Salt, acid generator, resist composition and method for producing resist pattern

Abstract

To provide a salt, a resist composition or the like that enables the production of a resist pattern with superior line edge roughness.SOLUTION: Disclosed is a salt represented by formula (I). In the formula, Q1 and Q2 each represent a fluorine atom or a perfluoroalkyl group, R1 and R2 each represent a hydrogen atom, z represents an integer of 0 to 6, X1 represents -CO-O-, -O-CO-, -O-CO-O- or -O-, L1 represents a single bond or a saturated hydrocarbon group, and -CH2- included in the group may be replaced by -O-, -S- or -CO-, A1 represents a substituted / unsubstituted monocyclic alicyclic hydrocarbon group, and -CH2- included in the group may be replaced by -O-, -S-, -SO2- or -CO-, Ra represents a substituted / unsubstituted cyclic hydrocarbon group, where, if Ra is an aromatic hydrocarbon group, the aromatic hydrocarbon group has at least one halogen atom, and Z+ represents an organic cation.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a salt for an acid generator used in the fine processing of semiconductors, an acid generator containing the salt, and a resist 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. TIFF0007659682000001.tif2747 Patent Document 2 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. Things are listed. TIFF0007659682000002.tif2752 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. TIFF0007659682000003.tif2770 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2007-161707 A [Patent Document 2] JP 2007-145824 A [Patent Document 3] JP 2008-074843 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. and providing a salt capable of forming a resist pattern with good line edge roughness (LER). The objective of the project is to: [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] A salt represented by formula (I). JPEG0007659682000004.jpg19115 [In formula (I), Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms; Represents a group. R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. It represents an alkyl group. z represents an integer of 0 to 6, and when z is 2 or more, a plurality of R 1 and R 2 are mutually They may be the same or different. X 1 is *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (however, * indicates C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ) represents the bonding position. ) represents the bonding position. L 1 represents a single bond or a saturated hydrocarbon group having 1 to 28 carbon atoms, -CH2- may be replaced by -O-, -S-, -SO2- or -CO-. . A 1 represents a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, The -CH2- contained in the cyclic hydrocarbon group may be replaced with -O-, -S-, -SO2- or -CO-. It may be replaced. R a represents a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. a but When the aromatic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group has at least one halogen atom. Z + represents an organic cation. [2]X 1 *-CO-O- or *-O-CO- (where * is C(R 1 )(R 2 )also is C(Q 1 )(Q 2 ) represents the bonding position with respect to the aryl group. [3] L 1 is a single bond, an alkanediyl group (provided that the -C H2- may be replaced by -O- or -CO-.) or an alkanediyl group and an alicyclic group. A group formed by combining with a cyclic saturated hydrocarbon group (provided that the -C H2- may be replaced by -O- or -CO-, and the alicyclic saturated hydrocarbon group The -CH2- may be replaced by -O-, -S-, -SO2- or -CO-. The salt according to [1] or [2], wherein [4]R a an alicyclic ring having 3 to 18 carbon atoms which may have a hydroxyl group or a fluorine atom or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a hydroxyl group. The salt according to any one of [1] to [3]. [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 structural unit having an acid labile group is a structural unit represented by formula (a1-1) and a structural unit represented by formula (a The resist composition according to [6], which contains at least two kinds of structural units represented by 1-2). TIFF0007659682000005.tif3885 [In formula (a1-1) and formula (a1-2), L a1 and L a2are each independently -O- or *-O-(CH2) k1 -CO-O- In the formula, k1 represents an integer of 1 to 7, and * represents a bond to —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 further contains a structural unit represented by formula (a2-A): The resist composition according to item [6] or [7]. TIFF0007659682000006.tif3843[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 a52each 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] Furthermore, the present invention relates to a method for producing a polymer comprising the steps of [6] to [9], which further comprises the steps of: The resist composition according to any one of the above.

[11] (1) A resist composition according to any one of [6] to

[10] above, which is applied onto a substrate. A process of (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 using the salt of the present invention, it is possible to obtain good line edge roughness. A resist pattern can be produced using a laser elimination process (LER). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In this specification, the term "(meth)acrylic monomer" refers to a monomer having a structure such as "CH2=CH-CO-" Monomers having the structure "CH2=C(CH3)-CO-" and monomers having the structure "CH2=C(CH3)-CO-" Similarly, "(meth)acrylate" and "(Meth)acrylic acid" refers to a compound selected from the group consisting of acrylate and methacrylate. "At least one selected from the group consisting of acrylic acid and methacrylic acid" and "at least one selected from the group consisting of acrylic acid and methacrylic acid "CH2=C(CH3)-CO-" or "CH2=CH-C When a structural unit having "O-" is exemplified, structural units having both groups are also included. In addition, in the groups described in this specification, straight chain structures and branched structures are For those which can have both structures, either one is acceptable. It means a group in which two or more of the indicated groups are bonded together with their valences appropriately changed. When present, all stereoisomers are included. In this specification, the term "solid content of a resist composition" refers to the fraction of the total amount of the resist composition that is This refers to the total of all components excluding the solvent (E) described below.

[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)".

[0009] In formula (I), Q 1 , Q 2 , R 1 and R 2 As the perfluoroalkyl group, Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoropropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorot Examples of the groups include an ert-butyl group, a perfluoropentyl group, and a perfluorohexyl group. . Q 1 and Q 2 are each independently preferably a trifluoromethyl group or a fluorine atom. and more preferably a fluorine atom. R 1 and R 2 are each independently preferably a hydrogen atom or a fluorine atom. It is preferred that z is 0 or 1. X 1 *-CO-O- or *-O-CO-(* is C(R 1 )(R 2 ) or C(Q 1 ) (Q 2 ) is preferably a bond to the ring.

[0010] L 1 The divalent saturated hydrocarbon group represented by the formula (I) is an alkanediyl group, a monocyclic or polycyclic and a combination of two or more of these groups. (For example, a divalent hydrocarbon group formed from an alicyclic hydrocarbon group and an alkanediyl group) good. 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. L 1 The -CH2- contained in the divalent saturated hydrocarbon group having 1 to 28 carbon atoms is -O-, -S It may be replaced by -, -SO2- or -CO-. L 1 The -CH2- contained in the divalent saturated hydrocarbon group having 1 to 28 carbon atoms represented by the formula , -S-, -SO2- or -CO-, the number of carbon atoms before the substitution is The number of carbon atoms in the hydrocarbon group. L 1 is a saturated hydrocarbon group having 1 to 28 carbon atoms (the -CH2- contained in the saturated hydrocarbon group is , -O-, -S-, -SO2- or -CO- may be substituted. However, a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that the alkanediyl group -CH2- may be replaced with -O- or -CO-.) or an alkyl group having 1 to 4 carbon atoms. A group formed by combining an alkanediyl group with an alicyclic saturated hydrocarbon group (provided that the alkanediyl group The -CH2- contained in the alicyclic group may be replaced by -O- or -CO-. The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S-, -SO2- or -CO-. It is preferable that the alkyl group is a single bond, an alkanediyl group having 1 to 4 carbon atoms, or ... a combination of an alkanediyl group or an alkanediyl group having 1 to 4 carbon atoms with an alicyclic saturated hydrocarbon group Group (provided that -CH2- contained in the alkanediyl group is replaced by -O- or -CO-) It is more preferable that the alkyl group is a single bond or an alkanediyl group having 1 to 4 carbon atoms. or a group formed by combining an alkanediyl group having 1 to 4 carbon atoms with an adamantanediyl group. (However, -CH2- contained in the alkanediyl group is replaced with -O- or -CO-. In this case, the number of alkanediyl groups is preferably 2 or more. It may be combined with an adamantanediyl group.

[0011] A 1 The divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms is preferably a monocyclic or polycyclic divalent Examples of the alkyl group include alicyclic hydrocarbon groups. Examples of the monocyclic divalent alicyclic hydrocarbon group include a cyclobutane-1,3-diyl group, a cyclobutane-1,3-diyl group, Pentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1 ,5-diyl groups and the like. Examples of polycyclic divalent alicyclic hydrocarbon groups include norbornane-1,4-diyl group, norbornane-1,4-diyl group, Adamantane-2,5-diyl group, Adamantane-2,2-diyl group, Adamantane-1,5- Examples thereof include a diyl group and an adamantane-2,6-diyl group. A 1 The substituents which the alicyclic hydrocarbon group may have include halogen atoms, hydroxy groups, etc. , cyano group, carboxy group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms groups and groups in which two or more of these groups are combined. 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 Examples of the alkyl group include an aryl group and a nonyl group. 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. Examples of the group combining two or more of these include an alkoxycarbonyl group having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms and alkylcarbonyloxy groups having 2 to 13 carbon atoms, etc. Examples include: Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and an alkylcarbonyloxy group having 2 to 13 carbon atoms are each independently selected from the above-mentioned alkyl groups or alkoxy groups. It represents a group in which a carbonyl group or a carbonyloxy group is bonded to a silyl group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy group, and 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. A 1 The divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by the following formula (I) is one substituent or the same Alternatively, it may have a plurality of different substituents. A 1 The -CH2- contained in the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms is -O-, - It may be replaced by -S-, -CO- or -SO2-. A 1 In the case where the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by the formula The -CH2- contained in the alicyclic hydrocarbon group is replaced with -O-, -S-, -CO- or -SO2-. When the hydrocarbon group is replaced, the number of carbon atoms before the replacement is regarded as the number of carbon atoms of the hydrocarbon group.

[0012] A 1 The divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms represented by the formula (I) is a cyclopentanediyl group. a monocyclic divalent alicyclic hydrocarbon group such as a cyclohexanediyl group (wherein the alicyclic hydrocarbon group The -CH2- contained may be replaced by -O-, -S-, -CO- or -SO2-. ), and is preferably a cyclopentanediyl group or a cyclohexanediyl group. It is more preferable that the aryl group is a cyclohexanediyl group, and it is even more preferable that the aryl group is a cyclohexanediyl group.

[0013] R a The cyclic hydrocarbon group having 3 to 18 carbon atoms represented by the formula (I) is a monocyclic or polycyclic alicyclic Examples of the hydrocarbon group include saturated hydrocarbon groups and aromatic hydrocarbon groups.

[0014] Examples of the monocyclic alicyclic saturated hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, Examples thereof include a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include a norbornyl group and an adamantyl group. Some examples include: Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group.

[0015] R a The substituents which the cyclic hydrocarbon group may have include halogen atoms, hydroxyl groups, group, cyano group, carboxy group, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms Examples of the alkyl group include a silyl group and a group in which two or more of these groups are combined. 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 Examples of the alkyl group include an aryl group and a nonyl group. 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. Examples of the group combining two or more of these include an alkoxycarbonyl group having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms and alkylcarbonyloxy groups having 2 to 13 carbon atoms. Some examples include: 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 group, and 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. R a The cyclic hydrocarbon group having 3 to 18 carbon atoms represented by the formula (I) has one or more substituents. It may have.

[0016] R a The cyclic hydrocarbon group having 3 to 18 carbon atoms represented by the formula (I) is a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. 18 alicyclic hydrocarbon groups or aromatic hydrocarbon groups having 6 to 18 carbon atoms and a halogen atom. It is preferable that the alkyl group has 1 to 12 carbon atoms, the hydroxyl group or the fluorine atom is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a fluorine atom, or More preferably, it is an aromatic hydrocarbon group having 1 to 8 carbon atoms, and more preferably, it is an alkyl group having 1 to 12 carbon atoms, a hydrocarbyl group, or a cycloalkyl group having 1 to 8 carbon atoms. a monocyclic alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have an oxy group or a fluorine atom, or A phenyl group having a fluorine atom is more preferred.

[0017] Examples of the anion (I) include the following anions. -1), Formula (Ia-4), Formula (Ia-5), Formula (Ia-8) to Formula (Ia-12), Formula (I a-14), formula (Ia-17), formula (Ia-18), formula (Ia-21) ~ formula (Ia-25) ) is preferred. TIFF0007659682000007.tif194152

[0018] TIFF0007659682000008.tif90144

[0019] 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. TIFF0007659682000009.tif76115In equations (b2-1) to (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, It represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the chain hydrocarbon group The hydrogen atoms contained in the alkyl group are hydroxyl groups, alkoxy groups having 1 to 12 carbon atoms, and fatty acids having 3 to 12 carbon atoms. The alicyclic group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms, aliphatic hydrocarbon groups having 1 to 18 carbon atoms, may be substituted with an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group is replaced by a halogen atom, a hydroxyl group, or a C1 It may be substituted with up to 12 alkoxy groups. R b4 and R b5 are bonded together to form a ring with the sulfur atom to which they are attached The -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. good. R b7 and R b8 each independently represents a hydroxyl group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms; 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. Rb9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or a chain hydrocarbon group having 3 to 4 carbon atoms, Represents 36 alicyclic hydrocarbon groups. R b9 and R b10 are bonded together to form a ring with the sulfur atom to which they are attached The -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. Good too. R b11 is a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, It represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. R b12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a hydrogen atom contained in the chain hydrocarbon is It may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aromatic hydrocarbon group The hydrogen atom is preferably an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group. R b11 and R b12 means that they are bonded together to form a ring including the -CH-CO- to which they are attached. The -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. It is also possible. R b13 ~R b18 each independently represents a hydroxyl group or an aliphatic hydrocarbon group having 1 to 12 carbon atoms; Or an alkoxy group having 1 to 12 carbon atoms. L b31 represents a sulfur atom or an oxygen atom. o2, p2, s2, and t2 each independently represent an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R 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.

[0020] 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 group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group 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. TIFF0007659682000010.tif11158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms. Examples of alicyclic hydrocarbon groups in which hydrogen atoms are replaced by aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl, dimethylcyclohexyl, 2-methyladamantan-2-yl, 2-ethyl 2-Isopropyladamantan-2-yl group, methylnor Examples of the alkyl group include a bornyl group and an isobornyl group. In the alicyclic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably Preferably, it is 20 or less. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a biphenylyl group, a naphthyl group, and a fluoro group. The aromatic hydrocarbon group may be a chain hydrocarbon group or an aryl group such as a phenanthryl group. may have an alicyclic hydrocarbon group, and an aromatic hydrocarbon group (a tricyclic hydrocarbon group) having a chain hydrocarbon group. aryl group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert- Butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc. ) and aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexylphenyl group, p -adamantylphenyl group, etc. In addition, when the aromatic hydrocarbon group contains 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.

[0021] 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.

[0022] 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. TIFF0007659682000011.tif23144R 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.

[0023] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF0007659682000012.tif79158

[0024] TIFF0007659682000013.tif74143

[0025] Examples of the cation (b2-2) include the following cations. TIFF0007659682000014.tif17120

[0026] Examples of the cation (b2-3) include the following cations. TIFF0007659682000015.tif23121

[0027] Examples of the cation (b2-4) include the following cations. TIFF0007659682000016.tif94136

[0028] TIFF0007659682000017.tif31141

[0029] Examples of the salt (I) include the salts listed in Table 1. For example, in Table 1, salt (I-1) is composed of an anion represented by formula (Ia-1) and a cation represented by formula (b2-c-1): The salt is shown below. TIFF0007659682000018.tif2892 [Table 1] TIFF0007659682000020.tif223154 TIFF0007659682000021.tif223154 TIFF0007659682000022.tif223154 TIFF0007659682000023.tif223154 TIFF0007659682000024.tif223154 TIFF0007659682000025.tif57145

[0030] Among them, salt (I) is salt (I-1), salt (I-4), salt (I-5), salt (I-8) ~ Salt (I-12), salt (I-14), salt (I-17), salt (I-18), salt (I-19), Salt (I-22), Salt (I-23), Salt (I-26) ~ Salt (I-30), Salt (I-32), Salt (I-35), Salt (I-36), Salt (I-37), Salt (I-40), Salt (I-41), Salt (I-44) ~ Salt (I-48), Salt (I-50), Salt (I-53), Salt (I-54), Salt (I-55), Salt (I-58), Salt (I-59), Salt (I-62) ~ Salt (I-66), Salt (I-68), Salt (I-71), Salt (I-712), Salt (I-73), Salt (I-76) , salt (I-77), salt (I-80) ~ salt (I-84), salt (I-86), salt (I-89) , salt(I-90), salt(I-91), salt(I-94), salt(I-95), salt(I-98) ~Salt(I-102), Salt(I-104), Salt(I-107), Salt(I-108), Salt(I -109), salt (I-112), salt (I-113), salt (I-116) ~ salt (I-120) ), salt(I-122), salt(I-125), salt(I-126), salt(I-127), salt( I-130), salt (I-131), salt (I-134) ~ salt (I-138), salt (I-14 0), salt(I-143), salt(I-144), salt(I-145), salt(I-148), salt (I-149), salt (I-152) ~ salt (I-156), salt (I-158), salt (I-1 61), salt (I-162), salt (I-163), salt (I-166), salt (I-167), Salt (I-170) ~ Salt (I-174), Salt (I-176), Salt (I-179), Salt (I- Salt (I-180), salt (I-201) to salt (I-250) are preferred.

[0031] <Method for producing salt (I)> In the salt (I), X 1 is -CO-O- (salt represented by formula (I1)) For example, the salt represented by formula (I1-a) is reacted with carbonyldiimidazole in a solvent. and then reacting the compound with a compound represented by formula (I1-b) to produce the compound. can be done. TIFF0007659682000026.tif29155 (wherein all symbols have the same meanings as defined above.) Solvents for this reaction include chloroform, acetonitrile, and the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0032] Examples of the salt represented by formula (I1-a) include the salts represented by the following formula: It can be produced by the method described in 08-127367. TIFF0007659682000027.tif2843 Examples of the compound represented by formula (I1-b) include compounds represented by the following formula, and are commercially available. It is easily available from the market and can be easily produced by known methods. do. TIFF0007659682000028.tif44160

[0033] In the salt (I), X 1 is *-O-CO-O- (a salt represented by formula (I2)) For example, the salt represented by formula (I2-a) is reacted with carbonyldiimidazole in a solvent. After reacting the resulting compound, the resulting compound is further reacted with a compound represented by formula (I1-b) to produce the compound It is possible. The salt represented by formula (I2) can be prepared, for example, by the reaction of a compound represented by formula (I1-b) with a carbo and nildiimidazole in a solvent, and then further reacting the compound represented by formula (I2-a) It can also be prepared by reacting TIFF0007659682000029.tif63163 (wherein all symbols have the same meanings as defined above.) Solvents for this reaction include chloroform, acetonitrile, and the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours. Examples of the salt represented by formula (I2-a) include the salts represented by the following formula: It can be produced by the method described in Publication No. 12-193170. TIFF0007659682000030.tif2843

[0034] In the salt (I), X 1 is *-O-CO- (salt represented by formula (I3)) For example, the compound represented by formula (I3-b) is reacted with carbonyldiimidazole in a solvent. and then further reacting with a salt represented by formula (I2-a) This can be done. TIFF0007659682000031.tif33167 (wherein all symbols have the same meanings as above.) Solvents for this reaction include chloroform, acetonitrile, and the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours. The compound represented by formula (I3-b) includes the compound represented by the following formula: It can be easily obtained from the market. TIFF0007659682000032.tif25127

[0035] In the salt (I), X 1 The salt represented by formula (I4) in which is -O- is represented by the formula (I2 -a) and a compound represented by formula (I1-b) in a solvent in the presence of a base. It can be obtained by reacting. TIFF0007659682000033.tif23165 (wherein all symbols have the same meanings as defined above.) The base in this reaction includes potassium hydroxide and the like. The solvent for this reaction may be acetonitrile or the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0036] In the salt (I), L 1 But *-L I4 -Ad-L I5 -O-CO-OL I6 -salt ( A salt represented by formula (I5) (L I4 , L I5 and L I6 are each independently a single bond or a carbon atom represents an alkanediyl group having a molecular weight of 6 to 6; L I4 , L I5 and L I6 At least one of the following has 1 to 6 carbon atoms Ad represents an adamantanediyl group, and * represents X. 1 The bond position with For example, a salt represented by formula (I5-a) and a compound represented by formula (I5-b) The compound can be produced by reacting the compound (I) with the compound (II) in a solvent. TIFF0007659682000034.tif48119 (wherein all symbols have the same meanings as defined above.) The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours. Solvents for this reaction include chloroform, acetonitrile, and the like. Examples of the salt represented by formula (I5-a) include the salt represented by the following formula: It can be produced by the method described in US Pat. No. 5,399,323. TIFF0007659682000035.tif25128 The compound represented by formula (I5-b) is, for example, a compound represented by formula (I1-b). Some examples include:

[0037] <Acid generator> The acid generator of the present invention is an acid generator containing a salt (I). The salt (I) may be used alone. Alternatively, two or more of them may be used in combination. 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.

[0038] 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. 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.

[0039] 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. TIFF0007659682000036.tif2862[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms; It represents a aryl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, The -CH2- contained in the alkyl group may be replaced with -O- or -CO-, and the divalent saturated carbon atom A hydrogen atom contained in the hydrogen group may be substituted with a fluorine atom or a hydroxy group. Y is a methyl group which may have a substituent or a C3-1 8, and -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by -S-, -SO2- or -CO-. Z + represents an organic cation.

[0040] 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.

[0041] 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. L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The replaced group is, for example, a group represented by any one of formulas (b1-1) to (b1-3). The groups represented by formulae (b1-1) to (b1-3) and their specific examples are In the examples of the groups represented by formulae (b1-4) to (b1-11), * and ** represent bonding sites. represents the position, and * represents a bond to -Y.

[0042] TIFF0007659682000037.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. The --CH2-- contained in the hydrogen atom may be replaced by --O-- or --CO--. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), 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. The --CH2-- contained in the hydrogen atom may be replaced by --O-- or --CO--. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxy groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the saturated carbon atom may be substituted with fluorine atoms or hydroxy groups. The --CH2-- contained in the hydrogen atom may be replaced by --O-- or --CO--. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0043] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group When -CH2- is replaced by -O- or -CO-, the number of carbon atoms before the replacement is The number of carbon atoms in the hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 The divalent saturated hydrocarbon groups are the same as those of the above. do. L 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 -CH2- contained in the divalent saturated hydrocarbon group is replaced with -O- or -CO-. Good too. L 1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The replaced group is preferably a group represented by formula (b1-1) or formula (b1-3).

[0044] 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. TIFF0007659682000038.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The -CH2- contained therein may be replaced by -O- or -CO-. L b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, The hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b9 and L b10 The total number of carbon atoms is 20 or less. In formula (b1-6), L b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. However, L b11 and L b12 The total number of carbon atoms is 21 or less. In formula (b1-7), L b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms. L b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The --CH2-- contained in the hydrogen atom may be replaced by --O-- or --CO--. L b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, 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, The contained --CH2-- 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.

[0045] L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms is preferred. L b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms is preferred. L b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms. L b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. L b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably A single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms is preferred.

[0046] 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: TIFF0007659682000039.tif23139 formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less. 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.

[0047] Examples of the group represented by formula (b1-4) include the following. TIFF0007659682000040.tif16154

[0048] Examples of the group represented by formula (b1-5) include the following. TIFF0007659682000041.tif78163

[0049] Examples of the group represented by formula (b1-6) include the following. TIFF0007659682000042.tif26166

[0050] Examples of the group represented by formula (b1-7) include the following. TIFF0007659682000043.tif62153

[0051] Examples of the group represented by formula (b1-8) include the following. TIFF0007659682000044.tif23150

[0052] Examples of the group represented by formula (b1-2) include the following. TIFF0007659682000045.tif30161

[0053] Examples of the group represented by formula (b1-9) include the following. TIFF0007659682000046.tif44137

[0054] Examples of the group represented by formula (b1-10) include the following. TIFF0007659682000047.tif92166

[0055] Examples of the group represented by formula (b1-11) include the following. TIFF0007659682000048.tif85164

[0056] The alicyclic hydrocarbon group represented by Y includes those represented by the formulae (Y1) to (Y11) and (Y36) to (Y38). Examples of the group include a group represented by the formula (Y38). The -CH2- contained in the alicyclic hydrocarbon group represented by Y is -O-, -S(O)2- or - When the group is replaced by CO-, the number of the CO- may be one or more. Examples of the groups include those represented by the formulae (Y12) to (Y35) and (Y39) to (Y41). can be.

[0057] The alicyclic hydrocarbon group represented by TIFF0007659682000049.tif86166Y 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 (Y41) 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) or (Y40), and more preferably a group represented by formula (Y11), formula (Y1 5), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula ( Y39) or a group represented by formula (Y40). The alicyclic hydrocarbon group represented by Y is represented by the formula (Y28) to the formula (Y35), the formula (Y39) to the formula (Y In the case of a spiro ring such as 40), the alkanediyl group between the two oxygen atoms is one or more It is preferable that the alkanediyl group contained in the ketal structure has a fluorine atom. Of these, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom. .

[0058] The substituent of the methyl group represented by Y is a halogen atom, a hydroxyl group, a methyl group having 3 to 1 carbon atoms, 6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -( CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 teeth, Alkyl groups having 1 to 16 carbon atoms, alicyclic hydrocarbon groups having 3 to 16 carbon atoms, aromatic groups having 6 to 18 carbon atoms represents an aromatic hydrocarbon group or a group combining these; ja represents an integer of 0 to 4; It is included in the alkyl group having 1 to 16 carbon atoms and the alicyclic hydrocarbon group having 3 to 16 carbon atoms. -CH2- may be replaced by -O-, -S(O)2- or -CO-. Some examples include: The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms which may be substituted with an aryloxy group; an alicyclic group having 3 to 16 carbon atoms; Hydrocarbon groups, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, carbon Aralkyl groups having 7 to 21 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms, and glycidyloxy groups. , -(CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, 8 or a combination thereof; ja is any one of 0 to 4; It represents an integer. It is included in the alkyl group having 1 to 16 carbon atoms and the alicyclic hydrocarbon group having 3 to 16 carbon atoms. The -CH2- contained therein may be replaced by -O-, -S(O)2- or -CO-. ) etc.

[0059] 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 alkyl group include a carbonyl group and an adamantyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a p-methyl group, and a phenyl group. p-tert-butylphenyl group, p-adamantylphenyl group; aryl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6 -diethylphenyl group, 2-methyl-6-ethylphenyl group, and other aryl groups. . 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 etc. 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 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. 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. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. etc.

[0060] Y includes the following: TIFF0007659682000050.tif141163

[0061] Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. More preferably, it is an adamantyl group which may have a substituent. The -CH2- constituting the adamantyl group is replaced with -CO-, -S(O)2- or -CO-. Y is more preferably an adamantyl group, a hydroxyadamantyl group, group, an oxoadamantyl group, or a group represented by the following formula: TIFF0007659682000051.tif85140

[0062] The anion in the salt represented by formula (B1) is represented by the formulas (B1-A-1) to (B1- A-55) (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 5) is more preferable.

[0063] TIFF0007659682000052.tif154166

[0064] TIFF0007659682000053.tif85146

[0065] TIFF0007659682000054.tif138166

[0066] TIFF0007659682000055.tif70167

[0067] TIFF0007659682000056.tif110144

[0068] TIFF0007659682000057.tif124167 Here R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably Preferably, the alkyl group has 1 to 4 carbon atoms, the alicyclic hydrocarbon group has 5 to 12 carbon atoms, or a combination thereof. A group formed by combining these groups, more preferably a methyl group, an ethyl group, or a cyclohexyl group. or an adamantyl group. A4is a single bond or an alkanediyl group having 1 to 4 carbon atoms . 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.

[0069] The anion in the salt represented by formula (B1) is preferably a compound represented by formula (B1a-1) to formula (B1a-2). B1a-34) are examples of anions represented by the formula: TIFF0007659682000058.tif126154

[0070] TIFF0007659682000059.tif93139

[0071] TIFF0007659682000060.tif152163

[0072] Among them, the compounds represented by formulae (B1a-1) to (B1a-3) and (B1a-7) to (B1a- 16), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a- 34) is preferably an anion represented by any one of the following:

[0073] 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. It is. Z1 in formula (B1) + can be the same as the cation (I) in the salt (I). .

[0074] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation. The acid generator (B) is preferably a compound represented by the formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) ~ Formula (B1a-16), Formula (B1a-18), Formula ( B1a-19), an anion represented by any one of formulas (B1a-22) to (B1a-34) and a combination of the cation (b2-1) or the cation (b2-3).

[0075] The acid generator (B) is preferably one represented by formula (B1-1) to formula (B1-48), 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 (B1-48) are particularly preferred. TIFF0007659682000061.tif62150

[0076] TIFF0007659682000062.tif72164

[0077] TIFF0007659682000063.tif85161

[0078] TIFF0007659682000064.tif68160

[0079] TIFF0007659682000065.tif87144

[0080] JPEG0007659682000066.jpg60154

[0081] TIFF0007659682000067.tif68163

[0082] 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.

[0083] <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)").

[0084] <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 Examples include:

[0085] <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. TIFF0007659682000068.tif2298[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms, R represents an alicyclic hydrocarbon group having 3 to 20 carbon atoms or a combination thereof; a1 and R a2 are bonded to each other and form, together with the carbon atom to which they are bonded, an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Form. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.] TIFF0007659682000069.tif2378[In formula (2), R a1' and R a2' each independently represents a hydrogen atom or a carbon atom having 1 to 12 carbon atoms; represents a hydrogen atom, and R a3' represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2' and R a3' Mutually They bond to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and X. The -CH2- contained in the hydrocarbon group and the heterocyclic group is replaced by -O- or -S-. It is also possible. X represents an oxygen atom or a sulfur atom. na′ represents 0 or 1. * represents a bond.]

[0086] 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 ( * represents a bond.) etc. a1 , R a2 and R a3 The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 16. TIFF0007659682000070.tif10159As a group combining an alkyl group and an alicyclic hydrocarbon group, for example, methylcyclohexane xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group , adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. do. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form an alicyclic hydrocarbon group, -C(R a1 )(Ra2 )(R a3 The alicyclic hydrocarbon group preferably has 3 carbon atoms. ~12. * represents a bond to -O-. TIFF0007659682000071.tif35158

[0087] 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. The aromatic hydrocarbon group includes a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, nyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, Silyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethyl Examples of the aryl group include aryl groups such as phenyl group and 2-methyl-6-ethylphenyl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. aryl-cyclohexyl groups such as phenylcyclohexyl groups; aralkyl groups such as benzyl groups; Examples thereof include the aryl group. 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 a3' )-XR a2' Examples of the ring include the following: represents the binding site. TIFF0007659682000072.tif18124Ra1' and R a2' At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0088] 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 bond. TIFF0007659682000073.tif74158

[0089] Specific examples of the group (2) include the following groups. * represents a bond. TIFF0007659682000074.tif67153

[0090] 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.

[0091] 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.

[0092] 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. TIFF0007659682000075.tif46149 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or *-O-(CH2) k1 -CO- k1 represents an integer of 1 to 7, and * represents a bonding site with -CO-. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups or combinations thereof. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 18 carbon atoms, or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0093] 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-(CH2) k01 -CO-O- (wherein k01 is preferably an integer of 1 to 4, more preferably 1. ), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 The alkyl group, alicyclic hydrocarbon group and As a group formed by combining these, R in formula (1) 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) preferably has 1 to 6 carbon atoms, and more preferably More preferably, it is a methyl group or an ethyl group, and even more preferably, it is a methyl group. R a6 and R a7 The alkyl group in the formula (I) preferably has 1 to 6 carbon atoms, and more preferably It is preferably a methyl group, an ethyl group, or an isopropyl group, and more preferably an ethyl group or an isopropyl group. It is a pyridine group. R a02 , R a03 , R a04 , R a6 and R a7The 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 It is preferred that the total number of carbon atoms in combination with the group is 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.

[0094] 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. TIFF0007659682000076.tif58150

[0095] 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. TIFF0007659682000077.tif48131

[0096] 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 The structural unit represented by (a1-2-6) is preferred. TIFF0007659682000078.tif37161

[0097] 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 %.

[0098] 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)"). TIFF0007659682000079.tif3766[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1-6 alkyl group which may have a halogen atom represents an alkyl group represented by the formula: R a33 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of R a33 are mutual may be the same or different. R a34 and R a35 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R a36 represents a hydrocarbon group having 1 to 20 carbon atoms, or R a35 and R a36 are combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH2- contained in the alkyl group and the divalent hydrocarbon group is replaced by -O- or -S-. That's fine.]

[0099] 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. , an aromatic hydrocarbon group, and R in formula (2) a1' and R a2' The same groups as those shown in the above are particularly preferred. To, R a36 Examples of the alkyl group include an alkyl group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these Examples include:

[0100] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. is more preferred, and a methoxy group is even more preferred. la is preferably 0 or 1, and more preferably 0. R a34 is preferably a hydrogen atom. R a35 is preferably an alkyl group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms, more preferably More preferably, it is a methyl group or an ethyl group. R a36 The hydrocarbon group is preferably an alkyl group having 1 to 18 carbon atoms, Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is an alkyl group having 1 to 18 carbon atoms, a group having 3 to 1 R is an alicyclic aliphatic hydrocarbon group having 8 or an aralkyl group having 7 to 18 carbon atoms. a36 In The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 In The aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

[0101] -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid) and is eliminated to form a hydroxyl group.

[0102] 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 in the structural unit (a1-4) a32 In accordance with A structural unit in which the hydrogen atom in the aryl group is replaced by a methyl group is preferable. Structural units represented by formulas (a1-4-1) to (a1-4-5) and (a1-4-10), respectively Examples include: TIFF0007659682000080.tif69157

[0103] 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 10 to 95 mol %, more preferably 15 to 90 mol %, based on the total of the structural units. More preferably, the content is 20 to 85 mol %, and even more preferably, the content is 20 to 70 mol %. %, and particularly preferably 20 to 60 mol %.

[0104] 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. TIFF0007659682000081.tif4253 formula (a1-5), R a8 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Represents an acetylene atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 Represents a bond 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.

[0105] 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 aryl group include the ethyl group and the trifluoromethyl group. In formula (a1-5), R a8 is a hydrogen atom, a methyl group, or a trifluoromethyl group. preferable. L 51 is preferably an oxygen atom. L 52 and L 53 Of these, it is preferred that one is -O- and the other is -S-. It is preferable that s1 is 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or -CH2-CO-O-.

[0106] 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. TIFF0007659682000082.tif31130

[0107] 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.

[0108] Further, examples of the structural unit (a1) include the following structural units. TIFF0007659682000083.tif27161

[0109] 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 10 to 95 mol % based on the total structural units of the resin (A), and more preferably 15 to 95 mol %. More preferably, the content is from 20 to 85 mol %, and even more preferably, the content is from 20 to 70 mol %. More preferably, the range is 20 to 60 mol %, and particularly preferably, the range is 10 to 40 mol %. I wish.

[0110] 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.

[0111] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may also 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 preferably used. In addition, ArF excimer laser (193 nm) or the like is used. In this case, the structural unit (a2) may be a structural unit (a2) having an alcoholic hydroxyl group. ) is preferred, and the structural unit (a2-1) described below is more preferred. As a2), one type may be contained alone, or two or more types may be contained.

[0112] The structural unit (a2) having a phenolic hydroxy group is represented by the formula (a2 -A) (hereinafter sometimes referred to as "structural unit (a2-A)"). can be. TIFF0007659682000084.tif3843[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 It represents the bond to the carbon atom. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52each 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.]

[0113] 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.

[0114] *-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.

[0115] 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 a52is preferably a methylene group or an ethylene group.

[0116] A a50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable.

[0117] 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 to bind to

[0118] 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. TIFF0007659682000085.tif42166

[0119] 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 preferably 65 mol %, and more preferably 20 to 50 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.

[0120] 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: TIFF0007659682000086.tif3753 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents a bond to -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.

[0121] In formula (a2-1), L a3 is preferably -O-, -O-(CH2) f1-CO-O- (wherein f1 represents an integer of 1 to 4), and more preferably —O—. R a14 is preferably a methyl group. R a15 is preferably a hydrogen atom. R a16 is preferably a hydrogen atom or a hydroxy group. o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0122] 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. TIFF0007659682000087.tif50138

[0123] 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 %.

[0124] <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:

[0125] 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. TIFF0007659682000088.tif46148[In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH2) k3 -CO-O -(k3 represents an integer of 1 to 7). L a7 , -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -C OOL a9 -CO-O- or *-OL a8 -O-CO-L a9 Represents -O-. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Represents a gen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Ra22 , 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.]

[0126] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in propyl, isopropyl, butyl, sec-butyl and tert-butyl groups Examples of alkyl groups include the following. R a24 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine atoms. Children are mentioned. R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, groups, butyl groups, sec-butyl groups, tert-butyl groups, pentyl groups, and hexyl groups. Preferred are alkyl groups having 1 to 4 carbon atoms, and more preferred are methyl groups or is an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Fluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group group, triiodomethyl group, and the like. L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane group, -1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, penta hexane-1,5-diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2- Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane -1,4-diyl group and 2-methylbutane-1,4-diyl group.

[0127] In formulas (a3-1) to (a3-3), L a4 , L a5 and L a6 are each independently Preferably, -O- or *-O-(CH2) k3 In -CO-O-, k3 is 1 to 4 A group having any integer, more preferably -O- and *-O-CH2-CO-O-, and more preferably Of these, an oxygen atom is preferred. R a18 , R a19 , R a20 and 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.

[0128] In formula (a3-4), R a24is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A group, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom. It is a hydrogen atom or a methyl group. R a25 is preferably a carboxy group, a cyano group or a methyl group. L a7 is preferably -O- or *-OL a8 -CO-O-, more preferably -O -, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF0007659682000089.tif4928(in the formula, R a24 , L a7 has the same meaning as above.)

[0129] 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.

[0130] TIFF0007659682000090.tif114164

[0131] 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 %.

[0132] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF0007659682000091.tif3066[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, The -CH2- contained in the group may be replaced with -O- or -CO. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain hydrocarbon group and a monocyclic or polycyclic alicyclic hydrocarbon group. groups, as well as groups formed by combining these groups.

[0133] 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 bond): TIFF0007659682000092.tif11159 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0134] 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: TIFF0007659682000093.tif4552[In formula (a4-0), R 5 represents a hydrogen atom or a methyl group. L 4a represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms. L 3a is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. It represents a fluorocycloalkanediyl group. R 6 represents a hydrogen atom or a fluorine atom.

[0135] L 4a The divalent aliphatic saturated hydrocarbon group in Straight-chain alkanediyl groups such as pan-1,3-diyl group and butane-1,4-diyl group, ethoxylated propane-1,1-diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2- Branched groups such as methylpropane-1,3-diyl and 2-methylpropane-1,2-diyl groups alkanediyl groups. L 3a The perfluoroalkanediyl group in the formula (I) is a difluoromethylene group, Fluoroethylene 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 xanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group yl group, perfluoroadamantanediyl group, and the like.

[0136] L 4a is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond, a methylene group. L3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably or a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0137] 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. TIFF0007659682000094.tif95165

[0138] TIFF0007659682000095.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, The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. A a41 represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent, or a group represented by the formula (ag 1), where A a41 and R a42 At least one of the following is a substituent: It has a halogen atom (preferably a fluorine atom). TIFF0007659682000096.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 a42each independently represents -O-, -CO-, -CO-O-, or -O-CO - represents. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * is a bond, and the * on the right is -O-CO-R a42 It is a combination with .

[0139] 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, Manthyl group, norbornyl group, and polycyclic alicyclic saturated groups such as the following groups (* represents a bond): and hydrocarbon groups. TIFF0007659682000097.tif11159 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an aryl group with one or more alicyclic saturated hydrocarbon groups. Examples of the saturated alicyclic hydrocarbon group include -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl Examples of the alkyl group include an aryl group, an alkanediyl group, an alicyclic saturated hydrocarbon group, and an alkyl group.

[0140] R a42The substituents which may be contained in the formula (a-g3) include a halogen atom and a The halogen atom may be at least one selected from the group consisting of fluorine, arylene ... Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. TIFF0007659682000098.tif965[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O- (* represents R a42 (represents a bond with ). A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . * represents a bond.] 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 .

[0141] 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 bond): TIFF0007659682000099.tif11159 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0142] R a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, and / or an aliphatic hydrocarbon group having a group represented by formula (a-g3) is preferably This is more preferable. R a42 When is an aliphatic hydrocarbon group having a halogen atom, it is preferable that More preferably, it is a perfluoroalkyl group or a perfluoro and preferably a perfluoroalkyl group having 1 to 6 carbon atoms. and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, Examples of perfluorocycloalkyl include fluoroheptyl and perfluorooctyl groups. Examples of the alkyl group include a perfluorocyclohexyl group. R a42 is an aliphatic 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. In the case where the substituent is a group represented by formula (a-g3), , the number is preferably one.

[0143] R a42 is an aliphatic hydrocarbon having a group represented by formula (a-g3), R a42 Yes, More preferably, it is a group represented by formula (a-g2). TIFF0007659682000100.tif879[In formula (a-g2), A a46 represents a divalent aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. Represents. X a44 represents *-O-CO- or *-CO-O- (* represents A a46 (represents a bond with ). 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 a bond to the carbonyl group.

[0144] A a46 The aliphatic 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.

[0145] A preferred structure of the group represented by formula (a-g2) is the following structure (* represents a carbonyl group). (It is a combination with ). TIFF0007659682000101.tif13161

[0146] 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.

[0147] A in the group represented by formula (a-g1) a42 , A a43 and A a44 The divalent saturated hydrocarbon Examples of the substituent include linear or branched alkanediyl groups and monocyclic divalent alicyclic hydrocarbon groups, as well as and a group formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, Propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3 -diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Examples of the aryl group include the aryl group. 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.

[0148] In the group represented by formula (a-g2), X a42 is -O-, -CO-, -CO-O- or Examples of the -O-CO- group include the following groups. In the following examples, * and Each ** represents a bond, and ** is -O-CO-R. a42 It is a combination with. TIFF0007659682000102.tif54162

[0149] 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: TIFF0007659682000103.tif167144

[0150] TIFF0007659682000104.tif66134

[0151] As the structural unit represented by formula (a4-1), a structural unit represented by formula (a4-2) is preferred. I wish. TIFF0007659682000105.tif4365[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, H2- may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The total number of carbon atoms in the molecule is limited to 21.

[0152] 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 the same groups as 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.

[0153] 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.

[0154] Examples of the structural unit (a4) include a structural unit represented by formula (a4-3). TIFF0007659682000106.tif5670[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 a bond with .) Represents. A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may contain a fluorine atom. However, A f13 and Af14 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.

[0155] L 5 The alkanediyl group in a41 Alkaline in the divalent saturated hydrocarbon group Examples of the phenyl group include the same groups as those exemplified for the phenyl group. A f13 The divalent saturated hydrocarbon group which may have a fluorine atom in or a divalent aliphatic saturated hydrocarbon group which may have a fluorine atom and a is preferably a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkane divalent It is a yl group. The divalent aliphatic hydrocarbon group which may have a fluorine atom is preferably a methylene group, an ethylene group, alkanediyl groups such as aryl, propanediyl, butanediyl, and pentanediyl groups; Difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, Perfluoroalkanediyl groups such as fluorobutanediyl and perfluoropentanediyl groups Examples of the aryl group 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.

[0156] 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.

[0157] 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.

[0158] The structural unit (a4) also includes a structural unit represented by the formula (a4-4). TIFF0007659682000107.tif4466[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -or-(CH2) j4 - CO-O-(CH2) j5 - represents. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0159] 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.

[0160] In formula (a4-4), A f21 As an example, -(CH2) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0161] 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. TIFF0007659682000108.tif87160

[0162] 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.

[0163] <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): . TIFF0007659682000109.tif3971[In formula (a5-1), R 51 represents a hydrogen atom or a methyl group. R 52 represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and the water contained in the alicyclic hydrocarbon group The atom may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. L 55 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the formula (I) may be replaced with -O- or -CO-.

[0164] 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.

[0165] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula (I) is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * and ** each represent a bond, and * represents a bond to an oxygen atom. TIFF0007659682000110.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 It represents a bond 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 , Lx6 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.

[0166] 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 x9is 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.

[0167] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF0007659682000111.tif53135

[0168] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF0007659682000112.tif23130

[0169] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF0007659682000113.tif15145

[0170] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF0007659682000114.tif26115

[0171] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0172] 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. TIFF0007659682000115.tif75150

[0173] TIFF0007659682000116.tif36152 When the resin (A) has the structural unit (a5), the content of the structural unit (a5) is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and more preferably 3 to 15 mol %. % is more preferred.

[0174] <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 The structural unit described in JP-A-2016-79235 is an example, and the side chain may include a sulfonate group or a cyclic alkyl group. or a structural unit having a carboxylate group and an organic cation, or a structural unit having a sulfonio group on the side chain It is preferable that the structural unit has an organic anion.

[0175] 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: TIFF0007659682000117.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon may be The hydrogen atom contained in the alkyl group is replaced by a halogen atom or a alkyl group having 1 to 10 carbon atoms which may have a halogen atom. 6 may be substituted with an alkyl or hydroxy group. A X1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atom contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. . RA -represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: Z.A. + represents an organic cation.

[0176] 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 trifluoroalkyl groups. perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group Examples of the alkyl group include a perfluoropentyl group and a perfluorohexyl group. X III3The 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 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 norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane Divalent polycyclic alicyclic saturated carbons such as cyclohexyl-1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like. A saturated hydrocarbon group in which -CH2- has been replaced with -O-, -S- or -CO- Examples of the divalent group include those represented by the formulae (X1) to (X53). The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-. The number of carbon atoms in front of each is 17 or less. In the following formula, * and ** represent binding sites. * is A X1 represents the binding site with TIFF0007659682000118.tif145161

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

[0178] ZA in formula (II-2-A') + is the cation Z in salt (I). + The same thing was mentioned. Can be obtained.

[0179] The structural unit represented by the formula (II-2-A') is a structural unit represented by the formula (II-2-A) It is preferable that: TIFF0007659682000119.tif38108 [In formula (II-2-A), R III3 , X III3 and Z.A. + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom, or a phenyl group having 1 to 6 carbon atoms; When z is 2 or more, multiple R III2 and R III4 are identical to each other may be the same or may be 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. R III2 , R III4 , Q a and Q b and a perfluoroalkyl group having 1 to 6 carbon atoms represented by the following formula: For details, see Q below. 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.

[0180] 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. TIFF0007659682000120.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and Z.A. + has the same meaning as above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents an integer of 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon The hydrogen atoms contained in the group may be substituted with halogen atoms or hydroxy groups. 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.

[0181] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). More preferred are structural units in which TIFF0007659682000121.tif5288 [In formula (II-2-A-2), R III3 , R III5 and Z.A. + has the same meaning as above. m and n each independently represent 1 or 2.

[0182] Examples of the structural unit represented by formula (II-2-A') include the following structural units and the International Examples of the structural units include those described in Publication No. 2012 / 050015. + is an organic cation Represents. TIFF0007659682000122.tif79163

[0183] TIFF0007659682000123.tif82153

[0184] 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 TIFF0007659682000124.tif3791 [In formula (II-1-1), A II1 represents a single bond or a divalent linking group. R II1 represents a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. R II2 and R II3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 Reach BiR II3 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. R II4is 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 -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or Specifically, X may be replaced with -CO-. III3 2 with 1 to 18 carbon atoms The examples of the alkyl group include the same ones as those of the 4-valent saturated hydrocarbon group.

[0185] The structural unit containing a cation in formula (II-1-1) may be any of the structural units represented by the following formula: Some examples include: TIFF0007659682000125.tif80143

[0186] TIFF0007659682000126.tif99139

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

[0188] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF0007659682000127.tif43135

[0189] Examples of sulfonylmethide anions include the following: TIFF0007659682000128.tif29123

[0190] Examples of carboxylate anions include the following: TIFF0007659682000129.tif51153

[0191] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF0007659682000130.tif98159

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

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

[0194] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s), i.e. That is, it is a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably a cyclohexyl group or a structural unit having a cyclopentyl group) and (a1-4), Preferably, at least two types are used, and more preferably, the structural unit (a1-1) and the structural unit (a1-2) are used. At least two of the positions (a1-2) are selected from the group consisting of 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 determined by gel permeation chromatography under the conditions described in the Examples. It is.

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

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

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

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

[0199] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound and an acid generator (B). The quencher (C) content is The amount is preferably about 0.01 to 5 mass % based on the solid content of the resist composition. 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.

[0200] 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, Ethyldibutylamine 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)ethane, 1,2-di(4-pyridyl)ethene, 1,3-Di(4-pyridyl)propane, 1,2-Di(4-pyridyloxy)ethane, Di( 2-Pyridyl) ketone, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide amine, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Among them, preferred are aromatic amines such as diisopropylaniline, and more preferred are aromatic amines such as diisopropylaniline. Examples include 2,6 - diisopropyl aniline. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropyl ammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethyl ammonium hydroxide, 3 - (trifluoromethyl)phenyltrimethylammonium hydroxide, tetra - n - butylammonium salicylate, choline, and the like. are mentioned.

[0201] 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 acid generated from the acid generator (B) has a lower acidity than the acid The salt that generates is usually a salt with an acid dissociation constant of the acid generated from the salt of - 3 < pKa, preferably is a salt of - 1 < pKa < 7, and more preferably a salt of 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP - A - 2015 - 147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and salts described in JP - A - 2012 - 229206 JP - A - 2012 - 6908, JP - A - 2012 - 72109, JP - A - 2011 - 3 9502, and JP - A - 2011 - 191745. Preferably, the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is the weak acid inner salt (D). (B) is the weak acid inner salt (D). TIFF0007659682000131.tif85165

[0202] Examples of the weak acid inner salt (D) include the following salts. TIFF0007659682000132.tif71165

[0203] When the resist composition contains a quencher (C), the content of the quencher (C) is The amount of the photoresist is usually from 0.01 to 5 mass %, preferably from 0.01 to 3 mass %, based on the solid content of the resist composition. Mass percent.

[0204] <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.

[0205] Preparation of Resist Composition The resist composition of the present invention comprises a salt (I) and a resin (A), and, if necessary, an acid generator (B), resins other than resin (A), solvent (E), quencher (C) and other components (F The order of mixing is arbitrary and is not particularly limited. The temperature during mixing ranges from 10 to 40°C, depending on the type of resin, solvent (E The appropriate temperature can be selected depending on the solubility of the solvent in the solvent. The mixing time depends on the mixing temperature. Depending on the situation, an appropriate time can be selected from 0.5 to 24 hours. There is no limitation, 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

[0206] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) applying the resist composition of the present invention onto a substrate; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating. To apply the resist composition onto a substrate, a commonly used device such as a spin coater is used. The substrate can be an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be cleaned, and an anti-reflection film or the like may be formed on the substrate. It may be possible. The composition after coating is dried to remove the solvent and form a composition layer. For example, the solvent can be evaporated using a heating device such as a hot plate (prebaking). The heating temperature is 50 to 200°C. It is preferable that the heating time is 10 to 180 seconds. The pressure during the process is 1 to 1.0×10 5 It is preferable that the pressure is about Pa. The obtained composition layer is usually exposed using an exposure machine. The exposure light source may be a KrF excimer laser (wavelength 248 nm), an ArF excimer Lasers in the ultraviolet range such as F2 excimer laser (wavelength 157 nm) and F2 laser (wavelength 193 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert the wavelength and emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range, electron beams, Various types of light sources can be used, such as those that irradiate ultraviolet light (EUV). In this case, the irradiation of these radiations is sometimes collectively called "exposure". Exposure is usually carried out through a mask corresponding to the desired pattern. In the case of lines, exposure may be performed by direct writing without using a mask. The composition layer after exposure is subjected to a heat treatment (so-called heat treatment) in order to promote the deprotection reaction of the acid labile group. The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150 degrees Celsius. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of the method include the dip method, the paddle method, the spray method, and the dynamic dispense method. The development temperature is preferably, for example, 5 to 60° C., and the development time is, for example, 5 The time is preferably 300 seconds or less. By selecting the type of developer as follows: Either a positive resist pattern or a negative resist pattern can be produced. When a positive resist pattern is produced from the resist composition of the present invention, a developer An alkaline developer is used. The alkaline developer is any of the various alkaline solutions used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples of the aqueous solution ... ethyl)trimethylammonium hydroxide (commonly known as choline) include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers are ketones such as 2-hexanone and 2-heptanone. Solvents; glycol ether ethers such as propylene glycol monomethyl ether acetate Steryl solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and the like aromatic hydrocarbon solvents. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, The content is preferably from 95% by mass to 100% by mass, and more preferably substantially only an organic solvent. More preferred. Among them, organic developers include those containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass. Preferably, the content is 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the components are qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 10%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. It is preferable to wash the resist pattern after development with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and any solvent containing a general organic solvent may be used. Any suitable solvent may be used, preferably an alcohol or ester solvent. After cleaning, it is preferable to remove any rinsing liquid remaining on the substrate and the pattern.

[0207] <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 resist compositions for V exposure, particularly resist compositions for ArF excimer laser exposure, It is suitable as a resist composition for EB exposure or EUV exposure. , and is useful in semiconductor microfabrication. EXAMPLES

[0208] 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."

[0209] Example 1: Synthesis of a salt represented by formula (I-1) TIFF0007659682000133.tif41165 13 parts of the salt represented by formula (I-1-a) and 20 parts of chloroform were mixed and incubated at 23°C for 30 The mixture was stirred for 10 minutes. 5.05 parts of the compound represented by formula (I-1-b) was added to the resulting mixture. The mixture was added and stirred at 50° C. for 2 hours. 5.41 parts of the compound was added, and the mixture was stirred at 50°C for 3 hours, and then cooled to 23°C. To the resulting mixture, 70 parts of chloroform and 25 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred for 23 h. After stirring at ℃ for 30 minutes, the organic layer was separated and extracted. After adding 30 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. The obtained organic layer was concentrated, and the concentrated residue was diluted with 10 parts of acetonitrile and Add 90 parts of tert-butyl methyl ether, stir at 23°C for 30 minutes, and then remove the supernatant. The liquid was removed and the filtrate was concentrated to obtain 11.98 parts of the salt represented by formula (I-1). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 339.1

[0210] Example 2: Synthesis of a salt represented by formula (I-18) TIFF0007659682000134.tif78150 9.54 parts of the salt represented by formula (I-18-a) and 30 parts of chloroform were mixed and heated at 23°C. The mixture was stirred at rt for 30 minutes. Compound 2.49 represented by formula (I-1-c) was added to the resulting mixture. parts of ion-exchanged water was added to the mixture, and the mixture was stirred at 23° C. for 8 hours. The mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. 20 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was then separated to obtain an organic layer. To the obtained organic layer, 30 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was separated and washed with water five times. The organic layer was concentrated. Then, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to give the compound of formula (I- 7.19 parts of the salt represented by formula 18) were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 547.2

[0211] Example 3: Synthesis of a salt represented by formula (I-127) TIFF0007659682000135.tif45163 12.23 parts of the salt represented by formula (I-127-a) and 20 parts of chloroform were mixed, and The mixture was stirred at 3° C. for 30 minutes. Compound 5 represented by formula (I-1-b) was added to the resulting mixture. 05 parts of toluene was added, and the mixture was stirred at 50° C. for 2 hours. c) 5.41 parts of the compound represented by the formula (1) was added, and the mixture was stirred at 50° C. for 3 hours. The mixture was cooled to 70 parts of chloroform and 25 parts of a 5% aqueous solution of oxalic acid. After stirring at 23°C for 30 minutes, the organic layer was separated and extracted. Thirty parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes, after which the organic layer was separated and taken out. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with acetonitrile. 5 parts of tert-butyl methyl ether and 95 parts of tert-butyl methyl ether were added, and the mixture was stirred at 23°C for 30 minutes. The supernatant was removed and the mixture was concentrated to obtain 10.49 parts of a salt represented by formula (I-127). obtained. MASS(ESI(+)Spectrum):M + 237.1 MASS(ESI(-)Spectrum):M - 339.1

[0212] Example 4: Synthesis of salt represented by formula (I-4) TIFF0007659682000136.tif37164 13 parts of the salt represented by formula (I-1-a) and 20 parts of chloroform were mixed and incubated at 23°C for 30 The mixture was stirred for 10 minutes. 5.05 parts of the compound represented by formula (I-1-b) was added to the resulting mixture. The mixture was added with 1,000 ml of ethyl acetate and stirred at 50° C. for 2 hours. 5.49 parts of the compound was added, and the mixture was stirred at 50°C for 3 hours, and then cooled to 23°C. To the resulting mixture, 70 parts of chloroform and 25 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred for 23 h. After stirring at ℃ for 30 minutes, the organic layer was separated and extracted. After adding 30 parts of the mixture and stirring at 23°C for 30 minutes, the organic layer was separated and taken out. The organic layer obtained was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether. Add 50 parts of ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 10.12 parts of the salt represented by the formula (I-4) was obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 355.1

[0213] Example 5: Synthesis of salt represented by formula (I-9) TIFF0007659682000137.tif45163 13 parts of the salt represented by formula (I-1-a) and 20 parts of chloroform were mixed and incubated at 23°C for 30 The mixture was stirred for 10 minutes. 5.05 parts of the compound represented by formula (I-1-b) was added to the resulting mixture. The mixture was added with 1,000 ml of ethyl acetate and stirred at 50° C. for 2 hours. The mixture was stirred at 50°C for 3 hours and then cooled to 23°C. To the resulting mixture, 70 parts of chloroform and 25 parts of a 5% aqueous oxalic acid solution were added and the mixture was stirred for 23 h. After stirring at ℃ for 30 minutes, the organic layer was separated and extracted. After adding 30 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 7 times. The obtained organic layer was concentrated, and the concentrated residue was diluted with 10 parts of acetonitrile and Add 90 parts of tert-butyl methyl ether, stir at 23°C for 30 minutes, and then remove the supernatant. The liquid was removed and the filtrate was concentrated to obtain 11.98 parts of the salt represented by formula (I-9). MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 369.0

[0214] Example 6: Synthesis of salt represented by formula (I-203) TIFF0007659682000138.tif29120 25 parts of the compound represented by formula (I-203-a) and 125 parts of acetonitrile are mixed, After stirring at 23° C. for 30 minutes, the mixture was cooled to 5° C. The resulting mixture was added with sodium borohydride. A mixed solution of 1.00 parts of thorium and 15.00 parts of ion-exchanged water was added dropwise over 1 hour, and then The mixture was stirred at 5°C for 2 hours and then concentrated. The concentrated residue was mixed with 400 parts of chloroform and Add 200 parts of ion-exchanged water and stir at 23°C for 30 minutes, then separate the mixture and take out the organic layer. 200 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23°C for 30 minutes. The organic layer was extracted by washing with water. This water washing procedure was repeated five times. The obtained organic layer was concentrated. The concentrated mixture was then passed through a column (Silica gel 60N (spherical, neutral) 100-210 μm; Kanto Chemical ( The mixture was separated using a developing solvent (manufactured by Eppendorf, Inc., n-heptane / ethyl acetate = 1 / 1) to obtain 12.64 parts of the salt represented by the formula (I-203-c) were obtained. TIFF0007659682000139.tif38166 Four parts of the salt represented by formula (I-1-a) and 50 parts of acetonitrile were mixed and incubated at 23° C. for 30 minutes. The mixture was stirred for 1 minute. 1.71 parts of the compound represented by formula (I-1-b) was added to the resulting mixture. The mixture was added and stirred at 50° C. for 2 hours. The mixture was stirred at 50°C for 8 hours and then cooled to 23°C. To the resulting mixture, 150 parts of chloroform and 10 parts of a 5% aqueous solution of oxalic acid were added. After stirring at 23°C for 30 minutes, the organic layer was separated. After adding 50 parts of exchanged water and stirring at 23° C. for 30 minutes, the mixture was separated and the organic layer was taken out. The water washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated residue was diluted with 200 ml of n-heptane. The mixture was stirred at 23°C for 30 minutes, and then filtered to obtain the compound represented by formula (I-203). 3.42 parts of the salt were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 395.2

[0215] Example 7: Synthesis of a salt represented by formula (I-17) TIFF0007659682000140.tif64133 9.13 parts of the salt represented by formula (I-17-a) and 30 parts of chloroform were mixed and heated at 23°C. The mixture was stirred at rt for 30 minutes. Compound 2.49 represented by formula (I-1-c) was added to the resulting mixture. parts of ion-exchanged water was added to the mixture, and the mixture was stirred at 23° C. for 8 hours. The mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. 20 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23°C for 30 minutes. The mixture was then separated to obtain an organic layer. To the obtained organic layer, 30 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was separated and washed with water five times. The organic layer was concentrated. Then, 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether were added to the concentrated residue. After stirring at 23° C. for 30 minutes, the supernatant was removed and the mixture was concentrated to give the compound of formula (I- 7.88 parts of the salt represented by formula 17) were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 517.2

[0216] Example 8: Synthesis of a salt represented by formula (I-205) TIFF0007659682000141.tif70154 9.13 parts of the salt represented by formula (I-17-a) and 30 parts of chloroform were mixed and heated at 23°C. The mixture was stirred at room temperature for 30 minutes. Compound 3 represented by formula (I-203-c) was added to the resulting mixture. 26 parts of ion-exchanged water was added to the mixture, and the mixture was stirred at 23° C. for 8 hours. 0 parts was added, and the mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated and taken out. 20 parts of 5% oxalic acid aqueous solution was added to the layer, stirred at 23°C for 30 minutes, and then the organic layer was separated. To the obtained organic layer, 30 parts of ion-exchanged water was added and stirred at 23° C. for 30 minutes. The organic layer was then separated and washed with water five times. After condensation, the concentrated residue was mixed with 3 parts of acetonitrile and 30 parts of tert-butyl methyl ether. After stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated to give a product of the formula ( 8.22 parts of the salt represented by I-205) were obtained. MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 573.3

[0217] Example 9: Synthesis of salt represented by formula (I-204) TIFF0007659682000142.tif36166 3.87 parts of the salt represented by formula (I-204-a) and 50 parts of acetonitrile were mixed, and 2 The mixture was stirred at 3° C. for 30 minutes. Compound 1 represented by formula (I-1-b) was added to the resulting mixture. 71 parts of toluene was added, and the mixture was stirred at 50° C. for 2 hours. 2.39 parts of the compound represented by 3-c) was added, and the mixture was stirred at 50° C. for 8 hours. The mixture was cooled to 3° C. To the resulting mixture, 150 parts of chloroform and 1 part of a 5% aqueous solution of oxalic acid were added. 0 parts was added, and the mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated and taken out. 50 parts of ion-exchanged water was added to the layer, and the mixture was stirred at 23°C for 30 minutes, and then the organic layer was separated. This water washing procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated residue was diluted with n-heptane. The mixture was stirred at 23° C. for 30 minutes, and then filtered to obtain a product of the formula (I-2 04) 3.35 parts of a salt represented by the formula: MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 425.2

[0218] 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. TIFF0007659682000143.tif39164

[0219] Synthesis Example 1: Synthesis of Resin A1 As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer ( Monomer (a1-1) and monomer (a2-1-1) were used, and the molar ratio of monomer (a1-1) -3): Monomer (a1-2-5): Monomer (a2-1-1): Monomer (a3-1- 1)) was mixed in a ratio of 14:45:2.5:38.5, and 1.5 mass of the total monomers were mixed. A solution was prepared by adding 2 times the amount of propylene glycol monomethyl ether acetate. In addition, azobisisobutyronitrile and azobis(2,4-dimethylvaleronyl) were used as initiators. Tolyl) was added at 1 mol% and 3 mol% based on the total monomer amount, respectively, and these were mixed at 73 The mixture was heated at 5° C. for about 5 hours. The reaction mixture was poured into a large amount of a mixed solvent of methanol and water. The resin was allowed to settle and filtered. The resulting resin was again diluted with propylene glycol monohydrate. The solution obtained by dissolving in methyl ether acetate was poured into a methanol / water mixed solvent. The resin was precipitated with 0.05% NaOH and filtered, and the reprecipitation procedure was repeated twice to obtain a resin with a weight average molecular weight of 7. .9×10 3 Resin A1 was obtained in a yield of 88%. This resin A1 has the following structural units: It is something. TIFF0007659682000144.tif31131

[0220] Synthesis Example 2: Synthesis of Resin X1 Monomer (a4-1-4) was used as the monomer, and the monomer was added in an amount 1.5 times the total amount of monomers. To this solution, azobisisobutyric acid was added as an initiator. Valeronitrile and azobis(2,4-dimethylvaleronitrile) were added to the total monomer amount. These were heated at 75°C for about 5 hours. The reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin. The weight average molecular weight of the product was 1.7×10 4 Resin X1 was obtained in a yield of 77%. has the following structural unit: TIFF0007659682000145.tif3426

[0221] Synthesis Example 3 [Synthesis of Resin A3] 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 An aqueous acid solution was added, and the mixture was stirred for 6 hours, after which the layers were separated. The resin was precipitated by pouring it into a filter and collecting it through filtration, and the weight-average molecular weight was about 5.3×10 3 Resin A3 (copolymer) was obtained in a yield of 78%. This resin A3 has the following structural units: It has. TIFF0007659682000146.tif28126

[0222] <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]

[0223] <Resin> A1, X1: Resin A1, Resin X1 <Salt (I)> I-1: A salt represented by formula (I-1) I-4: A salt represented by formula (I-4) I-9: A salt represented by formula (I-9) I-17: A salt represented by formula (I-17) I-18: A salt represented by formula (I-18) I-127: A salt represented by the formula (I-127) I-203: A salt represented by the formula (I-203) I-204: A salt represented by the formula (I-204) I-205: A salt represented by the formula (I-205) <Acid generator> IX-1: A salt represented by formula (IX-1) (Examples of JP 2007-161707 A) (synthesized according to TIFF0007659682000148.tif2747

[0224] IX-2: A salt represented by the formula (IX-2) (Example of JP 2007-145824 A) (synthesized according to TIFF0007659682000149.tif2752IX-3: A salt represented by formula (IX-3) (Example of JP 2008-074843 A) (synthesized according to TIFF0007659682000150.tif2770<Quencher(C)> D1: (Tokyo Chemical Industry Co., Ltd.) TIFF0007659682000151.tif1831<solvent> Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-Heptanone 20 parts γ-butyrolactone 3.5 parts

[0225] <Production and Evaluation of Resist Patterns> A silicon wafer was coated with an organic anti-reflective coating composition (ARC-29; Nissan Chemical Co., Ltd.). The wafer was then coated with a 78 nm thick film and baked at 205°C for 60 seconds. An organic anti-reflective film was formed. Next, the above resist composition was applied onto the organic anti-reflective film. The silicon was spin-coated so that the film thickness after drying was 160 nm. The wafer is placed on a direct hot plate at the temperature listed in the "PB" column of Table 2 for 60 seconds. The silicon wafer on which the composition layer was formed was subjected to liquid immersion exposure. ArF excimer stepper for light (XT:1900Gi; ASML, NA=1.35, 3 / 4Annular XY polarization, line and space pattern (line and Exposure was performed using a mask to form a space pitch of 180 nm / line of 104 nm. The amount of liquid was changed stepwise during exposure. Ultrapure water was used as the immersion medium. After exposure, post-heat the film on a hot plate for 60 seconds at the temperature specified in the "PEB" column of Table 2. The composition layer on the silicon wafer was then exposed to a developer. Using a 2.38% aqueous solution of tetramethylammonium hydroxide as the solvent, the temperature was adjusted to 60°C at 23°C. A resist pattern was produced by performing puddle development for 2 seconds.

[0226] The resist pattern thus obtained was exposed to an exposure dose that gave a line pattern width of 80 nm. The efficacy sensitivity was calculated.

[0227] <Line Edge Roughness Evaluation (LER)> The obtained resist pattern was observed with a scanning electron microscope to check the amplitude of the unevenness of the wall surface. The amplitude of the measurement is shown in Table 3 as LER (nm). [Table 3] The fluctuation of the unevenness of the sidewall surface of the resist pattern in the compositions 1 to 9 is compared with that in the comparative compositions 1 to 3. The width of the crack was small, and the line edge roughness was evaluated as good.

[0228] <Preparation of resist composition> As shown in Table 4, 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 4]

[0229] <Resin> A3: Resin A3 <Salt (I)> I-1: A salt represented by formula (I-1) I-9: A salt represented by formula (I-9) I-203: A salt represented by the formula (I-203) I-204: A salt represented by the formula (I-204) <Acid generator> IX-1: A salt represented by formula (IX-1) (Examples of JP 2007-161707 A) (synthesized according to TIFF0007659682000154.tif2747

[0230] IX-2: A salt represented by the formula (IX-2) (Example of JP 2007-145824 A) (synthesized according to TIFF0007659682000155.tif2752IX-3: A salt represented by formula (IX-3) (Example of JP 2008-074843 A) (synthesized according to TIFF0007659682000156.tif2770<Quencher(C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF0007659682000157.tif4349<Solvent(E)> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0231] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer is heated on a direct hot plate with hexamethyldisilazane. The silicon wafer was treated at 90° C. for 60 seconds. 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 4 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, the film was post-exposed on a hot plate for 60 seconds at the temperature shown in the "PEB" column of Table 4. 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. The resulting resist pattern (line and space pattern) was observed with a scanning electron microscope. Considering that the line width and space width of a line and space pattern with a pitch of 60 nm are 1: The exposure amount at which the sensitivity became 1 was defined as the effective sensitivity.

[0232] Line Edge Roughness Evaluation (LER): Sidewall of resist pattern produced at effective sensitivity The amplitude of the unevenness of the surface was measured using a scanning electron microscope to obtain the line edge roughness. The results are shown in Table 5. [Table 5] Compared with Comparative Compositions 4 to 6, Compositions 10 to 13 show unevenness of the sidewall surface of the resist pattern. The fluctuation range was small, and the line edge roughness evaluation was good. [Industrial Applicability]

[0233] The salt of the present invention and the resist composition containing the salt have good line edge roughness and are semi-transparent. It is useful for microfabrication of conductors.

Claims

1. A salt represented by formula (I): [In formula (I), Q 1 and Q. 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R 1 and R 2 represents a hydrogen atom. z represents an integer of 0 to 6, and when z is 2 or more, a plurality of R 1 and R 2 may be the same or different from each other. X 1 is *-CO-O-, *-O-CO-, *-O-CO-O- or *-O- (however, * indicates C(R 1 ) (R 2 ) or C(Q 1 ) (Q 2 ) represents the bonding position. L 1 represents a single bond or a saturated hydrocarbon group having 1 to 28 carbon atoms, and the —CH 2 - may be replaced by -O-, -S- or -CO-. A 1 represents a divalent monocyclic alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the —CH ２ - is -O-, -S-, -SO ２ It may be replaced by --or --CO--. R a represents a cyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. a When is an aromatic hydrocarbon group, the aromatic hydrocarbon group has at least one halogen atom. Z + represents an organic cation.

2. X 1 is *-CO-O- or *-O-CO- (where * is C(R 1 ) (R 2 ) or C( Q 1 ) (Q 2 2. The salt according to claim 1, wherein:

3. L 1 is a single bond, an alkanediyl group (provided that the alkanediyl group contains —CH 2 - may be replaced by -O- or -CO-; or a group formed by combining an alkanediyl group with an alicyclic saturated hydrocarbon group (provided that the -CH 2 - may be replaced by -O- or -CO-, and -CH contained in the alicyclic saturated hydrocarbon group 2 - is -O-, -S-, -SO ２ 3. The salt according to claim 1 or 2, wherein:

4. R ａ is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a hydroxy group or a fluorine atom, or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a hydroxy group.

5. An acid generator comprising the salt according to any one of claims 1 to 4.

6. A resist composition comprising the acid generator according to claim 5 and a resin having an acid labile group.

7. 7. The resist composition according to claim 6, wherein the resin having an acid labile group contains at least two kinds of structural units represented by formula (a1-1) and 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 a bond to --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.

8. 8. The resist composition according to claim 6, wherein the resin having an acid labile group further contains a structural unit represented by formula (a2-A). [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.

9. 9. The resist composition according to claim 6, further comprising a salt capable of generating an acid having a weaker acidity than the acid generated from the acid generator.

10. 10. The resist composition according to claim 6, further comprising a resin that includes a structural unit having a fluorine atom.

11. (1) A step of applying a resist composition according to any one of claims 6 to 10 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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