A5] Monomers include acetoxystyrene, monomer (a1-2-13), and monomer (a6 -1) Using the molar ratio [acetoxystyrene:monomer (a1-2-13):monomer Mix (a6-1) in a ratio of 35:45:20, and further, this mono - Add methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all monomers to the mixture. Mixed. To the resulting mixture, azobisisobutyronitrile and azobis( 2,4-dimethylvaleronitrile) is added at 1.2 mol% and 3 mol% respectively relative to the total amount of monomer. 0.6 mol% was added, and these were heated at 73°C for about 5 hours. Then, the total amount was added to the polymerization reaction solution. 25% tetramethylammonium hydrochloride at 1.5 times the total mass of the nomer. After adding the sid aqueous solution and stirring for 12 hours, the mixture was separated. The recovered organic layer contained a large amount of n-H By pouring it into butan to precipitate the resin, filtering and recovering it, the weight-average molecular weight is approximately 5.5 × 10 3 Resin A5 was obtained in a yield of 79%. This resin A5 has the following structural units. That is the case. TIFF0007912654000119.tif30126

[0228] Synthesis Example 6 [Synthesis of Resin A6] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer ( Using a3-4-2) and monomer (a1-4-19), the molar ratio [monomer (a1- 2-6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (a1-4 Mix the monomers in the ratio of -19) to 53:3:12:32, and further, this monomer To the mixture, add methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all monomers. Combined. To the resulting mixture, azobisisobutyronitrile and azobis(2) were added as initiators. ,4-dimethylvaleronitrile) is added at 1.2 mol% and 3 mol% respectively relative to the total amount of monomer. 6 mol% was added, and these were heated at 73°C for approximately 5 hours. After that, the entire monopolymer was added to the polymerization reaction solution. A p-toluenesulfonic acid aqueous solution (2.5 by weight) is added in an amount equal to 2.0 times the total mass of the amount of Mer. %) was added, stirred for 12 hours, and then separated. The recovered organic layer contained a large amount of n-heptane. By pouring it into the solution to precipitate the resin, and then filtering and recovering it, the weight-average molecular weight is approximately 5.5 × 10⁻⁶. 3 Resin A6 was obtained in a yield of 74%. This resin A6 has the following structural units: ru. TIFF0007912654000120.tif37129

[0229] Synthesis Example 7 [Synthesis of Resin A7] As monomers, monomer (a1-2-6), monomer (a2-1-3), monomer ( Using a3-4-2) and monomer (a1-4-20), the molar ratio [monomer (a1- 2-6): Monomer (a2-1-3): Monomer (a3-4-2): Monomer (a1-4 Mix the monomers in the ratio of 53:3:12:32, and further, this monomer To the mixture, add methyl isobutyl ketone in an amount equal to 1.5 times the total mass of all monomers. Combined. To the resulting mixture, azobisisobutyronitrile and azobis(2) were added as initiators. ,4-dimethylvaleronitrile) is added at 1.2 mol% and 3 mol% respectively relative to the total amount of monomer. 6 mol% was added, and these were heated at 73°C for approximately 5 hours. After that, the entire monopolymer was added to the polymerization reaction solution. A p-toluenesulfonic acid aqueous solution (2.5 by weight) is added in an amount equal to 2.0 times the total mass of the amount of Mer. %) was added, stirred for 12 hours, and then separated. The recovered organic layer contained a large amount of n-heptane. By pouring it into the solution and allowing the resin to precipitate, then filtering and recovering it, the weight-average molecular weight is approximately 5.2 × 10⁻⁶. 3 Resin A7 was obtained in a yield of 66%. This resin A7 has the following structural units: ru. TIFF0007912654000121.tif37129

[0230] <Preparation of the resist composition> As shown in Table 1, the following components were mixed, and the resulting mixture contained fluorine with a pore size of 0.2 μm. The resist composition was prepared by filtering through a resin filter. [Table 1]

[0231] <Resin> A1~A7: Resin A1~Resin A7 <Acid Generator (B)> B1-43: Salt represented by formula (B1-43) (Implementation of Japanese Patent Publication No. 2016-47815) (Synthesized according to the example) TIFF0007912654000123.tif4381<Compound (I)> I-1: Compound represented by formula (I-1) I-3: Compound represented by formula (I-3) I-6: Compound represented by formula (I-6) I-12: Compound represented by formula (I-12) I-16: Compound represented by formula (I-16) I-25: Compound represented by formula (I-25) I-28: Compound represented by formula (I-28) I-37: Compound represented by formula (I-37) I-46: Compound represented by formula (I-46) I-61: Compound represented by formula (I-61) I-77: Compound represented by formula (I-77) IX-1: Compound represented by formula (IX-1) IX-2: Compound represented by formula (IX-2) IX-3: Compound represented by formula (IX-3) TIFF0007912654000124.tif107168<Quencher(C)> C1: Synthesized by the method described in Japanese Patent Publication No. 2011-39502 TIFF0007912654000125.tif4347<solvent> Propylene glycol monomethyl ether acetate, 400 units Propylene glycol monomethyl ether, 100 parts γ-Butyrolactone 5 parts

[0232] (Electron beam exposure evaluation of resist composition: butyl acetate development) A 6-inch silicon wafer is subjected to hexamethyldisilaza on a direct hot plate. The silicon wafer was treated at 90°C for 60 seconds using a solvent. The resist composition was then applied to this silicon wafer. The layer was spin-coated to a thickness of 0.04 μm. Then, direct hot plated... On the grid, the composition layer was formed by pre-baking for 60 seconds at the temperature shown in the "PB" column of Table 1. On the composition layer formed on the surface, an electron beam lithography machine [Hitachi Ltd.'s "HL-800D"] was used. Using 50 keV, the exposure level is changed in steps to create a line and space pattern. I drew it directly. After exposure, post-exposure is performed on a hot plate at the temperature shown in the "PEB" column of Table 1 for 60 seconds. Jar baking was performed. Next, the composition layer on this silicon wafer was treated with acetic acid as the developer. Using butyl (manufactured by Tokyo Chemical Industry Co., Ltd.), dynamic dispensing was performed at 23°C for 20 seconds. A resist pattern was obtained by developing the material according to the specified method. The obtained resist pattern (line and space pattern) is observed using a scanning electron microscope. I guess the line width and space width of the 60nm line and space pattern are in a 1:1 ratio. The exposure amount was defined as the effective sensitivity.

[0233] Line Edge Roughness Evaluation (LER): Sidewall of a resist pattern manufactured with effective sensitivity. The amplitude of surface irregularities was measured using a scanning electron microscope to determine the line edge roughness. The results are shown in Table 2. [Table 2] [Industrial applicability]

[0234] The resist composition of the present invention has a line edge roughness (LE) of the resulting resist pattern. Because it has excellent R) properties, it is suitable for 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), L 1 This represents an alkanediyl group having 1 to 6 carbon atoms, which may have a single bond or substituents. R １ This represents a halogen atom or a haloalkyl group having 1 to 12 carbon atoms. R ２ is, *-X １ -Ph-L １ -OH represents the -OH group, and * represents the bonding site with the benzene ring. X 1 This represents -O-. Ph represents a phenylene group which may have substituents. m2 represents an integer from 1 to 4, and when m2 is 2 or greater, multiple R ２ They may be identical or different from one another. R ３ represents a halogen atom, a hydroxy group, a haloalkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms, and -CH contained in the alkyl group 2 - may be substituted with -O- or -CO-. m3 represents an integer from 0 to 3, and when m3 is 2 or greater, multiple R ３ They may be identical or different from each other, provided that 1 ≤ m² + m³ ≤ 4.

2. L １ The resist composition according to claim 1, wherein the group is an alkanediyl group having 1 to 4 carbon atoms, which may have a single bond or a halogen atom.

3. In equation (I), m² is 1, R ２ However, L in the benzene ring 1 The resist composition according to claim 1 or 2, wherein the bond is located at the meta or para position relative to the bonding position.

4. The aforementioned Ph is the same as the aforementioned X １ - and the L １ Having one or two substituents other than -OH, The resist composition according to any one of claims 1 to 3, wherein the substituents are independently a halogen atom or a fluorinated alkyl group having 1 to 6 carbon atoms.

5. R ３ However, fluorine atoms, iodine atoms, hydroxyl groups, C1-C3 alkyl fluorides, or C1-C3 alkyl groups (the alkyl group contains -CH 2 The resist composition according to any one of claims 1 to 4, wherein - may be replaced by -O- or -CO-.

6. A resist composition according to any one of claims 1 to 5, 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.

7. The resist composition according to any one of claims 1 to 6, 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.

8. In formula (a2-A), At least one hydroxyl group is present in the benzene ring. a50 The resist composition according to claim 7, wherein the bond is located at the meta position relative to the bonding position.

9. The resist composition according to any one of claims 1 to 8, 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 perfluoroalkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. 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-. Z ＋ This represents an organic cation.

10. The resist composition according to any one of claims 1 to 9, further comprising a salt that generates an acid with a lower acidity than the acid generated from the acid generator.

11. (1) A step of applying the resist composition according to any one of claims 1 to 10 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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