Resist composition and method for producing resist pattern

Abstract

To provide a resist composition from which a resist pattern can be produced with a good pattern collapse margin (PCM).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). [In the formula (I), L1 and R1 each represent a substituted / unsubstituted hydrocarbon group, and -CH2- in the group may be substituted with -O-, -S- or the like; X1 represents -CO-O-, -O-CO- or the like; R2 represents a halogen atom or an alkyl group; and m1 represents an integer of 1-3 and m2 represents an integer of 0-4].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. TIFF2025060725000001.tif3357 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. TIFF2025060725000002.tif33127 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. TIFF2025060725000003.tif2854 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. TIFF2025060725000004.tif3362 [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. The present invention provides a resist composition that forms a resist pattern with good pattern collapse resistance (PCM). The objective of the project is to provide [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF2025060725000005.tif3499 [In formula (I), L 1 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, -CH 2 -, -O-, -S-, -SO 2 - or -CO- may be substituted. stomach. X 1 represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O-; *L 1 It represents the binding site with R 1 represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, -CH 2 -, -O-, -S-, -SO 2 - or -CO- may be substituted. stomach. m1 represents an integer of 1 to 3, and when m1 is 2 or more, a plurality of L 1 , X 1 and R 1 may be the same or different from each other. 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 an organic cation. [2]R 1 However, the cyclic hydrocarbon group has 3 to 18 carbon atoms (the cyclic hydrocarbon group has a substituent). ) (the —CH 2 - is -O-, -S-, -SO 2 - or -CO-.) [3] L 1 The salt according to [1] or [2], wherein [4] The salt according to any one of [1] to [3], wherein m1 is 2. [5] An acid generator comprising the salt according to any one of [1] to [4]. [6] A resist composition comprising the acid generator according to [5] and a resin having an acid labile group. [7] 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 [6], which contains at least one selected from the group consisting of structural units represented by Store composition. TIFF2025060725000006.tif4291 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or *-O-(CH 2 ) 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. [8] The resin having an acid labile group contains a structural unit represented by formula (a2-A). [6] Or The resist composition according to [7]. TIFF2025060725000007.tif4654[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.] [9] 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 6] to [8].

[10] (1) A resist composition according to any one of [6] to [9] is applied onto a substrate. process, (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) developing the heated composition layer; A method for producing a resist pattern comprising the steps of: Effect of the Invention

[0006] By using a resist composition containing the salt of the present invention, it is possible to obtain good resistance to pattern collapse ( Resist patterns can be produced using a photochromic membrane (PCM). 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)". TIFF2025060725000008.tif3499 [wherein all symbols have the same meanings as defined above.]

[0009] In formula (I), L 1 The divalent hydrocarbon group in the formula (I) is preferably a divalent hydrocarbon group such as an alkanediyl group. acyclic hydrocarbon groups, monocyclic or polycyclic divalent alicyclic hydrocarbon groups, divalent aromatic hydrocarbon groups and groups in which two or more of these groups are combined (for example, alicyclic hydrocarbon groups). and an alkanediyl group). Examples of the alkanediyl group include a methylene group, an ethylene group, and a propane-1,3-diyl group. Butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group , heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,1 2-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, Pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,16-diyl group linear alkanediyl groups such as alkane-1,17-diyl groups; and 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 and branched alkanediyl groups such as 2-methylbutane-1,4-diyl. The number of carbon atoms in the lucanediyl group is preferably 1 to 12, and more preferably 1 to 9. More preferably, it is 1 to 6, and even more preferably, it is 1 to 4. The monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group is preferably cyclobutane-1,3-dicyclic. Cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclo A monocyclic divalent alicyclic group such as a cycloalkanediyl group, e.g., a cyclooctane-1,5-diyl group. Saturated hydrocarbon groups; and 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 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 18, and more preferably It is preferably 3 to 16, and more preferably 3 to 12. The divalent aromatic hydrocarbon group includes a phenylene group, a naphthylene group, an anthrylene group, a biphenyl group, Examples of aromatic hydrocarbon groups include arylene groups such as a phenylene group and a phenanthrylene group. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. and more preferably 6 to 10. As a group which combines two or more of these, a combination of an alicyclic saturated hydrocarbon group and an alkanediyl group is preferable. and groups combining an aromatic hydrocarbon group and an alkanediyl group. . Examples of the group combining an alicyclic saturated hydrocarbon group and an alkanediyl group include -2 cycloaliphatic saturated hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent cycloaliphatic saturated Alicyclic saturated hydrocarbon group, alkanediyl group, -alkanediyl group, divalent saturated alicyclic hydrocarbon group --etc. Examples of the group combining an aromatic hydrocarbon group and an alkanediyl group include a -2-valent Aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group -alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-, etc. . L 1 -CH contained in a divalent hydrocarbon group having 1 to 28 carbon atoms 2 - is -O-, -S-, -SO 2 It may be replaced by - or -CO-. L 1 -CH contained in the hydrocarbon group having 1 to 28 carbon atoms 2 - is -O-, -S-, -SO 2 When the carbon atom is replaced with - or -CO-, the number of carbon atoms before the replacement is the number of carbon atoms of the hydrocarbon group. Let us assume that.

[0010] L 1 The substituents which may be contained in the alkyl group include a hydroxy group, a carboxy group, a halogen atom, a silyl group, and the like. Ano group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms; an alkylcarbonyl group having 2 to 13 carbon atoms; Examples of the alkyl group include an alkylcarbonyloxy group and a combination thereof. 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. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a bromine group, and a butyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group etc. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms is the above-mentioned alkyl or alkoxy group. The aryl group represents a group having a carbonyl group or a carbonyloxy group bonded to the aryl group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy carbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 13 carbon atoms. Examples of the aryl group include an acetyl group, a propionyl group, and a butyryl group, and the like. The alkylcarbonyloxy group of 3 is an acetyloxy group, a propionyloxy group, butyryloxy group and the like. The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. Preferably, it is an alkyl group having 1 to 4 carbon atoms or a halogen atom, and more preferably, it is methyl. It is more preferably a group or a fluorine atom.

[0011] L 1 represents an alkanediyl group having 1 to 4 carbon atoms (provided that the -C H 2 - may be replaced by -O- or -CO-.) A group formed by combining a diyl group with an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that the alkyl group -CH contained in the phenyl group 2 - may be replaced by -O- or -CO-, -CH contained in alicyclic hydrocarbon group 2 -, -O-, -S-, -SO 2 -or-CO- or an alkanediyl group having 1 to 4 carbon atoms and a substituent. and an aromatic hydrocarbon group having 6 to 18 carbon atoms (provided that the alkanediyl -CH 2 - may be replaced by -O- or -CO-. and an alkanediyl group having 1 to 4 carbon atoms are preferred, and an alkanediyl group having 1 to 4 carbon atoms and an alkanediyl group having 1 to 4 carbon atoms are preferred. A group formed by combining an alicyclic hydrocarbon group having 3 to 18 carbon atoms (provided that the alkanediyl group Included -CH 2 - may be replaced by -O- or -CO-; or a carbon number of 1 A group formed by combining an alkanediyl group of any one of the above to 4 and a phenylene group which may have a substituent ( However, the -CH contained in the alkanediyl group 2 - is replaced by -O- or -CO- It is more preferable that the alkanediyl group has 1 to 4 carbon atoms. is more preferred, and a methylene group or an ethylene group is even more preferred.

[0012] R 1 The hydrocarbon group in the above is an aliphatic hydrocarbon group (alkyl group, alkenyl group, Aromatic hydrocarbon groups and the like, Examples of the groups include groups formed by combining The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, Examples of the alkyl group include an n-undecyl group and an n-dodecyl group. The number of carbon atoms in the alkyl group is preferably The carbon number of the alkyl group is preferably 1 to 9, and more preferably 1 to 4. 2, more preferably 1 to 9, even more preferably 1 to 6, and even more preferably Usually 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. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spiro rings, and may be saturated or The monocyclic alicyclic hydrocarbon group may be, for example, cyclopropyl. group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo Monocyclic cycloalkyl groups such as octyl, cyclononyl, cyclodecyl, and cyclododecyl groups Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl. Examples of the cycloalkyl groups include polycyclic cycloalkyl groups such as adamantyl groups and norbornyl groups. The number of carbon atoms in the hydrocarbon group is preferably 3 to 18, more preferably 3 to 16, and further It is more preferably 5 to 16. Specific examples of the alicyclic hydrocarbon group include the groups shown below. TIFF2025060725000009.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 to 18, more preferably 6 to 14, and even more preferably It is 6 to 10.

[0013] In the case of a combination of groups, the above groups each having a different valence (such as an alkanediyl group, ... cycloalkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) Good too. The group formed by the combination is an aromatic hydrocarbon group and a chain hydrocarbon group. A group that combines (for example, aromatic hydrocarbon group-alkanediyl group-*, alkyl group-aromatic aromatic hydrocarbon group-*), groups combining alicyclic and chain hydrocarbon groups (e.g. , alicyclic hydrocarbon group-alkanediyl group-*, alkyl group-alicyclic hydrocarbon group-*), aromatic A group that combines an aromatic hydrocarbon group and an alicyclic hydrocarbon group (e.g., an aromatic hydrocarbon group-alicyclic Cyclic hydrocarbon group-*, alicyclic hydrocarbon group-aromatic hydrocarbon group-*). Represents the binding site. Aromatic hydrocarbon groups - alkanediyl groups -* include aryl groups such as benzyl and phenethyl groups. Examples include ralkyl groups. Examples of the alkyl group-aromatic hydrocarbon group-* include a tolyl group and a xylyl group. Alicyclic hydrocarbon groups - alkanediyl groups - * include cyclohexylmethyl groups, cyclohexylmethyl groups, Hexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 -1-methylethyl, and the like. Examples of alkyl groups - alicyclic hydrocarbon groups -* include methylcyclohexyl, dimethylcyclohexyl, cyclohexyl group, 2-alkyladamantan-2-yl group, etc. Examples of the alkyl groups include alkyl groups. Examples of aromatic hydrocarbon groups - alicyclic hydrocarbon groups -* include phenyladamantyl groups. can be done. Alicyclic hydrocarbon groups - aromatic hydrocarbon groups -* include adamantylphenyl groups, etc. can be done.

[0014] -CH contained in the hydrocarbon group 2 Examples of the group in which - is replaced by -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, -CH contained in alicyclic hydrocarbon groups 2 - is -O-, -CO- or -SO 2 -in Examples of the substituted group include the groups shown below. TIFF2025060725000010.tif68154 -CH contained in the hydrocarbon group 2 -, -O-, -S-, -SO 2 - or -CO- When the carbon atom is replaced, the number of carbon atoms before the replacement is regarded as the total number of carbon atoms of the hydrocarbon group. The number may be one or more.

[0015] R 1 The substituents which the hydrocarbon group may have include halogen atoms, cyano groups, carbon atoms, An alkyl group having a number of 1 to 12 (the —CH 2 - is -O-, -S-, -C O- or -SO 2 - 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, -CH contained in an alkyl group 2 - is replaced by -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. As for the hydroxyl group (-CH contained in the methyl group), 2 - is replaced by -O-) , carboxyl group (-CH contained in ethyl group 2 -CH 2 - is replaced by -O-CO- alkoxy group (a group in which -CH 2 - to -O- substituted group), alkoxycarbonyl group (-C at any position in the alkyl group) H 2 -CH 2 - is replaced by -O-CO-), alkylcarbonyl group (alkyl Any position of -CH 2 - is replaced by -CO-), alkylcarbo Nyloxy group (-CH at any position in the alkyl group) 2 -CH 2 -But -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. R 1 The hydrocarbon group in may have one or more substituents.

[0016] R 1 The hydrocarbon group in is a cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon The group may have a substituent. 2 -teeth , -O-, -S-, -SO 2- or -CO- may be substituted. preferable.

[0017] The hydrocarbon group containing a cyclic hydrocarbon group is preferably a monocyclic or polycyclic alicyclic group having 3 to 18 carbon atoms. Hydrocarbon groups of the formula and cyclic hydrocarbon groups such as aromatic hydrocarbon groups having 6 to 18 carbon atoms, or a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms and a group having 6 carbon atoms Cyclic hydrocarbon groups such as aromatic hydrocarbon groups with carbon atoms of 1 to 18 and chain hydrocarbon groups (alkyl groups) with carbon atoms of 1 to 6 and groups obtained by arbitrarily combining an aryl group with an aryl group, an alkenyl group, or an alkynyl group. The alicyclic hydrocarbon group, aromatic hydrocarbon group, and chain hydrocarbon group are the same as those described above. Some examples include:

[0018] 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) Ru-CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by alicyclic hydrocarbon groups and chain hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups) The combined group (the —CH 2 - is -O-, -S-, -CO- or -SO 2 -) 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) Reru-CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by ) 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, which group is X 1 In addition, the above groups may be bonded to Groups such as alkanediyl groups, alkanetriyl groups, cycloalkanediyl groups, cycloalkanediyl groups, R may contain a phenyl group, etc. 1 Hydrocarbon groups including cyclic hydrocarbon groups in The total number of carbon atoms is, for example, 3 to 24, preferably 4 to 18, and more preferably 5 to 16. I wish.

[0019] 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 -CH contained in cyclic hydrocarbon groups 2 - is -O-, -S-, -CO- or -SO 2 -Placed (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 Reru-CH 2 - is -O-, -S-, -CO- or -SO 2 - may be replaced by ), Aromatic hydrocarbon groups such as tolyl and xylyl groups. -CH 2 - is -O-, -S-, -CO- or -SO 2 -Replaced by (or Methylcyclohexylmethyl group, etc., chain hydrocarbon group-alicyclic hydrocarbon group-chain hydrocarbon group -* (-CH contained in the chain hydrocarbon group and the alicyclic hydrocarbon group)2 - is -O-, -S-, -CO- or -SO 2 -), Aromatic hydrocarbon groups such as benzyl groups and phenethyl groups - Acyclic hydrocarbon groups -* (said acyclic hydrocarbon groups -CH contained in hydrogen group 2 - is -O-, -S-, -CO- or -SO 2 -Replaced by (may be Aromatic hydrocarbon group - Aromatic hydrocarbon group - Aromatic hydrocarbon group -* (such as a tolylmethyl group) Hydrocarbon groups in the formula -CH 2 - is -O-, -S-, -CO- or -SO 2 -Place may be replaced), Aromatic hydrocarbon group-alicyclic hydrocarbon group-* (such as phenyladamantyl group) -CH contained in hydrogen radical 2 - is -O-, -S-, -CO- or -SO 2 -Replaced by (It may be possible to Alicyclic hydrocarbon groups such as cyclohexylphenyl group and adamantylphenyl group - aromatic Hydrocarbon group -* (-CH contained in the alicyclic hydrocarbon group) 2 - is -O-, -S-, -CO -OR-SO 2 -), etc., where * is X 1 Bond with Represents the binding site.

[0020] The substituent that the cyclic hydrocarbon group may have is a halogen atom, a cyano group, a carbon number 1 to 12 alkyl groups (-CH 2 - is -O-, -S-, -CO -OR-SO 2 - may be substituted). Halogen atoms, alkyl groups having 1 to 12 carbon atoms (including —CH 2 -teeth, -O-, -S-, -CO- or -SO 2 - may be substituted) are as described above. The examples include the same groups as those mentioned above.

[0021] 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 -CH contained in the alicyclic hydrocarbon group 2 -, -O-, -S-, -SO 2 -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, Hydrocarbon groups in the formula -CH 2 -, -O-, -S-, -SO 2 -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, Hydrocarbon groups in the formula -CH 2 -, -O-, -S-, -SO 2 -or-CO- It is more preferable that the aryl group is substituted.

[0022] Contains a cyclic hydrocarbon group having 3 to 18 carbon atoms (the cyclic hydrocarbon group may have a substituent). Examples of the hydrocarbon group include: Preferably, the hydrocarbon group contains an alicyclic hydrocarbon group having 3 to 18 carbon atoms (the alicyclic hydrocarbon The group may have a substituent. 2 - is -O-, -S-, -SO 2 - or -CO-), or an 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 -CH 2 -, -O-, -S-, -SO 2 - or -CO- replaced (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 hydrocarbon group may have one or more -CH 2 - is -O-, -S-, - SO 2 - or -CO-), or an 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. -CH 2 -, -O-, -S-, -SO 2 may be replaced by - 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 -CH contained in the alicyclic hydrocarbon group may be 2 -, -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 combined group contains -CH 2 -, -O-, -S-, -SO 2 -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. -CH 2 -, -O-, -S-, -SO 2 - or -CO- replaced (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 alicyclic hydrocarbon group may have -CH 2 -, -O-, -S-, -SO 2 - or -CO- may be substituted), 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 combined group may include -CH 2-, -O-, -S-, -SO 2 -or -CO- may be substituted).

[0023] m1 is an integer of 1 to 3, preferably 1 or 2, and more preferably 2. If 1 is 1 or 2, then SO 3 - For the above, the following structure having m substitution is preferred. It is nice. TIFF2025060725000011.tif38135

[0024] 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.

[0025] Examples of the anion (I) include the following anions. -1) ~ Formula (Ia-8), Formula (Ia-14), Formula (Ia-15) ~ Formula (Ia-23), Formula Preferred are anions represented by formula (Ia-29) and formula (Ia-30). TIFF2025060725000012.tif247159

[0026] TIFF2025060725000013.tif232161

[0027] Z + The organic cations include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations and Among these, organic sulfonium cations are and organic iodonium cations are preferred, with arylsulfonium cations being more preferred. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter , and may be referred to as "cation (b2-1)" etc. depending on the formula number.

[0028] TIFF2025060725000014.tif48166In 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 ring may contain -CH 2 - may be replaced by -O-, -S- or -CO- good. R b7 and R b8 each independently represents a halogen atom, a hydroxyl group, or 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 ring may contain -CH 2 - is replaced by -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 b12represents 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 ring may have -CH 2 - is 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 b14 are 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.

[0029] 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. TIFF2025060725000015.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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] R b4 and R b5 and form a ring together with the sulfur atom to which they are attached: 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. TIFF2025060725000016.tif23143

[0034] R b9 and R b10 The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. 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 combining with may be monocyclic, polycyclic, aromatic or non-aromatic. 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.

[0035] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2025060725000017.tif80158

[0036] TIFF2025060725000018.tif99143

[0037] Examples of the cation (b2-2) include the following cations. TIFF2025060725000019.tif18150

[0038] Examples of the cation (b2-3) include the following cations. TIFF2025060725000020.tif26140

[0039] Examples of the cation (b2-4) include the following cations. TIFF2025060725000021.tif82166

[0040] The salt (I) is a combination of the above-mentioned anions and the above-mentioned organic cations, which are optionally The salt (I) is preferably a salt represented by the formula (Ia-1) to the formula (Ia-8) ), formula (Ia-14), formula (Ia-15) ~ formula (Ia-23), formula (Ia-29), formula ( Ia-30), and a cation (b2-1), a cation (b2 -2) or a combination with a cation (b2-3).

[0041] Examples of the salt (I) include the salts shown in Table 1. In the following table, each symbol corresponds to the above-mentioned A The symbols are attached to structures that represent anions or cations. For example, salt (I-1) is a salt of the formula (Ia -1) and a cation represented by formula (b2-c-1) and represents the salt shown below. TIFF2025060725000022.tif3981 [Table 1] TIFF2025060725000024.tif223154 TIFF2025060725000025.tif223154 TIFF2025060725000026.tif223154 TIFF2025060725000027.tif223154 TIFF2025060725000028.tif177156 Among them, salt (I) is salt (I-1) to salt (I-8), salt (I-14), salt (I-15) ) ~ Salt (I-23), Salt (I-29), Salt (I-30), Salt (I-34) ~ Salt (I-41 ), salt (I-47), salt (I-48) ~ salt (I-56), salt (I-62), salt (I-63) ), salt (I-67) ~ salt (I-74), salt (I-80), salt (I-81) ~ salt (I-89) ), salt (I-95), salt (I-96), salt (I-100) ~ salt (I-107), salt (I- 113), salt (I-114) ~ salt (I-122), salt (I-128), salt (I-129) , salt(I-133)~salt(I-140), salt(I-146), salt(I-147)~salt(I -155), salt (I-161), salt (I-162), salt (I-166) ~ salt (I-173) ), salt (I-179), salt (I-180) ~ salt (I-188), salt (I-194), salt ( I-195), salt (I-199) ~ salt (I-206), salt (I-212), salt (I-21 3) Salt (I-221), salt (I-227), and salt (I-228) are preferred.

[0042] <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 TIFF2025060725000029.tif44165 [wherein all symbols have the same meanings as above. X represents a chlorine atom, a bromine atom, Iodine atom or CH 3 SO 4 represents.] 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.

[0043] 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. TIFF2025060725000030.tif116167

[0044] The salt represented by formula (Ib) is a salt represented by formula (Ic) and a salt represented by formula (Id) The compound can be produced by reacting the compound with a base in a solvent in the presence of a base catalyst. TIFF2025060725000031.tif41168 [wherein all symbols have the same meanings as defined above.] Examples of bases include potassium carbonate, potassium iodide, pyridine, and triethylamine. Can be obtained. 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.

[0045] Examples of the salt represented by formula (Ic) include the salt represented by the following formula: It can be easily obtained. TIFF2025060725000032.tif2184 Examples of the compound represented by formula (Id) include the compounds represented by the following formula: It can be easily obtained from the market and can also be easily produced by known methods. . TIFF2025060725000033.tif32163

[0046] [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.

[0047] 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.

[0048] 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.

[0049] 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. TIFF2025060725000034.tif2861[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 b1represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, -CH 2 - may be replaced by -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. 4, and the -CH 2 -, -O-, - S(O) 2 It may be replaced by - or -CO-. Z1 + represents an organic cation.

[0050] Q b1 and Q b2 The 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.

[0051] 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.

[0052] L b1 -CH contained in a divalent saturated hydrocarbon group represented by 2 - is replaced by -O- or -CO-. The replaced group is, for example, a group represented by any one of formulas (b1-1) to (b1-3). In addition, the formulae (b1-1) to (b1-3) and specific examples thereof, such as the formula ( In the groups represented by formulae (b1-4) to (b1-11), * represents a bonding site with -Y.

[0053] TIFF2025060725000035.tif26117[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. -CH contained in hydrogen radical 2 - may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 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. -CH contained in hydrogen radical 2 - 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 b7represents 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. -CH contained in hydrogen radical 2 - 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.]

[0054] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group -CH 2 When - 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 b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, 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 divalent saturated hydrocarbon group contains -CH 2 - is replaced by -O- or -CO- Good too.

[0055] L b1 -CH contained in a divalent saturated hydrocarbon group represented by 2 - is replaced by -O- or -CO-. 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. TIFF2025060725000036.tif49119[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, -CH 2 - 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, -CH contained in hydrogen radical 2 - 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, The 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, Included -CH 2 - may be replaced by -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, The 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 b10is 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.

[0056] 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: TIFF2025060725000037.tif23140[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 alkylcarbonyloxy group may be substituted. 2 - is -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 alkylcarbonyloxy group may be substituted. 2 - is -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 b26represents 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 alkylcarbonyloxy group may be substituted. 2 - is -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.]

[0057] 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.

[0058] Examples of the group represented by formula (b1-4) include the following. TIFF2025060725000038.tif16150

[0059] Examples of the group represented by formula (b1-5) include the following. TIFF2025060725000039.tif72148

[0060] Examples of the group represented by formula (b1-6) include the following. TIFF2025060725000040.tif29150

[0061] Examples of the group represented by formula (b1-7) include the following. TIFF2025060725000041.tif64150

[0062] Examples of the group represented by formula (b1-8) include the following. TIFF2025060725000042.tif23150

[0063] Examples of the group represented by formula (b1-2) include the following. TIFF2025060725000043.tif31161

[0064] Examples of the group represented by formula (b1-9) include the following. TIFF2025060725000044.tif43138

[0065] Examples of the group represented by formula (b1-10) include the following. TIFF2025060725000045.tif89157

[0066] Examples of the group represented by formula (b1-11) include the following. TIFF2025060725000046.tif81158

[0067] 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). -CH contained in the alicyclic hydrocarbon group represented by Y 2 - 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). can be. The alicyclic hydrocarbon group represented by TIFF2025060725000047.tif83168Y 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 40), or a spiro ring containing an oxygen atom, such as formula (Y42) or formula (Y43), The alkanediyl group between the two oxygen atoms preferably has one or more fluorine atoms. In addition, among the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

[0068] 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, -( CH 2 ) ja -CO-OR b1 Group or -(CH 2 ) 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 alkyl group and the alicyclic hydrocarbon group each represent a -CH 2 - is -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 -CH 2 - 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, -(CH 2 ) ja -CO-OR b1 Group or -(CH 2 ) 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 - is -O-, -S(O) 2 - or -CO-, 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.

[0069] 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 biphenyl group, a naphthyl group, an anthracene group, and an aryl group. Examples of the aromatic hydrocarbon group include aryl groups such as an alkyl 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. -CH in the alkyl group 2 - is -O-, -S(O) 2 - or -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. -CH contained in alicyclic hydrocarbon group 2 - is -O-, -S(O) 2 - or -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.

[0070] Y includes the following: TIFF2025060725000048.tif155167

[0071] 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 -CH constituting an adamantyl group 2 - is -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

[0072] 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.

[0073] TIFF2025060725000049.tif143153

[0074] TIFF2025060725000050.tif64156

[0075] TIFF2025060725000051.tif87146

[0076] TIFF2025060725000052.tif160156

[0077] TIFF2025060725000053.tif165161 Here R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is preferably a methyl group or an ethyl group. i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms. Preferably, the alkyl group has 1 to 4 carbon atoms, an alicyclic hydrocarbon group has 5 to 12 carbon atoms, or More preferably, a methyl group, an ethyl group, a cyclohexyl group, L is a phenyl group or an adamantyl group. A41 is a single bond or an alkanediyl having 1 to 4 carbon atoms. It is a base. Q b1 and Q b2 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.

[0078] 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: TIFF2025060725000054.tif125153

[0079] TIFF2025060725000055.tif92138

[0080] TIFF2025060725000056.tif167156

[0081] 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.

[0082] 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. The arylsulfonium cation is preferably the cation Z in formula (I). + Similar to Some examples include:

[0083] 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) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), an aniline represented by any one of formulas (B1a-22) to (B1a-38) A combination of on and the cation (b2-1) or the cation (b2-3) is also included.

[0084] 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. TIFF2025060725000057.tif61150

[0085] TIFF2025060725000058.tif72163

[0086] TIFF2025060725000059.tif79150

[0087] TIFF2025060725000060.tif64150

[0088] TIFF2025060725000061.tif87145

[0089] JPEG2025060725000062.jpg63157

[0090] TIFF2025060725000063.tif152169

[0091] 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.

[0092] [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)").

[0093] <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.

[0094] <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. TIFF2025060725000064.tif2197[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.] TIFF2025060725000065.tif2379[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 —CH group contained in the hydrocarbon group and the heterocyclic group 2- 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.]

[0095] 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. TIFF2025060725000066.tif11161 Examples of the group combining an alkyl group and an alicyclic hydrocarbon group include 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 )(Ra3 The alicyclic hydrocarbon group preferably has 3 carbon atoms. ~12. * indicates the bonding site with -O-. TIFF2025060725000067.tif34158

[0096] 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, and a phenanthryl group. Examples of suitable aryl groups include aryl groups such as aryl groups. 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 ring together with the carbon atom to which they are bonded and X. -C(R a1' )(R a2' )-XR a3' Examples of the ring include the following: represents the binding site. TIFF2025060725000068.tif18125R a1' and R a2' At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0097] 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. TIFF2025060725000069.tif74158

[0098] Specific examples of the group (2) include the following groups: * represents a bonding site. TIFF2025060725000070.tif67153

[0099] 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.

[0100] 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.

[0101] 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. TIFF2025060725000071.tif46150 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or *-O-(CH 2 ) 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.

[0102] R a01 , R a4 and R a5 is preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or -O-(CH 2 ) 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 in the alicyclic hydrocarbon group is preferably 5 to 12, and more preferably 5 to 10. The group consisting of a combination of an alkyl group and an alicyclic hydrocarbon group is The total number of carbon atoms in combination with the group is preferably 18 or less. R a02 and 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.

[0103] 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. TIFF2025060725000072.tif59150

[0104] 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. TIFF2025060725000073.tif49132

[0105] 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. TIFF2025060725000074.tif36161

[0106] 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 %.

[0107] 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)"). TIFF2025060725000075.tif3667[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 -CH group contained in the divalent hydrocarbon group 2 - is replaced by -O- or -S- That's fine.]

[0108] 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: TIFF2025060725000076.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.

[0109] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33is 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.

[0110] -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid) and is eliminated to form a hydroxyl group.

[0111] 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). TIFF2025060725000077.tif69158

[0112] 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 %.

[0113] 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. TIFF2025060725000078.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 *-(CH 2 ) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 It 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.

[0114] 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 a single bond or -CH 2 -CO-O- is preferred.

[0115] 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. TIFF2025060725000079.tif31130

[0116] 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.

[0117] Further, examples of the structural unit (a1) include the following structural units. TIFF2025060725000080.tif26160

[0118] 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.

[0119] 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.

[0120] <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.

[0121] 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. TIFF2025060725000081.tif4348[In formula (a2-A), R a50 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. 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.]

[0122] 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.

[0123] *-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-OA a52 -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.

[0124] 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.

[0125] A a50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- Preferred are single bonds, *-CO-O- or *-CO-O-CH 2-CO-O- A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable.

[0126] 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

[0127] 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. TIFF2025060725000082.tif42166

[0128] 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.

[0129] 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: TIFF2025060725000083.tif3958 formula (a2-1), L a3 is -O- or *-O-(CH 2 ) 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.

[0130] In formula (a2-1), L a3 is preferably -O-, -O-(CH 2 ) 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 a16is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0131] 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. TIFF2025060725000084.tif53151

[0132] 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 %.

[0133] <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:

[0134] 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. TIFF2025060725000085.tif52164 [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-(CH 2 ) 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 is -CH 2 - 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.]

[0135] 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 La9 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.

[0136] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferably is -O- or *-O-(CH 2 ) k3 In -CO-O-, k3 is any one of 1 to 4 Groups which are integers, more preferably -O- and *-O-CH 2 -CO-O-, 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.

[0137] 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 a7is preferably -O- or *-OL a8 -CO-O-, more preferably -O -, -O-CH 2 -CO-O- or -OC 2 H 4 -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)'. TIFF2025060725000086.tif4151 (in the formula, R a24 , L a7 has the same meaning as above.)

[0138] 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.

[0139] TIFF2025060725000087.tif112162

[0140] 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 %.

[0141] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025060725000088.tif3167[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, -CH 2 - may be replaced by -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.

[0142] 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): TIFF2025060725000089.tif11158 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.

[0143] 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: TIFF2025060725000090.tif4651[In formula (a4-0), R 5 represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl 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.

[0144] L 4a 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, and other linear alkanediyl groups; ethane-1,1- Diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane Branched alkanediyl groups such as 2-methylpropane-1,3-diyl and 2-methylpropane-1,2-diyl groups Examples of the aryl group include the aryl 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.

[0145] 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.

[0146] 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. TIFF2025060725000091.tif94165

[0147] TIFF2025060725000092.tif4466[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, -CH contained in the hydrocarbon group 2 - 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 a41 and R a42 At least one of the following is a substituent: It has a halogen atom (preferably a fluorine atom). TIFF2025060725000093.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 , Xa41 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

[0148] 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 hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, Cycloalkyl groups such as cycloheptyl and cyclooctyl; decahydronaphthyl, adipyl, Polycyclic alicyclic groups such as manthyl, norbornyl and the following groups (* indicates a bonding site): Examples include saturated hydrocarbon groups. TIFF2025060725000094.tif11158 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.

[0149] 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. TIFF2025060725000095.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 When 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 .

[0150] A a45 The 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): TIFF2025060725000096.tif11158 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.

[0151] 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.

[0152] 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). TIFF2025060725000097.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.]

[0153] A a46 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.

[0154] 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 TIFF2025060725000098.tif13161

[0155] 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.

[0156] 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.

[0157] In the group represented by formula (a-g1), X a42is -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 TIFF2025060725000099.tif54163

[0158] 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: TIFF2025060725000100.tif165143

[0159] TIFF2025060725000101.tif67132

[0160] An example of the structural unit (a4) is a structural unit represented by the formula (a4-2). TIFF2025060725000102.tif4364[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, H 2 - 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.

[0161] 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.

[0162] 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.

[0163] Examples of the structural unit (a4) include a structural unit represented by formula (a4-3). TIFF2025060725000103.tif5672[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 It 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.

[0164] 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.

[0165] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The 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.

[0166] 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.

[0167] The structural unit (a4) also includes a structural unit represented by the formula (a4-4). TIFF2025060725000104.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH 2 ) j1 -, -(CH 2 ) j2 -O-(CH 2 ) j3 -or-(CH 2 ) j4 - CO-O-(CH 2 ) 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.]

[0168] 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.

[0169] In formula (a4-4), Af21 As an example, -(CH 2 ) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0170] 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. TIFF2025060725000105.tif87160

[0171] 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.

[0172] <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): . TIFF2025060725000106.tif3871[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, Included in -CH2 - may be replaced by -O- or -CO-.

[0173] 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 55 The 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.

[0174] L 55 -CH contained in the divalent saturated hydrocarbon group represented by 2 - 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. TIFF2025060725000107.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 x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. In formula (L1-3), L x5 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.

[0175] 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.

[0176] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF2025060725000108.tif54136

[0177] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2025060725000109.tif23130

[0178] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2025060725000110.tif15145

[0179] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2025060725000111.tif26115

[0180] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0181] 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. TIFF2025060725000112.tif112150When resin (A) has structural unit (a5), its content is the total of all structural units of 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.

[0182] <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.

[0183] 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: TIFF2025060725000113.tif36105[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, Ru-CH 2 - 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.

[0184] 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 following 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 X1 Examples 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.

[0185] 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.

[0186] -CH contained in saturated hydrocarbon groups 2 - is replaced by -O-, -S- or -CO- Examples of the divalent group include those represented by the formulae (X1) to (X53). and -CH contained in saturated hydrocarbon groups 2 - is replaced by -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 It represents the binding site with TIFF2025060725000114.tif145161

[0187] 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.

[0188] ZA in formula (II-2-A') + is the cation Z in salt (I). + The same thing was mentioned. Can be obtained.

[0189] 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: TIFF2025060725000115.tif38110[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.

[0190] 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, please refer to 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.

[0191] 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. TIFF2025060725000116.tif5677 [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, -CH 2 - 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.

[0192] 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.

[0193] 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 TIFF2025060725000117.tif5187 [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.

[0194] 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 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. TIFF2025060725000118.tif87163

[0195] 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 TIFF2025060725000119.tif3692[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 following 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 II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated hydrocarbon having 1 to 18 carbon atoms. The divalent saturated hydrocarbon group includes a -CH 2 - 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.

[0196] 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. TIFF2025060725000120.tif84130

[0197] 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).

[0198] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2025060725000121.tif35134

[0199] Examples of sulfonylmethide anions include the following: TIFF2025060725000122.tif29123

[0200] Examples of carboxylate anions include the following: TIFF2025060725000123.tif41155

[0201] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2025060725000124.tif94155

[0202] 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 %.

[0203] The resin (A) may have structural units other than the above-mentioned structural units. The positions include structural units known in the art.

[0204] 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.

[0205] <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 in the case of resin (A).

[0206] 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.

[0207] 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.

[0208] <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.

[0209] <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, 2,2’ - dipyridylamine, 2,2’ - dipicolylamine, bipyridine, etc. are mentioned, preferably diisopropyl aniline is mentioned, more preferably 2,6 - diisopropyl aniline is mentioned. As the ammonium salt, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3 - (trifluoromethyl)phenyltrimethylammonium hydroxide, tetra - n - butylammonium salicylate, and choline, etc. are mentioned.

[0210] The acidity of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is usually a salt with an acid dissociation constant of the acid generated from the salt of - 3 < pKa, preferably a salt of - 1 < pKa < 7, and more preferably a salt of 0 < pKa < 5. As the salt that generates an acid with a lower acidity than the acid not generated from the acid generator (B), the salts represented by the 9502 and JP-A 2011-191745. As the salt that generates an acid weaker in acidity than the acid generated from (B), preferably, (B) A salt that generates a carboxylic acid that is weaker in acidity than the acid generated from (B) (carboxylate anion) embedded image), and more preferably a weak acid inner salt (D). TIFF2025060725000125.tif85165

[0211] Examples of the weak acid inner salt (D) include the following salts. TIFF2025060725000126.tif72165

[0212] <Other Ingredients> The resist composition of the present invention may further contain components other than the above-mentioned components (hereinafter referred to as “other components”) as necessary. (F)) may be contained. There are no particular limitations on other components (F). However, additives known in the resist art, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc., may be used. Agents, dyes, etc. can be used.

[0213] 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

[0214] <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 Laser (wavelength 193 nm), F 2 Ultraviolet lasers such as excimer lasers (wavelength 157 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.

[0215] <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

[0216] 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."

[0217] Example 1: Synthesis of a salt represented by formula (I-1) TIFF2025060725000127.tif35157 3 parts of a salt represented by formula (I-1-a), 1.55 parts of potassium carbonate and dimethylformamide The mixture was stirred at 23°C for 30 minutes, and then heated to 50°C. Add 5.43 parts of a compound represented by formula (I-1-b) and 0.46 parts of potassium iodide to The mixture was stirred at 50°C for 20 hours and then cooled to 23°C. Add 50 parts of chloroform and 25 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the mixture. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 7.35 parts of the salt represented by the formula (I-1-c) was obtained. TIFF2025060725000128.tif37166 7.35 parts of a salt represented by formula (I-1-c), 3.23 parts of a salt represented by formula (I-1-d) 10 parts of ion-exchanged water, 50 parts of chloroform, and 25 parts of ethyl acetate were mixed and incubated at 23°C. The mixture was stirred for 8 hours. 25 parts of a 5% aqueous oxalic acid solution was added to the resulting mixture, and the mixture was stirred for 30 minutes at 23°C. After stirring for 10 minutes, the organic layer was separated and separated. After adding the water and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. To the concentrated residue obtained, 30 parts of tert-butyl methyl ether was added, After stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound represented by formula (I-1). 7.02 parts of the salt represented by the formula were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 657.2

[0218] Example 2: Synthesis of a salt represented by formula (I-16) TIFF2025060725000129.tif25158 2.51 parts of a salt represented by formula (I-16-a), 0.78 parts of potassium carbonate and dimethyl phosphatase The mixture was stirred at 23°C for 30 minutes and then heated to 50°C. A mixed solution containing 2.72 parts of a compound represented by formula (I-1-b) and 0.23 parts of potassium iodide The mixture was stirred at 50°C for 20 hours and then cooled to 23°C. Add 50 parts of chloroform and 25 parts of ion-exchanged water to the mixture and stir 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. Thereby, 4.71 parts of a salt represented by the formula (I-16-c) was obtained. TIFF2025060725000130.tif34166 4.65 parts of a salt represented by formula (I-16-c), 3.2 parts of a salt represented by formula (I-1-d) Mix 3 parts of ethyl acetate, 10 parts of ion-exchanged water, 50 parts of chloroform, and 25 parts of ethyl acetate at 23°C. The mixture was stirred at 23° C. for 8 hours. 25 parts of a 5% aqueous oxalic acid solution was added to the resulting mixture and the mixture was stirred at 23° C. for 3 hours. After stirring for 10 minutes, the organic layer was separated and extracted. After adding the water, the mixture was stirred at 23°C for 30 minutes, and the organic layer was separated. This was repeated 5 times. 30 parts of tert-butyl methyl ether was added to the concentrated residue obtained. After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound of formula (I-16) 4.29 parts of a salt represented by the formula (II) were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 407.1

[0219] Example 3: Synthesis of salt represented by formula (I-100) TIFF2025060725000131.tif431577.35 parts of a salt represented by formula (I-1-c), 3 parts of a salt represented by formula (I-100-d). 81 parts of the alcohol, 50 parts of chloroform and 25 parts of ethyl acetate were mixed and stirred at 23° C. for 8 hours. To the resulting mixed solution, 25 parts of a 5% aqueous oxalic acid solution was added and stirred at 23°C for 30 minutes. The organic layer was separated and separated. 25 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23° C. After stirring for 30 minutes, the organic layer was separated and washed with water five times. To the concentrated residue, 30 parts of tert-butyl methyl ether was added, and the mixture was stirred at 23°C for 30 minutes. After stirring, the supernatant was removed and the mixture was concentrated to obtain a salt represented by formula (I-100) 7. It sold .72 copies. MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 657.2

[0220] Example 4: Synthesis of a salt represented by formula (I-15) TIFF2025060725000132.tif32152 3 parts of a salt represented by formula (I-1-a), 1.55 parts of potassium carbonate and dimethylformamide The mixture was stirred at 23°C for 30 minutes, and then heated to 50°C. Add 4.27 parts of the compound represented by formula (I-15-b) and 0.46 parts of potassium iodide to the mixture. The mixture was stirred at 50°C for 20 hours and then cooled to 23°C. Add 50 parts of chloroform and 25 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the liquid. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 6.25 parts of a salt represented by the formula (I-15-c) was obtained. TIFF2025060725000133.tif401636.23 parts of a salt represented by formula (I-15-c), 3.2 parts of a salt represented by formula (I-1-d) Mix 3 parts of ethyl acetate, 10 parts of ion-exchanged water, 50 parts of chloroform, and 25 parts of ethyl acetate at 23°C. The mixture was stirred at 23° C. for 8 hours. 25 parts of a 5% aqueous oxalic acid solution was added to the resulting mixture and the mixture was stirred at 23° C. for 3 hours. After stirring for 10 minutes, the organic layer was separated and extracted. After adding the water, the mixture was stirred at 23°C for 30 minutes, and the organic layer was separated. This was repeated 5 times. 30 parts of tert-butyl methyl ether was added to the concentrated residue obtained. After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound of formula (I-15 5.89 parts of a salt represented by the formula (II) were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 553.2

[0221] Example 5: Synthesis of salt represented by formula (I-6) TIFF2025060725000134.tif41163 3 parts of a salt represented by formula (I-1-a), 1.55 parts of potassium carbonate and dimethylformamide The mixture was stirred at 23°C for 30 minutes, and then heated to 50°C. Add 8.65 parts of the compound represented by formula (I-6-b) and 0.46 parts of potassium iodide to The mixture was stirred at 50°C for 20 hours and then cooled to 23°C. Add 50 parts of chloroform and 25 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the mixture. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 10.75 parts of the salt represented by the formula (I-6-c) was obtained. TIFF2025060725000135.tif46168 10.46 parts of a salt represented by formula (I-6-c), 3.2 parts of a salt represented by formula (I-1-d) Mix 3 parts of ethyl acetate, 10 parts of ion-exchanged water, 50 parts of chloroform, and 25 parts of ethyl acetate at 23°C. The mixture was stirred at 23° C. for 8 hours. 25 parts of a 5% aqueous oxalic acid solution was added to the resulting mixture and the mixture was stirred at 23° C. for 3 hours. After stirring for 10 minutes, the organic layer was separated and extracted. After adding the water, the mixture was stirred at 23°C for 30 minutes, and the organic layer was separated. This was repeated 5 times. 30 parts of tert-butyl methyl ether was added to the concentrated residue obtained. After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound represented by formula (I-6) 10.22 parts of a salt represented by the formula: MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 945.2

[0222] Example 6: Synthesis of salt represented by formula (I-114) TIFF2025060725000136.tif45163 6.23 parts of a salt represented by formula (I-15-c), 3 parts of a salt represented by formula (I-100-d) Mix 0.81 parts of ethyl acetate, 10 parts of ion-exchanged water, 50 parts of chloroform, and 25 parts of ethyl acetate. The mixture was stirred at 3° C. for 8 hours. 25 parts of a 5% aqueous oxalic acid solution was added to the resulting mixed solution, and the mixture was heated to 23° C. After stirring for 30 minutes at 40° C., the organic layer was separated and separated. After adding 25 parts of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. The above procedure was repeated five times. 30 parts of tert-butyl methyl ether was added to the concentrated residue obtained. After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to give the compound of formula (I- 114) 6.74 parts of the salt represented by the formula: MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 553.2

[0223] Example 7: Synthesis of a salt represented by formula (I-105) TIFF2025060725000137.tif45162 10.46 parts of a salt represented by formula (I-5-c), 3 parts of a salt represented by formula (I-100-d) Mix 0.81 parts of ethyl acetate, 10 parts of ion-exchanged water, 50 parts of chloroform, and 25 parts of ethyl acetate. The mixture was stirred at 3° C. for 8 hours. 25 parts of a 5% aqueous oxalic acid solution was added to the resulting mixed solution, and the mixture was heated to 23° C. After stirring for 30 minutes at 40° C., the organic layer was separated and separated. After adding 25 parts of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. The above procedure was repeated five times. 30 parts of tert-butyl methyl ether was added to the concentrated residue obtained. After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to give the compound of formula (I- 10.62 parts of the salt represented by formula (105) were obtained. MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 945.2

[0224] Example 8: Synthesis of salt represented by formula (I-4) TIFF2025060725000138.tif36163 3 parts of a salt represented by formula (I-1-a), 1.55 parts of potassium carbonate and dimethylformamide The mixture was stirred at 23°C for 30 minutes, and then heated to 50°C. Add 5.47 parts of the compound represented by formula (I-4-b) and 0.46 parts of potassium iodide to The mixture was stirred at 50°C for 20 hours and then cooled to 23°C. Add 50 parts of chloroform and 25 parts of ion-exchanged water, stir at 23°C for 30 minutes, and then separate the mixture. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. As a result, 7.53 parts of a salt represented by the formula (I-4-c) was obtained. TIFF2025060725000139.tif35167 7.39 parts of a salt represented by formula (I-4-c), 3.23 parts of a salt represented by formula (I-1-d) 10 parts of ion-exchanged water, 50 parts of chloroform, and 25 parts of ethyl acetate were mixed and incubated at 23°C. The mixture was stirred for 8 hours. 25 parts of a 5% aqueous oxalic acid solution was added to the resulting mixture, and the mixture was stirred for 30 minutes at 23°C. After stirring for 10 minutes, the organic layer was separated and separated. After adding the water and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. To the concentrated residue obtained, 30 parts of tert-butyl methyl ether was added, After stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the compound represented by formula (I-4). 6.89 parts of the salt represented by the formula were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 661.2

[0225] 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. TIFF2025060725000140.tif4179

[0226] 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. TIFF2025060725000141.tif29124

[0227] 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: TIFF2025060725000142.tif2887

[0228] <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]

[0229] <Resin> A1, A2: Resin A1, Resin A2 <Salt (I)> I-1: A salt represented by formula (I-1) I-4: A salt represented by formula (I-4) I-6: A salt represented by formula (I-6) I-15: A salt represented by formula (I-15) I-16: A salt represented by formula (I-16) I-100: A salt represented by the formula (I-100) I-105: A salt represented by the formula (I-105) I-114: A salt represented by the formula (I-114) <Acid generator> IX-1 IX-2 IX-3 IX-4 IX-5 TIFF2025060725000144.tif68161<Quencher(C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF2025060725000145.tif3849<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0230] (Electron beam exposure evaluation of resist composition: Alkaline development) 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. The layer was spin-coated to a thickness of 0.04 μm. The substrate was prebaked for 60 seconds at the temperature shown in the "PB" column of Table 2 to form a composition layer. The composition layer formed on the wafer was then subjected to an electron beam lithography machine (ELS-F1 manufactured by Elionix Co., Ltd.). The exposure dose was gradually changed to obtain a line and space pattern. A line (pitch 60 nm / line width 30 nm) was directly written. After exposure, post-exposure was performed for 60 seconds on a hot plate at the temperature shown in the "PEB" column of Table 2. The jar was baked and then immersed in 2.38% tetramethylammonium hydroxide aqueous solution. A resist pattern was obtained by puddle development in a solution for 60 seconds. In the obtained resist pattern, the line width and space of the line and space pattern were The exposure amount at which the ratio of the source width to the source width becomes 1:1 was defined as the effective sensitivity.

[0231] <Pattern Collapse Evaluation (PCM) Evaluation> The more light exposure, the thinner the line pattern becomes, and the more likely the pattern will disappear. The numbers indicate the number of times that the line pattern formed with an exposure amount greater than the effective sensitivity is destroyed due to collapse or peeling. The minimum line width (nm) of the resist pattern where no turn loss was observed is shown in Table 3. As shown in. [Table 3] Compared with the comparative compositions 1 to 5, the resist pattern disappearance was not observed in the compositions 1 to 16. The minimum line width of the pattern was small, and the evaluation of pattern collapse was good. From the above results, it can be seen that the salt of the present invention and the resist composition containing the salt have excellent resistance to pattern collapse. It can be seen that (PCM) is good. [Industrial Applicability]

[0232] The salt of the present invention and the resist composition containing the salt have excellent pattern collapse resistance (PCM). This makes it useful for microfabrication of semiconductors.

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), L 1 represents a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and the —CH 2 - is -O-, -S-, -SO ２ It may be replaced by --or --CO--. X 1 represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O-, and * represents L 1 represents the binding site with R 1 represents a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and the —CH 2 - is -O-, -S-, -SO ２ It may be replaced by --or --CO--. m1 represents an integer of 1 to 3, and when m1 is 2 or more, a plurality of L 1 , X 1 and R 1 may be the same or different from each other. 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 an organic cation. [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 -, * is -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. R 1 However, a hydrocarbon group (containing a —CH 2 - is -O-, -S-, -SO ２ 2. The resist composition according to claim 1, wherein:

3. L １ 3. The resist composition according to claim 1, wherein is an alkanediyl group having 1 to 4 carbon atoms.

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. 6. 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.

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

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