JP2020007299A - Salt, acid generator, resist composition, and method for producing resist pattern - Google Patents

Abstract

To provide a salt capable of producing a resist pattern having a good mask error factor (MEF).SOLUTION: The salt is represented by formula (I) [where Rrepresents a fluorine atom or the like; nn1 represents an integer of 1-5; Rrepresents a C1-8 alkyl group which may have a fluorine atom, or the like; nn2 represents an integer of 0-5; Qand Qeach independently represent a fluorine atom or the like; Lrepresents a C1-24 saturated hydrocarbon group or the like; and Yrepresents a C3-18 alicyclic hydrocarbon group which may have a substituent, or the like].SELECTED DRAWING: None

Description

  The present invention relates to a salt for an acid generator used for fine processing of a semiconductor, an acid generator containing the salt, a resist composition, and a method for producing a resist pattern.

Patent Literature 1 describes a salt represented by the following formula.

JP 2018-43952 A

  The present invention provides a salt capable of producing a resist pattern with a better mask error factor (MEF) than a resist pattern formed from a resist composition containing the above salt.

The present invention includes the following inventions.
[1] A salt represented by the formula (I).
[In the formula (I),
R ¹ represents a fluorine atom or a C 1-6 perfluoroalkyl group.
nn1 represents an integer of 1 to 5, when nn1 is 2 or more, plural ^{R 1} may be the same or different from each other.
R ² represents an alkyl group having 1 to 8 carbon atoms which may have a fluorine atom, and —CH ₂ — contained in the alkyl group may be replaced by —O— or —CO—.
nn2 represents an integer of 0 to 5, when nn2 is 2 or more, plural ^{R 2} may be the same or different from each other.
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ¹ represents a saturated hydrocarbon group having 1 to 24 carbon atoms, —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O— or —CO—, and the saturated hydrocarbon group May be substituted with a fluorine atom or a hydroxy group.
Y ¹ represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and is included in the alicyclic hydrocarbon group. -CH ₂ - is, -O -, - SO ₂ - or -CO- may be replaced with. ]
[2] The salt according to [1], wherein R ¹ is a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms.
[3] The salt of [1] or [2], wherein nn2 is any integer of 1 to 5.
[4] An acid generator containing the salt according to any one of [1] to [3].
[5] A resist composition comprising the acid generator according to [4] and a resin having an acid labile group.
[6] The resist according to [5], wherein the structural unit having an acid labile group includes at least two types of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2). Composition.
[In the formulas (a1-1) and (a1-2),
L ^a1 and L ^a2 independently of one another, -O- or _{* -O- (CH 2) k1 -CO} -O- the stands, k1 represents an integer of 1-7, * the binding of -CO- Represent hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent 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 any integer of 0 to 14.
n1 represents any integer of 0-10.
n1 ′ represents any integer of 0 to 3. ]
[7] The resist composition according to [5] or [6], further comprising a salt that generates an acid having a lower acidity than the acid generated from the acid generator.
[8] The resist composition according to any one of [5] to [7], further comprising a resin containing a structural unit having a fluorine atom.
[9] (1) a step of applying the resist composition according to any one of [5] to [8] on a substrate;
(2) drying the composition after application to form a composition layer;
(3) exposing the composition layer to light,
A method for producing a resist pattern, comprising: (4) a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

  By using the resist composition using the salt of the present invention, a resist pattern can be manufactured with a good mask error factor (MEF).

In the present specification, “(meth) acrylic monomer” refers to a monomer having a structure of “CH ₂ ＣＨCH—CO—” and a monomer having a structure of “CH ₂ ＣC (CH ₃ ) —CO—”. At least one selected from the group consisting of: Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one selected from the group consisting of acrylate and methacrylate” and “at least one selected from the group consisting of acrylic acid and methacrylic acid,” respectively. Means. When a structural unit having “CH ₂ ＣC (CH ₃ ) —CO—” or “CH ₂ ＣＨCH—CO—” is exemplified, a structural unit having both groups is also exemplified. Shall be. In addition, any of the groups described in this specification that can have both a linear structure and a branched structure may be used. The term “combined group” means a group in which two or more of the exemplified groups are bonded, and the valence of these groups may be appropriately changed depending on the bonding form. If stereoisomers are present, they include all stereoisomers.
In the present specification, the “solid content of the resist composition” means the sum of components excluding a solvent (E) described later from the total amount of the resist composition.

<Salt represented by formula (I)>
The present invention relates to a salt represented by the formula (I) (hereinafter sometimes referred to as “salt (I)”).
Of the salt (I), the side having a negative charge may be referred to as “anion (I)” and the side having a positive charge may be referred to as “cation (I)”.
Examples of the perfluoroalkyl group for R ¹ include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, and the like. Is mentioned.
R ¹ is preferably a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, and more preferably a fluorine atom or a trifluoromethyl group.
nn1 is preferably 1, 2 or 5, and more preferably 1 or 5.
When nn1 is 1, the substitution position of R ¹ is preferably para to the iodine atom, and when nn2 is 2, the substitution position of R ¹ is both meta position to the iodine atom. It is preferred that

Examples of the alkyl group having 1 to 8 carbon atoms for R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. No. The carbon number of the alkyl group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.
When —CH ₂ — contained in the alkyl group represented by R ² is replaced by —O— or —CO—, the number of carbon atoms before the replacement is defined as the total number of carbon atoms of the alkyl group. In the alkyl group represented by R ² , the —CH ₂ — contained in the alkyl group is replaced with —O— or —CO—, and the hydroxy group (—CH ₂ — contained in the methyl group is —O— ), A carboxy group (a group in which —CH ₂ —CH ₂ — contained in an ethyl group is replaced by —O—CO—), an alkoxy group having 1 to 5 carbon atoms (a group having 2 to 6 carbon atoms) A group in which —CH ₂ — contained in the alkyl group is replaced by —O—; an alkoxycarbonyl group having 2 to 5 carbon atoms (—CH ₂ —CH ₂ — contained in the alkyl group having 3 to 6 carbon atoms); but groups replaced with -O-CO-), -CH ₂ contained in the alkyl group of the alkyl group (2-6 carbon atoms having 2 to 6 carbon atoms - is replaced by a -CO- group), An alkylcarbonyloxy group having 2 to 5 carbon atoms (an alkyl carbonyloxy group having 3 to 6 carbon atoms) —CH ₂ —CH ₂ — contained in the kill group may be replaced by —CO—O—).
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group and a heptyloxy group.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethlicicarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, and the like.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butoxycarbonyloxy group, and the like.

R ² preferably has an alkyl group having 1 to 3 carbon atoms (-CH _2- contained in the alkyl group may be replaced by -O- or -CO-) or a fluorine atom. It is an alkoxy group having 1 to 7 carbon atoms which may be a methyl group, a methoxy group or a fluorinated alkoxy group having 1 to 7 carbon atoms.
nn2 is preferably 1 or 3.
When nn2 is 1, the substitution position of R ² is preferably para to the iodine atom, and when nn2 is 3, the substitution position of R ² is ortho to para position with respect to the iodine atom. Is preferred.

Examples of the cation (I) include the following cations. Among them, Formulas (Ic-1) to (Ic-4), Formula (Ic-7), Formula (Ic-8), Formula (Ic-11), Formula (Ic-11) The cation represented by (Ic-12) is preferable.

Examples of the perfluoroalkyl group having 1 to 6 carbon atoms for Q ¹ and Q ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, and a perfluorotert-butyl group. , A perfluoropentyl group and a perfluorohexyl group.
Preferably, Q ¹ and Q ² are each independently a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

Examples of the divalent saturated hydrocarbon group for L ¹ include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a group formed by combining two or more of the groups.
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 Linear groups such as tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group Alkanediyl 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, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclooctane-1,5-diyl group; Divalent alicyclic saturated hydrocarbon group;
Polycyclic divalent saturated alicyclic hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group And the like.

-CH ₂ contained in the divalent saturated hydrocarbon group represented by L ¹ - as has been replaced by -O- or -CO- group, for example, the formula (b1-1) ~ formula (b1-3) And a group represented by any of the following: Note that, in the groups represented by the formulas (b1-1) to (b1-3) and the groups represented by the formulas (b1-4) to (b1-11), which are specific examples, * and * * represents the binding site, * represents a bond to -Y ^1.

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

In the groups represented by the formulas (b1-1) to (b1-3), when —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— or —CO—, the carbon before replacement is Let the number be the carbon number of the saturated hydrocarbon group.
Examples of the divalent saturated hydrocarbon group include the same as the divalent saturated hydrocarbon group for L ^b1 .

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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
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, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group; —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—.
Table Examples is replaced by -O- or -CO- group, with group represented by the formula (b1-1) or the formula (b1-3) - -CH ₂ contained in the divalent saturated hydrocarbon group represented by L ¹ Are preferred.

Examples of the group represented by the formula (b1-1) include groups represented by the formulas (b1-4) to (b1-8).
[In the formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In the formula (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group 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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In the 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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In the 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, wherein -CH _2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO-. Is also good.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group .
However, the total number of carbon atoms of L ^b13 ~L ^b15 is 19 or less.
In the formula (b1-8),
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group 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, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group .
However, the total carbon number of L ^{b16 to} L ^b18 is 19 or less. ]
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.
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.
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.

Examples of the group represented by the formula (b1-3) include groups represented by the formulas (b1-9) to (b1-11).
In the formula (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon 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, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Is also good. -CH ₂ contained in the alkylcarbonyloxy group - may be replaced by -O- or -CO-, hydrogen atoms contained in the alkylcarbonyloxy group may be substituted by a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In the formula (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon 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, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Is also good. -CH ₂ contained in the alkylcarbonyloxy group - may be replaced by -O- or -CO-, hydrogen atoms contained in the alkylcarbonyloxy group may be substituted by a hydroxy group.
However, the total carbon number of L ^b21 , L ^b22 and L ^b23 is 21 or less.
In the formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon 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, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Is also good. -CH ₂ contained in the alkylcarbonyloxy group - may be replaced by -O- or -CO-, hydrogen atoms contained in the alkylcarbonyloxy group may be substituted by a hydroxy group.
However, L ^b24, the total number of carbon atoms of L ^b25 and L ^b26 is 21 or less.

  In the groups represented by the formulas (b1-9) to (b1-11), when the hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the number of carbon atoms before the substitution is represented by The number of carbon atoms of the saturated hydrocarbon group.

  Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group, an adamantylcarbonyloxy group, and the like.

Examples of the group represented by the formula (b1-4) include the following.

Examples of the group represented by the formula (b1-5) include the following.

Examples of the group represented by the formula (b1-6) include the following.

Examples of the group represented by the formula (b1-7) include the following.

Examples of the group represented by the formula (b1-8) include the following.

Examples of the group represented by the formula (b1-2) include the following.

Examples of the group represented by the formula (b1-9) include the following.

Examples of the group represented by the formula (b1-10) include the following.

Examples of the group represented by the formula (b1-11) include the following.

Examples of the alicyclic hydrocarbon group represented by Y ¹ include groups represented by formulas (Y1) to (Y11) and formulas (Y36) to (Y38).
When —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y ¹ is replaced by —O—, —S (O) ₂ — or —CO—, the number may be one, or two or more. May be. Examples of such a group include groups represented by Formulas (Y12) to (Y35) and Formulas (Y39) to (Y41). * Represents a bonding position of the ^{L 1.}

The alicyclic hydrocarbon group represented by Y ¹ is preferably a group represented by formulas (Y1) to (Y20), (Y26), (Y27), (Y30), (Y31), or (Y39). ) Or a formula (Y40), more preferably a formula (Y11), a formula (Y15), a formula (Y16), a formula (Y20), a formula (Y26), a formula (Y27), A group represented by the formula (Y30), the formula (Y31), the formula (Y39) or the formula (Y40), more preferably the formula (Y11), the formula (Y15), the formula (Y20), the formula (Y30), It is a group represented by the formula (Y39) or (Y40).
When the alicyclic hydrocarbon group represented by Y ¹ is a spiro ring containing an oxygen atom represented by the formulas (Y28) to (Y35), (Y39) or (Y40), two oxygen atoms The intervening alkanediyl group preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

Examples of the substituent of the methyl group represented by Y ¹ include a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group, and-. (CH ₂ ) _ja —CO—O—R ^b1 group or — (CH ₂ ) _ja —O—CO—R ^b1 group (where R ^b1 is an alkyl group having 1 to 16 carbon atoms, 3 to 16 carbon atoms) Represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof, and ja represents an integer of any of 0 to 4. An alkyl group having 1 to 16 carbon atoms. And —CH ₂ — contained in the alicyclic hydrocarbon group having 3 to 16 carbon atoms may be replaced with —O—, —S (O) ₂ —, or —CO—. .
Examples of the substituent of the alicyclic hydrocarbon group represented by Y ¹ include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, and an alicyclic group having 3 to 16 carbon atoms. Formula hydrocarbon group, C1-C12 alkoxy group, C6-C18 aromatic hydrocarbon group, C7-C21 aralkyl group, C2-C4 alkylcarbonyl group, glycidyloxy group,- (CH ₂ ) _ja —CO—O—R ^b1 group or — (CH ₂ ) _ja —O—CO—R ^b1 group (where R ^b1 is an alkyl group having 1 to 16 carbon atoms, 3 to 16 carbon atoms) Represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof, and ja represents an integer of any of 0 to 4. An alkyl group having 1 to 16 carbon atoms. , and -CH ₂ - contained in the alicyclic hydrocarbon group having 3 to 16 carbon atoms - are _{-O -, - S (O)} 2 -. Or -CO- in may be replaced), and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, and the like.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group. Examples of the aromatic hydrocarbon group having a chain hydrocarbon group include a tolyl group, a xylyl group, and a cumenyl group. , A mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group and the like, and an aromatic group having an alicyclic hydrocarbon group. Examples of the hydrocarbon group include a p-cyclohexylphenyl group and a p-adamantylphenyl group.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, and nonyl. Group, decyl group, undecyl group, dodecyl group and the like.
Examples of the alkyl group substituted with a hydroxy group include a hydroxyalkyl group such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

The Y ^1, include the following.

Y ¹ is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an alicyclic hydrocarbon group substituted with a hydroxy group, further preferably it is also good adamantyl group optionally having a substituent, -CH 2 constituting the alicyclic hydrocarbon group or an adamantyl group _- is -CO -, - S (O) 2 - or -CO- in has been replaced You may. Y ¹ is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by the following, and particularly preferably a hydroxyadamantyl group or an oxoadamantyl group, or a group containing these.

As the anion (I), an anion represented by the formulas (IA-1) to (IA-55) [hereinafter referred to as "anion (IA-1)" according to the formula number There is. Are preferred, and the formulas (IA-1) to (IA-4), the formula (IA-9), the formula (IA-10), the formulas (IA-24) to the formula (IA-24) (IA-33), Formulas (IA-36) to (IA-40), and Formulas (IA-47) to (IA-55). Anions are more preferred.

Here, R ^{i2 to} R ⁱ⁷ each independently represent, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is formed, for example, by a chain hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a combination thereof. And more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. ^LA41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.
Q ^b1 and Q ^b2 represent the same meaning as described above.
Specific examples of the sulfonic acid anion in the salt represented by the formula (B1) include anions described in JP-A-2010-204646.

Preferred examples of the anion (I) include anions represented by the formulas (Ia-1) to (Ia-34).

  Among them, the formulas (Ia-1) to (Ia-3) and the formulas (Ia-7) to (Ia-19) and the formulas (Ia-22) to (Ia-22) Ia-34) is preferred.

Specific examples of the salt (I) include salts obtained by arbitrarily combining the above cation and anion. Specific examples of the salt (I) are shown in the following table.
In the following table, each symbol represents the symbol attached to the structure representing the above-described anion or cation. For example, the salt (I-1) is a salt composed of an anion represented by the formula (Ia-1) and a cation represented by the formula (Ic-1), and is a salt shown below.

  Among them, the salt (I) is a salt (I-1) to a salt (I-6), a salt (I-13) to a salt (I-17), a salt (I-30) to a salt (I-35), Salt (I-42) to salt (I-46), salt (I-59) to salt (I-64), salt (I-71) to salt (I-75), salt (I-88) to salt (I-93), salt (I-100) to salt (I-104), salt (I-117) to salt (I-122), salt (I-129) to salt (I-133), salt ( I-146) to salt (I-151), salt (I-158) to salt (I-162), salt (I-175) to salt (I-180), salt (I-187) to salt (I -191), salt (I-204) to salt (I-209), salt (I-216) to salt (I-220), salt (I-233) to salt (I-238), salt (I- 245) to salt (I-249), salt (I-262) to salt (I-26) ), Salts (I-274) to salt (I-278), salts (I-291) to salt (I-296), salts (I-303) to salt (I-307), and salts (I-320). Salt (I-325), salt (I-332) to salt (I-336), salt (I-349) to salt (I-354), salt (I-361) to salt (I-365), Salts (I-378) to (I-383) and salts (I-390) to (I-394) are preferred.

<Method for producing salt (I)>
The salt (I) can be produced by reacting a salt represented by the formula (Ia) with a salt represented by the formula (Ib) in a solvent.
(In the formula, all symbols represent the same meaning as described above.)
Examples of the solvent in this reaction include chloroform, acetonitrile, ion-exchanged water and the like.
The reaction temperature is usually 0 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

Examples of the salt represented by the formula (Ia) include a salt represented by the following formula, which can be easily obtained from the market. In addition, it can be easily manufactured by a known method.
Examples of the salt represented by the formula (Ib) include a salt represented by the following formula. These salts can be obtained by a method similar to the method described in JP-A-2011-116747.

<Acid generator>
The acid generator of the present invention is an acid generator containing the salt (I). One kind of the salt (I) may be contained, or two or more kinds of the salt (I) may be contained.
The acid generator of the present invention may contain, in addition to the salt (I), an acid generator known in the field of resist (hereinafter sometimes referred to as “acid generator (B)”). The acid generator (B) may be used alone or in combination of two or more.

  The acid generator (B) may be either nonionic or ionic. Examples of the nonionic acid generator include sulfonate esters (eg, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg, disulfone, Ketosulfone, sulfonyldiazomethane) and the like. Representative examples of the ionic acid generator include onium salts containing onium cations (eg, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of the anion of the onium salt include a sulfonic acid anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, and 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. 3,914,407, European Patent No. 126,712, etc. The compounds capable of generating an acid by the radiation described in (1) can be used. Further, a compound produced by a known method may be used. The acid generator (B) may be used in combination of two or more.

The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”).
[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O— or —CO—; A hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and-is included in the alicyclic hydrocarbon group. CH ₂ — may be replaced by —O—, —S (O) ₂ — or —CO—.
Z1 ⁺ represents an organic cation. ]
Q ^b1 , Q ^b2 , L ^b1 and Y in the formula (B1) are the same as Q ¹ , Q ² , L ¹ and Y ^{1 in the} above formula (I), respectively.

The anion in the acid generator (B1) is preferably the same as the anion (I) in the salt (I), and the anions represented by the formulas (B1a-1) to (B1a-34) are preferable. .

  Among them, the formulas (B1a-1) to (B1a-3) and the formulas (B1a-7) to (B1a-16), the formula (B1a-18), the formula (B1a-19), and the formula (B1a-22) ) To (B1a-34).

Examples of the organic cation of Z1 ⁺ include an organic onium cation, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. Among these, an organic sulfonium cation and an organic iodonium cation are preferable, and an aryl sulfonium cation is more preferable. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) (hereinafter, may be referred to as “cation (b2-1)” or the like depending on the formula number). No.

In the formulas (b2-1) to (b2-4),
R ^{b4 to} R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms; The hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group which may be substituted is a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b4 and R ^b5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring is -O-, -S- or It may be replaced by -CO-.
R ^b7 and R ^b8 each independently represent a hydroxy group, 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, a plurality of R ^b7 may be the same or different, and when n2 is 2 or more, a plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring is -O-, -S- or It may be replaced by -CO-.
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the aliphatic hydrocarbon. May be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or a carbon atom having 1 to 12 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may be bonded to each other to form a ring including —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring includes —O— and —S -Or -CO-.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, 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 any integer of 0 to 5.
q2 and r2 each independently represent an integer from 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13 are the same or different. When p2 is 2 or more, a plurality of R ^b14 are the same or different. When q2 is 2 or more, a plurality of R ^b15 are the same or different. , When r2 is 2 or more, a plurality of R ^b16 are the same or different; when s2 is 2 or more, a plurality of R ^b17 are the same or different; when t2 is 2 or more, a plurality of R ^b18 are the same or different. different.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and an alkyl group of a 2-ethylhexyl group. No. In particular, the aliphatic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, Cycloalkyl groups such as a heptyl group, a cyclooctyl group and a cyclodecyl group are exemplified. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.
In particular, the alicyclic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

  Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, and a 2-ethyladamantan-2-yl group. , 2-isopropyladamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which a hydrogen atom has been substituted with an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group. The aromatic hydrocarbon group having a chain hydrocarbon group (tolyl group, xylyl group, cumenyl group, mesityl group) Group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and an aromatic hydrocarbon group having an alicyclic hydrocarbon group ( p-cyclohexylphenyl group, p-adamantylphenyl group, etc.). In addition, when an aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, it has a C1-C18 chain hydrocarbon group and a C3-C18 alicyclic hydrocarbon group. Is preferred.
Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the aliphatic hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, and naphthylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, a pentylcarbonyloxy group Hexylcarbonyloxy group, octylcarbonyloxy group and 2-ethylhexylcarbonyloxy group.

The ring formed by R ^b4 and R ^b5 together with the sulfur atom to which they are bonded may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated. May be a ring of The ring includes a ring having 3 to 18 carbon atoms, and is preferably a ring 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, for example, the following rings. * Represents a binding site.

The ring formed by R ^b9 and R ^b10 together may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated ring. The ring may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothiophenium ring), a thiane-1-ium ring, a 1,4-oxathian-4-ium ring and the like can be mentioned.
The ring formed by R ^b11 and R ^b12 together may be any of a monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated ring. The ring may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring, oxonorbornane ring, oxoadamantane ring and the like.

Among the cations (b2-1) to cations (b2-4), the cation (b2-1) is preferable.
Examples of the cation (b2-1) include the following cations.

Examples of the cation (b2-2) include the following cations.

Examples of the cation (b2-3) include the following cations.

Examples of the cation (b2-4) include the following cations.

  The acid generator (B) is a combination of the above-mentioned sulfonic acid anion and the above-mentioned organic cation, and these can be arbitrarily combined. As the acid generator (B), preferably, the formulas (B1a-1) to (B1a-3), the formulas (B1a-7) to (B1a-16), the formulas (B1a-18), and the formulas (B1a-) 19), and a combination of an anion represented by any one of formulas (B1a-22) to (B1a-34) with a cation (b2-1) or a cation (b2-3).

As the acid generator (B), those represented by the formulas (B1-1) to (B1-48) are preferable. Among them, those containing an arylsulfonium cation are preferable, and the formula (B1-1) To (B1-3), (B1-5) to (B1-7), (B1-11) to (B1-14), (B1-20) to (B1-26), Those represented by the formulas (B1-29) and (B1-31) to (B1-48) are particularly preferable.

  When the salt (I) and the acid generator (B) are contained as the acid generator, the ratio of the content of the salt (I) to the acid generator (B) (mass ratio; salt (I): acid generator ( B)) is usually from 1:99 to 99: 1, preferably from 2:98 to 98: 2, more preferably from 5:95 to 95: 5, still more preferably from 10:90 to 90:90. : 10, particularly preferably 15:85 to 85:15.

<Resist composition>
The resist composition of the present invention contains an acid generator containing a salt (I) and a resin having an acid labile group (hereinafter sometimes referred to as “resin (A)”). Here, the term “acid-labile group” refers to a group having a leaving group, the leaving group being eliminated by contact with an acid, and the structural unit having a hydrophilic group (for example, a hydroxy group or a carboxy group). It means a group to be converted into a unit.
The resist composition of the present invention preferably contains a quencher such as a salt that generates an acid having a lower acidity than the acid generated from the acid generator (hereinafter sometimes referred to as “quencher (C)”). And a solvent (hereinafter sometimes referred to as “solvent (E)”).

<Acid generator>
In the resist composition of the present invention, the content of the acid generator is preferably from 1 part by mass to 40 parts by mass, more preferably from 3 parts by mass to 35 parts by mass, per 100 parts by mass of the resin (A) described below. Or less, more preferably 10 to 35 parts by mass.

<Resin (A)>
The resin (A) has a structural unit having an acid labile group (hereinafter, may be referred to as “structural unit (a1)”). The resin (A) preferably further contains a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include a structural unit having no acid labile group (hereinafter, may be referred to as a “structural unit (s)”), a structural unit (a1), and a structural unit other than the structural unit (s). A structural unit (for example, a structural unit having a halogen atom described below (hereinafter sometimes referred to as a “structural unit (a4)”), and a structural unit having a non-eliminable hydrocarbon group described below (hereinafter referred to as a “structural unit (a5)”) And other structural units derived from monomers known in the art.

<Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”).
The acid labile group contained in the resin (A) includes a group represented by the formula (1) (hereinafter, also referred to as a group (1)) and / or a group represented by the formula (2) (hereinafter, a group (2) ) Is also preferred.
[In the formula (1), R ^a1 , R ^a2 and R ^a3 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group obtained by combining these. R ^a1 and R ^a2 are bonded to each other to form an alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
ma and na each independently represent 0 or 1, and at least one of ma and na represents 1.
* Represents a binding site. ]
[In formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a heterocyclic group having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and are included in the hydrocarbon group and the heterocyclic group; CH ₂ - may be replaced by -O- or -S-.
X represents an oxygen atom or a sulfur atom.
na ′ represents 0 or 1.
* Represents a binding site. ]

The alkyl group in which R ^a1, R ^a2 and a R ^a3, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group.
The alicyclic hydrocarbon group for R ^a1 , R ^a2 and R ^a3 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bonding site). R ^a1, the number of carbon atoms in the alicyclic hydrocarbon group R ^a2 and R ^a3 is preferably 3 to 16.
Examples of a group obtained by combining an alkyl group and an alicyclic hydrocarbon group include, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, and a norbornyl group. And an ethyl group.
Preferably, ma is 0 and na is 1.
When R ^a1 and R ^a2 are bonded to each other to form a non-aromatic hydrocarbon ring, examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) include the following rings. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * Represents a binding site to -O-.

Examples of the hydrocarbon group for R ^{a1 ′} , R ^{a2 ′} and R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these.
Examples of the alkyl group and the alicyclic hydrocarbon group include the same groups as those described for R ^a1 , R ^a2 and R ^a3 .
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group.
Examples of the combined group include a group obtained by combining the above-described alkyl group and an alicyclic hydrocarbon group (for example, a cycloalkylalkyl group), an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (p-methyl). Phenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic hydrocarbon group Aromatic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.) and aryl-cycloalkyl groups such as phenylcyclohexyl group.
When R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a heterocyclic ring together with the carbon atom and X to which they are bonded, —C (R ^{a1 ′} ) (R ^{a3 ′} ) —X—R ^{a2 ′} includes the following: Ring. * Represents a binding site.
Preferably, at least one of R ^{a1 ′} and R ^{a2 ′} is a hydrogen atom.
na ′ is preferably 0.

The group (1) includes the following groups.
In the formula (1), R ^a1 , R ^a2 and R ^a3 are alkyl groups, ma = 0 and na = 1. As the group, a tert-butoxycarbonyl group is preferable.
In the formula (1), R ^a1 and R ^a2 together with the carbon atom to which they are attached form an adamantyl group, R ^a3 is an alkyl group, ma = 0 and na = 1. .
In the formula (1), a group wherein R ^a1 and R ^a2 are each independently an alkyl group, R ^a3 is an adamantyl group, ma = 0, and na = 1.
Specific examples of the group (1) include the following groups. * Represents a binding site.

Specific examples of the group (2) include the following groups. * Represents a binding site.

  The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond, more preferably a (meth) acrylic monomer having an acid labile group.

  Among the (meth) acrylic monomers having an acid labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferable. When a resin (A) having a structural unit derived from a monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used for a resist composition, the resolution of a resist pattern can be improved.

As a structural unit derived from the (meth) acrylic monomer having the group (1), a structural unit represented by the formula (a1-0) (hereinafter, sometimes referred to as a structural unit (a1-0)), a formula ( a1-1) (hereinafter may be referred to as a structural unit (a1-1)) or a structural unit represented by the formula (a1-2) (hereinafter referred to as a structural unit (a1-2)). In some cases). Preferably, it is at least one structural unit selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2). These may be used alone or in combination of two or more.
[In the formulas (a1-0), (a1-1) and (a1-2),
L ^a01, L ^a1 and L ^a2 each independently, -O- or _{* -O- (CH 2) k1 -CO} -O- the stands, k1 represents an integer of 1-7, and * Represents a binding site to —CO—.
R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 each independently ^represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining these.
m1 represents any integer of 0 to 14.
n1 represents any integer of 0-10.
n1 'represents any integer of 0-3. ]

R ^a01 , R ^a4 and R ^a5 are preferably a methyl group.
L ^a01 , L ^a1 and L ^a2 are preferably an oxygen atom or * -O- (CH ₂ ) _k01 -CO-O- (however, k01 is preferably an integer of 1 to 4, more preferably Is 1.), more preferably an oxygen atom.
Examples of the alkyl group, alicyclic hydrocarbon group, and a combination thereof in R ^a02 , R ^a03 , R ^a04 , R ^a6, and R ^a7 include the groups listed in R ^a1 , R ^a2, and R ^a3 in Formula (1). And the same groups as mentioned above.
The alkyl group in R ^a02, R ^a03, and R ^a04 is preferably 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, more preferably a methyl group.
The alkyl group for R ^a6 and R ^a7 preferably has 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and still more preferably an ethyl group or an isopropyl group.
^{R a02, R a03, R a04} , the number of carbon atoms in the alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably 5 to 12, more preferably from 5 to 10.
The group obtained by combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less obtained by combining the alkyl group and the alicyclic hydrocarbon group.
^Ra02 and ^Ra03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group.
^Ra04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
R ^a6 and R ^a7 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and further preferably an ethyl group or an isopropyl group.
m1 is preferably an integer of any of 0 to 3, and more preferably 0 or 1.
n1 is preferably an integer of any of 0 to 3, and more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

The structural unit (a1-0), for example, the R ^a01 in equation (a1-0-1) structural units and structural units represented by any one of the - formula (a1-0-12) (a1-0) Examples include a structural unit in which a corresponding methyl group is replaced by a hydrogen atom, and a structural unit represented by any of formulas (a1-0-1) to (a1-0-10) is preferable.

Examples of the structural unit (a1-1) include a structural unit derived from a monomer described in JP-A-2010-204646. Above all, a methyl group corresponding to R ^a4 in the structural unit represented by any of the formulas (a1-1-1) to (a1-1-4) and the structural unit (a1-1) was replaced with a hydrogen atom. Structural units are preferable, and structural units represented by any of formulas (a1-1-1) to (a1-1-4) are more preferable.

The structural unit (a1-2) corresponds to the structural unit represented by any of the formulas (a1-2-1) to (a1-2-6) and R ^a5 in the structural unit (a1-2). Examples include a structural unit in which a methyl group is replaced by a hydrogen atom, and a structural unit represented by Formula (a1-2-2), Formula (a1-2-5), or Formula (a1-2-6) is preferable.

When the resin (A) contains the structural unit (a1-0), its content is usually 1 to 60 mol%, preferably 3 to 50 mol%, based on all structural units of the resin (A). And more preferably 5 to 40 mol%.
When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is based on all structural units of the resin (A).
Usually, it is 10 to 95 mol%, preferably 15 to 90 mol%, more preferably 15 to 85 mol%, further preferably 20 to 75 mol%, and still more preferably 20 to 70 mol%. It is.

Examples of the structural unit having the group (2) in the structural unit (a1) include a structural unit represented by the formula (a1-4) (hereinafter, may be referred to as “structural unit (a1-4)”). .
[In the formula (a1-4),
^Ra32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 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, acryloyl. Represents an oxy group or a methacryloyloxy group.
la represents any integer of 0-4. When la is 2 or more, a plurality of ^Ra33 may be the same or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 may represent a hydrocarbon group having 1 to 20 carbon atoms, R ^a35 and R ^a36 are bonded to each other to with -C-O-which they are attached to form a divalent hydrocarbon group having 2 to 20 carbon atoms, -CH ₂ contained in the hydrocarbon group of the hydrocarbon group and the divalent - is - It may be replaced by O- or -S-. ]

^Examples of the alkyl group for ^Ra32 and ^Ra33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
Examples of the halogen atom for R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, , 2,2-tetrafluoroethyl, ethyl, perfluoropropyl, 2,2,3,3,3-pentafluoropropyl, propyl, perfluorobutyl, 1,1,2,2,3,3 , 4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, perfluorohexyl, etc. Is mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further preferable.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like.
As the hydrocarbon group for R ^a34, R ^a35 and R ^a36, an alkyl group, an alicyclic hydrocarbon group, aromatic hydrocarbon groups, and groups formed by combining these.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bonding site).
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group.
Examples of the combined group include a group obtained by combining the above-described alkyl group and alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert- An aromatic hydrocarbon group having a butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, or an alicyclic hydrocarbon group ( aryl-cyclohexyl groups such as p-cyclohexylphenyl group, p-adamantylphenyl group) and phenylcyclohexyl group. In particular, R ^a36 is an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. Is mentioned.

In the formula (a1-4), R ^a32 is preferably a hydrogen atom.
As ^Ra33 , an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is further preferable.
As la, 0 or 1 is preferable, and 0 is more preferable.
^Ra34 is preferably a hydrogen atom.
^Ra35 is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, and more preferably a methyl group or an ethyl group.
The hydrocarbon group of ^Ra36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. It is a group formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group for R ^a36 are preferably unsubstituted. Aromatic hydrocarbon group for R ^a36 is an aromatic ring preferably has an aryloxy group having 6 to 10 carbon atoms.

^{-OC (R a34) (R a35} ) -O-R a36 in the structural unit (a1-4) is desorbed by contact with an acid (e.g. p- toluenesulfonic acid) to form a hydroxy group.

Examples of the structural unit (a1-4) include a structural unit derived from a monomer described in JP-A-2010-204646. Preferably, hydrogen atom corresponding to R ^a32 in equation (a1-4-1) represented respectively to Formula (a1-4-12) structural units and structural units (a1-4) is replaced by a methyl group structure Units, and more preferably, structural units represented by formulas (a1-4-1) to (a1-4-5) and (a1-4-10).

  When the resin (A) contains the structural unit (a1-4), its content is preferably from 10 to 95 mol%, preferably from 15 to 90 mol%, based on the total of all the structural units of the resin (A). Mol%, more preferably 20 to 85 mol%, still more preferably 20 to 70 mol%, and particularly preferably 20 to 60 mol%.

Examples of the structural unit derived from the (meth) acrylic monomer having the group (2) include a structural unit represented by the formula (a1-5) (hereinafter, also referred to as “structural unit (a1-5)”). Can be
In the formula (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or _{* - (CH 2) h3 -CO} -L 54 - represents, h3 represents an integer of 1 to 4, * represents a binding site with L ^51.
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent —O— or —S—.
s1 represents an integer of any of 1 to 3.
s1 ′ represents an integer from 0 to 3.

Examples of the halogen atom include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoro group. And a methyl group.
In the formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
Of L ⁵² and L ^53, one of -O-, and is preferably other is -S-.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 represents a single bond or * -CH ₂ -CO-O- are preferable.

Examples of the structural unit (a1-5) include a structural unit derived from a monomer described in JP-A-2010-61117. Among them, the structural units represented by the formulas (a1-5-1) to (a1-5-4) are preferable, and represented by the formula (a1-5-1) or the formula (a1-5-2). Structural units are more preferred.

  When the resin (A) contains the structural unit (a1-5), its content is preferably from 1 to 50 mol%, more preferably from 3 to 45 mol%, based on all structural units of the resin (A). , 5 to 40 mol% is still more preferable, and 5 to 30 mol% is still more preferable.

The structural unit (a1) also includes the following structural units.

  When the resin (A) contains the above structural units such as (a1-3-1) to (a1-3-7), the content is 10 to 10% of the total structural units of the resin (A). 95 mol% is preferable, 15 to 90 mol% is more preferable, 20 to 85 mol% is further preferable, 20 to 70 mol% is further more preferable, and 20 to 60 mol% is particularly preferable.

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “monomer (s)”). As the monomer for deriving the structural unit (s), a monomer having no acid labile group known in the resist field can be used.
The structural unit (s) preferably has a hydroxy group or a lactone ring. Structure having a hydroxy group and not having an acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or having a lactone ring and having no acid labile group Use of a resin having units (hereinafter sometimes referred to as “structural unit (a3)”) in the resist composition of the present invention can improve the resolution of a resist pattern and the adhesion to a substrate.

<Structural unit (a2)>
The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When manufacturing a resist pattern from the resist composition of the present invention, when using a high energy ray such as a KrF excimer laser (248 nm), an electron beam or EUV (ultra-ultraviolet light) as an exposure light source, the structural unit (a2) is used. It is preferable to use a structural unit (a2) having a phenolic hydroxy group. When an ArF excimer laser (193 nm) or the like is used, a structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2), and a structural unit (a2-1) or a structural unit (a2) described later. -A) is more preferably used. As the structural unit (a2), one type may be included alone, or two or more types may be included.

Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-A) (hereinafter, may be referred to as “structural unit (a2-A)”).
[In the formula (a2-A),
^Ra50 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, acryloyl. Represents an oxy group or a methacryloyloxy group.
A ^a50 represents a single bond or ^{* -X a51 - (A a52 -X} a52) nb - represents, * represents a binding site to the carbon atom to which -R ^a50 binds.
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent -O-, ^-CO -O-, or -O-CO-.
nb represents 0 or 1.
mb represents any integer of 0-4. When mb is any integer of 2 or more, a plurality of R ^a51 may be the same or different. ]

^Examples of the halogen atom for ^Ra50 include a fluorine atom, a chlorine atom and a bromine atom.
^Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom at R ^a50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 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, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl and perfluoro A hexyl group.
^Ra50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.
^Examples of the alkyl group for ^Ra51 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
^Examples of the alkoxy group for ^Ra51 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy 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 is even more preferred.
^Examples of the alkylcarbonyl group for R ^a51 include an acetyl group, a propionyl group, and a butyryl group.
^Examples of the alkylcarbonyloxy group for ^Ra51 include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
^Ra51 is preferably a methyl group.

^{* -X a51 - (A a52 -X} a52) nb - The, * - O -, * - CO-O -, * - O-CO -, * - CO-O-A a52 -CO-O-, * -O-CO- ^Aa52 -O-, * ^-OAa52 -CO-O-, * -CO- ^OAa52 -O- ^CO- , * -O-CO- ^Aa52- O-CO -. Especially, * -CO-O-, * -CO- ^OAa52- CO-O- or * ^-OAa52- CO-O- is preferable.

Examples of the alkanediyl group include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, and 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 and the like.
A ^a52 is preferably a methylene group or an ethylene group.

A ^a50 is preferably a single bond, * -CO-O- or * -CO-O-A ^a52 -CO-O-, and a single bond, * -CO-O- or * -CO-O-CH It is more preferably _2- CO-O-, even more preferably a single bond or * -CO-O-.

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 bonded to the para position.

  Examples of the structural unit (a2-A) include structural units derived from monomers described in JP-A-2010-204634 and JP-A-2012-12577.

Examples of the structural unit (a2-A) include structural units represented by Formulas (a2-2-1) to (a2-2-6) and Formulas (a2-2-1) to (a2-2-2-). ^Examples of the structural unit represented by 6) include a structural unit in which a methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom. The structural unit (a2-A) is a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-3), or a structural unit represented by the formula (a2-2-6). Structural unit represented by the formula (a2-2-1), structural unit represented by the formula (a2-2-3) or structural unit represented by the formula (a2-2-6): It is preferable that the methyl unit corresponding to R ^a50 in the structural unit (a2-A) is a structural unit in which a hydrogen atom is replaced.

When the resin (A) contains the structural unit (a2-A), the content of the structural unit (a2-A) is preferably from 5 to 80 mol%, more preferably from all structural units. It is 10 to 70 mol%, further preferably 15 to 65 mol%, and still more preferably 20 to 65 mol%.
The structural unit (a2-A) can be included in the resin (A) by, for example, polymerizing using the structural unit (a1-4) and then treating with an acid such as p-toluenesulfonic acid. After polymerization using acetoxystyrene or the like, the resin (A) can be made to contain the structural unit (a2-A) by treating with an alkali such as tetramethylammonium hydroxide.

Examples of the structural unit having an alcoholic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).
In the formula (a2-1),
L ^a3 is, -O- or _{* -O- (CH 2) k2 -CO} -O- the stands,
k2 represents any integer of 1 to 7. * Represents a binding site to -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents any integer of 0-10.

Formula (a2-1), L ^a3 is preferably, -O -, - O- (CH 2) f1 -CO-O- and is (wherein f1 represents an integer of 1 to 4) And more preferably -O-.
R ^a14 is preferably a methyl group.
^Ra15 is preferably a hydrogen atom.
^Ra16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of any of 0 to 3, more preferably 0 or 1.

Examples of the structural unit (a2-1) include a structural unit derived from a monomer described in JP-A-2010-204646. Structural units represented by any of formulas (a2-1-1) to (a2-1-6) are preferable, and structural units represented by formulas (a2-1-1) to (a2-1-4) are preferable. The structural unit represented by the formula (a2-1-1) or the formula (a2-1-3) is more preferable.

  When the resin (A) contains the structural unit (a2-1), its content is usually from 1 to 45 mol%, preferably from 1 to 40 mol%, based on all the structural units of the resin (A). Yes, more preferably 1 to 35 mol%, still more preferably 1 to 20 mol%, and still more preferably 1 to 10 mol%.

<Structural unit (a3)>
The lactone ring of the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. May be. Preferably, a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) is exemplified.

The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3) or the formula (a3-4). One of these may be contained alone, or two or more thereof may be contained.
[In the formula (a3-1), the formula (a3-2), the formula (a3-3) and the formula (a3-4),
L ^a4, L ^a5 and L ^a6 each independently, -O- or _{* -O- (CH 2) k3 -CO} -O- (k3 represents. An integer of 1-7) is represented by Represents a group.
L ^a7 is, -O -, * - O- L a8 -O -, * - O-L a8 -CO-O -, * - O-L a8 -CO-O-L a9 -CO-O- or * Represents -O- ^La8- O-CO- ^La9- O-.
^La8 and ^La9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bonding site with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represent a hydrogen atom or a methyl group.
R ^a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
X ^a3 represents —CH ₂ — or an oxygen atom.
^Ra21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents an integer of any of 0 to 5.
q1 represents any integer of 0 to 3.
r1 represents any integer of 0 to 3.
w1 represents an integer of any of 0 to 8.
When p1, q1, r1 and / or w1 are 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same or different. ]

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group. Can be
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
^Examples of the alkyl group for ^Ra24 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. And more preferably a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom at ^Ra24 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluoropentyl group. Examples include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.
The alkanediyl group in ^La8 and ^La9 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 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, Examples include a 4-diyl group and a 2-methylbutane-1,4-diyl group.

Formula (a3-1) ~ formula ^{(a3-3), L a4, L} a5 and L ^a6 are each independently preferably -O- _{or, * - O- (CH 2)} k3 -CO-O- in, k3 groups is any integer of 1 to 4, more preferably -O- _{and, * - O-CH 2 -CO} -O-, more preferably an oxygen atom.
R ^a18 , R ^a19 , R ^a20 and R ^a21 are preferably a methyl group.
^Ra22 and ^Ra23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of any of 0 to 2, and more preferably 0 or 1.

In the formula (a3-4), R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group. It is.
^Ra25 is preferably a carboxy group, a cyano group or a methyl group.
L ^a7 is preferably -O- or * -O-L ^a8 -CO-O-, more preferably an _{-O -, - O-CH 2} -CO-O- or _-O-C 2 _{H 4} - CO-O-.
w1 is preferably an integer of 0 to 2, more preferably 0 or 1.
Particularly, the formula (a3-4) is preferably the formula (a3-4) ′.
(In the formula, R ^a24 and L ^a7 represent the same meaning as described above.)

Examples of the structural unit (a3) include a monomer described in JP-A-2010-204646, a monomer described in JP-A-2000-122294, and a structure derived from a monomer described in JP-A-2012-41274. Units. As the structural unit (a3), the formula (a3-1-1), the formula (a3-1-2), the formula (a3-2-1), the formula (a3-2-2), the formula (a3-3-3) 1), a structural unit represented by any one of formulas (a3-3-2) and formulas (a3-4-1) to (a3-4-12), and the structural unit represented by the formula (a3-1) ) To (a3-4), a structural unit in which a methyl group corresponding to R ^a18 , R ^a19 , R ^a20 and R ^a24 is replaced by a hydrogen atom is preferable.

When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). , More preferably 10 to 60 mol%.
Further, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the content of the structural unit (a3-4) is respectively based on the total structural units of the resin (A). Therefore, 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is further preferable.

<Structural unit (a4)>
Examples of the structural unit (a4) include the following structural units.
[In the formula (a4),
R ⁴¹ represents a hydrogen atom or a methyl group.
R ⁴² represents a saturated hydrocarbon group having a halogen atom having 1 to 24 carbon atoms, -CH ₂ contained in the saturated hydrocarbon group - may be replaced by -O- or -CO. ]
Examples of the saturated hydrocarbon group represented by R ⁴² include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.

Examples of the chain-type saturated hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Is mentioned.
As the monocyclic or polycyclic alicyclic saturated hydrocarbon group, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group and the following And a polycyclic alicyclic saturated hydrocarbon group such as a group (* represents a bonding site).
Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic saturated hydrocarbon groups, and include a -alkanediyl group. -Alicyclic saturated hydrocarbon group,-alicyclic saturated hydrocarbon group-alkyl group,-alkanediyl group-alicyclic saturated hydrocarbon group-alkyl group, and the like.

Examples of the structural unit (a4) include a structural unit represented by the formula (a4-0), a structural unit represented by the formula (a4-1), and a structural unit represented by the formula (a4-4). .
[In the formula (a4-0),
R ⁵⁴ represents a hydrogen atom or a methyl group.
L ^4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^3a represents a perfluoroalkyl cycloalkanediyl group perfluoro alkanediyl group or 3 to 12 carbon atoms having 1 to 8 carbon atoms.
R ⁶⁴ represents a hydrogen atom or a fluorine atom. ]

^Examples of the alkanediyl group for L ^4a include a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, an ethane-1,1-diyl group, And branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group. Can be

The perfluoroalkanediyl group for L ^3a includes a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a 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, perfluorohep 2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluoro An octane-3,3-diyl group, a perfluorooctane-4,4-diyl group and the like can be mentioned.
^Examples of the perfluorocycloalkanediyl group in L ^3a include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

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

The structural unit (a4-0), a methyl group corresponding to R ⁵⁴ may be mentioned a structural unit replacing a hydrogen atom in the structural units in the structural units and the following structural units shown below (a4-0).

[In the formula (a4-1),
^Ra41 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, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— or —CO—. You may.
A ^a41 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1). However, at least one of A ^a41 and R ^a42 has a halogen atom (preferably a fluorine atom) as a substituent.
[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a single bond or a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
X ^a41 and X ^a42 each independently represent -O-, -CO-, ^-CO -O-, or -O-CO-.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* Is a binding site, and * on the right side is a binding site to -O-CO- ^Ra42 . ]

^Examples of the saturated hydrocarbon group for ^Ra42 include a chain saturated hydrocarbon group, a monocyclic or polycyclic saturated alicyclic hydrocarbon group, and a group formed by combining these.

Examples of the chain-type saturated hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. And the like.
Examples of the monocyclic or polycyclic saturated alicyclic hydrocarbon group include cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloalkyl group such as cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group and the following. And a polycyclic alicyclic hydrocarbon group such as a group (* represents a bond).
Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more saturated alicyclic hydrocarbon groups, and a -alkanediyl group -Saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkyl group, -alkanediyl group-saturated alicyclic hydrocarbon group-alkyl group, and the like.

^Examples of the substituent that ^Ra42 may have include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, * ^-O -CO- or * -CO-O- (* represents a binding site to ^Ra42 ).
A ^a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
* Represents a binding site. ]
However, in R ^a42 -X ^a43 -A ^a45, when R ^a42 has no halogen atom, A ^a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms and having at least one halogen atom.

^Examples of the saturated hydrocarbon group for A ^a45 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. An alkyl group such as a group; a monocyclic alicyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups ( * Represents a bond.) And a polycyclic alicyclic hydrocarbon group.
Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups. Alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, and the like.

R ^a42 is preferably a saturated hydrocarbon group ^optionally having a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by the formula (a-g3).
When R ^a42 is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and further preferably a carbon number of 1 to 1. And is particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When ^Ra42 is a saturated hydrocarbon group having a group represented by the formula (a-g3), the total carbon number of ^Ra42 including the number of carbon atoms contained in the group represented by the formula (a-g3) The number is preferably 15 or less, more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably one.

When R ^a42 is a saturated hydrocarbon group having a group represented by the formula (a-g3), R ^a42 is more preferably a group represented by the formula (a-g2).
[In the formula (a-g2),
A ^a46 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents * ^-O -CO- or * -CO-O- (* represents a binding site to A ^a46 ).
A ^a47 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
However, the total number of carbon atoms of A ^a46 , A ^a47 and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.
* Represents a bonding site with a carbonyl group. ]

The carbon number of the saturated hydrocarbon group for A ^a46 is preferably 1 to 6, and more preferably 1 to 3.
The carbon number of the saturated hydrocarbon group of A ^a47 is preferably 4 to 15, more preferably 5 to 12, and A ^a47 is more preferably a cyclohexyl group or an adamantyl group.

The preferred structure of the group represented by the formula (a-g2) is the following structure (* is a bonding site with a carbonyl group).

^Examples of the alkanediyl group in A ^a41 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. Linear alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, Examples include a branched alkanediyl group such as a 2-methylbutane-1,4-diyl group.
^Examples of the substituent in the alkanediyl group represented by A ^a41 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

^Examples of the divalent saturated hydrocarbon group represented by A ^a42 , A ^a43 and A ^{a44 in} the group represented by the formula (a-g1) include a linear or branched divalent alkyl group and a monocyclic divalent oil. Examples include a cyclic saturated hydrocarbon group, and a divalent saturated hydrocarbon group formed by combining an alkyl group and an alicyclic saturated hydrocarbon group. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, Examples thereof include a 2-methylpropane-1,3-diyl group and a 2-methylpropane-1,2-diyl group.
^Examples of the substituent of the divalent saturated hydrocarbon group represented by A ^a42 , A ^a43 and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

In the group represented by the formula (a-g1), ^{examples of the} group in which X ^a42 is —O—, ^—CO— , ^—CO —O—, or —O—CO— include the following groups. In the following examples, * and ** each represent a binding site, and ** is a binding site to -O-CO- ^Ra42 .

As the structural unit represented by the formula (a4-1), a methyl group corresponding to R ^a41 in the following structural unit and a structural unit represented by the formula (a4-1) in the following structural unit is a hydrogen atom. Replaced structural units.

Examples of the structural unit represented by the formula (a4-1) include a structural unit represented by the formula (a4-2) and a structural unit represented by the formula (a4-3).
[In the 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, -CH ₂ contained in the alkanediyl group - may be replaced by -O- or -CO-.
R ^f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and a fluorine atom.
However, the upper limit of the total number of carbon atoms of L ⁴⁴ and R ^f6 are 21. ]

Alkanediyl group having 1 to 6 carbon atoms L ⁴⁴ include the same groups as those exemplified in A ^a41.
As the saturated hydrocarbon group for R ^f6 , the same groups as those exemplified for R ⁴² can be mentioned.
The alkanediyl group in L ^44, preferably alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

Examples of the structural unit represented by Formula (a4-2) include structural units represented by Formulas (a4-1-1) to (a4-1-11). A structural unit in which the methyl group corresponding to R ^f5 in the structural unit (a4-2) is replaced with a hydrogen atom is also exemplified as the structural unit represented by the formula (a4-2).

[In the 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.
X ^f12 represents * -O-CO- or * -CO-O- (* represents a binding site to A ^f13 ).
A ^f14 represents a C 1 to C 17 saturated hydrocarbon group which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 has a fluorine atom, and the upper limit of the total carbon number of L ⁵ , A ^f13 and A ^f14 is 20. ]

^Examples of the alkanediyl group for L ⁵ include the same groups as those exemplified for the alkanediyl group for A ^a41 .

As the divalent saturated hydrocarbon group ^optionally having a fluorine atom for A ^f13 , preferably a divalent chain-type saturated hydrocarbon group optionally having a fluorine atom or having a fluorine atom A divalent alicyclic saturated hydrocarbon group, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain-type saturated hydrocarbon group which may have a fluorine atom include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group and a pentanediyl group; a difluoromethylene group, a perfluoroethylene group, And perfluoroalkanediyl groups such as perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.
The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, a perfluoroadamantanediyl group, and the like.

Or saturated hydrocarbon group which may have a saturated hydrocarbon group and a fluorine atom of A ^f14 include the same groups as those exemplified with R ^a42. Among them, trifluoromethyl group, difluoromethyl 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, Fluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group, perfluorooctyl group, etc. Alkyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, Fluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyl dimethyl group, norbornyl group, norbornylmethyl group, perfluoro adamantyl group, a perfluoroalkyl adamantylmethyl group and the like are preferable.

In the formula (a4-3), L ⁵ is preferably an ethylene group.
The divalent saturated hydrocarbon group of A ^f13 is preferably a group containing a chain saturated hydrocarbon group having 1 to 6 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and preferably has 2 to 3 carbon atoms. A chain saturated hydrocarbon group is more preferred.
The saturated hydrocarbon group of A ^f14 is preferably a group containing a chain saturated hydrocarbon group having 3 to 12 carbon atoms and a group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and is preferably a chain saturated hydrocarbon group having 3 to 10 carbon atoms. A group containing a hydrocarbon group and an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms is more preferable. Among them, A ^f14 is preferably a group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. .

Examples of the structural unit represented by the formula (a4-3) include structural units represented by the formulas (a4-1′-1) to (a4-1′-11). A structural unit in which the methyl group corresponding to R ^f7 in the structural unit (a4-3) is replaced with a hydrogen atom is also exemplified as the structural unit represented by the formula (a4-3).

Examples of the structural unit (a4) also include a structural unit represented by Formula (a4-4).
[In the formula (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 _{is, - (CH 2) j1 -} , - (CH 2) j2 -O- (CH 2) j3 - or _{- (CH 2) j4 -CO-} O- (CH 2) j5 - represents a.
j1 to j5 each independently represent an integer of any of 1 to 6.
R ^f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and having a fluorine atom. ]

^As the saturated hydrocarbon group for R ^f22 , those similar to the saturated hydrocarbon group represented by R ^a42 in the formula (a4-1) can be mentioned. R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, and an alkyl group having 1 to 10 carbon atoms having a fluorine atom is preferable. More preferably, an alkyl group having 1 to 6 carbon atoms having a fluorine atom is further preferable.

In formula (A4-4), as the _{^{A f21, - (CH 2)}} j1 - , more preferably an ethylene group or a methylene group, more preferably a methylene group.

Examples of the structural unit represented by the formula (a4-4) include a structural unit represented by the following formula and a methyl group corresponding to R ^f21 in the structural unit (a4-4): Structural units replaced by atoms are included.

  When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, and more preferably 3 to 15 mol%, based on all structural units of the resin (A). -10 mol% is more preferred.

<Structural unit (a5)>
Examples of the non-eliminated hydrocarbon group contained in the structural unit (a5) include groups having a linear, branched, or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).
[In the 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 a hydrogen atom contained in the alicyclic hydrocarbon group 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, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O— or —CO—. . ]

The alicyclic hydrocarbon group for R ⁵² may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
Aliphatic hydrocarbon groups having 1 to 8 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and octyl. An alkyl group such as -ethylhexyl group.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-hydroxyadamantyl group and a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group for L ⁵⁵ include a divalent chain saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably a divalent chain saturated hydrocarbon group. .
Examples of the divalent chain saturated hydrocarbon group include alkanediyl groups such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, and a pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated hydrocarbon group include a cycloalkanediyl group such as a cyclopentanediyl group and a cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

-CH ₂ contained in the divalent saturated hydrocarbon group represented by L ⁵⁵ - is, the group replaced by -O- or -CO-, for example, by the formula (L1-1) ~ formula (L1-4) The groups represented are mentioned. In the following formulas, * and ** each represent a bond, and * represents a bonding site with an oxygen atom.
In the formula (L1-1),
X ^x1 represents * -O-CO- or * -CO-O- (* represents a binding site to L ^X1 ).
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, the total carbon number of L ^x1 and L ^x2 is 16 or less.
In the 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, the total carbon number of L ^x3 and L ^x4 is 17 or less.
In the 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 represent a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^x5 , L ^x6 and L ^x7 is 15 or less.
In the formula (L1-4),
L ^x8 and L ^{x9 each} represent a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of L ^x8 , L ^x9 and W ^x1 is 15 or less.
L ^x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably 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, and more preferably a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
^Lx4 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 a methylene group or an ethylene group.
^Lx6 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.
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 a single bond or a methylene group.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably 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.

Examples of the group represented by the formula (L1-1) include the following divalent groups.

Examples of the group represented by the formula (L1-2) include the following divalent groups.

Examples of the group represented by the formula (L1-3) include the following divalent groups.

Examples of the group represented by the formula (L1-4) include the following divalent groups.

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

The structural unit (a5-1), a methyl group corresponding to R ⁵¹ may be mentioned a structural unit replacing a hydrogen atom in the structural units in the structural units and the following structural units shown below (a5-1).
When the resin (A) has the structural unit (a5), its content is preferably from 1 to 30 mol%, more preferably from 2 to 20 mol%, based on all the structural units of the resin (A). ~ 15 mol% is more preferred.

<Structural unit (II)>
The resin (A) may further contain a structural unit capable of decomposing upon exposure to light to generate an acid (hereinafter, may be referred to as “structural unit (II)”). Specific examples include a structural unit described in JP-A-2006-79235, a structural unit having a sulfonate group or a carboxylate group and an organic cation in a side chain or a structural unit having a sulfonio group and an organic anion in a side chain. It is preferred that

The structural unit having a sulfonate group or a carboxylate group in the side chain and an organic cation is preferably a structural unit represented by the formula (II-2-A ′).
[In the formula (II-2-A ′),
X ^III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the saturated hydrocarbon group may be replaced by -O-, -S- or -CO-. The hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group.
A ^X1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
RA ^- represents a sulfonate or carboxylate groups.
R ^III3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
ZA ⁺ represents an organic cation. ]

Examples of the halogen atom represented by R ^III3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^III3, the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 The same is mentioned.
Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A ^x1 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a 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, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like. No.
Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted by A ^X1 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, and a perfluorotert-butyl group. -Butyl group, perfluoropentyl group, perfluorohexyl group and the like.
Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by ^XIII3 include a linear or branched alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a combination of these.
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 Linear alkanediyl groups such as, dodecane-1,12-diyl group; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Alkanediyl groups such as pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 , 4-diyl group, Cycloalkanediyl groups such as looctane-1,5-diyl group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group And other divalent polycyclic alicyclic saturated hydrocarbon groups.
Examples of the case where —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —S— or —CO— include divalent groups represented by Formulas (X1) to (X53). No. However, -CH ₂ contained in a saturated hydrocarbon group - is, -O -, - number of carbon atoms before replacing with S- or -CO- is respectively 17 or less. In the following formulas, * and ** represent the binding site, and * represents a binding site with A ^x1.

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.

Examples of the organic cation represented by ZA ⁺ include those similar to the organic cation Z1 ⁺ in the acid generator (B1).

The structural unit represented by the formula (II-2-A ′) is preferably a structural unit represented by the formula (II-2-A).
[In the formula (II-2-A), R ^III3 , X ^III3 and ZA ⁺ represent the same meaning as described above.
z2A represents any integer of 0 to 6.
R ^III2 and R ^III4 each independently represent a hydrogen atom, a fluorine atom or a C 1-6 perfluoroalkyl group, and when z is 2 or more, a plurality of R ^III2 and R ^III4 are the same as each other; Or different.
Q ^a and Q ^b are each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. ]
^{Examples of} the C 1-6 perfluoroalkyl group represented by R ^III2 , R ^III4 , Q ^a and Q ^b include the same as the C 1-6 perfluoroalkyl group represented by Q ^b1 described below. .

The structural unit represented by the formula (II-2-A) is preferably a structural unit represented by the formula (II-2-A-1).
[In the formula (II-2-A-1),
R ^III2 , R ^III3 , R ^III4 , Q ^a , Q ^b and ZA ⁺ represent the same meaning as described above.
R ^III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
z2A1 represents an integer of any of 0 to 6.
X ^I2 represents a divalent saturated hydrocarbon group of 1 to 11 carbon atoms, -CH ₂ contained in the saturated hydrocarbon group - is -O -, - it is replaced in S- or -CO- The hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group. ]
Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by R ^III5 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, Examples thereof include a linear or branched alkyl group such as a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group.
Examples of the divalent saturated hydrocarbon group represented by X ^I2 include the same as the divalent saturated hydrocarbon group represented by X ^III3 .

As the structural unit represented by the formula (II-2-A-1), a structural unit represented by the formula (II-2-A-2) is more preferable.
[In formula (II-2-A-2), R ^III3 , R ^III5 and ZA ⁺ represent the same meaning as described above.
m and n each independently represent 1 or 2. ]

Examples of the structural unit represented by the formula (II-2-A ′) include the following structural units and the structural units described in WO2012 / 050015. ZA ⁺ represents an organic cation.

The structural unit having a sulfonio group and an organic anion in the side chain is preferably a structural unit represented by the formula (II-1-1).
[In the 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 represent a hydrocarbon group having 1 to 18 carbon atoms, and R ^II2 and R ^II3 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded.
R ^II4 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
A ^- represents an organic anion. ]
Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^II1 include a phenylene group and a naphthylene group.
Examples of the hydrocarbon group represented by R ^II2 and R ^II3 include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these. Specific examples include the same hydrocarbon groups as R ^{a1 ′} , R ^{a2 ′} and R ^{a3 ′} .
Examples of the halogen atom represented by R ^II4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^II4 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 The same is mentioned.
Examples of the divalent linking group represented by A ^II1 include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group is It may be replaced by -O-, -S- or -CO-. Specific examples include the same divalent saturated hydrocarbon groups having 1 to 18 carbon atoms represented by ^XIII3 .

Examples of the structural unit containing a cation in the formula (II-1-1) include the following structural units.

Examples of the organic anion represented by A ⁻ include a sulfonate anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylate anion. The organic anion represented by A ⁻ is preferably a sulfonate anion, and examples of the sulfonate anion include the same as the anion (I) described above.

Examples of the sulfonylimide anion represented by A ⁻ include the following.

Examples of the sulfonylmethide anion include the following.

Examples of the carboxylate anion include the following.

Examples of the structural unit represented by the formula (II-1-1) include the following structural units.

  When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably from 1 to 20 mol% based on all structural units of the resin (A). Preferably it is 2 to 15 mol%, more preferably 3 to 10 mol%.

  The resin (A) may have a structural unit other than the structural units described above, and examples of such a structural unit include structural units known in the art.

The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s), that is, a copolymer of the monomer (a1) and the monomer (s).
The structural unit (a1) is preferably a group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2) (preferably, the structural unit having a cyclohexyl group and a cyclopentyl group). And more preferably at least two, and further preferably at least two selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2).
The structural unit (s) is preferably at least one selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit (a2-1) or a structural unit (a2-A). The structural unit (a3) is preferably a group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a structural unit represented by the formula (a3-4). At least one selected from

Each of the structural units constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, a radical polymerization method) using a monomer that leads to these structural units. be able to. The content of each structural unit of the resin (A) can be adjusted by the amount of the monomer used for polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, and still more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, and still more preferably). Is 15,000 or less). In the present specification, the weight average molecular weight is a value obtained by gel permeation chromatography under the conditions described in Examples.

<Resins other than resin (A)>
The resist composition of the present invention preferably uses a resin other than the resin (A) in combination.
Examples of the resin other than the resin (A) include a resin containing a structural unit (a4) or a structural unit (a5) (hereinafter, sometimes referred to as a resin (X)).
As the resin (X), a resin containing the structural unit (a4) is preferable.
In the resin (X), the content of the structural unit (a4) is preferably at least 30 mol%, more preferably at least 40 mol%, based on the total of all the structural units of the resin (X). , 45 mol% or more.
Examples of the structural unit that the resin (X) may further have include a structural unit (a2), a structural unit (a3), and a structural unit derived from other known monomers. Among them, the resin (X) is preferably a resin composed of only the structural unit (a4) and / or the structural unit (a5), and more preferably a resin composed of only the structural unit (a4).

Each of the structural units constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, a radical polymerization method) using a monomer for deriving these structural units. can do. The content of each structural unit of the resin (X) can be adjusted by the amount of the monomer used for polymerization.
The weight average molecular weight of the resin (X) is independently preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).
When the resist composition contains the resin (X), the content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the resin (A). It is preferably 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, particularly preferably 1 to 8 parts by mass.

  The content of the resin (A) in the resist composition is preferably from 80% by mass to 99% by mass, more preferably from 90% by mass to 99% by mass, based on the solid content of the resist composition. When a resin other than the resin (A) is contained, the total content of the resin (A) and the resin other than the resin (A) is from 80% by mass to 99% by mass based on the solid content of the resist composition. Or less, and more preferably 90% by mass or more and 99% by mass or less. The solid content of the resist composition and the content of the resin with respect to the solid content can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Solvent (E)>
The content of the solvent (E) in the resist composition is usually from 90% by mass to 99.9% by mass, preferably from 92% by mass to 99% by mass, more preferably from 94% by mass to 99% by mass. % Or less. The content of the solvent (E) can be measured by a known analytical means such as liquid chromatography or gas chromatography.
Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; Esters; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; One kind of the solvent (E) may be used alone, or two or more kinds may be used.

<Quencher (C)>
Examples of the quencher (C) include a basic nitrogen-containing organic compound and a salt that generates an acid having a lower acidity than the acid generated from the acid generator (B). The content of the quencher (C) is preferably about 0.01 to 5% by mass based on the solid content of the resist composition.
Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Amines include aliphatic amines and aromatic amines. Aliphatic amines include primary, secondary and tertiary amines.
Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, trihexylamine Heptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, Rudicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyl Didecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2'-methylenebisaniline, imidazole, 4-methyli Dazole, pyridine, 4-methylpyridine, 1,2-di (2-pyridyl) ethane, 1,2-di (4-pyridyl) ethane, 1,2-di (2-pyridyl) ethene, 1,2-di (4-pyridyl) ethene, 1,3-di (4-pyridyl) propane, 1,2-di (4-pyridyloxy) ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide, 4, Examples include 4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipicolylamine, bipyridine and the like, preferably aromatic amines such as diisopropylaniline, more preferably 2,6-diisopropyl Aniline is mentioned.
Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, and 3- (trifluoromethyl) phenyltrimethyl. Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like.

The acidity of a salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is represented by an acid dissociation constant (pKa). The salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is a salt whose acid dissociation constant of the acid generated from the salt is usually −3 <pKa, preferably −1 <pKa. It is a salt with pKa <7, and more preferably a salt with 0 <pKa <5.
Examples of the salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) include a salt represented by the following formula and a salt represented by the formula (D) described in JP-A-2015-147926. (Hereinafter sometimes referred to as “weak acid inner salt (D)”), JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, and JP-A-2011-39502. And the salts described in JP-A-2011-191745. The salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is preferably a weak acid inner salt (D).

Examples of the weak acid inner salt (D) include the following salts.

  When the resist composition contains the quencher (C), the content of the quencher (C) is usually 0.01 to 5% by mass, preferably 0.01 to 5% by mass, based on the solid content of the resist composition. 3% by mass.

<Other ingredients>
The resist composition of the present invention may contain components other than the above-described components (hereinafter, sometimes referred to as “other components (F)”) as necessary. The other component (F) is not particularly limited, and additives known in the resist field, for example, a sensitizer, a dissolution inhibitor, a surfactant, a stabilizer, a dye, and the like can be used.

<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), a resin other than the resin (A), a solvent (E), and a quencher (C). And other components (F). The mixing order is arbitrary and is not particularly limited. An appropriate temperature can be selected from 10 to 40 ° C. depending on the type of the resin and the like and the solubility of the resin and the like in the solvent (E). An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to perform filtration using a filter having a pore size of about 0.003 to 0.2 μm.

<Resist pattern manufacturing method>
The method for producing a resist pattern according to the present invention includes:
(1) a step of applying the resist composition of the present invention on a substrate,
(2) drying the composition after application to form a composition layer;
(3) exposing the composition layer to light,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.
The application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.
By drying the composition after application, the solvent is removed to form a composition layer. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called prebaking), or using a decompression device. The heating temperature is preferably from 50 to 200 ° C., and the heating time is preferably from 10 to 180 seconds. The pressure at the time of drying under reduced pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.
The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. The exposure light source, which emits laser light in a UV-region such as a KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser source (YAG or semiconductor laser Etc.), use various types of laser light, such as one that emits harmonic laser light in the far ultraviolet or vacuum ultraviolet region by converting the wavelength of the laser light from the above, and one that irradiates an electron beam or ultra-ultraviolet light (EUV). Can be. In the present specification, irradiating these radiations may be collectively referred to as “exposure”. At the time of exposure, the exposure is usually performed through a mask corresponding to the required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.
The composition layer after the exposure is subjected to a heat treatment (so-called post-exposure bake) in order to promote a deprotection reaction at the acid labile group. The heating temperature is usually about 50 to 200C, preferably about 70 to 150C.
The heated composition layer is usually developed using a developing solution using a developing device. Examples of the developing method include a dip method, a paddle method, a spray method, a dynamic dispense method, and the like. The development temperature is preferably, for example, 5 to 60 ° C., and the development time is, for example, preferably 5 to 300 seconds. By selecting the type of the developer as follows, a positive resist pattern or a negative resist pattern can be produced.
When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as a developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. For example, an aqueous solution of tetramethylammonium hydroxide or (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline) may be mentioned. The alkali developer may contain a surfactant.
After the development, it is preferable to wash the resist pattern with ultrapure water, and then remove water remaining on the substrate and the pattern.
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 “organic developer”) is used as a developer.
Examples of the organic solvent contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether. Ether solvents; amide solvents such as N, N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole.
The content of the organic solvent in the organic developer is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and further preferably substantially only the organic solvent.
Among them, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is preferably from 50% by mass to 100% by mass, more preferably from 90% by mass to 100% by mass, and substantially butyl acetate and / or 2% by mass. More preferably it is only heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a type different from the organic developer.
It is preferable to wash the developed resist pattern with a rinse solution. The rinsing solution is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and is preferably an alcohol solvent or an ester solvent.
After the cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

<Applications>
The resist composition of the present invention includes a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure or a resist composition for EUV exposure, particularly ArF It is suitable as a resist composition for excimer laser exposure, and is useful for fine processing of semiconductors.

The present invention will be described more specifically with reference to examples. In the examples, "%" and "part" representing the content or the use amount are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography. The analysis conditions for gel permeation chromatography are as follows.
Column: TSKgel Multipore HXL-M x 3 + guardcolumn (Tosoh Corporation)
Eluent: tetrahydrofuran Flow rate: 1.0 mL / min
Detector: RI detector Column temperature: 40 ° C
Injection volume: 100 μl
Molecular weight standard: Standard polystyrene (manufactured by Tosoh Corporation)
The structure of the compound was confirmed by measuring the molecular ion peak using mass spectrometry (LC: 1100, manufactured by Agilent, MASS: LC / MSD, manufactured by Agilent). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

Example 1 Synthesis of Salt Represented by Formula (I-2)
5.40 parts of the salt represented by the formula (I-2-a), 4.42 parts of the salt represented by the formula (I-2-b), 36 parts of chloroform and 24 parts of ion-exchanged water were added, and 23 After stirring at 2 ° C. for 2 hours, liquid separation was performed to take out an organic layer. 15 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes. This washing operation was repeated five times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes. Then, the supernatant was removed and concentrated to obtain the compound represented by the formula (I-2). ) Was obtained.
MASS (ESI (+) Spectrum): M ⁺ 391.0
MASS (ESI (-) Spectrum): M ^- 339.1

Example 2: Synthesis of salt represented by formula (I-3)
5.40 parts of the salt represented by the formula (I-2-a), 4.25 parts of the salt represented by the formula (I-3-b), 36 parts of chloroform and 24 parts of ion-exchanged water were added, and 23 After stirring at 2 ° C. for 2 hours, liquid separation was performed to take out an organic layer. 15 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes. This washing operation was repeated five times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes. Then, the supernatant was removed and concentrated to obtain the compound represented by the formula (I-3). 5.81 parts of a salt represented by the following formula: were obtained.
MASS (ESI (+) Spectrum): M ⁺ 391.0
MASS (ESI (-) Spectrum): M ^- 323.0

Example 3 Synthesis of Salt Represented by Formula (I-176)
5.28 parts of the salt represented by the formula (I-176-a), 4.42 parts of the salt represented by the formula (I-2-b), 36 parts of chloroform and 24 parts of ion-exchanged water were added, and 23 After stirring at 2 ° C. for 2 hours, liquid separation was performed to take out an organic layer. 15 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes. This washing operation was repeated five times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes. Then, the supernatant was removed and concentrated to obtain the compound of the formula (I-176). 3.92 parts of the salt represented by
MASS (ESI (+) Spectrum): M ⁺ 379.0
MASS (ESI (-) Spectrum): M ^- 339.1

Example 4: Synthesis of salt represented by formula (I-177)
5.28 parts of the salt represented by the formula (I-176-a), 4.25 parts of the salt represented by the formula (I-3-b), 36 parts of chloroform and 24 parts of ion-exchanged water were added, and 23 After stirring at 2 ° C. for 2 hours, liquid separation was performed to take out an organic layer. 15 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes. This washing operation was repeated five times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, and the mixture was stirred at 23 ° C. for 30 minutes. Then, the supernatant was removed and concentrated to obtain the compound represented by the formula (I-177). ) Was obtained.
MASS (ESI (+) Spectrum): M ⁺ 379.0
MASS (ESI (-) Spectrum): M ^- 323.0

Example 5: Synthesis of salt represented by formula (I-292)
5.55 parts of the salt represented by the formula (I-292-a), 4.42 parts of the salt represented by the formula (I-2-b), 36 parts of chloroform and 24 parts of ion-exchanged water were added, and 23 After stirring at 2 ° C. for 2 hours, liquid separation was performed to take out an organic layer. 15 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes. This washing operation was repeated five times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, the mixture was stirred at 23 ° C. for 30 minutes, the supernatant was removed, and the mixture was concentrated to obtain the compound represented by the formula (I-292). ) Was obtained.
MASS (ESI (+) Spectrum): M ⁺ 401.0
MASS (ESI (-) Spectrum): M ^- 339.1

Example 6: Synthesis of salt represented by formula (I-293)
5.55 parts of the salt represented by the formula (I-292-a), 4.25 parts of the salt represented by the formula (I-3-b), 36 parts of chloroform and 24 parts of ion-exchanged water were added, and 23 After stirring at 2 ° C. for 2 hours, liquid separation was performed to take out an organic layer. 15 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes. This washing operation was repeated five times. After concentrating the obtained organic layer, 30 parts of tert-butyl methyl ether was added to the concentrated residue, the mixture was stirred at 23 ° C. for 30 minutes, the supernatant was removed, and the mixture was concentrated to obtain the compound represented by the formula (I-293). ) Was obtained.
MASS (ESI (+) Spectrum): M ⁺ 401.0
MASS (ESI (-) Spectrum): M ^- 323.0

Synthesis of Resin The compounds (monomers) used in the synthesis of the resin (A) are shown below. Hereinafter, these compounds are referred to as “monomer (a1-1-3)” or the like according to the formula number.

Synthesis Example 1: Synthesis of resin A1 As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-3), and monomer (a3-4-2) were used. The molar ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2)] is 45: 14: 2.5: 38. 5, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of monomers was added to form a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators based on the total amount of monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol and water to precipitate the resin, and the resin is filtered twice to perform a reprecipitation operation twice. Resin A1 having a molecular weight of 7.6 × 10 ³ was obtained with a yield of 68%. This resin A1 has the following structural units.

Synthesis Example 2: Synthesis of Resin X1 A monomer (a5-1-1) and a monomer (a4-0-12) were used as monomers, and the molar ratio [monomer (a5-1-1): monomer (a4-0-) was used. 12)] was mixed at a ratio of 50:50, and a solution was prepared by adding methyl isobutyl ketone 1.2 times by mass of the total amount of monomers. To this solution, azobis (2,4-dimethylvaleronitrile) as an initiator was added at 3 mol% based on the total amount of monomers, and the mixture was heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and this resin was filtered to obtain a resin X1 having a weight average molecular weight of 1.0 × 10 ^{4 in} a yield of 91%. This resin X1 has the following structural units.

<Preparation of resist composition>
As shown in Table 2, the following components were mixed, and the resulting mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

<Resin>
A1, X1: Resin A1, Resin X1
<Acid generator (B)>
B1-21: A salt represented by the formula (B1-21) (synthesized according to the examples in JP-A-2012-224611).
B1-22: Salt represented by the formula (B1-22) (synthesized according to the example of JP-A-2012-224611)
IX-1: Salt represented by formula (IX-1) (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Quencher (C)>
D1: (Tokyo Chemical Industry Co., Ltd.)
<Solvent>
Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts

<Manufacture of resist pattern and its evaluation>
A composition for an organic anti-reflection film (ARC-29; manufactured by Nissan Chemical Industries, Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds, so that a 78 nm-thick organic reflection film is formed on the wafer. An prevention film was formed. Next, the above resist composition was applied (spin-coated) on the organic antireflection film so that the film thickness after drying was 85 nm. After the application, the silicon wafer was prebaked on a direct hot plate at the temperature described in the “PB” column of Table 2 for 60 seconds to form a composition layer. An ArF excimer stepper for liquid immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light) was used to form a contact hole pattern (hole pitch 90 nm) on the silicon wafer on which the composition layer was formed. (Hole diameter: 55 nm) using a mask for forming the exposure stepwise. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed on a hot plate at a temperature described in the “PEB” column of Table 2 for 60 seconds. Then, the composition layer on the silicon wafer is developed by a dynamic dispense method at 23 ° C. for 20 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution to form a negative resist pattern. Manufactured.

  In the resist pattern obtained after the development, the exposure amount at which the hole diameter formed using the mask was 45 nm was defined as the effective sensitivity.

<Mask error factor (MEF) evaluation>
With respect to the effective sensitivity, a resist pattern was formed using a mask having a mask hole diameter (hole diameter of a light-transmitting portion of the mask) of 57 nm, 56 nm, 55 nm, 54 nm, and 53 nm (hole pitch was 90 nm). The slope of the regression line when the mask hole diameter was plotted on the horizontal axis and the hole diameter of the resist pattern formed (transferred) on the substrate by exposure was plotted on the vertical axis was calculated as the MEF value.
Table 3 shows the results. Numerical values in parentheses indicate MEF values.

In comparison with Comparative Composition 1, Compositions 1 to 12 had a smaller slope of the regression line, and had a better mask error factor (MEF) evaluation.

  Since the resist composition containing the compound of the present invention can obtain a resist pattern having a good mask error factor (MEF), it is suitable for fine processing of semiconductors and is extremely useful in industry.

Claims (9)

A salt represented by the formula (I).
[In the formula (I),
R ¹ represents a fluorine atom or a C 1-6 perfluoroalkyl group.
nn1 represents an integer of 1 to 5, when nn1 is 2 or more, plural ^{R 1} may be the same or different from each other.
R ² represents an alkyl group having 1 to 8 carbon atoms which may have a fluorine atom, and —CH ₂ — contained in the alkyl group may be replaced by —O— or —CO—.
nn2 represents an integer of 0 to 5, when nn2 is 2 or more, plural ^{R 2} may be the same or different from each other.
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ¹ represents a saturated hydrocarbon group having 1 to 24 carbon atoms, —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O— or —CO—, and the saturated hydrocarbon group May be substituted with a fluorine atom or a hydroxy group.
Y ¹ represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and is included in the alicyclic hydrocarbon group. -CH ₂ - is, -O -, - SO ₂ - or -CO- may be replaced with. ] The salt according to claim 1, wherein R ¹ is a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms.   3. The salt according to claim 1, wherein nn2 is an integer of any one of 1 to 5.   An acid generator containing the salt according to claim 1.   A resist composition comprising the acid generator according to claim 4 and a resin having an acid labile group. The resist composition according to claim 5, wherein the structural unit having an acid labile group includes at least two types of a structural unit represented by Formula (a1-1) and a structural unit represented by Formula (a1-2).
[In the formulas (a1-1) and (a1-2),
L ^a1 and L ^a2 independently of one another, -O- or _{* -O- (CH 2) k1 -CO} -O- the stands, k1 represents an integer of 1-7, * the binding of -CO- Represent hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent 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 any integer of 0 to 14.
n1 represents any integer of 0-10.
n1 ′ represents any integer of 0 to 3. ]   7. The resist composition according to claim 5, further comprising a salt that generates an acid having a lower acidity than the acid generated from the acid generator.   The resist composition according to claim 5, further comprising a resin containing a structural unit having a fluorine atom. (1) applying the resist composition according to any one of claims 5 to 8 onto a substrate;
(2) drying the composition after application to form a composition layer;
(3) exposing the composition layer to light,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern comprising: