Resist composition and method for producing resist pattern

Abstract

To provide a salt which allows a resist pattern having good CD uniformity (CDU) to be produced, and a resist composition containing the salt.SOLUTION: The resist composition contains: an acid generator containing a salt represented by formula (I); and a resin containing a structural unit having an acid-labile group and a structural unit represented by formula (a2-A).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Patent Document 1 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Things are listed. TIFF2025066748000001.tif3457 Patent Document 2 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Each item is listed. TIFF2025066748000002.tif33129 Patent Document 3 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Things are listed. TIFF2025066748000003.tif2955 Patent Document 4 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Things are listed. TIFF2025066748000004.tif3461 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2004-203858 A [Patent Document 2] JP 2005-097254 A [Patent Document 3] Japanese Patent Application Publication No. 09-244234 [Patent Document 4] JP 2017-088865 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention relates to a resist pattern formed from a resist composition containing the above salt. To provide a resist composition which forms a resist pattern with good CD uniformity (CDU) The objective is to: [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF2025066748000005.tif3083 [In formula (I), m1 represents an integer of 1 to 3. R 1 is a cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a substituent). The -CH2- contained in the hydrocarbon group represents -O-, -S-, It may be replaced by -SO2- or -CO-. R 2 represents a halogen atom or an alkyl group having 1 to 6 carbon atoms. m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R 2 are the same They may be the same or different. Z + represents a cation represented by formula (Z-1), formula (Z-2) or formula (Z-3). TIFF2025066748000006.tif55135 [In the formula (Z-1), formula (Z-2) and formula (Z-3), R 11 represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , R 31 , R 32 and R 33 Yes, that each independently represents a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, or a It represents a hydrocarbon group, and -CH2- contained in the hydrocarbon group is replaced by -O- or -CO-. It's okay to know. m12 represents an integer of 0 to 4, and when m12 is 2 or more, a plurality of R 12 Mutually They may be the same or different. m13 represents an integer of 0 to 5, and when m13 is 2 or more, a plurality of R 13 Mutually They may be the same or different. m14 represents an integer of 0 to 5, and when m14 is 2 or more, a plurality of R 14 Mutually They may be the same or different. m21 represents an integer of 0 to 4, and when m21 is 2 or more, a plurality of R 21 Mutually They may be the same or different. m22 represents an integer of 0 to 4, and when m22 is 2 or more, a plurality of R 22 Mutually They may be the same or different. m23 represents an integer of 0 to 5, and when m23 is 2 or more, a plurality of R 23 Mutually They may be the same or different. m31 represents an integer of 0 to 5, and when m31 is 2 or more, a plurality of R 31 Mutually They may be the same or different. m32 represents an integer of 0 to 4, and when m32 is 2 or more, a plurality of R 32 Mutually They may be the same or different. m33 represents an integer of 0 to 2, and when m33 is 2 or more, a plurality of R 33 Mutually They may be the same or different. n3 represents 0 or 1.] [2]R1 However, the hydrocarbon group containing an alicyclic hydrocarbon group having 5 to 16 carbon atoms (the alicyclic hydrocarbon The hydrocarbon group may have a substituent, and the -CH2- contained in the hydrocarbon group may be -O-, -S-, - The salt according to [1], wherein -SO2- or -CO- may be substituted. [3] The salt according to [1] or [2], wherein m1 is 2. [4] An acid generator comprising the salt according to any one of [1] to [3]. [5] A resist composition comprising the acid generator according to [4] and a resin having an acid labile group. [6] The resin having an acid labile group is a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1- 2) The residue according to [5], which contains at least one selected from the group consisting of structural units represented by Store composition. TIFF2025066748000007.tif4192 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or *-O-(CH2) k1 -CO-O- In the formula, k1 represents an integer of 1 to 7, and * represents a bonding site with —CO—. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 18 carbon atoms, represents a hydrocarbon group of the formula: m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. [7] The resin having an acid labile group contains a structural unit represented by formula (a2-A). [5] Or The resist composition according to [6]. TIFF2025066748000008.tif4753[In formula (a2-A), R a50 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: R a51 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or * -X a51 -(A a52 -X a52 ) nb - stands for -R. a50 Combined represents the bonding site with the carbon atom. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, R in Numbers a51 may be the same or different.] [8] The composition further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. The resist composition according to any one of items 5] to [7]. [9] (1) A process for applying the resist composition according to any one of [5] to [8] onto a substrate. About (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A method for producing a resist pattern, comprising the step of developing the composition layer after heating. Effect of the Invention

[0006] By using a resist composition containing the salt of the present invention, good CD uniformity (CDU ) to produce a resist pattern. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In this specification, the term "(meth)acrylic monomer" refers to an acrylic monomer and "(Meth)acrylate" and "at least one methacrylic monomer" are used. The terms "(meth)acrylic acid" and "(meth)acrylic acid" have the same meaning. In the case where the structure can be either a straight chain structure or a branched structure, either one is acceptable. The term "combined group" refers to a group in which two or more of the exemplified groups are combined with their valences appropriately changed. "Derived from" or "derived from" refers to a polymerizable C=C bond contained in the molecule. is polymerized to become a -CC- group. If stereoisomers exist, all stereoisomers are Includes isomers.

[0008] [Salt represented by formula (I)] The present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In salt (I), the side with a negative charge is called an anion (I) and the side with a positive charge is called a cationic salt (I). It is sometimes called "On(I)". TIFF2025066748000009.tif3085 [wherein all symbols have the same meanings as defined above.]

[0009] In formula (I), R 1 The hydrocarbon group containing a cyclic hydrocarbon group in the formula (I) is a monocyclic or is a polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms, etc. or a combination thereof, a monocyclic or polycyclic group having 3 to 18 carbon atoms alicyclic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 18 carbon atoms, etc. 1 to 6 chain hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups) in any combination Examples of the group include a group obtained by combining the

[0010] The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spiro rings, and may be saturated or The alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, or an unsaturated group. group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclo monocyclic cycloalkyl groups such as cyclononyl, cyclodecyl, and cyclododecyl groups; and polycyclic cycloalkyl groups such as a norbornyl group, a norbornyl group, and an adamantyl group. The alicyclic hydrocarbon group preferably has 3 to 16 carbon atoms, and more preferably has 5 to 16 carbon atoms. It is preferably 6 to 16, more preferably 6 to 12. Specific examples of the alicyclic hydrocarbon group include the groups shown below. TIFF2025066748000010.tif40151 Aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthryl, Examples of aromatic hydrocarbon groups include aryl groups such as phenanthryl and binaphthyl groups. The prime number is preferably 6-14, and more preferably 6-10.

[0011] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl Examples of the alkyl group include an alkyl group such as a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9, and even more preferably Preferably, it is 1 to 6, and even more preferably, it is 1 to 4. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, and a butenyl group. isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples of such groups include an octynyl group, an isooctynyl group, and a nonenyl group. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, Examples thereof include a nonynyl group.

[0012] The combined groups are: A group in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined (including the above-mentioned combined group) -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. alicyclic hydrocarbon groups and chain hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups) The combined group (the -CH2- contained in the combined group is -O-, -S-, -CO- or -SO2-) and aromatic hydrocarbon groups and chain hydrocarbon groups (a A group combining an alkyl group, an alkenyl group, or an alkynyl group (including such a combined group) -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. ) are mentioned. In addition, in the combination, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, chain hydrocarbon groups ( The alkyl groups, alkenyl groups, alkynyl groups, etc. may each be a combination of two or more. In addition, any of the groups may be bonded to the oxygen atom. Different groups (alkanediyl, alkanetriyl, cycloalkanediyl, cycloa R may contain a glycantriyl group, etc. 1 Hydrocarbons containing cyclic hydrocarbon groups in The total number of carbon atoms in the alkyl group is, for example, 3 to 24, preferably 4 to 18, and more preferably 5 to 16. This is more preferable.

[0013] Specific examples of the combined groups include: Adamantyl methyl group, adamantyl ethyl group, cyclohexyl methyl group, cyclohexyl Alicyclic hydrocarbon groups, such as cyclohexane, etc., - chain hydrocarbon groups -* (said chain hydrocarbon groups and said alicyclic The -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -CO- or -SO2-. (It may be replaced), Chain alkyl groups such as methyladamantyl groups, methylcyclohexyl groups, and dimethylcyclohexyl groups Acyclic hydrocarbon groups - alicyclic hydrocarbon groups - * (The chain hydrocarbon groups and alicyclic hydrocarbon groups -CH2- may be replaced by -O-, -S-, -CO- or -SO2-. ), Aromatic hydrocarbon groups such as tolyl and xylyl groups. The -CH2- in the group is replaced by -O-, -S-, -CO- or -SO2-. (or Methylcyclohexylmethyl group, etc., chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group The -CH2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group is -O-, -S-, -CO- or -SO2- may be substituted, Aromatic hydrocarbon groups such as benzyl groups and phenethyl groups - Acyclic hydrocarbon groups -* (said acyclic hydrocarbon groups The -CH2- contained in the hydrogen group is replaced with -O-, -S-, -CO- or -SO2-. (may be Aromatic hydrocarbon group - Aromatic hydrocarbon group - Aromatic hydrocarbon group -* (such as a tolylmethyl group) The -CH2- contained in the hydrocarbon group of the formula may be replaced with -O-, -S-, -CO- or -SO2-. may be replaced), Aromatic hydrocarbon group-alicyclic hydrocarbon group-* (such as phenyladamantyl group) The -CH2- in the hydride group is replaced by -O-, -S-, -CO- or -SO2-. (It may be possible to Alicyclic hydrocarbon groups such as cyclohexylphenyl group and adamantylphenyl group - aromatic Hydrocarbon group -* (-CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -CO - or -SO2-) etc. In this case, * is an oxygen atom. represents the binding site of

[0014] R 1 The -CH2- contained in the hydrocarbon group represented by the following formula is -O-, -S-, -CO- or - When replaced with SO2-, the number of carbon atoms before the replacement is regarded as the total number of carbon atoms in the hydrocarbon group. The number of the elements may be one, two or more. Examples of the hydrocarbon group in which -CH2- is replaced with -O- or -CO- include: Alkoxy groups such as hydroxyl, carboxyl, methoxy, ethoxy, and butoxy groups cycloalkoxy groups such as cyclohexyloxy groups; cyclohexylmethoxy groups such as cyclohexylmethoxy groups; alkylalkoxy groups, alkylcarbonyl groups such as acetyl groups, methoxycarbonyl groups alkoxycarbonyl groups such as acetyloxy group, alkylcarbonyloxy groups such as butadiene, alkoxycarbonyloxy groups such as alkoxycarbonyloxy groups, aromatic groups such as benzoyloxy groups, Examples thereof include an aromatic hydrocarbon group-carbonyloxy group. In addition, the -CH2- contained in the alicyclic hydrocarbon group is -O-, -CO- or -SO2-. Examples of the substituted group include the groups shown below. TIFF2025066748000011.tif68154

[0015] The substituent that the cyclic hydrocarbon group may have is a halogen atom, a cyano group, a carbon number An alkyl group having 1 to 12 groups (the -CH2- contained in the alkyl group is not limited to -O-, -S-, -CO - or -SO2- may be substituted). Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl The number of carbon atoms in the alkyl group is preferably 1 to 9, and more preferably 1 to 9. Preferably, it is 1 to 6, and more preferably, it is 1 to 4. As a substituent, -CH2- in the alkyl group is replaced with -O- or -CO-. When a group is substituted with a substituted aryl group, the number of carbon atoms before the substitution is the total number of carbon atoms in the alkyl group. For example, a hydroxy group (a group in which the -CH2- in a methyl group is replaced with -O-) The carboxyl group (-CH2-CH2- in the ethyl group is replaced with -O-CO- alkoxy group (an alkyl group in which -CH2- at any position is replaced by -O-) substituted group), alkoxycarbonyl group (-C at any position in the alkyl group) H2-CH2- replaced by -O-CO-), alkylcarbonyl group (alkyl any position of -CH2- in the alkyl group is replaced with -CO-), Nyloxy group (wherein any -CH2-CH2- at any position in the alkyl group is -CO-O- (groups replaced with) and the like. The alkoxy group includes an alkoxy group having 1 to 11 carbon atoms. For example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, oxy group, Ctyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, un The number of carbon atoms in the alkoxy group is preferably 1 to 6, and more preferably 1 to 6. It is more preferably 1 to 4. The alkoxycarbonyl group, the alkylcarbonyl group and the alkylcarbonyloxy group are The above-mentioned alkyl or alkoxy group is bonded to a carbonyl or carbonyloxy group. Represents a group. The alkoxycarbonyl group includes an alkoxycarbonyl group having 2 to 11 carbon atoms. Examples of such groups include methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl groups. Examples of the alkylcarbonyl group include alkylcarbonyl groups having 2 to 12 carbon atoms. Examples of the alkyl groups include an acetyl group, a propionyl group, and a butyryl group. Examples of the carbonyloxy group include alkylcarbonyloxy groups having 2 to 11 carbon atoms. Examples include an acetyloxy group, a propionyloxy group, and a butyryloxy group. The alkoxycarbonyl group preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 6, and more preferably 2 to 6. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 6, and more preferably Usually it is 2 to 4. The cyclic hydrocarbon group may have one substituent or multiple substituents.

[0016] The cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a substituent) is An alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon group may have a substituent, The -CH2- contained in the alicyclic hydrocarbon group is -O-, -S-, -SO2- or -CO-. or an aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic hydrocarbon group may be replaced by The hydrogen group may have a substituent, An alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon group is an alkyl group having 1 to 4 carbon atoms). may have one or more selected from the group consisting of a cycloaliphatic group, a hydroxyl group and a fluorine atom, The -CH2- contained in the hydrocarbon group of the formula may be replaced with -O-, -S-, -SO2- or -CO-. may be substituted), or an aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic hydrocarbon group is one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and a fluorine atom. More preferably, An alicyclic hydrocarbon group having 5 to 16 carbon atoms (the alicyclic hydrocarbon group is an alkyl group having 1 to 4 carbon atoms). may have one or more selected from the group consisting of a cycloaliphatic group, a hydroxyl group and a fluorine atom, The -CH2- contained in the hydrocarbon group of the formula may be replaced with -O-, -S-, -SO2- or -CO-. It is more preferable that the aryl group is substituted.

[0017] R 1 A cyclic hydrocarbon group having 3 to 18 carbon atoms represented by the following formula (the cyclic hydrocarbon group has a substituent): The hydrocarbon group containing Preferably, the hydrocarbon group contains an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon The group may have a substituent, and the -CH2- contained in the hydrocarbon group may be -O-, -S-, -SO2- or -CO- may be substituted), or aromatic carbon having 6 to 18 carbon atoms A hydrocarbon group containing a fluorinated group (the aromatic hydrocarbon group may have a substituent, and the hydrocarbon group The -CH2- in the group is replaced by -O-, -S-, -SO2- or -CO-. (or may be) More preferably, the hydrocarbon group contains an alicyclic hydrocarbon group having 3 to 18 carbon atoms. The hydrogen group is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and a fluorine atom. The -CH2- contained in the hydrocarbon group may have one or more of -O-, -S-, - may be replaced by -SO2- or -CO-), or aromatic carbon having 6 to 18 carbon atoms Hydrocarbon groups containing hydrogen groups (the aromatic hydrocarbon groups are alkyl groups, hydroxyl groups, etc. having 1 to 4 carbon atoms). The hydrocarbon group may have one or more atoms selected from the group consisting of a silyl group and a fluorine atom. -CH2- may be replaced by -O-, -S-, -SO2- or -CO-. ) and More preferably, the alicyclic hydrocarbon group has 3 to 18 carbon atoms. having one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and a fluorine atom; The -CH2- contained in the alicyclic hydrocarbon group may be -O-, -S-, -SO2- or -CO-), an alicyclic hydrocarbon group having 3 to 18 carbon atoms and A group combining an alicyclic hydrocarbon group having 1 to 6 carbon atoms (the alicyclic hydrocarbon group is an alicyclic hydrocarbon group having 1 to 4 carbon atoms). may have one or more selected from the group consisting of an alkyl group, a hydroxyl group, and a fluorine atom, The -CH2- contained in the combined group is -O-, -S-, -SO2- or -CO-. may be substituted), an aromatic hydrocarbon group having 6 to 18 carbon atoms (the aromatic hydrocarbon group is one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and a fluorine atom; or an aromatic hydrocarbon group having 6 to 18 carbon atoms and an open chain hydrocarbon group having 1 to 6 carbon atoms. A group combining a fluorine atom and a fluorine atom (the aromatic hydrocarbon group is an alkyl group having 1 to 4 carbon atoms, a hydride group, and the combination of the above may have one or more selected from the group consisting of an oxy group and a fluorine atom. The -CH2- in the group is replaced by -O-, -S-, -SO2- or -CO-. (or may be) Even more preferably, it is an alicyclic hydrocarbon group having 5 to 16 carbon atoms (the alicyclic hydrocarbon group is One or more selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, and a fluorine atom. The -CH2- contained in the alicyclic hydrocarbon group may be -O-, -S-, -SO 2- or -CO-), or an alicyclic hydrocarbon having 5 to 16 carbon atoms A group formed by combining a group with a chain hydrocarbon group having 1 to 4 carbon atoms (the alicyclic hydrocarbon group has having one or more groups selected from the group consisting of 1 to 4 alkyl groups, hydroxyl groups, and fluorine atoms; The -CH2- contained in the combined group may be -O-, -S-, -SO2- or -CO- may be substituted). m1 is an integer of 1 to 3, preferably 1 or 2, and more preferably 2. If 1 is 1 or 2, SO3 - For the above, the following structure having m substitution is preferred. It is nice. TIFF2025066748000012.tif31111

[0018] R 2 Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 4, and more preferably Usually it is 1 to 3. R 2 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Can be obtained. m2 is an integer of 0 to 4, and preferably an integer of 0 to 2. In one embodiment, m2 is preferably 0. In another embodiment, m2 is Preferably, m2 is 1 or 2. When m2 is 1, R 2 is a halogen atom Preferably, R 2 It is more preferable that m2 is a fluorine atom or an iodine atom. If, R 2 One of the groups is a halogen atom, and the other is a halogen atom or an alkyl group having 1 to 4 carbon atoms. R 2 One of the atoms is a fluorine atom or an iodine atom, and the other is a fluorine atom. It is more preferable that the alkyl group is an iodine atom or an alkyl group having 1 to 3 carbon atoms.

[0019] Examples of the anion (I) include the following anions. -1) to formula (Ia-9), formula (Ia-11), formula (Ia-16) to formula (Ia-20) The anions which are preferred are TIFF2025066748000013.tif224157

[0020] TIFF2025066748000014.tif74146

[0021] In the anion (I), SO3 - Electron-withdrawing ability due to the ester group at the meta position to the group When only one ester group is present, the electron-withdrawing ability of the ester group is greater than when two ester groups are present. In the resist composition described below, the line edge roughness during resist pattern formation is It can effectively affect the LER. 1 has a leaving group and reacts with an acid Upon contact, the leaving group is eliminated to form a hydrophilic group (e.g., a hydroxyl group or a carboxyl group). This is believed to be more pronounced when the compound has a structure that allows the compound to be bonded to the substrate.

[0022] R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , R 31 , R 32 and R 3 3 The fluorinated alkyl group having 1 to 4 carbon atoms is an alkyl group having 1 to 4 carbon atoms and a fluorine atom. A perfluoroalkyl group having 1 to 4 carbon atoms (such as a trifluoromethyl group, a pentafluoromethyl group, fluoroethyl group, heptafluoropropyl group, nonafluorobutyl group), and 2,2, 2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluoro Examples of such groups include a fluorobutyl group and a 3,3,4,4,4-pentafluorobutyl group. R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , R 31 , R 32 and R 33 Carbon Examples of the hydrocarbon group having a number of 1 to 12 include chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups and groups formed by combining these groups. The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group The number of carbon atoms in the alkyl group is preferably 1 to 9, and more preferably 1 It is preferably from 1 to 6, and more preferably from 1 to 4. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the hydrogen group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. monocyclic cycloalkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups; Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, and the like. Examples of the alicyclic hydrocarbon group include polycyclic cycloalkyl groups such as a cycloalkyl group and a norbornyl group. The number of carbon atoms is preferably 3 to 10. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. The group preferably has 6 to 10 carbon atoms. Examples of groups formed by combining these include methylcyclohexyl group, dicyclohexyl group, Methylcyclohexyl group, 2-alkyladamantan-2-yl group, 1-(adamantane -1-yl) alkan-1-yl group, methylnorbornyl group, isobornyl group, etc. a group combining an alkyl group with an alicyclic hydrocarbon group, an aralkyl group such as a benzyl group or a phenethyl group, etc. When -CH2- in a hydrocarbon group is replaced with -O- or -CO-, The number of carbon atoms before the substitution is regarded as the total number of carbon atoms in the hydrocarbon group. Examples of the hydrocarbon group in which -CH2- is replaced with -O- or -CO- include: Hydroxy group; carboxyl group; methoxy group, ethoxy group, butoxy group, etc., with 1 to 1 carbon atoms 1) Alkoxy groups; alkylcarbonyl groups having 2 to 12 carbon atoms, such as acetyl groups; alkoxycarbonyl groups having 2 to 11 carbon atoms, such as a butoxycarbonyl group; alkylcarbonyloxy groups having 2 to 11 carbon atoms, such as ethyloxy groups; benzoyloxy groups, etc. Examples of the aromatic hydrocarbon group having 7 to 11 carbon atoms-carbonyloxy group include:

[0023] R 11 is preferably a fluorine atom or a trifluoromethyl group. m12 is preferably an integer of 0 to 2, and more preferably 0 or 2. preferable. m13 and m14 are preferably an integer of 0 to 3, and are preferably 0, 1 or 3. It is more preferable that there is. R 12 is preferably a halogen atom or a fluorinated alkyl group having 1 to 4 carbon atoms. More preferably, the fluorine atom is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. A fluorine atom or a trifluoromethyl group is more preferred. R 13 and R 14 each independently represents a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, A fluorine atom, a fluorine group having 1 to 4 carbon atoms, or an alkyl group having 1 to 6 carbon atoms is preferred. More preferably, the alkyl group is a perfluoroalkyl group or an alkyl group having 1 to 4 carbon atoms. It is more preferably a nitrogen atom, a trifluoromethyl group or a methyl group. m21 and m22 each independently represent an integer of 0 to 2. , 0 or 1 is more preferable. m23 is preferably an integer of 0 to 3, more preferably 0 or 1. preferable. R 21 and R 22 are each independently preferably a halogen atom, and It is preferable that it is a child. R 23 is a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 12 carbon atoms. It is preferably a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 4 carbon atoms. More preferably, it is an alkyl group. It is preferable that m31 and m32 each independently represent an integer of 0 to 2. , 0 or 1 is more preferable. It is preferable that m33 is 0 or 1. R 31 , R 32 and R 33 each independently represents a hydrocarbon group having 1 to 12 carbon atoms (the The -CH2- contained in the hydrogen group may be replaced with -O-. Preferably, an alkyl group having 1 to 8 carbon atoms (-CH2- contained in the alkyl group is replaced by -O-) It is more preferable that the alkyl group has 1 to 4 carbon atoms (the alkyl group may be substituted). The -CH2- contained in the alkyl group may be replaced by -O-. Preferred. It is preferred that n3 is 1.

[0024] The cation of the salt (I) is represented by the following formulas (Ic-1) to (Ic-34). Examples of cations include: TIFF2025066748000015.tif196151

[0025] TIFF2025066748000016.tif133151

[0026] Among them, the formulas (Ic-1) to (Ic-6), (Ic-13), and (Ic- 15), Formula (Ic-17), Formula (Ic-18), Formula (Ic-23), Formula (Ic- Cations represented by formula (Ic-1), formula (Ic-4), formula (I-27) are preferred. c-5), Formula (Ic-15), Formula (Ic-17), Formula (Ic-18), Formula (Ic -23), and the cation represented by formula (Ic-27) are more preferred.

[0027] Examples of the salt (I) include the salts listed in Table 1. For example, in Table 1, salt (I-1) is composed of an anion represented by formula (Ia-1) and a cation represented by formula (Ic-1). The salt is a salt represented by the formula: TIFF2025066748000017.tif3483 [Table 1] TIFF2025066748000019.tif223154 TIFF2025066748000020.tif223154 TIFF2025066748000021.tif223154 TIFF2025066748000022.tif223154 TIFF2025066748000023.tif223154 Among them, salt (I) is salt (I-1) to salt (I-7), salt (I-11), salt (I-17) ), salt (I-18), salt (I-21) ~ salt (I-27), salt (I-31), salt (I-37) ), salt (I-38), salt (I-41) ~ salt (I-47), salt (I-51), salt (I-57) ), salt (I-58), salt (I-61) ~ salt (I-67), salt (I-71), salt (I-77) ), salt (I-78), salt (I-81) ~ salt (I-87), salt (I-91), salt (I-97) ), salt (I-98), salt (I-101) ~ salt (I-107), salt (I-117), salt (I -118), salt (I-121) ~ salt (I-126), salt (I-137), salt (I-138) ), salt (I-141) ~ salt (I-146), salt (I-151), salt (I-157), salt ( I-158), salt (I-161) ~ salt (I-167), salt (I-171), salt (I-17 7), salt (I-178), salt (I-181) ~ salt (I-187), salt (I-191), salt (I-197), salt (I-198), salt (I-201) ~ salt (I-207), salt (I-2 11), salt (I-217), salt (I-218), salt (I-221) ~ salt (I-227), Salt (I-231), salt (I-237) and salt (I-238) are preferred.

[0028] <Method for producing salt (I)> The salt (I) can be prepared by reacting a salt represented by formula (Ia) with a salt represented by formula (Ib) in a solvent. It can be produced by reacting TIFF2025066748000024.tif35155 [wherein all symbols have the same meanings as above. X represents a chlorine atom, a bromine atom, It represents an iodine atom or CH3SO4. Solvents include chloroform, monochlorobenzene, dimethylformamide, and acetonitrile. tolyl, ethyl acetate, water, etc. The reaction temperature is usually 15° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0029] Examples of the salt represented by formula (Ia) include the salt represented by the following formula, and are readily available on the market. These compounds are readily available and can be easily produced by known methods. TIFF2025066748000025.tif116154

[0030] Examples of the salt represented by formula (Ib) include the salt represented by the following formula: It is readily available and can be easily produced by known methods. TIFF2025066748000026.tif100166

[0031] [Acid Generator] The acid generator of the present invention is an acid generator containing a salt (I). Alternatively, two or more types of salt (I) may be contained. In addition to the salt (I), the acid generator of the present invention may be an acid generator known in the resist field (hereinafter, “acid generator”). The acid generator (B) may be used alone. Alternatively, two or more of them may be used in combination.

[0032] The acid generator (B) may be either a nonionic or ionic acid generator. Biocides include sulfonate esters (e.g., 2-nitrobenzyl esters, aromatic sulfonates, etc.). sulfonates, oximesulfonates, N-sulfonyloxyimides, sulfonyloxyketones ton, diazonaphthoquinone 4-sulfonate), sulfones (e.g. disulfone, ketone Examples of ionic acid generators include oni Onium salts containing ion cations (e.g. diazonium salts, phosphonium salts, sulfonium salts) The anion of the onium salt is typically a sulfonate anion. ion, sulfonylimide anion, sulfonylmethide anion, etc.

[0033] Examples of the acid generator (B) include those described in JP-A-63-26653 and JP-A-55-164824. JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate an acid when exposed to radiation, such as those described in US Pat. No. 5,312,712, can be used. In addition, a compound produced by a known method may be used. The acid generator (B) may be a compound containing two or more kinds of compounds. They may also be used in combination.

[0034] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)", except for salt (I).) It is. TIFF2025066748000027.tif2862[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms; It represents a aryl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, The -CH2- contained in the alkyl group may be replaced with -O- or -CO-, and the divalent saturated carbon atom A hydrogen atom contained in the hydrogen group may be substituted with a fluorine atom or a hydroxy group. Y is a methyl group which may have a substituent or a methyl group having 3 to 2 carbon atoms which may have a substituent. The -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + represents an organic cation.

[0035] Q b1 and Q b2The perfluoroalkyl group represented by the formula (I) is a trifluoromethyl group, a perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a perfluorohexyl group and a perfluorohexyl group. Q b1 and Q b2 are each independently a fluorine atom or a trifluoromethyl group. It is preferable that both are fluorine atoms.

[0036] L b1 The divalent saturated hydrocarbon group in the formula (I) is a straight-chain alkanediyl group, a branched alkanediyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A group formed by combining two or more of these may also be used. 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 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 branched alkanediyl groups such as 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-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 carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like.

[0037] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The replaced group is, for example, a group represented by any one of formulas (b1-1) to (b1-3). The groups represented by formulae (b1-1) to (b1-3) and their specific examples are In the examples of the groups represented by formulae (b1-4) to (b1-11), * represents the bond to -Y. Represents rank. TIFF2025066748000028.tif26118[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. The --CH2-- contained in the hydrogen atom 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), Lb4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. The --CH2-- contained in the hydrogen atom 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 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxy groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. The --CH2-- contained in the hydrogen atom may be replaced by --O-- or --CO--. However, L b6 and L b7 The total number of carbon atoms is 23 or less. * and ** represent binding sites, and * represents the binding site with Y.]

[0038] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group When -CH2- is replaced by -O- or -CO-, the number of carbon atoms before the replacement is The number of carbon atoms in the hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 The divalent saturated hydrocarbon groups are the same as those of the above. do. L b2is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, The hydrogen atoms contained in the radicals may be substituted with fluorine atoms. L b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, The hydrogen atoms contained in the hydride group may be substituted with fluorine atoms. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, A hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The -CH2- contained in the divalent saturated hydrocarbon group is replaced with -O- or -CO-. Good too.

[0039] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The replaced group is preferably a group represented by formula (b1-1) or formula (b1-3). The group represented by formula (b1-1) is preferably any of the groups represented by formulas (b1-4) to (b1-8). Examples of such groups include those mentioned above. TIFF2025066748000029.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The -CH2- contained therein may be replaced by -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, The hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The --CH2-- contained in the hydrogen atom may be replaced by --O-- or --CO--. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, A hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The contained --CH2-- may be replaced by --O-- or --CO--. L b17represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, A hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b16 ~L b18 The total number of carbon atoms is 19 or less. * and ** represent binding sites, and * represents the binding site with Y.] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms is preferred. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms is preferred. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms is preferred.

[0040] The group represented by formula (b1-3) is represented by formulas (b1-9) to (b1-11), Examples of the groups include those represented by the following formula: TIFF2025066748000030.tif24139[In formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less. * and ** represent binding sites, and * represents the binding site with Y.]

[0041] In addition, in the groups represented by formulae (b1-9) to (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0042] Examples of the group represented by formula (b1-4) include the following. TIFF2025066748000031.tif16151

[0043] Examples of the group represented by formula (b1-5) include the following. TIFF2025066748000032.tif72149

[0044] Examples of the group represented by formula (b1-6) include the following. TIFF2025066748000033.tif29149

[0045] Examples of the group represented by formula (b1-7) include the following. TIFF2025066748000034.tif63151

[0046] Examples of the group represented by formula (b1-8) include the following. TIFF2025066748000035.tif23150

[0047] Examples of the group represented by formula (b1-2) include the following. TIFF2025066748000036.tif30160

[0048] Examples of the group represented by formula (b1-9) include the following. TIFF2025066748000037.tif44137

[0049] Examples of the group represented by formula (b1-10) include the following. TIFF2025066748000038.tif88158

[0050] Examples of the group represented by formula (b1-11) include the following. TIFF2025066748000039.tif81158

[0051] The alicyclic hydrocarbon group represented by Y includes those represented by the formulae (Y1) to (Y11) and (Y36) to (Y38). Examples of the group include a group represented by the formula (Y38). The -CH2- contained in the alicyclic hydrocarbon group represented by Y is -O-, -S(O)2- or - When the group is replaced by CO-, the number of the CO- may be one or more. Examples of the groups include those represented by the formulae (Y12) to (Y35) and (Y39) to (Y43). * is L b1 represents the binding site with The alicyclic hydrocarbon group represented by TIFF2025066748000040.tif83166Y is preferably a group represented by the formula (Y1) to the formula (Y20), the formula (Y21) to the formula (Y22) Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y43) and more preferably a group represented 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 the formula (Y40), the formula (Y42) or the formula (Y43), and more preferably Or formula (Y11), formula (Y15), formula (Y20), formula (Y26), formula (Y27), formula ( Y30), formula (Y31), formula (Y39), formula (Y40), formula (Y42) or formula (Y43) It is a group represented by the following formula: The alicyclic hydrocarbon group represented by Y is represented by the formula (Y28) to the formula (Y35), the formula (Y39), the formula (Y In the case of a spiro ring containing an oxygen atom, such as those represented by formula (Y40), formula (Y42), formula (Y43), etc., two The alkanediyl group between the oxygen atoms preferably has one or more fluorine atoms. Among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom has Preferably, the fluorine atoms are unsubstituted.

[0052] The substituent of the methyl group represented by Y is a halogen atom, a hydroxyl group, a methyl group having 3 to 1 carbon atoms, 6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -( CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 teeth, Alkyl groups having 1 to 16 carbon atoms, alicyclic hydrocarbon groups having 3 to 16 carbon atoms, aromatic groups having 6 to 18 carbon atoms represents an aromatic hydrocarbon group or a group combining these; ja represents an integer of 0 to 4; The -CH2- contained in the alkyl group and the alicyclic hydrocarbon group represents -O-, -S(O )2- or -CO-, and the alkyl group, the alicyclic hydrocarbon group, and The hydrogen atoms contained in the aromatic hydrocarbon group are replaced by hydroxy groups or fluorine atoms. It may be possible to use.) The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxyl group, an alkyl group having 1 to 16 carbon atoms which may be substituted with an alkoxy group (the alkyl group -CH2- may be replaced by -O- or -CO-.) A cyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, Glycidyloxy group, -(CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO -R b1 group (in the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon having 3 to 16 carbon atoms. ja represents a cyclic group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. represents an integer of 0 to 4. The —CH 2- may be replaced by -O-, -S(O)2- or -CO-, and the alkyl group The hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group are each independently selected from the group consisting of a hydroxyl group and a hydroxy group. may be substituted with a fluorine atom.

[0053] Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexane group, and a cyclohexane group. Cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, Examples of the alicyclic hydrocarbon group include a chain hydrocarbon group. Examples of the alkyl group include a methylcyclohexyl group and a dimethylcyclohexyl group. The alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms. be. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and the like. Examples of the aromatic hydrocarbon group include aryl groups such as an alkyl group and an aryl group such as a phenyl group and a phenanthryl group. The aromatic hydrocarbon group may have a hydrocarbon group or an alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a chain hydrocarbon group. Hydrogen group (tolyl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p- tert-Butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group Aromatic hydrocarbon groups having alicyclic hydrocarbon groups (e.g., p-cyclohexylphenyl groups, etc.) The number of carbon atoms in the aromatic hydrocarbon group is , preferably 6 to 14, and more preferably 6 to 10. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromoalkyl group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group , 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group The number of carbon atoms in the alkyl group is preferably 1 to 12, and more preferably 1 It is preferably from 1 to 9, more preferably from 1 to 6, and even more preferably from 1 to 4. Examples of alkyl groups substituted with hydroxy groups include hydroxymethyl groups, hydroxy Examples of such groups include hydroxyalkyl groups such as an ethyl group. The aralkyl group includes a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and the like. Examples of the alkyl group include ethyl and naphthylethyl groups. The -CH2- in the alkyl group is replaced with -O-, -S(O)2-, -CO-, etc. The groups that can be used include an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkoxy ... alkyl, carbonyl, and oxy groups, or combinations thereof. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy group. The number of carbon atoms of the alkoxy group is preferably 1 to 12. It is preferably 1 to 6, and more preferably 1 to 4. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. The number of carbon atoms of the alkoxycarbonyl group is preferably Preferably, it is 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 12, and more preferably It is preferably 2-6, and more preferably 2-4. Examples of the alkylcarbonyloxy group include an acetyloxy group and a propionyloxy group. The number of carbon atoms of the alkylcarbonyloxy group is preferably Preferably, it is 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. Examples of the combined group include a group in which an alkoxy group and an alkyl group are combined, a group combining an alkoxy group and an alkoxy group; and a group combining an alkoxy group and an alkylcarbonyloxy group. Some examples include: Examples of the group consisting of an alkoxy group and an alkyl group include a methoxymethyl group, Alkoxyalkyl groups such as methoxyethyl, ethoxyethyl, and ethoxymethyl groups; The number of carbon atoms in the alkoxyalkyl group is preferably 2 to 12, and more preferably The number is preferably 2 to 6, and more preferably 2 to 4. Examples of the combination of an alkoxy group and an alkoxy group include a methoxymethoxy group, a meth alkoxyalkoxy groups such as oxyethoxy group, ethoxymethoxy group, and ethoxyethoxy group; The number of carbon atoms in the alkoxyalkoxy group is preferably 2 to 12, and more preferably It is preferably 2 to 6, and more preferably 2 to 4. Examples of a group that combines an alkoxy group and an alkylcarbonyl group include methoxyacetyl. Alkoxy groups such as methoxypropionyl groups, ethoxyacetyl groups, and ethoxypropionyl groups. The number of carbon atoms in the alkoxyalkylcarbonyl group is Preferably, it is 3 to 13, more preferably 3 to 7, and further preferably 3 to 5. be. Examples of the combination of an alkoxy group and an alkylcarbonyloxy group include methoxy groups. Cetyloxy group, methoxypropionyloxy group, ethoxyacetyloxy group, ethoxy Examples of such groups include alkoxyalkylcarbonyloxy groups such as propionyloxy groups. The number of carbon atoms in the koxyalkylcarbonyloxy group is preferably 3 to 13, and more preferably The number is preferably 3 to 7, and more preferably 3 to 5. The -CH2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S(O)2-, -CO-, etc. The replaced groups are represented by formulae (Y12) to (Y35) and formulae (Y39) to (Y43). Examples of such groups include those mentioned above.

[0054] Y includes the following: TIFF2025066748000041.tif153164

[0055] Y is preferably an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent. and more preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. More preferably, it is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. An adamantyl group which may have a substituent is more preferred, and the alicyclic hydrocarbon group Or, the -CH2- constituting the adamantyl group is replaced with -CO-, -S(O)2- or -CO-. Y is preferably an adamantyl group, a hydroxyadamantyl group, a methyl group, an oxoadamantyl group, or a group represented by the formula (Y42), the formula (Y100) to the formula (Y114), It is a group that is

[0056] The anion in the salt represented by formula (B1) is represented by the formulas (B1-A-1) to (B1- A-59) (hereinafter, "anion (B1-A-1), etc." according to the formula number) Formula (B1-A-1) to Formula (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 9) is more preferable.

[0057] TIFF2025066748000042.tif142153

[0058] TIFF2025066748000043.tif64156

[0059] TIFF2025066748000044.tif87146

[0060] TIFF2025066748000045.tif87156

[0061] TIFF2025066748000046.tif236161

[0062] Here, R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably is a methyl group or an ethyl group. i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably Preferably, the alkyl group has 1 to 4 carbon atoms, the alicyclic hydrocarbon group has 5 to 12 carbon atoms, or a combination thereof. A group formed by combining these groups, more preferably a methyl group, an ethyl group, or a cyclohexyl group. or an adamantyl group. A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q b1 and Qb2 has the same meaning as above. Specific examples of the anion in the salt represented by formula (B1) include those described in JP-A-2010-20 Examples of the anions include those described in US Pat. No. 4,646.

[0063] The anion in the salt represented by formula (B1) is preferably a compound represented by formula (B1a-1) to formula (B1a-2). B1a-38) are examples of anions represented by the formula: TIFF2025066748000047.tif125154

[0064] TIFF2025066748000048.tif93139

[0065] TIFF2025066748000049.tif167156

[0066] Among them, the formulae (B1a-1) to (B1a-3) and the formulae (B1a-7) to (B1a-1 6), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a-3) 8) is preferred.

[0067] Z1 + Examples of the organic cation include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations and Among these, organic sulfonium cations are Preferred are iodonium and organic iodonium cations, and more preferred are arylsulfonium cations. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter In some cases, they are referred to as "cation (b2-1)" depending on the formula number.

[0068] TIFF2025066748000050.tif47167In equations (b2-1) to (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, It represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the chain hydrocarbon group The hydrogen atoms contained in the alkyl group are hydroxyl groups, alkoxy groups having 1 to 12 carbon atoms, and fatty acids having 3 to 12 carbon atoms. The alicyclic 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, aliphatic hydrocarbon groups having 1 to 18 carbon atoms, may be substituted with an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group is replaced by a halogen atom, a hydroxyl group, or a C1 It may be substituted with up to 12 alkoxy groups. R b4 and R b5 are bonded together to form a ring with the sulfur atom to which they are attached The -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. good. R b7 and R b8 each independently represents a halogen atom, a hydroxyl group, a fatty acid having 1 to 12 carbon atoms, It represents an aliphatic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. m2 and n2 each independently represent an integer of 0 to 5. When m2 is 2 or more, multiple R b7 may be the same or different, and when n2 is 2 or more, R in Numbers b8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or a chain hydrocarbon group having 3 to 4 carbon atoms, Represents 36 alicyclic hydrocarbon groups. R b9 and R b10 are bonded together to form a ring with the sulfur atom to which they are attached The -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. Good too. R b11 is a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, It represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the chain hydrocarbon group are It may be substituted with an aromatic hydrocarbon group having a prime number of 6 to 18, and the aromatic hydrocarbon group The hydrogen atom is preferably an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group. R b11 and R b12 means that they are bonded together to form a ring including the -CH-CO- to which they are attached. The -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. It is also possible. R b13 ~R b18 each independently represents a hydroxyl group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms; Or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, r2 When is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 teeth Identical or different, when t2 is 2 or more, multiple R b18 are the same or different. The aliphatic hydrocarbon group refers to a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and An example of the alkyl group is 2-ethylhexyl. In particular, R b9 ~R b12 The chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the hydrogen group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. cycloalkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl and adamantyl groups. , norbornyl group, and the following groups. TIFF2025066748000051.tif10158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms. Examples of alicyclic hydrocarbon groups in which hydrogen atoms are replaced by aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl, dimethylcyclohexyl, 2-methyladamantan-2-yl, 2-ethyl 2-Isopropyladamantan-2-yl group, methylnor Examples of the alkyl group include a bornyl group and an isobornyl group. In the alicyclic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably Preferably, it is 20 or less. Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may be an open-chain hydrocarbon group or an alicyclic hydrocarbon group. It may have a cyclic group, and an aromatic hydrocarbon group having a chain hydrocarbon group (such as a tolyl group, a xylyl group, phenyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and alicyclic carbons Aromatic hydrocarbon groups having a hydride group (p-cyclohexylphenyl group, p-adamantyl phenyl group, etc. In addition, when the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, A chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples thereof include the aryl group. Examples of the chain hydrocarbon group in which a hydrogen atom is replaced by an aromatic hydrocarbon group include a benzyl group, a phenoxy group, and the like. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples of such groups include aralkyl groups. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be done. Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. The alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, and an ethyl Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group Si group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples thereof include an oxy group and a 2-ethylhexylcarbonyloxy group. R b4 and R b5 When combined with the sulfur atom to which they are attached, the ring they form is The ring may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated. The ring may be one having 3 to 18 carbon atoms, and preferably one having 4 to 18 carbon atoms. The ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples include the rings shown below, where * represents a binding site. TIFF2025066748000052.tif24143R b9 and R b10 The ring formed by and together can be monocyclic, polycyclic, aromatic, or nonaromatic. The ring may be either a saturated or unsaturated ring. Examples of the ring include a 3-membered ring to a 12-membered ring. Preferably, it is a 3- to 7-membered ring. For example, a thiolane-1-ium ring (tetrahydrothio ophenium ring), thian-1-ium ring, 1,4-oxathiane-4-ium ring, etc. Can be obtained. R b11 and R b12 The ring formed by and together can be monocyclic, polycyclic, aromatic, or nonaromatic. The ring may be either a saturated or unsaturated ring. Examples of the ring include a 3-membered ring to a 12-membered ring. and preferably a 3- to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring , oxonorbornane ring, oxoadamantane ring, etc.

[0069] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2025066748000053.tif116158

[0070] TIFF2025066748000054.tif60127

[0071] Examples of the cation (b2-2) include the following cations. TIFF2025066748000055.tif18150

[0072] Examples of the cation (b2-3) include the following cations. TIFF2025066748000056.tif26140

[0073] Examples of the cation (b2-4) include the following cations. TIFF2025066748000057.tif82165

[0074] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation. The acid generator (B) is preferably a compound represented by the formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) ~ Formula (B1a-16), Formula (B1a-18), Formula ( B1a-19), an anion represented by any one of formulas (B1a-22) to (B1a-38) and a combination of the cation (b2-1) or the cation (b2-3).

[0075] The acid generator (B) is preferably a compound represented by formula (B1-1) to formula (B1-56), Among them, those containing an arylsulfonium cation 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 Those represented by formulas (B1-31) to (B1-56) are particularly preferred. JPEG2025066748000058.jpg62150

[0076] TIFF2025066748000059.tif72164

[0077] TIFF2025066748000060.tif114158

[0078] TIFF2025066748000061.tif113145

[0079] JPEG2025066748000062.jpg66162

[0080] TIFF2025066748000063.tif152169

[0081] In the case where the acid generator contains a salt (I) and an acid generator (B), the salt (I) and the acid generator (B) The ratio of the contents of the salt (I):acid generator (B) (mass ratio; salt (I):acid generator (B)) is usually 1:99 to 99:1. The ratio is preferably 2:98 to 98:2, and more preferably 5:95 to 95:5. , more preferably 10:90 to 90:10, and particularly preferably 15:85 to 85: It is 15. In the resist composition of the present invention, the total content of the acid generator is 00 parts by mass, preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass The amount is preferably from 3 to 35 parts by mass, and more preferably from 3 to 40 parts by mass.

[0082] [Resist Composition] The resist composition of the present invention comprises an acid generator containing a salt (I) and a resin having an acid labile group (hereinafter Here, the "acid labile group" refers to a group that is eliminated by When the structural unit is contacted with an acid, the leaving group is eliminated, and the structural unit becomes a hydrophilic group (e.g., a hydroxyl group). It means a group that converts into a structural unit having a silyl group or a carboxy group. The resist composition of the present invention generates an acid having a weaker acidity than the acid generated from the acid generator. It may contain a quencher such as a salt (hereinafter referred to as "quencher (C)"). It is preferable that the ink contains a solvent (hereinafter, sometimes referred to as "solvent (E)").

[0083] <Resin (A)> Resin (A) contains a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). The resin (A) may further contain a structural unit other than the structural unit (a1). As the structural unit other than the structural unit (a1), a structural unit not having an acid labile group ( (hereinafter sometimes referred to as "structural unit (s)"), structural unit (a1) and structural unit (s) other than (for example, a structural unit having a halogen atom described later (hereinafter referred to as "structural unit (a4) "), a structural unit having a non-leaving hydrocarbon group described below (hereinafter referred to as a "structural unit ( a5) and other structural units derived from monomers known in the art etc.

[0084] <Structural unit (a1)> The structural unit (a1) is a monomer having an acid labile group (hereinafter referred to as "monomer (a1)"). In some cases, 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 preferred. TIFF2025066748000064.tif2298[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, R represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms or a combination thereof; a1 and R a2 are bonded to each other and form, together with the carbon atom to which they are bonded, an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Form. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * denotes a binding site.] TIFF2025066748000065.tif2278[In formula (2), R a1' and R a2' each independently represents a hydrogen atom or a carbon atom having 1 to 12 carbon atoms; represents a hydrogen atom, and R a3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2' and R a3' Mutually They bond to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. The -CH2- contained in the hydrocarbon group and the heterocyclic group is replaced by -O- or -S-. It is also possible. X represents an oxygen atom or a sulfur atom. na′ represents 0 or 1. * denotes a binding site.]

[0085] R a1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, Examples of the alkyl group include a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl 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 cyclohexyl group, cycloalkyl groups such as butyl and cyclooctyl groups. Examples of the alkyl group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group ( * indicates a binding site.) etc. a1 , R a2 and R a3 The carbon of the alicyclic hydrocarbon group The number is preferably 3 to 16. TIFF2025066748000066.tif10159As a group combining an alkyl group and an alicyclic hydrocarbon group, for example, methylcyclohexane xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group , adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. do. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form an alicyclic hydrocarbon group, -C(R a1 )(R a2 )(R a3 The alicyclic hydrocarbon group preferably has 3 carbon atoms. ~12. * indicates the bonding site with -O-. TIFF2025066748000067.tif35158

[0086] R a1' , R a2' and R a3' The hydrocarbon group in the formula (I) is an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups formed by combining these groups. The alkyl group and the alicyclic hydrocarbon group are R a1 , R a2 and R a3 The same groups as those listed in Can be obtained. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group and the like. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl group), aralkyl group (e.g., benzyl group), alkyl group Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group) , xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6 -ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl phenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group (phenyl cyclohexyl group, etc. R a2' and R a3' are bonded to each other to form a heterocyclic group together with the carbon atom to which they are bonded and X. When forming, -C(R a1' )(R a2' )-XR a3' Examples of the ring include the following rings. * denotes a binding site. TIFF2025066748000068.tif19124R a1' and R a2' At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0087] Examples of the group (1) include the following groups. In formula (1), R a1, R a2 and R a3 is an alkyl group, ma=0, and na=1 The group is preferably a tert-butoxycarbonyl group. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamantane. Forming a ethyl group, R a3 is an alkyl group, ma=0, and na=1. In formula (1), R a1 and R a2 are each independently an alkyl group; R a3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following groups: * represents a binding site. TIFF2025066748000069.tif74158

[0088] Specific examples of the group (2) include the following groups: * represents a bonding site. TIFF2025066748000070.tif67153

[0089] The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond. More preferably, it is a (meth)acrylic monomer having an acid labile group.

[0090] Of the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of such a bulky structure include those having an alicyclic hydrocarbon group. A resin (A) having a structural unit derived from a monomer (a1) having the above structure is used in a resist composition. This can improve the resolution of the resist pattern.

[0091] As a structural unit derived from a (meth)acrylic monomer having a group (1), 0) (hereinafter, may be referred to as structural unit (a1-0)), -1) (hereinafter, may be referred to as structural unit (a1-1)) or a1-2) (hereinafter, may be referred to as structural unit (a1-2)). Preferably, the structural unit (a1-1) is selected from the group consisting of the structural unit (a1-2) These may be used alone or in combination of two or more. They may be used in combination. TIFF2025066748000071.tif46149 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or *-O-(CH2) k1 -CO- k1 represents an integer of 1 to 7, and * represents a bonding site with -CO-. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups or combinations thereof. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 18 carbon atoms, or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0092] R a01 , R a4and R a5 is preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or *-O-(CH2) k01 -CO-O- (wherein k01 is preferably an integer of 1 to 4, more preferably 1. ), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 The alkyl group, alicyclic hydrocarbon group and Examples of the combined group include R a1 , R a2 and R a3 The same groups as those listed in can be. R a02 , R a03 , and R a04 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. A methyl group or an ethyl group is more preferable, and a methyl group is even more preferable. do. R a6 and R a7 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably More preferably, it is a methyl group, an ethyl group, or an isopropyl group, and even more preferably, it is an ethyl group. Or an isopropyl group. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms of the alicyclic hydrocarbon group is preferably 5 to It is preferably 12, and more preferably 5 to 10. The group consisting of a combination of an alkyl group and an alicyclic hydrocarbon group is It is preferred that the total number of carbon atoms in combination with the group is 18 or less. R a02and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl It is a phenyl group or an ethyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms. is preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. be. R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl group, an ethyl group, or an isopropyl group, and more preferably an ethyl group or an isopropyl group. It is. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0093] Examples of the structural unit (a1-0) include those represented by the formulae (a1-0-1) to (a1-0-12): and R in the structural unit (a1-0) a01 Methionine equivalent The structural units represented by the formulae (a1-0-1) to (a1-0- -10) is preferred. TIFF2025066748000072.tif58150

[0094] Examples of the structural unit (a1-1) include those described in JP-A-2010-204646. Among them, structural units derived from the monomers of formula (a1-1-1) to formula (a1-1-2) are included. -1-4) and R in the structural unit (a1-1) a4 Equivalent to The structural units represented by the formulas (a1-1-1) to (a1-1-2) are preferably those in which the methyl group is replaced by a hydrogen atom. A structural unit represented by any one of a1-1-4) is more preferable. TIFF2025066748000073.tif48132

[0095] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to (a1-2-6). The structural unit represented by the formula (a1-2) is R a5 The methyl group corresponding to The structural units represented by the formula (a1-2-2), the formula (a1-2-5) and the formula A structural unit represented by any one of (a1-2-6) is preferred. TIFF2025066748000074.tif37161

[0096] Resin (A) is a structural unit (a1-0) and / or a structural unit (a1-1) and / or a structural unit When the unit (a1-2) is included, the total content of these units relative to the total structural units of the resin (A) is: It is usually 10 to 95 mol %, preferably 15 to 90 mol %, more preferably 20 The content is preferably from 25 to 85 mol %, more preferably from 25 to 80 mol %, and even more preferably from 25 to 80 mol %. It is 30 to 75 mol %.

[0097] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of the structural unit include a structural unit (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF2025066748000075.tif3766[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1-6 alkyl group which may have a halogen atom represents an alkyl group represented by the formula: R a33 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of R a33 are mutual may be the same or different. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH2- contained in the alkyl group and the divalent hydrocarbon group is replaced by -O- or -S-. That's fine.]

[0098] R a32 and R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the alkyl group include propyl, butyl, pentyl and hexyl groups. An alkyl group having 1 to 4 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even more preferred. R a32 and R a33 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl. group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoro Ethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoro 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, Examples of the alkyl group include an alkyl group, a hexyl group, and a perfluorohexyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, Among them, alkoxy groups having 1 to 4 carbon atoms are particularly preferred. A methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. . Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Examples thereof include a thyloxy group. R a34 , R a35 and R a36 The hydrocarbon group in the formula (I) is an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups combining these. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples include a silyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aryl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, The following groups (* indicates a bonding site): Some examples include: TIFF2025066748000076.tif10151 Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples of the aryl group include a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl p-adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36 As for the carbon number 1-18, an alkyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Examples of the groups include groups formed by combining these.

[0099] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. is more preferred, and a methoxy group is even more preferred. la is preferably 0 or 1, and more preferably 0. R a34 is preferably a hydrogen atom. R a35 is preferably an alkyl group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms, more preferably More preferably, it is a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is an alkyl group having 1 to 18 carbon atoms, a group having 3 to 1 R is an alicyclic aliphatic hydrocarbon group having 8 or an aralkyl group having 7 to 18 carbon atoms. a36 In The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 In The aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0100] -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid) and is eliminated to form a hydroxyl group.

[0101] Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers represented by the formula (a1-4-1) to (a1-4-2) are preferably included. -4-12) and R a32 The hydrogen atom corresponding to More preferably, the structural units represented by the formula (a1-4-1) to the formula (a1-4- 5), and structural units represented by formula (a1-4-10). TIFF2025066748000077.tif68157

[0102] When the resin (A) has the structural unit (a1-4), the content thereof is determined based on the total structure of the resin (A). It is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, based on the total of the structural units. It is more preferable that the content is 10 to 40 mol %.

[0103] The structural unit derived from a (meth)acrylic monomer having the group (2) is represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can also be mentioned. can be. TIFF2025066748000078.tif4253 formula (a1-5), R a8 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Represents an acetylene atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 represents the binding site with L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0104] Examples of the halogen atom include a fluorine atom and a chlorine atom, with a fluorine atom being preferred. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group Examples of the alkyl group include the ethyl group and the trifluoromethyl group. In formula (a1-5), R a8 is a hydrogen atom, a methyl group, or a trifluoromethyl group. preferable. L 51 is preferably an oxygen atom. L 52 and L 53 Of these, it is preferred that one is -O- and the other is -S-. It is preferable that s1 is 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or -CH2-CO-O-.

[0105] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers represented by the formula (a1-5-1) to the formula (a1-5- 4), and the structural units represented by the formula (a1-5-1) or the formula (a1-5-2) are preferred. ) is more preferred. TIFF2025066748000079.tif31129

[0106] When the resin (A) has the structural unit (a1-5), the content thereof is determined based on the total structure of the resin (A). The content of the copolymer is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0107] Further, examples of the structural unit (a1) include the following structural units. TIFF2025066748000080.tif27161

[0108] When the resin (A) contains structural units such as those of (a1-3-1) to (a1-3-7) The content of the aryl group is preferably 5 to 60 mol %, more preferably 5 to 5 0 mol % is more preferable, and 10 to 40 mol % is even more preferable.

[0109] Structural unit(s) The structural unit (s) is a monomer that does not have an acid labile group (hereinafter referred to as "monomer (s)"). The monomer from which the structural unit (s) is derived is an acid-inhibiting monomer known in the resist field. Monomers that do not have stabilizing groups can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. A structural unit having an oxy group and no acid labile group (hereinafter referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid labile group (hereinafter referred to as "structural unit" When a resin having the structural unit (a3) ​​is used in the resist composition of the present invention, For example, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0110] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may be a carboxylic hydroxy group. When a resist pattern is produced from the resist composition of the present invention, the exposure light source is KrF Using high energy rays such as excimer laser (248 nm), electron beam or EUV (extreme ultraviolet light) In this case, the structural unit (a2) is a structural unit having a phenolic hydroxy group ( a2) is preferred, and it is more preferred to use the structural unit (a2-A) described below. When using an ArF excimer laser (193 nm) or the like, the structural unit (a2) is The structural unit (a2) having an alcoholic hydroxy group is preferred, and the structural unit (a2) described below is It is more preferable to use the structural unit (a2) alone. It may contain two or more kinds.

[0111] In the structural unit (a2), the structural unit having a phenolic hydroxy group is represented by the formula (a 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") is can be done. TIFF2025066748000081.tif4247[In formula (a2-A), R a50is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group. R a51 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - stands for -R. a50 Combined represents the bonding site with the carbon atom. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O-, or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, R in Numbers a51 may be the same or different.]

[0112] R a50 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. can be. R a50 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom is, for example, tri Fluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2 -Trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoroethyl group 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluoropropyl group, Fluorobutyl 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 Examples of the alkyl group include ethyl, pentyl, hexyl and perfluorohexyl groups. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or is more preferably an ethyl group, and further preferably a hydrogen atom or a methyl group. R a51 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. can be done. R a51 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an iso Examples of the group include a propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group or an ethoxy group is more preferred. A toxyl group is more preferred. R a51 The alkylcarbonyl group in the formula (I) is an acetyl group, a propionyl group, or a butyl group. Examples of the alkyl group include an aryl group. R a51 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, Examples of the alkyl groups include an alkyloxy group and a butyryloxy group. R a51 is preferably a methyl group.

[0113] *-X a51 -(A a52 -X a52 ) nb - includes *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OAa52 -O-CO-, *-O-CO-A a52 -O-CO-, Among them, *-CO-O- and *-CO-OA are the most common. a52 -CO-O- or *- Office Automation a52 -CO-O- is preferred.

[0114] Examples of the alkanediyl group include a methylene group, an ethylene group, and a 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 and 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group.

[0115] A a50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable.

[0116] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the ortho or para position of the benzene ring, and more preferably to the para position. It is more preferred that the carboxyl group is bonded to the

[0117] Examples of the structural unit (a2-A) include those described in JP-A-2010-204634 and JP-A-2012- Examples of structural units include those derived from monomers described in US Pat. No. 5,12577. The structural unit (a2-A) is represented by the formulas (a2-2-1) to (a2-2-6). In the structural units and the structural units represented by formulae (a2-2-1) to (a2-2-6), R in unit (a2-A) a50 A structural unit in which a methyl group corresponding to the above is replaced by a hydrogen atom. The structural unit (a2-A) is a structural unit represented by the formula (a2-2-1), a2-2-3), a structural unit represented by formula (a2-2-6) and a structural unit represented by formula (a 2-2-1), a structural unit represented by formula (a2-2-3) or a structural unit represented by formula (a2 In the structural unit represented by (a2-A), R a50 Equivalent to It is preferable that the structural unit is a structural unit in which a methyl group is replaced with a hydrogen atom. TIFF2025066748000082.tif42166

[0118] Content of structural unit (a2-A) when structural unit (a2-A) is contained in resin (A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, based on all structural units. % by mole, more preferably 15 to 65 mol %, and even more preferably 20 to 65 mol %. It is 65 mol%. The structural unit (a2-A) can be prepared, for example, by polymerization of the structural unit (a1-4) followed by p-toluenesulfonyl chloride. It can be incorporated into the resin (A) by treating it with an acid such as benzenesulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating the resin with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0119] In the structural unit (a2), the structural unit having an alcoholic hydroxy group is represented by the formula ( a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") Some examples include: TIFF2025066748000083.tif4057 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents a bonding site with -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer of 0 to 10.

[0120] In formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0121] Examples of the structural unit (a2-1) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a2-1-1) to formula (a2-1-6) are included. ), and the structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) is preferred. A structural unit represented by any one of the formulas (a2-1-1) or (a2-1- The structural unit represented by 3) is more preferred. TIFF2025066748000084.tif53151

[0122] When the resin (A) contains the structural unit (a2-1), the content of the structural unit (a2-1) is determined based on the total amount of the structural units of the resin (A). The amount is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably It is preferably 1 to 35 mol %, more preferably 1 to 20 mol %, and even more preferably The content is usually 1 to 10 mol %.

[0123] <Structural unit (a3)> The lactone ring contained in the structural unit (a3) ​​is a β-propiolactone ring, a γ-butyrolactone ring, or It may be a monocyclic ring such as a lactone ring or a δ-valerolactone ring, or a condensation ring of a monocyclic lactone ring with another ring. It may be a γ-butyrolactone ring, an adamantane lactone ring, or a γ -Bridged ring containing a butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) Examples include:

[0124] The structural unit (a3) ​​is preferably represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or a structural unit represented by formula (a3-4). One of these may be contained alone, Two or more types may be contained. TIFF2025066748000085.tif50157 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH2) k3 -CO-O -(k3 represents an integer of 1 to 7). L a7 , -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -C OOL a9 -CO-O- or *-OL a8 -O-CO-L a9 Represents -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Represents a gen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 each independently represents a carboxy group, a cyano group, or a group having 1 to 10 carbon atoms; 4 represents an aliphatic hydrocarbon group. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a23 and / or R a25 may be the same or different.]

[0125] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in propyl, isopropyl, butyl, sec-butyl and tert-butyl groups Examples of alkyl groups include the following. R a24 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine atoms. Children are mentioned. R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, groups, butyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups. Preferred are alkyl groups having 1 to 4 carbon atoms, and more preferred are methyl groups or is an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Fluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group group, triiodomethyl group, and the like. L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane group, -1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, penta hexane-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 2-methylbutane-1,4-diyl group.

[0126] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably is -O- or *-O-(CH2) k3In -CO-O-, k3 is any one of 1 to 4 A group which is an integer, more preferably -O- and *-O-CH2-CO-O-, even more preferably Most of the atoms are oxygen atoms. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group, or a methyl group. It is. p1, q1 and r1 each independently represent an integer of preferably 0 to 2; More preferably, it is 0 or 1.

[0127] In formula (a3-4), R a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A group, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom. It is a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably -O- or *-OL a8 -CO-O-, more preferably -O -, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF2025066748000086.tif4151(in the formula, R a24 , L a7 has the same meaning as above.)

[0128] As the structural unit (a3), a monomer described in JP-A-2010-204646 can be used. , Monomers described in JP 2000-122294 A, and JP 2012-41274 A Examples of the structural unit (a3) ​​include structural units derived from the monomers described in the above publication. , formula (a3-1-1), formula (a3-1-2), formula (a3-2-1), formula (a3-2-2) , Formula (a3-3-1), Formula (a3-3-2) and Formula (a3-4-1) to Formula (a3-4-1 2), and in the structural unit, the structural unit represented by any one of the formulas (a3-1) to (a3-2) R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to Substituted structural units are preferred.

[0129] TIFF2025066748000087.tif115165

[0130] When the resin (A) contains the structural unit (a3), the total content of the structural unit (a3) ​​is the total content of all structural units of the resin (A). The amount is usually 5 to 70 mol %, preferably 10 to 65 mol %, more preferably Or, it is 10 to 60 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit The content of the units (a3-4) is 5 to 60 moles per total structural units of the resin (A). % by mole, more preferably 5 to 50 mol %, and further preferably 10 to 50 mol %.

[0131] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025066748000088.tif3066[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, The -CH2- contained in the group may be replaced with -O- or -CO-. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain hydrocarbon group and a monocyclic or polycyclic alicyclic hydrocarbon group. groups, as well as groups formed by combining these groups.

[0132] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexa Examples of the cycloaliphatic carbons include decyl, heptadecyl and octadecyl groups. The hydrogen group includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and cycloalkyl groups such as ethyl group; decahydronaphthyl group, adamantyl group, norbornyl group and polycyclic alicyclic hydrocarbon groups such as the following groups (* represents a bonding site): TIFF2025066748000089.tif11159 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0133] The structural unit (a4) may be any of the following: a4-3) and at least one structure selected from the group consisting of formula (a4-4) Units include: TIFF2025066748000090.tif4552[In formula (a4-0), R 5 represents a hydrogen atom or a methyl group. L 4arepresents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms. L 3a is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. Represents an orocycloalkanediyl group. R 6 represents a hydrogen atom or a fluorine atom.

[0134] L 4a The divalent aliphatic saturated hydrocarbon group in linear alkanediyl groups such as ethane-1,3-diyl group, butane-1,4-diyl group, -1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methyl- Branched alkyl groups such as 2-methylpropane-1,3-diyl and 2-methylpropane-1,2-diyl groups An example is an alkanediyl group. L 3a The perfluoroalkanediyl group in the formula (I) is a difluoromethylene group, Perfluoroethylene group, perfluoropropane-1,1-diyl 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 -diyl group, perfluorooctane-4,4-diyl group, and the like. L 3a The perfluorocycloalkanediyl group in the Sandiyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group Examples of the alkyl group include a perfluoroadamantanediyl group and a perfluoroadamantanediyl group.

[0135] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond. In the latter case, it is a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably Most commonly, it is a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0136] The structural unit (a4-0) may be any of the structural units shown below and the structural units ( a4-0) in R 5 The structural unit in which the methyl group corresponding to the can be. TIFF2025066748000091.tif95166

[0137] TIFF2025066748000092.tif4670[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, or a group represented by the formula (ag 1), where A a41and R a42 At least one of the following is a substituent: It has a halogen atom (preferably a fluorine atom). TIFF2025066748000093.tif1384 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represents a divalent alkyl group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 is a divalent aliphatic hydrocarbon having 1 to 5 carbon atoms which may have a single bond or a substituent. Represents a group. X a41 and X a42 each independently represents -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 the binding site, and the * on the right is -O-CO-R a42 This is the binding site for

[0138] R a42 The saturated hydrocarbon group in the formula (I) is preferably a chain saturated hydrocarbon group or a monocyclic or polycyclic alicyclic and groups formed by combining these. do. Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, heptyl group, Examples include xadecyl, heptadecyl and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic alicyclic groups such as adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include cyclic saturated hydrocarbon groups. TIFF2025066748000094.tif11159 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an aryl group with one or more alicyclic saturated hydrocarbon groups. Examples of the saturated alicyclic hydrocarbon group include -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl Examples of the alkyl group include an aryl group, an alkanediyl group, an alicyclic saturated hydrocarbon group, and an alkyl group.

[0139] R a42 The substituents of the formula (a-g3) are halogen atoms and groups represented by the formula (a-g3). The halogen atom may be at least one selected from the group consisting of fluorine atom, Examples of the atom include a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred. TIFF2025066748000095.tif965[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO-, or *-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . * stands for R a42 represents the binding site for However, R a42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a4 5 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom .

[0140] A a45The aliphatic hydrocarbon group in the formula (I) is a methyl group, an ethyl group, a propyl group, a butyl group, group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, penta Alkyl groups such as decyl, hexadecyl, heptadecyl, and octadecyl groups; Monocyclic groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups alicyclic hydrocarbon groups; as well as decahydronaphthyl, adamantyl, norbornyl and and polycyclic and alicyclic hydrocarbon groups such as the following groups (* represents a bonding site): TIFF2025066748000096.tif11159 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0141] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, More preferred is a saturated hydrocarbon group having an alkyl group and / or a group represented by formula (a-g3): I wish. R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom. More preferably, it is a saturated hydrocarbon group having a fluoroalkyl group or a perfluorosilyl group. Preferably, the alkyl group is a chloroalkyl group, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a perfluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro perfluorooctyl and perfluoroheptyl groups. Examples of the aryl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3), including the number of carbon atoms contained in the group represented by R a42 The total number of carbon atoms is preferably 15 or less. When the alkyl group has a group represented by formula (a-g3) as a substituent, The number is preferably one.

[0142] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 Yes, More preferably, it is a group represented by formula (a-g2). TIFF2025066748000097.tif879[In formula (a-g2), A a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. represent. X a44 represents **-O-CO- or **-CO-O- (** represents A a46 The binding site with represent). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 of At least one of them has at least one halogen atom. * indicates the bonding site with the carbonyl group.]

[0143] Aa46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. A a47 The aliphatic hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms. A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0144] A preferred structure of the group represented by formula (a-g2) is the following structure (* represents a carbonyl group). (This is the binding site for TIFF2025066748000098.tif14160

[0145] A a41 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 linear alkanediyl groups such as propane-1,2-diyl, butane-1,6-diyl; ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- and branched alkanediyl groups such as 2-methylbutane-1,4-diyl and the like. do. A a41 The substituent in the alkanediyl group is a hydroxy group or a C1-6 alkanediyl group. Examples of the alkyl group include an alkoxy group. A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably It is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

[0146] A in the group represented by formula (a-g1) a42 , A a43 and A a44 The divalent saturated hydrocarbon The substituents include linear or branched alkanediyl groups and monocyclic or polycyclic divalent alicyclic hydrocarbons. A divalent alicyclic hydrocarbon group is formed by combining an alkyl group and an alkanediyl group. Specifically, methylene group, ethylene group, propane-1,3-diamine group, etc. propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane -1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1 , 2-diyl group, etc. A a42 , A a43 and A a44 The substituent of the divalent saturated hydrocarbon group represented by is a hydroxy group. and alkoxy groups having 1 to 6 carbon atoms. It is preferred that s is 0.

[0147] In the group represented by formula (a-g1), X a42 is -O-, -CO-, -CO-O- or Examples of the -O-CO- group include the following groups. In the following examples, * and ** indicates each binding site, and ** is -O-CO-R a42 This is the binding site for TIFF2025066748000099.tif53162

[0148] The structural unit represented by formula (a4-1) includes 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 Examples of structural units that have been replaced include: TIFF2025066748000100.tif167144

[0149] TIFF2025066748000101.tif66133

[0150] An example of the structural unit (a4) is a structural unit represented by the formula (a4-2). TIFF2025066748000102.tif4365[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, H2- may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The total number of carbon atoms in the molecule is limited to 21.

[0151] L 44 The alkanediyl group having 1 to 6 carbon atoms is represented by A a41 As an example, the alkanediyl group in Examples of the groups include those mentioned above. R f6 The saturated hydrocarbon group of R a42 Examples of the groups include the same groups as those exemplified in the above. L 44 The alkanediyl group having 1 to 6 carbon atoms is preferably an alkanediyl group having 2 to 4 carbon atoms. A phenyl group is preferred, and an ethylene group is more preferred.

[0152] Examples of the structural unit represented by formula (a4-2) include the structural units represented by formulae (a4-1-1) to (a4 -1-11) are structural units represented by the following formulas. 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 mentioned as a structural unit.

[0153] Examples of the structural unit (a4) include a structural unit represented by formula (a4-3). TIFF2025066748000103.tif5771[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. vinegar. X f12 represents *-O-CO- or *-CO-O- (* represents A f13 represents the binding site with ). A f14 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 L has a fluorine atom. 5 , A f13 and A f14 The total number of carbon atoms in the molecule is limited to 20.

[0154] L 5 The alkanediyl group in a41 The alkanediyl group in The same groups as those mentioned above are included. A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in or a divalent chain saturated hydrocarbon group which may have a fluorine atom and a It is preferably a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkane dialkyl group. It is a aryl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include a methylene group, an ethylene alkanediyl groups such as propanediyl, butanediyl and pentanediyl groups; Fluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoro perfluoroalkanediyl groups such as perfluorobutanediyl and perfluoropentanediyl groups Examples thereof include the aryl group. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either a monocyclic or a polycyclic group. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexa Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and the like. diyl group, perfluoroadamantanediyl group, and the like. A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are represented by R a42 in The same groups as those exemplified above can be mentioned. Among them, trifluoromethyl group, difluoromethyl group, ethyl 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 perfluorohexyl group. Fluorinated alkyl groups such as fluorooctyl group, cyclopropylmethyl group, cyclopropyl group , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl group A methyl group and the like are preferred.

[0155] In formula (a4-3), L 5 is preferably an ethylene group. A f13The divalent saturated hydrocarbon group is a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent chain hydrocarbon group having 3 A group containing a divalent alicyclic hydrocarbon group having from 1 to 12 carbon atoms is preferred, and a divalent chain hydrocarbon group having from 2 to 3 carbon atoms is preferred. A base is more preferred. A f14 The saturated hydrocarbon group is a chain hydrocarbon group having 3 to 12 carbon atoms and an aliphatic hydrocarbon group having 3 to 12 carbon atoms. Groups containing cyclic hydrocarbon groups are preferred, and chain hydrocarbon groups having 3 to 10 carbon atoms and groups containing 3 to 1 More preferred is a group containing an alicyclic hydrocarbon group of A f14 is preferably carbon It is a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably, cyclopropylmethyl. groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups.

[0156] Examples of the structural unit represented by formula (a4-3) include the structural units represented by formulae (a4-1'-1) to (a 4-1'-11) are examples of structural units represented by the structural unit (a4-3). R f7 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-3). It is one of the structural units that can be mentioned.

[0157] The structural unit (a4) also includes a structural unit represented by the formula (a4-4). TIFF2025066748000104.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 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0158] R f22 The saturated hydrocarbon group of R a42 The saturated hydrocarbon group may be the same as that represented by the following formula: R f22 represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or a carbon An alicyclic hydrocarbon group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms and a fluorine atom is preferred. A fluorine atom-containing alkyl group having 1 to 6 carbon atoms is more preferred.

[0159] In formula (a4-4), A f21 As an example, -(CH2) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0160] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by the formula (a4-4), R f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced by aryl groups. TIFF2025066748000105.tif86160

[0161] When the resin (A) has the structural unit (a4), its content is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and more preferably 3 to 10 mol %. % is more preferred.

[0162] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) is a straight-chain, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The group is preferred. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1): . TIFF2025066748000106.tif3971[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in the alicyclic hydrocarbon group The atom may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the formula (I) may be replaced with -O- or -CO-.

[0163] R 52 The alicyclic hydrocarbon group in may be either a monocyclic or polycyclic group. Examples of the alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentene group, and the like. Examples of the polycyclic alicyclic hydrocarbon group include, for example, , adamantyl group and norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl Examples of the alkyl group include an octyl group and a 2-ethylhexyl group. Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group. do. R 52 is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and more preferably Examples thereof include an adamantyl group, a norbornyl group, and a cyclohexyl group. L 55The divalent saturated hydrocarbon group in the formula (I) is a divalent chain saturated hydrocarbon group or a divalent fatty acid group. Examples of the hydrocarbon group include cyclic saturated hydrocarbon groups, and preferably divalent chain saturated hydrocarbon groups. Examples of the divalent chain saturated hydrocarbon group include a methylene group, an ethylene group, and a propanediyl group. Examples of the alkyl groups include alkanediyl groups such as dialkyl groups, butanediyl groups, and pentanediyl groups. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of the saturated hydrocarbon group include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include adatomyl groups. Examples thereof include a manthanediyl group and a norbornanediyl group.

[0164] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula (I) is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. TIFF2025066748000107.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 It represents the binding site with . L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4represents 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 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. L x6 and L x7 each independently represents a single bond or a divalent aliphatic saturated carbon atom having 1 to 14 carbon atoms; Represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms. W x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms. However, L x8 , L x9 and W x1 The total number of carbon atoms is 15 or less.

[0165] L x1 is 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 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond. L x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is a methylene group or an ethylene group. L x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably A methylene group or an ethylene group is preferred. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond or a methylene group. L x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably Preferably, it is a single bond or a methylene group. W x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably , a cyclohexanediyl group, or an adamantanediyl group.

[0166] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF2025066748000108.tif54136

[0167] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2025066748000109.tif23130

[0168] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2025066748000110.tif15145

[0169] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2025066748000111.tif26114

[0170] L 55is preferably a single bond or a group represented by formula (L1-1).

[0171] The structural unit (a5-1) may be any of the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to the can be. TIFF2025066748000112.tif111151 When the resin (A) has the structural unit (a5), the content of the structural unit (a5) is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and more preferably 3 to 15 mol %. % is more preferred.

[0172] <Structural unit (II)> The resin (A) further includes a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit The structural unit (II) may specifically include is a structural unit described in JP 2016-79235 A, and has a sulfonate group in the side chain. or a structural unit having a carboxylate group and an organic cation, or a sulfonio group on the side chain and an organic anion.

[0173] The structural unit having a sulfonate group or a carboxylate group in the side chain is represented by the formula (II-2 -A') is preferably a structural unit represented by the formula: TIFF2025066748000113.tif35104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon may be The hydrogen atom contained in the alkyl group is replaced by a halogen atom or a alkyl group having 1 to 10 carbon atoms which may have a halogen atom. 6 may be substituted with an alkyl or hydroxy group. A X1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. . RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: Z.A. + represents an organic cation.

[0174] R III3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms and the like can be mentioned. R III3 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the formula: , R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by the following formula: Examples include: A X1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) 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, 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 yl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. . A X1Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Isopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert -butyl group, perfluoropentyl group, perfluorohexyl group, and the like.

[0175] X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched alkyl group. and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A combination of the above is 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, dodecane-1,12-diyl group, Linear alkanediyl groups such as decane-1,12-diyl group; butane-1,3-diyl group; 2-Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentamethylpropane Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohetane-1,3-diyl group, Cycloalkanediyl groups such as cyclohexanone-1,4-diyl group and cyclooctane-1,5-diyl group divalent monocyclic alicyclic saturated hydrocarbon radicals such as norbornane-1,4-diyl radical, norbornane-1,4-diyl radical, Adamantane-2,5-diyl group, Adamantane-1,5-diyl group, Adamantane-2,6- Examples of the divalent alkyl group include divalent polycyclic alicyclic saturated hydrocarbon groups such as a diyl group.

[0176] A saturated hydrocarbon group in which -CH2- has been replaced with -O-, -S- or -CO- Examples of the divalent group include those represented by the formulae (X1) to (X53). The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-. The number of carbon atoms in front of each is 17 or less. In the following formula, * and ** represent binding sites. * is A X1 represents the binding site with TIFF2025066748000114.tif145161

[0177] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0178] ZA in formula (II-2-A') + represents the cation Z1 in the salt represented by formula (B1). + The same can be mentioned.

[0179] The structural unit represented by the formula (II-2-A') is a structural unit represented by the formula (II-2-A) It is preferable that: TIFF2025066748000115.tif38108 [In formula (II-2-A), R III3 , X III3 and Z.A. + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom, or a phenyl group having 1 to 6 carbon atoms; When z2A is 2 or more, multiple R III2 and R III4 are mutually They may be the same or different. Q a and Q b each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents the alkyl group.

[0180] R III2 , R III4 , Q a and Q b The perfluoroalkyl group having 1 to 6 carbon atoms is represented by the formula: For details, see the Q b1 The above-mentioned perfluoroalkyl groups having 1 to 6 carbon atoms are the same as those represented by the following formula: can be done.

[0181] The structural unit represented by formula (II-2-A) is a structural unit represented by formula (II-2-A-1). It is preferable that the position is 1. TIFF2025066748000116.tif5577 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and Z.A. + has the same meaning as above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents an integer of 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon The hydrogen atoms contained in the group may be substituted with halogen atoms or hydroxy groups.

[0182] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, and a propyl group. propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl aryl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups. Examples of the alkyl group include linear or branched alkyl groups such as a decyl group. X I2 As the divalent saturated hydrocarbon group represented by the formula: III3 Divalent saturated hydrocarbon represented by The same as those in the group can be mentioned.

[0183] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). The structural unit is preferably TIFF2025066748000117.tif5288 [In formula (II-2-A-2), R III3 , R III5 and Z.A. + has the same meaning as above. m and n each independently represent 1 or 2.

[0184] Examples of the structural unit represented by formula (II-2-A') include the following structural units, R III3 The group corresponding to the methyl group is a hydrogen atom, a halogen atom (e.g., a fluorine atom) or a halogen atom An alkyl group having 1 to 6 carbon atoms which may have one or more atoms (for example, a trifluoromethyl group, etc.) and structural units described in International Publication No. 2012 / 050015. It can be done. + represents an organic cation. TIFF2025066748000118.tif85163

[0185] The structural unit having a sulfonio group and an organic anion in the side chain is represented by the formula (II-1-1): It is preferable that the structural unit is a structural unit that is TIFF2025066748000119.tif3791 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 Reach BiR II3 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. R II4 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I) include a phenylene group and and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, an alicyclic hydrocarbon group, an aromatic Examples of the alkyl group include aromatic hydrocarbon groups and groups formed by combining these groups. R a1’ , R a2’ and R a3’ The hydrocarbon groups are the same as those in the above. R II4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms and the like can be mentioned. R II4 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the formula: , R a8The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by the following formula: Examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated hydrocarbon having 1 to 18 carbon atoms. The -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or Specifically, X may be replaced with -CO-. III3 2 with 1 to 18 carbon atoms The examples of the alkyl group include the same ones as those of the 4-valent saturated hydrocarbon group.

[0186] The structural unit containing a cation in formula (II-1-1) includes the structural units represented by the following formula: BiR II4 The group corresponding to the methyl group in the formula (1) is a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. Examples include replaced structural units. TIFF2025066748000120.tif82125

[0187] A - As the organic anion represented by the formula (I), a sulfonate anion, a sulfonylimide anion, Examples of the anion include sulfonylmethide anion and carboxylate anion. - Represented by The organic anion is preferably a sulfonate anion. More preferably, it is an anion contained in the salt represented by formula (B1).

[0188] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2025066748000121.tif35134

[0189] Examples of sulfonylmethide anions include the following: TIFF2025066748000122.tif29123

[0190] Examples of carboxylate anions include the following: TIFF2025066748000123.tif41155

[0191] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2025066748000124.tif94155

[0192] When the resin (A) contains the structural unit (II), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 4 mol %, based on the total structural units of the oil (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0193] The resin (A) may have structural units other than the above-mentioned structural units. The positions include structural units known in the art.

[0194] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s), i.e. That is, it is a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably a cyclohexyl group or a structural unit having a cyclopentyl group) At least one selected from the group consisting of structural units, more preferably at least two and more preferably, the group consisting of the structural unit (a1-1) and the structural unit (a1-2). At least two selected from the above. The structural unit (s) is preferably selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably the structural unit (a2-1). The structural unit (a3) ​​is preferably represented by the formula (a3-1): a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-4) At least one unit selected from the group consisting of: Each structural unit constituting the resin (A) may be used alone or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (e.g., radical polymerization methods). The content of each structural unit in the resin (A) can be determined by the following procedure. This can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more). 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 In the present specification, the weight average molecular weight is preferably 1,000 or less, and more preferably 15,000 or less. The molecular weight is a value determined by gel permeation chromatography under the conditions described in the Examples. It is.

[0195] <Resins other than resin (A)> The resist composition of the present invention may contain a resin other than the resin (A). Examples of the resin other than the resin (A) include a resin containing the structural unit (a4) or the structural unit (a5). (hereinafter, may be referred to as resin (X)). As the resin (X), a resin containing the structural unit (a4) is preferable. It is preferable that the resin contains a structural unit having a fluorine atom. In resin (X), the content of the structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, and more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. Examples of the structural unit that the resin (X) may further have include the structural unit (a1), the structural unit (a2), structural unit (a3) ​​and structural units derived from other known monomers. Among these, the resin (X) is preferably composed only of the structural unit (a4) and / or the structural unit (a5). It is preferably a resin. Each structural unit constituting the resin (X) may be used alone or in combination of two or more kinds. Using monomers that derive these structural units, a known polymerization method (e.g., radical polymerization method) is performed. The content of each structural unit in the resin (X) can be determined by the following procedure. This can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more). 0 or more) and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight average molecular weight is the same as that for the resin (A).

[0196] When the resist composition of the present invention contains a resin (X), the content of the resin (X) is 100% by weight of the resin (A). The amount is preferably 1 to 60 parts by mass, and more preferably 1 to 50 parts by mass. More preferably, the amount is 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, and particularly preferably 1 to 40 parts by mass. The amount is preferably 1 to 8 parts by mass.

[0197] The content of the resin (A) in the resist composition is 8 to 100% based on the solid content of the resist composition. It is preferably 0% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. In addition, when a resin other than the resin (A) is contained, the resin (A) and the resin other than the resin (A) are preferably mixed. The total content of the resin is 80% by mass or more and 99% by mass or less based on the solid content of the resist composition. It is preferable that the content is 90% by mass or less, and more preferable that the content is 90% by mass or more and 99% by mass or less. In the present specification, the term "solid content of the resist composition" refers to the amount of the solvent (E The solid content of the resist composition and the resin content The rate is measured by known analytical means such as liquid chromatography or gas chromatography. It is possible.

[0198] <Solvent (E)> The content of the solvent (E) in the resist composition is usually 90% by mass or more and 99.9% by mass or less. It is preferably 92% by mass or more and 99% by mass or less, and more preferably 94% by mass or more. The content of the solvent (E) is 99% by mass or less. The content of the solvent (E) is measured, for example, by liquid chromatography or gas chromatography. This can be measured by known analytical means such as chromatography. The solvent (E) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate, and ethyl pyruvate; acetone, methyl isobutyl ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0199] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound and an acid generator (B). The resist composition may be a salt that generates an acid having a weaker acidity than the acid that generates the quencher. When (C) is contained, the content of the quencher (C) is based on the solid content of the resist composition. Generally, the content is about 0.01 to 15% by mass, and preferably about 0.1 to 10% by mass. It is more preferable that the content is about 0.1 to 5 mass %, and even more preferable that the content is about 0.1 to 3 mass %. It is even more preferable that it is expressed in mass %. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary Amines include secondary amines and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylamine, aniline, 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 amine, triethylamine, trimethylamine, tripropylamine, tributylamine, Tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine , methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine, Ethyldibutyrate diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylamine xylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropylamine Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine amine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -Dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridinium 4-Methylpyridine, 1,2-di(2-pyridyl)ethane, 1,2-di(4-pyridyl)ethane 1,2-di(2-pyridyl)ethene, 1,2-di(4-pyridyl)ethene, 1,3-Di(4-pyridyl)propane, 1,2-Di(4-pyridyloxy)ethane, Di( 2-Pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide amine, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Of these, diisopropylaniline is preferred, and 2,6-diisopropylaniline is more preferred. Propylaniline is an example. Ammonium salts include tetramethylammonium hydroxide, tetraisopropyl ammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl Ammonium hydroxide, tetraoctylammonium hydroxide, phenyl trime ethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium ammonium hydroxide, tetra-n-butylammonium salicylate, and choline. can be done.

[0200] The acidity of a salt that generates an acid weaker than the acid generated from the acid generator (B) is as follows: It is represented by the acid dissociation constant (pKa). An acid weaker in acidity than the acid generated from the acid generator (B) The salt that generates an acid is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 < pKa, preferably a salt of -1 < pKa < 7, and more preferably a salt of 0 < pKa < 5. Examples of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) include the salts represented by the following formula, the salts represented by formula (D) described in JP-A-2015-147926 (hereinafter, sometimes referred to as "weak acid inner salt (D)"), and JP-A-2012-229206 , JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 , JP-A-2011-191745. Examples of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) preferably include salts that generate carboxylic acids weaker in acidity than the acid generated from the acid generator (B) (salts having a carboxylic acid anion ), and more preferably weak acid inner salt (D). TIFF2025066748000125.tif85165

[0201] Examples of the weak acid inner salt (D) include the following salts. TIFF2025066748000126.tif71165

[0202] 〈Other components〉 The resist composition of the present invention may contain, if necessary, components other than the above-described components (hereinafter sometimes referred to as "other components (F)"). There is no particular limitation on the other components (F), and additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers , dyes, etc. can be used.

[0203] 〈Preparation of resist composition〉 ​​The resist composition of the present invention comprises a salt (I), a resin (A), an acid generator (B), and optionally Depending on the resin (A) used, the resin other than the resin (A), the solvent (E), the quencher (C) and its The composition can be prepared by mixing the other component (F) in any order. The temperature during mixing is not limited. It can be from 10 to 40°C depending on the type of resin, etc. An appropriate temperature can be selected depending on the solubility of the compound in the solvent (E) such as the above. The mixing time is Depending on the mixing temperature, the appropriate time can be selected from 0.5 to 24 hours. The mixing means is not particularly limited, and stirring and mixing, etc. can be used. After mixing the components, filter the mixture using a filter with a pore size of about 0.003 to 0.2 μm. It is preferable that

[0204] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) 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) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating. To apply the resist composition onto a substrate, a commonly used device such as a spin coater is used. The substrate can be an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be cleaned, and an anti-reflection film or the like may be formed on the substrate. It may be possible. The composition after coating is dried to remove the solvent and form a composition layer. For example, the solvent can be evaporated using a heating device such as a hot plate (prebaking). The heating temperature is 50 to 200°C. It is preferable that the heating time is 10 to 180 seconds. The pressure during the process is 1 to 1.0×10 5 It is preferable that the pressure is about Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure light source may be a KrF excimer laser (wavelength 248 nm), an ArF excimer Lasers in the ultraviolet range such as F2 excimer laser (wavelength 157 nm) and F2 laser (wavelength 193 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert the wavelength and emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range, electron beams, Various types of light sources can be used, such as those that irradiate ultraviolet light (EUV). In this case, the irradiation of these radiations is sometimes collectively called "exposure". Exposure is usually carried out through a mask corresponding to the desired pattern. In the case of lines, exposure may be performed by direct writing without using a mask. The composition layer after exposure is subjected to a heat treatment (so-called heat treatment) in order to promote the deprotection reaction of the acid labile group. The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150 degrees Celsius. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of the method include the dip method, the paddle method, the spray method, and the dynamic dispense method. The development temperature is preferably, for example, 5 to 60° C., and the development time is, for example, 5 The time is preferably 300 seconds or less. By selecting the type of developer as follows: Either a positive resist pattern or a negative resist pattern can be produced. When a positive resist pattern is produced from the resist composition of the present invention, a developer An alkaline developer is used. The alkaline developer is any of the various alkaline solutions used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples of the aqueous solution ... ethyl)trimethylammonium hydroxide (commonly known as choline) include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers are ketones such as 2-hexanone and 2-heptanone. Solvents; glycol ether ethers such as propylene glycol monomethyl ether acetate Steryl solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and the like aromatic hydrocarbon solvents. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, The content is preferably from 95% by mass to 100% by mass, and more preferably substantially only an organic solvent. More preferred. Among them, organic developers include those containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass. Preferably, the content is 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the components are qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 10%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. It is preferable to wash the resist pattern after development with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and any solvent containing a general organic solvent may be used. Any suitable solvent may be used, preferably an alcohol or ester solvent. After cleaning, it is preferable to remove any rinsing liquid remaining on the substrate and the pattern.

[0205] <Application> The resist composition of the present invention is a resist composition for exposure to a KrF excimer laser, Resist composition for exposure to ximer laser, resist composition for exposure to electron beam (EB) or EU A resist composition for V exposure, particularly a resist composition for electron beam (EB) exposure or EUV exposure The composition is suitable as a resist composition for semiconductor microfabrication. EXAMPLES

[0206] The present invention will be described in more detail with reference to examples. "%" and "parts" are by weight unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analytical conditions for gel permeation chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation) The structure of the compound was determined by mass spectrometry (LC: Agilent 1100, MASS: Agilent The molecular ion peak was measured using a LC / MSD (manufactured by Entec). In the examples, the value of this molecular ion peak is indicated as "MASS."

[0207] Example 1: Synthesis of a salt represented by formula (I-1) TIFF2025066748000127.tif49157 2.61 parts of a salt represented by formula (I-1-a) and 40 parts of chloroform and a compound represented by formula (I-1-b ) was mixed with 4.11 parts of a salt represented by the formula (I) and stirred at 23°C for 2 hours. 40 parts of oxalic acid solution was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated and taken out. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23° C. for 30 minutes. Then, the mixture was filtered to obtain 3.12 parts of the salt represented by the formula (I-1). MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 541.2

[0208] Example 2: Synthesis of a salt represented by formula (I-61) TIFF2025066748000128.tif49164 3.59 parts of a salt represented by formula (I-61-a), 40 parts of chloroform and 1.0 parts of a compound represented by formula (I-1- The mixture was stirred at 23° C. for 2 hours. Add 40 parts of 5% oxalic acid aqueous solution, stir at 23°C for 30 minutes, then separate the mixture and take out the organic layer. To the obtained organic layer, 40 parts of ion-exchanged water was added and stirred at 23° C. for 30 minutes, The organic layer was separated and washed with water five times. The organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23° C. for 30 minutes. This was followed by filtration to obtain 4.88 parts of the salt represented by the formula (I-61). MASS(ESI(+)Spectrum):M + 467.1 MASS(ESI(-)Spectrum):M - 541.2

[0209] Example 3: Synthesis of a salt represented by formula (I-141) TIFF2025066748000129.tif32126 23.70 parts of the compound represented by formula (I-141-a) and 47.4 parts of tetrahydrofuran The mixture was stirred at 23°C for 30 minutes, cooled to 10°C, and then added to magnesium sulfate. The Grignard solution was obtained by adding dropwise 2.73 parts of ethanol. A mixed solution of 6.68 parts of thionyl chloride and 13.36 parts of tetrahydrofuran was added at 10°C. The mixture was then stirred at 23° C. for 18 hours. 70 parts of ethyl acetate was added and stirred at 23°C for 30 minutes, and then the organic layer was separated. 35 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23° C. for 30 minutes, and then separated. The organic layer was extracted by washing with water. This water washing procedure was repeated three times. The obtained organic layer was concentrated. As a result, 11.00 parts of the salt represented by the formula (I-141-b) was obtained. TIFF2025066748000130.tif44126 7.34 parts of a compound represented by formula (I-141-b) and 7.34 parts of a compound represented by formula (I-141-c) The mixture was stirred at 23°C for 30 minutes and then cooled to 10°C. To the mixture, 6.67 parts of trifluorosulfonic anhydride was added at 10° C., and further The mixture was stirred at 23° C. for 18 hours. The reaction mixture was added with 33 parts of ion-exchanged water and chloroform. After adding 66 parts of ethanol and stirring at 23°C for 30 minutes, the mixture was separated and the organic layer was taken out. To the organic layer, 66 parts of a 5% aqueous solution of sodium hydrogen carbonate was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by distillation, and 66 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the organic layer was separated and washed with water three times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, After stirring at 23° C. for 30 minutes, the mixture was filtered to obtain a salt represented by formula (I-141-d). It yielded 3.25 copies. TIFF2025066748000131.tif46162 2.57 parts of a salt represented by formula (I-141-d), 2.7 parts of a salt represented by formula (I-1-b) 2 parts of chloroform and 20 parts of chloroform were mixed and stirred at 23°C for 2 hours. Add 10 parts of chloroform and 10 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the liquids. The organic layer was extracted by adding 10 parts of ion-exchanged water to the obtained organic layer and stirred at 23° C. for 30 minutes. After stirring, the organic layer was separated and washed with water five times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was diluted with 23 After stirring at ℃ for 30 minutes, the supernatant was removed and concentrated to obtain the compound represented by formula (I-141). 2.44 parts of the salt represented by the formula were obtained. MASS(ESI(+)Spectrum):M + 385.1 MASS(ESI(-)Spectrum):M - 541.2

[0210] Example 4: Synthesis of a salt represented by formula (I-161) TIFF2025066748000132.tif28118 30 parts of the salt represented by formula (I-161-a) and 90 parts of methanol were mixed and heated at 23°C for 3 After stirring for 10 minutes, 13.15 parts of dimethyl sulfate was added, and the mixture was stirred at 23°C for 4 hours. The concentrated residue was mixed with 100 parts of tert-butyl methyl ether and cooled to 23°C. After stirring for 30 minutes, the mixture was filtered to obtain 30.5% of the salt represented by formula (I-161-b). I got 4 copies. TIFF2025066748000133.tif37160 10 parts of a salt represented by formula (I-161-b), 4 parts of a compound represented by formula (I-161-c) 0.70 parts of chloroform and 60 parts of chloroform were mixed and stirred at 23°C for 30 minutes, and then anhydrous copper acetate ( 0.05 parts of II) was added, and the mixture was refluxed and stirred at 60° C. for 10 hours, and then concentrated. To the residue, 40 parts of tert-butyl methyl ether was added and stirred at 23°C for 30 minutes, The supernatant was removed and the mixture was concentrated to give 5.23 parts of a salt represented by formula (I-161-d). obtained. TIFF2025066748000134.tif39154 5.26 parts of a salt represented by formula (I-1-b), 3.4 parts of a salt represented by formula (I-161-d) 7 parts of ethyl acetate and 40 parts of chloroform were mixed and stirred at 23°C for 2 hours. Thirty parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes, after which the organic layer was separated and taken out. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated residue was treated with tert-butyl ether. Add 30 parts of ethyl methyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. Thereby, 5.11 parts of a salt represented by the formula (I-161) was obtained. MASS(ESI(+)Spectrum):M + 261.1 MASS(ESI(-)Spectrum):M - 541.2

[0211] Example 5: Synthesis of a salt represented by formula (I-181) TIFF2025066748000135.tif35100 5 parts of the salt represented by formula (I-181-a) and 25 parts of methanol were mixed and incubated at 23°C for 30 After stirring for 1 min, the mixture was added to an ion exchange resin (Shephadex R-QAE, manufactured by Aldrich). A-25) and the resulting solution was concentrated to give the compound represented by formula (I-181-b). 2.96 parts of the salt were obtained. TIFF2025066748000136.tif39152 5.26 parts of a salt represented by formula (I-1-b), 2.9 parts of a salt represented by formula (I-181-b) 3 parts of ethyl acetate and 40 parts of chloroform were mixed and stirred at 23°C for 2 hours. Thirty parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes, after which the organic layer was separated and taken out. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated residue was treated with tert-butyl ether. Add 30 parts of ethyl methyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. Thereby, 4.66 parts of a salt represented by the formula (I-181) was obtained. MASS(ESI(+)Spectrum):M + 279.1 MASS(ESI(-)Spectrum):M - 541.2

[0212] Example 6: Synthesis of salt represented by formula (I-201) TIFF2025066748000137.tif42160 10 parts of a salt represented by formula (I-161-b), 5 parts of a compound represented by formula (I-201-c) 0.62 parts of chloroform and 50 parts of chloroform were mixed and stirred at 23°C for 30 minutes, and then anhydrous copper acetate ( 0.05 parts of II) was added, and the mixture was refluxed and stirred at 60° C. for 10 hours, and then concentrated. To the residue, 30 parts of tert-butyl methyl ether was added and stirred at 23°C for 30 minutes, The supernatant was removed and the mixture was concentrated to give 5.09 parts of a salt represented by formula (I-201-d). obtained. TIFF2025066748000138.tif40167 5.26 parts of a salt represented by formula (I-1-b), 3.8 parts of a salt represented by formula (I-201-d) 1 part of ethyl acetate and 40 parts of chloroform were mixed and stirred at 23°C for 2 hours. Thirty parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes, after which the organic layer was separated and taken out. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated residue was treated with tert-butyl ether. Add 30 parts of ethyl methyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. Thereby, 4.19 parts of a salt represented by the formula (I-201) was obtained. MASS(ESI(+)Spectrum):M + 297.1 MASS(ESI(-)Spectrum):M - 541.2

[0213] Example 7: Synthesis of a salt represented by formula (I-221) TIFF2025066748000139.tif38139 3.92 parts of a salt represented by formula (I-161-b), a compound represented by formula (I-221-a) 1.34 parts of the product and 25 parts of chloroform were mixed and stirred at 23°C for 30 minutes. To the mixture, 0.02 parts of copper(II) diacetate monohydrate was added, and the mixture was then further reduced at 60°C for 4 hours. The mixture was stirred and concentrated. To the resulting residue, 35 parts of tert-butyl methyl ether was added, and the mixture was cooled to room temperature. After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound of formula (I-22 3.01 parts of the salt represented by 1-b) were obtained. TIFF2025066748000140.tif37154 5.25 parts of a salt represented by formula (I-1-b), 3.0 parts of a salt represented by formula (I-221-b) 0 parts of ethyl acetate and 40 parts of chloroform were mixed and stirred at 23°C for 2 hours. 15 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes, and then the organic layer was separated. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated residue was diluted with tert-butyl ether. Add 20 parts of methyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 3.99 parts of the salt represented by the formula (I-221) was obtained. MASS(ESI(+)Spectrum):M + 211.1 MASS(ESI(-)Spectrum):M - 541.2

[0214] Example 8: Synthesis of a salt represented by formula (I-2) TIFF2025066748000141.tif37122 4.88 parts of the salt represented by formula (I-2-a) and 25 parts of dimethylformamide are mixed, The mixture was stirred at 23° C. for 30 minutes. Compound 3 represented by formula (I-2-b) was added to the resulting mixture. 0.88 parts was added, and the mixture was stirred at 50°C for 2 hours. After stirring at 50° C. for 3 hours, 3.62 parts of the compound represented by formula (c) was added. C. to obtain a solution containing the salt represented by formula (I-2-d). TIFF2025066748000142.tif52164A solution containing a salt represented by formula (I-2-d) was added with 7.82 After stirring at 23°C for 2 hours, the organic layer was separated and the mixture was cooled to room temperature. To the obtained organic layer, 60 parts of ion-exchanged water was added and stirred at 23° C. for 30 minutes, The organic layer was separated and washed with water five times. The organic layer was filtered. The filtrate was then concentrated. The concentrated residue was diluted with tert-butyl methyl ether. After adding 40 parts of ethyl alcohol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 6.82 parts of the salt represented by the formula (I-2) was obtained. MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 349.1

[0215] Example 9: Synthesis of a salt represented by formula (I-3) TIFF2025066748000143.tif38136 2.92 parts of the salt represented by formula (I-3-a) and 25 parts of dimethylformamide were mixed, The mixture was stirred at 23° C. for 30 minutes. Compound 3 represented by formula (I-3-b) was added to the resulting mixture. 0.88 parts was added, and the mixture was stirred at 50° C. for 2 hours. After stirring at 50° C. for 3 hours, 3.62 parts of the compound represented by formula (c) was added. C. to obtain a solution containing the salt represented by formula (I-3-d). TIFF2025066748000144.tif47162A solution containing a salt represented by formula (I-3-d) was added with 7.82 g of a salt represented by formula (I-1-a). After stirring at 23°C for 2 hours, the organic layer was separated and the mixture was cooled to room temperature. To the obtained organic layer, 60 parts of ion-exchanged water was added and stirred at 23° C. for 30 minutes, The organic layer was separated and washed with water five times. The organic layer was filtered. The filtrate was then concentrated. The concentrated residue was diluted with tert-butyl methyl ether. After adding 40 parts of ethyl alcohol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 6.69 parts of the salt represented by the formula (I-3) was obtained. MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 541.2

[0216] Example 10: Synthesis of a salt represented by formula (I-4) TIFF2025066748000145.tif38121 4.88 parts of the salt represented by formula (I-4-a) and 25 parts of dimethylformamide are mixed, The mixture was stirred at 23° C. for 30 minutes. Compound 3 represented by formula (I-3-b) was added to the resulting mixture. 0.88 parts was added, and the mixture was stirred at 50° C. for 2 hours. After stirring at 50° C. for 3 hours, 3.62 parts of the compound represented by formula (c) was added. C. to obtain a solution containing the salt represented by formula (I-4-d). TIFF2025066748000146.tif53161A solution containing a salt represented by formula (I-4-d) was added with 7.82 After stirring at 23°C for 2 hours, the organic layer was separated and the mixture was cooled to room temperature. To the obtained organic layer, 60 parts of ion-exchanged water was added and stirred at 23° C. for 30 minutes, The organic layer was separated and washed with water five times. The organic layer was filtered. The filtrate was then concentrated. The concentrated residue was diluted with tert-butyl methyl ether. After adding 40 parts of ethyl alcohol and stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated. As a result, 3.61 parts of the salt represented by the formula (I-4) was obtained. MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 349.1

[0217] Example 11: Synthesis of salt represented by formula (I-7) TIFF2025066748000147.tif46164 2.61 parts of a salt represented by formula (I-1-a), 40 parts of chloroform and 1.0 parts of a salt represented by formula (I-7-b ) was mixed with 4.34 parts of a salt represented by the formula (I) and stirred at 23°C for 2 hours. 40 parts of oxalic acid solution was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was then separated and taken out. To the obtained organic layer, 40 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23° C. for 30 minutes. Then, filtration was carried out to obtain 2.39 parts of the salt represented by the formula (I-7). MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 573.2

[0218] Example 12: Synthesis of salt represented by formula (I-17) TIFF2025066748000148.tif48164 2.61 parts of a salt represented by formula (I-1-a), 40 parts of chloroform and 1.0 parts of a compound represented by formula (I-17- The mixture was stirred at 23° C. for 2 hours. Add 40 parts of 5% oxalic acid aqueous solution, stir at 23°C for 30 minutes, then separate the mixture and take out the organic layer. To the obtained organic layer, 40 parts of ion-exchanged water was added and stirred at 23° C. for 30 minutes, The organic layer was separated and washed with water five times. The organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23° C. for 30 minutes. This was followed by filtration to obtain 4.11 parts of the salt represented by the formula (I-17). MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 437.2

[0219] Example 13: Synthesis of a salt represented by formula (I-177) TIFF2025066748000149.tif381574.29 parts of a salt represented by formula (I-17-b), 3 parts of a salt represented by formula (I-161-d). 47 parts of toluene and 40 parts of chloroform were mixed and stirred at 23° C. for 2 hours. 30 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes, and then the organic layer was separated. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated residue was diluted with tert-butyl ether. Add 30 parts of ethyl methyl ether, stir at 23°C for 30 minutes, remove the supernatant, and By condensing, 5.88 parts of a salt represented by the formula (I-177) was obtained. MASS(ESI(+)Spectrum):M + 261.1 MASS(ESI(-)Spectrum):M - 437.2

[0220] Example 14: Synthesis of a salt represented by formula (I-157) TIFF2025066748000150.tif471622.57 parts of a salt represented by formula (I-141-d), 2 parts of a salt represented by formula (I-17-b). 22 parts of toluene and 20 parts of chloroform were mixed and stirred at 23° C. for 2 hours. Add 10 parts of chloroform and 10 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the liquid. The organic layer was extracted by adding 10 parts of ion-exchanged water to the obtained organic layer and stirred at 23° C. for 30 minutes. After stirring for 1 hour, the organic layer was separated and washed with water 5 times. After concentrating the organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and After stirring at 3° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to give the compound represented by formula (I-157): 3.38 parts of the salt represented by the formula: MASS(ESI(+)Spectrum):M + 385.1 MASS(ESI(-)Spectrum):M - 437.2

[0221] Example 15: Synthesis of a salt represented by formula (I-77) TIFF2025066748000151.tif49164 3.59 parts of a salt represented by formula (I-61-a), 40 parts of chloroform, and The mixture was stirred at 23° C. for 2 hours. Add 40 parts of 5% oxalic acid aqueous solution, stir at 23°C for 30 minutes, and then separate the mixture to remove the organic layer. To the obtained organic layer, 40 parts of ion-exchanged water was added and stirred at 23°C for 30 minutes. The organic layer was separated and separated. This water washing procedure was repeated five times. The obtained organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23°C for 30 minutes. This was followed by filtration to obtain 6.02 parts of the salt represented by the formula (I-77). MASS(ESI(+)Spectrum):M + 467.1 MASS(ESI(-)Spectrum):M - 437.2

[0222] Example 16: Synthesis of salt represented by formula (I-151) TIFF2025066748000152.tif45166 2.57 parts of a salt represented by formula (I-141-d), 4 parts of a salt represented by formula (I-151-b) 0.11 parts of toluene and 20 parts of chloroform were mixed and stirred at 23°C for 2 hours. 10 parts of chloroform and 10 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by distillation, and 10 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the organic layer was separated and washed with water 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue, After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound of formula (I-151 4.98 parts of a salt represented by the formula (I) were obtained. MASS(ESI(+)Spectrum):M + 385.1 MASS(ESI(-)Spectrum):M - 829.2

[0223] Example 17: Synthesis of salt represented by formula (I-81) TIFF2025066748000153.tif47150 3.14 parts of a salt represented by the formula (I-81-a), 40 parts of chloroform and The mixture was stirred at 23° C. for 2 hours. Add 40 parts of 5% oxalic acid aqueous solution, stir at 23°C for 30 minutes, then separate the mixture and take out the organic layer. To the obtained organic layer, 40 parts of ion-exchanged water was added and stirred at 23° C. for 30 minutes, The organic layer was separated and washed with water five times. The organic layer was concentrated. To the concentrated residue, 30 parts of tert-butyl methyl ether was added and stirred at 23° C. for 30 minutes. This was followed by filtration to obtain 4.29 parts of the salt represented by the formula (I-81). MASS(ESI(+)Spectrum):M + 399.1 MASS(ESI(-)Spectrum):M - 541.2

[0224] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-3)" etc. depending on their formula numbers. TIFF2025066748000154.tif4192

[0225] Synthesis Example 1 [Synthesis of Resin A1] As the monomer, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) was used, and the molar ratio [monomer (a1-4-2):monomer (a1-1 -3):monomer (a1-2-6) in a ratio of 38:24:38. Further, this monomer mixture was mixed with 1.5 times by mass of methyl ether based on the total mass of all monomers. Isobutyl ketone was mixed in the mixture. Azobisisobutyronite was added as an initiator to the mixture. Add 7 mol% of propylene to the total number of moles of all monomers, and heat the mixture at 85°C. The polymerization was carried out by heating at 40° C. for about 5 hours. After that, the polymerization reaction solution was diluted with p-toluenesulfone The acid solution was added, and the mixture was stirred for 6 hours, and then separated. The obtained organic layer was diluted with a large amount of n-heptane. The resin was precipitated by pouring it into a flask, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.3 × 10 3 Resin A1 (copolymer) was obtained in a yield of 78%. This resin A1 has the following structural units: This is what we do. TIFF2025066748000155.tif29126

[0226] Synthesis Example 2 [Synthesis of Resin A2] As the monomers, monomer (a1-4-2) and monomer (a1-2-6) were used. The molar ratio of monomer (a1-4-2):monomer (a1-2-6) was 38:62. The monomer mixture is mixed so that the total weight of all the monomers is equal to the total weight of the monomers. 1.5 times by mass of methyl isobutyl ketone was mixed into the obtained mixture. Azobisisobutyronitrile was added at 7 mol% based on the total moles of all monomers. The mixture was then heated at 85°C for about 5 hours to carry out polymerization. An aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 6 hours, and then separated. The resin was precipitated by pouring it into a large amount of n-heptane, and then filtered and collected to obtain the weight average The amount of molecules is about 5.4 x 10 3 Resin A2 (copolymer) was obtained in a yield of 89%. has the following structural unit: TIFF2025066748000156.tif2887

[0227] <Preparation of resist composition> As shown in Table 2, the following components were mixed, and the resulting mixture was passed through a fluorine-containing filter with a pore size of 0.2 μm. The mixture was filtered through a resin filter to prepare a resist composition. [Table 2]

[0228] <Resin> A1: Resin A1 A2: Resin A2 <Salt (I)> I-1: A salt represented by formula (I-1) I-2: A salt represented by formula (I-2) I-3: A salt represented by formula (I-3) I-4: A salt represented by formula (I-4) I-7: A salt represented by formula (I-7) I-17: A salt represented by formula (I-17) I-61: A salt represented by formula (I-61) I-77: A salt represented by the formula (I-77) I-81: A salt represented by formula (I-81) I-141: A salt represented by the formula (I-141) I-151: A salt represented by the formula (I-151) I-157: A salt represented by the formula (I-157) I-161: A salt represented by the formula (I-161) I-177: A salt represented by the formula (I-177) I-181: A salt represented by the formula (I-181) I-201: A salt represented by the formula (I-201) I-221: A salt represented by the formula (I-221) <Acid generator> IX-1 IX-2 IX-3 IX-4 IX-5 TIFF2025066748000158.tif70161<Quencher(C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF2025066748000159.tif3849<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0229] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer is heated on a direct hot plate with hexamethyldisilazane. The silicon wafer was treated at 90° C. for 60 seconds. Spin coating was performed so that the film thickness of the layer was 0.04 μm. Then, it was pre-baked for 60 seconds at the temperature shown in the "PB" column of Table 2 on a direct hot plate to form a composition layer. On the wafer, a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn using an electron beam lithography machine ["ELS-F1 25 125 keV" manufactured by Elionix, Inc.] while changing the exposure dose step by step. (Hole pitch 40 nm / hole diameter 17 nm) was directly drawn. After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 2 on a hot plate, and further paddle development was performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution to obtain a resist pattern. In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was defined as the effective sensitivity.

[0230]

[0231] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times for each hole, and the average value was defined as the average hole diameter of one hole. The average hole diameter of the patterns formed with a hole diameter of 17 nm within the same wafer was measured at 400 locations and used as the population to calculate the standard deviation. The results are shown in Table 3. The numerical values in the table indicate the standard deviation (nm).

Table 3

Industrial Applicability

[0232] The resist composition containing the salt of the present invention is a resist having good CD uniformity (CDU). Since a transparent pattern can be obtained, it is suitable for semiconductor microfabrication and is extremely useful industrially.

Claims

1. an acid generator containing a salt represented by formula (I); A resist composition comprising a resin that includes a structural unit having an acid labile group and a structural unit represented by formula (a2-A): [In formula (I), m1 represents an integer of 1 to 3. R １ represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a group in which an alicyclic hydrocarbon group having 3 to 18 carbon atoms is combined with an acyclic hydrocarbon group having 1 to 6 carbon atoms, or a group in which an aromatic hydrocarbon group having 6 to 18 carbon atoms is combined with an acyclic hydrocarbon group having 1 to 6 carbon atoms, The group formed by combining an alicyclic hydrocarbon group having 3 to 18 carbon atoms with a chain hydrocarbon group having 1 to 6 carbon atoms is alicyclic hydrocarbon group-chain hydrocarbon group-* (* represents a bonding site), The group formed by combining an aromatic hydrocarbon group having 6 to 18 carbon atoms with a chain hydrocarbon group having 1 to 6 carbon atoms is represented by the formula: aromatic hydrocarbon group-chain hydrocarbon group-* (* represents a bonding site), The —CH group contained in the alicyclic hydrocarbon group ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by When m1 is 1 or more, the alicyclic hydrocarbon group and the aromatic hydrocarbon group have no substituent, When m1 is 2 or more, the alicyclic hydrocarbon group is selected from the group consisting of a chlorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms (including —CH ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by -, provided that when the alicyclic hydrocarbon group is a spiro ring represented by formula (D31) to formula (D36), formula (D39) or formula (D40), the alicyclic hydrocarbon group may have a fluorine atom, When m1 is 2 or more, the aromatic hydrocarbon group is preferably a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms (including —CH ２ - is -O-, -S-, -CO- or -SO ２ - may be replaced by. R ２ represents a halogen atom or an alkyl group having 1 to 6 carbon atoms. m2 represents an integer of 0 to 4, and when m2 is 2 or more, a plurality of R ２ may be the same or different from each other. Z ＋ represents a cation represented by formula (Z-1), formula (Z-2) or formula (Z-3). [In the formula, * represents a binding site.] [In formula (Z-1), formula (Z-2) and formula (Z-3), R １１ represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R １２ , R １３ , R １４ , R ２１ , R ２２ , R ２３ , R ３１ , R ３２ and R ３３ each independently represents a halogen atom, a fluorinated alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 11 carbon atoms, an alkylcarbonyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 11 carbon atoms, an alkylcarbonyloxy group having 2 to 11 carbon atoms, or an aromatic hydrocarbon group-carbonyloxy group having 7 to 11 carbon atoms. m12 represents an integer of 0 to 2, and when m12 is 2 or more, a plurality of R １２ may be the same or different from each other. m13 represents an integer of 0 to 3, and when m13 is 2 or more, a plurality of R １３ may be the same or different from each other. m14 represents an integer of 0 to 3, and when m14 is 2 or more, a plurality of R １４ may be the same or different from each other. m21 represents an integer of 0 to 2, and when m21 is 2 or more, a plurality of R ２１ may be the same or different from each other. m22 represents an integer of 0 to 2, and when m22 is 2 or more, a plurality of R ２２ may be the same or different from each other. m23 represents an integer of 0 to 3, and when m23 is 2 or more, a plurality of R ２３ may be the same or different from each other. m31 represents an integer of 0 to 2, and when m31 is 2 or more, a plurality of R ３１ may be the same or different from each other. m32 represents an integer of 0 to 2, and when m32 is 2 or more, a plurality of R ３２ may be the same or different from each other. m33 represents an integer of 0 to 2, and when m33 is 2 or more, a plurality of R ３３ may be the same or different from each other. n3 represents 0 or 1. [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 - (A a52 -X a52 ) nｂ -, * represents -R a50 represents the bonding site with the carbon atom to which it is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents -O-, -CO-O- or -O-CO-. nb represents 0 or 1. mb represents an integer of 0 to 4. When mb is an integer of 2 or more, a plurality of R a51 may be the same or different.

2. 2. The resist composition according to claim 1, further comprising a salt capable of generating an acid having a weaker acidity than the acid generated from the acid generator.

3. R 1 is a hydrocarbon group containing an alicyclic hydrocarbon group having 5 to 16 carbon atoms (the alicyclic hydrocarbon group may have a substituent, and the —CH 2 - is -O-, -S-, -SO ２ 3. The resist composition according to claim 1, wherein:

4. 4. The resist composition according to claim 1, wherein m1 is 2.

5. 5. The resist composition according to claim 1, wherein the structural unit having an acid labile group comprises at least one of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2). [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or *-O-(CH ２ ) k1 represents --CO--O--, k1 represents an integer of 1 to 7, and * represents the bonding site with --CO--. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

6. (1) A step of applying the resist composition according to any one of claims 1 to 5 onto a substrate; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A method for producing a resist pattern, comprising the step of developing the composition layer after heating.

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