JP2019210465A - Resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

To provide a compound and a resist composition capable of producing a resist pattern having good CD uniformity.SOLUTION: A resin contains at least one selected from the group consisting of structural units represented by formula (IA) and formula (IB) and at least one selected from the group consisting of structural units represented by formula (a1-1) and formula (a1-2). Formula (IA): -(CH-C(R)-X-L(OH)(-OR)(-OR))-. Formula (IB): -(CH-C(R)-X-L(X-C(R)-CH)-)(-OR)(-OR))-. Formula (a1-1): -(CH-C(R)-CO-L- (optionally substituted adamantane). Formula (a1-2): -(CH-C(R)-CO-L- (optionally substituted cycloalkyl). [Xand Xeach represent -C(=O)O- or the like; Lrepresents a hydrocarbon group; Rand Rare bonded to each other to form a ring; and Land Leach represent -O- or the like.]SELECTED DRAWING: None

Description

  The present invention relates to a resin, a resist composition, a method for producing a resist pattern using the resist composition, and the like.

Patent Document 1 describes the following compounds.
Patent Document 2 describes a resist composition containing a resin having the following structural units.
Patent Document 3 describes the following compounds.

JP-T-2015-526426 JP 2007-155851 A JP 2014-009188 A

  The present invention provides a compound capable of producing a resist pattern with better CD uniformity (CDU) than a resist pattern formed from a resist composition containing the above resin.

The present invention includes the following inventions.
[1] At least one selected from the group consisting of a structural unit represented by formula (IA) and a structural unit represented by formula (IB), a structural unit represented by formula (a1-1), and a formula (a1 -2) Resin containing at least 1 chosen from the group which consists of a structural unit represented.
[In Formula (IA) and Formula (IB),
R ¹ and R ² each independently represents a hydrogen atom or a methyl group.
X ¹ and X ² each independently represent a group represented by any one of formulas (X ¹ -1) to (X ¹ -7).
(In the formula (X ¹ -1) to the formula (X ¹ -7),
*, ** represents a binding site, ** represents the bonding site to ^{L 1.} )
L ¹ represents an optionally substituted hydrocarbon group having 1 to 48 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or It may be replaced by —SO ₂ —.
R ³ and R ⁴ each independently represent a group represented by the formula (Aa) or a group represented by the formula (Ab), or R ³ and R ⁴ are bonded to each other and bonded to an oxygen atom Together with this, an acid labile ring is formed. ]
[In Formula (Aa), R ⁵ , R ⁶ and R ⁷ 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 ⁵ and R ⁶ are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
n represents 0 or 1.
* Represents a binding site. ]
[In Formula (Ab), R ⁸ and R ⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, R ⁹ and R ¹⁰ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and ^Xb , and —CH ₂ — contained in the hydrocarbon group and the heterocycle is — O- or -S- may be substituted.
^Xb represents an oxygen atom or a sulfur atom.
* Represents a binding site. ]
[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents —CO—. Represents the binding site.
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 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents any integer of 0 to 3. ]
[2] The resin according to [1], wherein L ¹ is a group represented by the formula (IIA) or a group represented by the formula (IIB).
[In Formula (IIA) and Formula (IIB),
L ⁴ and L ^{4 ′} each independently represent a C 1-24 hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the hydrocarbon group is — O—, —S—, —CO— or —SO ₂ — may be substituted.
L ² and L ³ each independently represent a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^{3 ′} represents an alkanetriyl group having 1 to 4 carbon atoms.
* A represents a bonding site with X ¹ , * b represents a bonding site with oxygen atom or X ² , * c represents a bonding site with oxygen atom in -OR ³ , * d represents in -OR ⁴ Represents the bonding site with the oxygen atom. ]
[3] L ⁴ and L ^{4 ′} are each independently a single bond, an alkanediyl group having 1 to 6 carbon atoms or an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. (—CH ₂ — contained in the alkanediyl group may be replaced by —O— or —CO—, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O— -, -S-, -CO- or -SO _2- may be substituted), L ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms, and L ³ is 1 carbon atom. The resin according to [1] or [2], which is an alkanediyl group of ˜4 and L ^{3 ′} is an alkanetriyl group having 1 to 4 carbon atoms.
[4] ^{X 1} has the formula ^(X 1 -1), one of which is a group represented by any one of formulas ^(X 1 -3) or Formula ^{(X 1 -4) [1]} ~ [3] The resin described in 1.
[5] A resist composition comprising the resin according to any one of [1] to [4] and an acid generator.
[6] The resist composition according to [5], wherein the acid generator contains a salt represented by the formula (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 divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — may be replaced by —O—, —S (O) ₂ — or —CO—.
Z ⁺ represents an organic cation. ]
[7] The resist composition according to [5] or [6], further comprising a salt that generates an acid having a lower acidity than an acid generated from an 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) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) A step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.
[10] A compound represented by formula (IA1) or formula (IB1).
[In Formula (IA1) and Formula (IB1),
R ¹ and R ² each independently represents a hydrogen atom or a methyl group.
X ¹¹ and X ²¹ each independently represent a group represented by any one of formula (X ¹ -2) to formula (X ¹ -7).
(In the formula (X ¹ -2) to the formula (X ¹ -7),
*, ** represents a binding site, ** represents the bonding site to ^{L 1.} )
L ¹ represents an optionally substituted hydrocarbon group having 1 to 48 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or It may be replaced by —SO ₂ —.
R ³ and R ⁴ each independently represent a group represented by the formula (Aa) or a group represented by the formula (Ab), or R ³ and R ⁴ are bonded to each other and bonded to an oxygen atom Together with this, an acid labile ring is formed. ]
[In Formula (Aa), R ⁵ , R ⁶ and R ⁷ 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 ⁵ and R ⁶ are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
n represents 0 or 1.
* Represents a binding site. ]
[In Formula (Ab), R ⁸ and R ⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, R ⁹ and R ¹⁰ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and ^Xb , and —CH ₂ — contained in the hydrocarbon group and the heterocycle is — O- or -S- may be substituted.
^Xb represents an oxygen atom or a sulfur atom.
* Represents a binding site. ]
[11] The compound according to [10], wherein L ¹ is a group represented by formula (IIA) or a group represented by formula (IIB).
[In Formula (IIA) and Formula (IIB),
L ⁴ and L ^{4 ′} each independently represent a C 1-24 hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the hydrocarbon group is — O—, —S—, —CO— or —SO ₂ — may be substituted.
L ² and L ³ each independently represent a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^{3 ′} represents an alkanetriyl group having 1 to 4 carbon atoms.
* A represents a bonding site with X ¹ , * b represents a bonding site with oxygen atom or X ² , * c represents a bonding site with oxygen atom in -OR ³ , * d represents in -OR ⁴ Represents the bonding site with the oxygen atom. ]

  By using a resist composition containing the resin of the present invention, a resist pattern can be produced with good CD uniformity (CDU).

In this specification, unless otherwise specified, “(meth) acrylate” means “at least one selected from the group consisting of acrylate and methacrylate”. The notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning. When structural units having “CH ₂ ═C (CH ₃ ) —CO—” or “CH ₂ ═CH—CO—” are exemplified, the structural units having both groups are also exemplified. Shall. The “combined group” means a group in which two or more exemplified groups are bonded, and the valence of these groups may be appropriately changed depending on the bonding form. Moreover, when a stereoisomer exists, all the stereoisomers are included.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described later from the total amount of the resist composition.

〔resin〕
The resin of the present invention has a structural unit represented by formula (IA) (hereinafter sometimes referred to as structural unit (IA)) and a structural unit represented by formula (IB) (hereinafter referred to as structural unit (IB)). At least one selected from the group consisting of: a structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) and formula (a1-2). A resin (hereinafter also referred to as “resin (A)”) containing at least one selected from the group consisting of structural units represented by the following (hereinafter also referred to as structural unit (a1-2)). .

<Structural Unit (IA) or Structural Unit (IB)>
In Formula (IA) and Formula (IB), X ¹ and X ² are groups represented by any one of Formula (X ¹ -1) to Formula (X ¹ -7). Among these, X ¹ is preferably a group represented by any ^one of the formula (X ¹ -1), the formula (X ¹ -3), and the formula (X ¹ -4), and the formula (X ¹ -1 ) Or a group represented by formula (X ¹ -4).
Examples of the hydrocarbon group having 1 to 48 carbon atoms of L ¹ include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkanetetrayl groups, alkenetetrayl groups, alkynetetrayl groups, and monocyclic or polycyclic groups. Alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and the like, and tetravalent hydrocarbon groups (for example, tetravalent aliphatic hydrocarbon groups and divalent groups) in which two or more of these groups are combined. 4 is a combination of a tetravalent hydrocarbon group, a tetravalent alicyclic hydrocarbon group or an aromatic hydrocarbon group, and one or more divalent aliphatic hydrocarbon groups. A tetravalent hydrocarbon group obtained by combining a trivalent hydrocarbon group, a trivalent or tetravalent alicyclic hydrocarbon group and / or an aromatic hydrocarbon group and an alkanediyl group, or the like.

Alkanetetrayl groups include methanetetrayl, ethanetetrayl, propanetetrayl, butanetetrayl, pentanetetrayl, hexanetetrayl, heptanetetrayl, octanetetrayl, nonanetetrayl A linear or branched alkanetetrayl group such as a group, a decanetetrayl group, an undecanetetrayl group, and a dodecanetetrayl group.
As alkenetetrayl group, ethenetetrayl group, propenetetrayl group, isopropenetetrayl group, butenetetrayl group, isobutenetetrayl group, tert-butenetetrayl group, pentenetetrayl group, hexenetetrayl group, Examples include a heptenetetrayl group, an octynetetrayl group, an isooctynetetrayl group, and a nonenetetrayl group.
The alkynetetrayl group includes propynetetrayl group, isopropynetetrayl group, butynetetrayl group, isobutynetetrayl group, tert-butynetetrayl group, pentynetetrayl group, hexynetetrayl group, octynetetra Yl group, noninetetrayl group and the like.
Examples of monocyclic alicyclic hydrocarbon groups include cyclobutanetetrayl groups, cyclopentanetetrayl groups, cyclohexanetetrayl groups, cyclohexenetetrayl groups, cyclooctanetetrayl groups, and the like. Can be mentioned.
The polycyclic alicyclic hydrocarbon group includes a polycyclic cycloalkanetetrayl group such as a norbornanetetrayl group, a norbornanetetrayl group, a 5-norbornenetetrayl group, an adamantanetetrayl group, and an adamantanetetrayl group. Can be mentioned.
Examples of the aromatic hydrocarbon group include a benzenetetrayl group, a naphthalenetetrayl group, and an anthracenetetrayl group.
Examples of the hydrocarbon group in which two or more kinds are combined include a group in which a chain hydrocarbon group, an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group are combined. Specifically, alkanetetrayl A combination of a group with a monovalent alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, or a methylene group contained in an alkanetetrayl group is a divalent alicyclic hydrocarbon group and / or a divalent Examples thereof include a group replaced with an aromatic hydrocarbon group, a trivalent or tetravalent alicyclic hydrocarbon group, and / or a group obtained by combining an aromatic hydrocarbon group and an alkanediyl group.

Examples of the substituent that the hydrocarbon group of L ¹ may have include a halogen atom and a cyano group.
A hydroxy group (a group in which —CH ₂ — contained in a methyl group is replaced with —O—), a carboxy group (—CH ₂ —CH ₂ — in an ethyl group is replaced with —O—CO—) Group), an alkoxy group having 1 to 12 carbon atoms (a group in which —CH ₂ — contained in an alkyl group having 2 to 13 carbon atoms is replaced by —O—), an alkoxycarbonyl group having 2 to 13 carbon atoms (carbon A group in which —CH ₂ —CH ₂ — contained in an alkyl group having 4 to 15 is replaced by —O—CO—, an alkylcarbonyl group having 2 to 13 carbon atoms (in an alkyl group having 3 to 14 carbon atoms) A group in which —CH ₂ — contained in is replaced by —CO—, an alkylcarbonyloxy group having 2 to 13 carbon atoms (—CH ₂ —CH ₂ — contained in an alkyl group having 4 to 15 carbon atoms), Group substituted by —CO—O—) is a hydrocarbon -CH ₂ contained in - is a group replaced by -O- or -CO-.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, undecyloxy group. Group, dodecyloxy group and the like.
The alkoxycarbonyl group having 2 to 13 carbon atoms, the alkylcarbonyl group having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms are groups in which a carbonyl group or a carbonyloxy group is bonded to the above-described alkyl group or alkoxy group. Represents.
Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group. Examples of the alkylcarbonyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group. Examples of the alkylcarbonyloxy group having 2 to 13 carbon atoms include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
The C1-C4 tetravalent hydrocarbon group represented by L ¹ may have one substituent or a plurality of substituents.

—CH ₂ — contained in the hydrocarbon group having 1 to 48 carbon atoms of L ¹ may be replaced by —O—, —S—, —CO— or —SO ₂ —.
When the hydrocarbon group having 1 to 48 carbon atoms of L ¹ has a substituent, or —CH ₂ — contained in the hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ —. When it is, the carbon number before the replacement is the carbon number of the hydrocarbon group.

L ¹ is preferably a group represented by the formula (IIA) or the formula (IIB).
[In Formula (IIA) and Formula (IIB),
L ⁴ and L ^{4 ′} each independently represent a C 1-24 hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the hydrocarbon group is — O—, —S—, —CO— or —SO ₂ — may be substituted.
L ² and L ³ each independently represent a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^{3 ′} represents an alkanetriyl group having 1 to 4 carbon atoms.
* A represents a bonding site with X ¹ , * b represents a bonding site with oxygen atom or X ² , * c represents a bonding site with oxygen atom in -OR ³ , * d represents in -OR ⁴ Represents the bonding site with the oxygen atom. ]

Examples of the hydrocarbon group having 1 to 24 carbon atoms of L ⁴ and L ^{4 ′} include aliphatic hydrocarbon groups (chain hydrocarbon groups such as alkanediyl groups, alkenediyl groups, alkynediyl groups, and monocyclic or polycyclic groups. A divalent alicyclic hydrocarbon group), a divalent aromatic hydrocarbon group, and the like, and a divalent hydrocarbon group in which two or more of these groups are combined may be used.

Examples of the alkanediyl group 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, a hexane-1,6-diyl group, and a 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 Linear alkanediyl groups such as groups;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Examples thereof include branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group.
Examples of the alkenediyl group include ethenediyl group, propenediyl group, isopropenediyl group, butenediyl group, isobutenediyl group, tert-butenediyl group, pentenediyl group, hexenediyl group, heptenediyl group, octynediyl group, isooctynediyl group, and nonenediyl group. .
Examples of the alkynediyl group include ethynediyl group, propynediyl group, isopropynediyl group, butynediyl group, isobutynediyl group, tert-butynediyl group, pentynediyl group, hexynediyl group, octynediyl group, and nonindiyl group.
Examples of the monocyclic divalent alicyclic hydrocarbon group include a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cyclohexene-3,6- Monocyclic cycloalkanediyl groups such as diyl group and cyclooctane-1,5-diyl group can be mentioned.
Examples of the polycyclic divalent alicyclic hydrocarbon group include norbornane-1,4-diyl group, norbornane-2,5-diyl group, 5-norbornene-2,3-diyl group, adamantane-1,5. -A polycyclic cycloalkanediyl group such as a diyl group and an adamantane-2,6-diyl group.
Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, and a phenanthrylene group.
Examples of the hydrocarbon group in combination of two or more include groups in which a chain hydrocarbon group and an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group are combined. Specifically, an alkanediyl group And a group in which an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group are combined, such as -cycloalkanediyl group-alkanediyl group-, -alkanediyl group-cycloalkanediyl group-, -alkanediyl Group-cycloalkanediyl group-alkanediyl group-, -alkanediyl group-aromatic hydrocarbon group-, -aromatic hydrocarbon group-alkanediyl group- and the like.

Examples of the substituent that the hydrocarbon group of L ⁴ and L ^{4 ′} may have include the same substituents as the substituent of the hydrocarbon group of L ¹ . Further, the group included by the substitution of —CH ₂ — in the hydrocarbon group is the same as the hydrocarbon group of L ¹ .
The divalent hydrocarbon group having 1 to 24 carbon atoms represented by L ⁴ and L ^{4 ′} may have one substituent or a plurality of substituents.

—CH ₂ — contained in the hydrocarbon group having 1 to 24 carbon atoms of L ⁴ and L ^{4 ′} may be replaced by —O—, —S—, —CO— or —SO ₂ —.
When the hydrocarbon group having 1 to 24 carbon atoms of L ⁴ and L ^{4 ′} has a substituent, or —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or —SO _2. When-is replaced, the carbon number before the replacement is the carbon number of the hydrocarbon group.

L ⁴ and L ^{4 ′} are each independently a single bond, an alkanediyl group having 1 to 6 carbon atoms or an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. (—CH ₂ — contained in the alkanediyl group may be replaced by —O— or —CO—, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, -S-, -CO- or -SO _2- may be substituted).
A single bond, an alkanediyl group having 1 to 6 carbon atoms, or * -an alicyclic hydrocarbon group having 3 to 18 carbon atoms-an alkanediyl group having 1 to 6 carbon atoms (the —CH ₂ — contained in the alkanediyl group is , -O- or -CO- may be substituted)-.
Single bond, alkanediyl group having 1 to 4 carbon atoms or * -adamantanediyl group -alkanediyl group having 1 to 4 carbon atoms (-CH _2- contained in the alkanediyl group is -O- or -CO- (It may be replaced)-is more preferable (* represents a binding site with X ¹ or X ² ).
L ⁴ and L ^{4 ′} may be groups different from each other, but are preferably the same group.

As the alkanediyl group of L ² and L ³ , a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, 2-methylpropane-1,3-diyl group, 2- Examples include branched alkanediyl groups such as methylpropane-1,2-diyl group.
Examples of the L3 ^′ alkanetriyl group include a methine group, an ethyne group, a propanetriyl group, and a butanetriyl group.
L ² and L ³ are each independently preferably a single bond or an alkanediyl group having 1 to 4 carbon atoms, and more preferably a single bond or a methylene group. L ² and L ³ may be groups different from each other, but are preferably the same group.
L ^{3 ′} is preferably an alkanetriyl group having 1 to 4 carbon atoms, and more preferably a methine group or an ethyne group.

In the group represented by the formula (Aa), examples of the alkyl group in R ⁵ , R ⁶ and R ⁷ 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. Can be mentioned.
The alicyclic hydrocarbon group for R ⁵ , R ⁶ and R ⁷ may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups 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 group (* represents a bonding site). R ^{5, R 6} and the carbon number of the alicyclic hydrocarbon group of ^{R 7} is preferably 3 to 16.
Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl An ethyl group etc. are mentioned.

In the group represented by the formula (Ab), examples of the hydrocarbon group in R ⁸ , R ⁹ and R ¹⁰ include a chain hydrocarbon group such as an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like. And groups formed by combining.
Examples of the alkyl group and alicyclic hydrocarbon group are the same as those described above.
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- Butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), an aromatic hydrocarbon group having an alicyclic hydrocarbon group ( p-cyclohexylphenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl groups (phenylcyclohexyl group etc.) and the like.
When R ⁹ and R ¹⁰ are bonded to each other to form a heterocyclic ring together with the carbon atom to which they are bonded and X ^b , -C (R ⁸ ) (R ⁹ ) -X ^b -R ¹⁰ includes the following rings: Can be mentioned. * Represents a binding site.
Of R ⁸ and R ⁹ , at least one is preferably a hydrogen atom.

Examples of the group represented by the formula (Aa) include the following groups. * Represents a binding site.

Examples of the group represented by the formula (Ab) include the following groups. * Represents a binding site.

The acid labile ring formed together with the oxygen atom to which R ³ and R ⁴ are bonded to each other is a monocyclic ring, a polycyclic ring or a spiro ring together with the two oxygen atoms bonded to L ¹ and L ^1. It may be formed. The total number of carbon atoms of ^{R 3} and ^{R 4} in this case is 1 to 20 and the like, 18 is preferred, 1 to 12 is more preferable.
When R ³ and R ⁴ are bonded to each other to form an acid labile ring together with the oxygen atom to which they are bonded, the following rings are exemplified.
R ³ and R ⁴ are preferably acid labile rings formed by bonding to each other. The acid labile ring here has a leaving group, the leaving group is eliminated by contact with an acid, and the structural unit has a hydrophilic group (for example, a hydroxy group or a carboxy group). It means the ring to be converted.

Examples of the structural unit (IA) include the structural units described below. The structural unit (IA) includes the structural unit (IA-1) to the structural unit (IA-8), the structural unit (IA-12), the structural unit (IA-13), the structural unit (IA-18), the structural unit ( IA-19) to the structural unit (IA-22), the structural unit (IA-1), the structural unit (IA-2), the structural unit (IA-5) to the structural unit (IA-7), The structural unit (IA-12), the structural unit (IA-13), the structural unit (IA-18), and the structural unit (IA-19) to the structural unit (IA-22) are more preferable.

Examples of the structural unit (IB) include the structural units described below. The structural unit (IB) includes the structural unit (IB-1) to the structural unit (IB-8), the structural unit (IB-12), the structural unit (IB-13), the structural unit (IB-18), and the structural unit ( IB-19), structural unit (IB-21), and structural unit (IB-22) are preferable, and structural unit (IB-1), structural unit (IB-2), and structural unit (IB-5) to Structural unit (IB-7), Structural unit (IB-12), Structural unit (IB-13), Structural unit (IB-18), Structural unit (IB-19), Structural unit (IB-21), Structural unit (IB-22) is more preferable.

In the structural units represented by formula (IA-1) to formula (IA-11), formula (IA-13), formula (IA-15), formula (IA-17) to formula (IA-22), In the structural unit in which the methyl group corresponding to R ¹ in (IA) is replaced with a hydrogen atom, and in the structural unit represented by the formula (IA-12), formula (IA-14), or formula (I-16), A structural unit in which a hydrogen atom corresponding to R ¹ in (IA) is replaced with a methyl group can also be given as a specific example of the structural unit (IA).
In the structural units represented by formula (IB-1) to formula (IB-11), formula (IB-13), formula (IB-15), formula (IB-17) to formula (IB-22), A structural unit in which a methyl group corresponding to R ¹ or R ² in (IB) is replaced with a hydrogen atom, and a structural unit represented by formula (IB-12), formula (IB-14), or formula (IB-16) In addition, a structural unit in which a hydrogen atom corresponding to R ¹ or R ² in formula (IB) is replaced with a methyl group can also be given as a specific example of the structural unit (IB).

The total content of the structural unit (IA) and the structural unit (IB) is usually 1 to 20 mol%, preferably 2 to 10 mol%, based on all monomers in the resin (A).
The resin (A) can contain one or both of the structural unit (IA) and the structural unit (IB). In any case, the structural unit (IA) and the structural unit (IB) may each contain two or more kinds.

<Structural Unit (a1-1) and Structural Unit (a1-2)>
The structural unit (a1-1) and the structural unit (a1-2) are represented by the following formulae.
[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents —CO—. Represents the binding site.
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 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents any integer of 0 to 3. ]

R ^a4 and R ^a5 are preferably methyl groups.
L ^a1 and L ^a2 are preferably an oxygen atom or * —O— (CH ₂ ) _k01 —CO—O— (where k01 is preferably any integer of 1 to 4, more preferably 1. More preferably an oxygen atom.
^Examples of the alkyl group for R ^a6 and R ^a7 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. Carbon number of the alkyl group in R ^a6 and R ^a7 is preferably 1-6, more preferably 1-4.
The alicyclic hydrocarbon group for R ^a6 and R ^a7 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups 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 group (* represents a bonding site). Carbon number of the alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably 3-8, more preferably 3-6.
Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, and norbornyl. An ethyl group etc. are mentioned. The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of the alkyl group and the alicyclic hydrocarbon 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 still more preferably an ethyl group or an isopropyl group.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably an integer of 0 to 2, and more preferably 0 or 1.

As a structural unit (a1-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Especially, the methyl group corresponding to R ^a4 in the structural unit represented by any one of the formulas (a1-1-1) to (a1-1-4) and the structural unit (a1-1) was replaced with a hydrogen atom. A structural unit is preferable, and a structural unit represented by any one of formulas (a1-1-1) to (a1-1-4) is more preferable.

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

The total content of the structural unit (a1-1) and / or the structural unit (a1-2) is usually 10 to 95 mol%, preferably 15 to 80 mol, based on all structural units of the resin (A). %, More preferably 15 to 75 mol%, still more preferably 20 to 70 mol%, and even more preferably 20 to 65 mol%.
The resin (A) preferably contains a structural unit (a1-1) and a structural unit (a1-2).

The resin (A) may further have a structural unit having an acid labile group other than the structural unit (a1-1) and the structural unit (a1-2).
As the structural unit having an acid labile group other than the structural unit (a1-1) and the structural unit (a1-2), for example, a structural unit represented by the formula (a1-0) (hereinafter, structural unit (a1- 0))). These may be used alone or in combination of two or more.
[In the formula (a1-0),
L ^a01 represents —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a binding site to —CO—.
R ^a01 represents 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 ^a01 is preferably a methyl group.
L ^a01 is preferably an oxygen atom or * —O— (CH ₂ ) _k01 —CO—O— (where k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably. Is an oxygen atom.
^Examples of the alkyl group for R ^a02 , R ^a03 and R ^a04 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. It is done.
The alicyclic hydrocarbon group for R ^a02 , R ^a03 and R ^a04 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups 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 group (* represents a bonding site). Carbon number of the alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 is preferably 3-16.
Examples of the group in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, methylcyclohexyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl An ethyl group etc. are mentioned.
The carbon number of the alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 is preferably 3-8, more preferably 3-6.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of the alkyl group and the alicyclic hydrocarbon group.
R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

As the structural unit (a1-0), for example, a structural unit represented by any one of formulas (a1-0-1) to (a1-0-12) and a methyl group corresponding to R ^a01 can be a hydrogen atom. The substituted structural unit is mentioned, The structural unit represented by either of Formula (a1-0-1)-Formula (a1-0-10) is preferable.

  When resin (A) contains a structural unit (a1-0), the content rate is 1-50 mol% normally with respect to all the structural units of resin (A), Preferably it is 3-40 mol%. Yes, more preferably 5 to 30 mol%.

As the structural unit having an acid labile group other than the structural unit (a1-1) and the structural unit (a1-2), a structural unit represented by the formula (a1-4) (hereinafter referred to as “structural unit (a1-4)”. ) ”))).
[In the formula (a1-4),
R ^a32 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 is 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 An oxy group or a methacryloyloxy group is represented.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ^a33 may be the same as 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 Together with —C—O— to which they are bonded to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent hydrocarbon group is — O- or -S- may be substituted. ]

^Examples of the alkyl group for R ^a32 and R ^a33 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 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, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, 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. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more 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, and a butyryloxy group.
As the hydrocarbon group for R ^a34, R ^a35 and R ^a36, an alkyl group, an alicyclic hydrocarbon group include aromatic hydrocarbon group, include the same groups as R ⁸ and R ⁹ of formula (Ab) It is done. In particular, as R ^a36 , 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 formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
As la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 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 for R ^a36 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 to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic 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 in R ^a36 are preferably unsubstituted. The aromatic hydrocarbon group for R ^a36 is preferably an aromatic ring having 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.

As a structural unit (a1-4), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Preferably, hydrogen atom corresponding to the structural units and R ^a32 each represented by formula (a1-4-1) ~ formula (a1-4-12) are exemplified a structural unit replacing a methyl group, more preferably , Structural units represented by formula (a1-4-1) to formula (a1-4-5) and formula (a1-4-10), respectively.

  When resin (A) has a structural unit (a1-4), it is preferable that the content rate is 5-60 mol% with respect to the sum total of all the structural units of resin (A), and 5-50 It is more preferable that it is mol%, and it is further more preferable that it is 10-40 mol%.

As the structural unit having an acid labile group other than the structural unit (a1-1) and the structural unit (a1-2), a structural unit represented by the formula (a1-5) (hereinafter “structural unit (a1-5)”) May also be mentioned).
In formula (a1-5),
R ^a8 represents a C 1-6 alkyl group optionally having a halogen atom, a hydrogen atom, or a halogen atom.
Z ^a1 represents a single bond or * — (CH ₂ ) _h3 —CO—L ⁵⁴ —, h3 represents any integer of 1 to 4, and * represents a binding site to L ⁵¹ .
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent —O— or —S—.
s1 represents any integer of 1 to 3.
s1 ′ represents any integer of 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 methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, fluoromethyl and trifluoro A methyl group is mentioned.
In 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 is preferably —O— and the other is preferably —S—.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

As a structural unit (a1-5), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-611117 is mentioned, for example. Among these, structural units each represented by formula (a1-5-1) to formula (a1-5-4) are preferable, and are represented by formula (a1-5-1) or formula (a1-5-2). A structural unit is more preferable.

  When resin (A) has a structural unit (a1-5), the content rate is preferable 1-50 mol% with respect to all the structural units of resin (A), and 3-45 mol% is more preferable. 5 to 40 mol% is more preferable.

As the structural unit having an acid labile group other than the structural unit (a1-1) and the structural unit (a1-2), for example, a structural unit represented by the formula (a1-0X) (hereinafter, structural unit (a1- 0X)))). Two or more types may be selected from the structural unit (a1-0X) and added to the resin (A).
[In the formula (a1-0X),
R ^X1 represents a hydrogen atom or a methyl group.
R ^x2 and R ^x3 each independently represent a saturated hydrocarbon group having 1 to 6 carbon atoms.
Ar ^X1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms. ]

Examples of the saturated hydrocarbon group for R ^x2 and R ^x3 include an alkyl group, an alicyclic hydrocarbon group, and a group formed by a combination thereof.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the aromatic hydrocarbon group represented by Ar ^X1 include aryl groups having 6 to 36 carbon atoms such as a phenyl group, a naphthyl group, and an anthryl group.
The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably a phenyl group.
Ar ^X1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group.
R ^X1 , R ^x2 and R ^x3 are each independently preferably a methyl group or an ethyl group, and more preferably a methyl group.

Examples of the structural unit (a1-0X) include the structural units described below. The structural unit (a1-0X) is preferably a structural unit (a1-0X-1) to a structural unit (a1-0X-3).

A compound in which the methyl group corresponding to R ^X1 is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a1-0X).

When resin (A) has a structural unit (a1-0X), it is preferable that the content rate is 5-60 mol% with respect to all the monomers in resin (A), and is 5-50 mol%. More preferably, it is more preferably 10 to 40 mol%.
The resin (A) may contain two or more structural units (a1-0X).

Examples of the structural unit having an acid labile group other than the structural unit (a1-1) and the structural unit (a1-2) include the following structural units.

  When resin (A) contains the said structural unit, the content rate is preferable with respect to all the structural units of resin (A), 5-60 mol% is more preferable, 5-50 mol% is more preferable, 10-40 mol % Is more preferable.

  Resin (A) is further a structural unit derived from a monomer having no acid labile group (hereinafter sometimes referred to as “monomer (s)”) other than a structural unit (hereinafter sometimes referred to as “structural unit (s)”). For example, a structural unit having a halogen atom (hereinafter sometimes referred to as “structural unit (a4)”), a structural unit having no halogen atom and having a non-leaving hydrocarbon group (hereinafter referred to as “structural unit ( a5) ”and / or other structural units derived from monomers known in the art.

<Structural unit (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. A structure having a hydroxy group and having no acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or a lactone ring and having no acid labile group If a resin having a unit (hereinafter sometimes referred to as “structural unit (a3)”) is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When a resist pattern is produced from the resist composition of the present invention, when a high energy beam such as a KrF excimer laser (248 nm), an electron beam or EUV (ultra-ultraviolet light) is used as an exposure light source, the structural unit (a2) It is preferable to use the structural unit (a2) having a phenolic hydroxy group. When using an ArF excimer laser (193 nm) or the like, the structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2), and the structural unit (a2-1) described later is more used. preferable. As a structural unit (a2), 1 type may be included independently and 2 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 sometimes referred to as “structural unit (a2-A)”).
[In the formula (a2-A),
R ^a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a51 is 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 An oxy group or a methacryloyloxy group is represented.
A ^a50 represents a single bond or ^* —X ^a51 — (A ^a52 —X ^a52 ) _nb —, and * represents a bonding site to the carbon atom to which —R ^a50 is bonded.
A ^a52 represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent —O—, ^—CO —O— or —O—CO—.
nb represents 0 or 1.
mb represents an integer of 0 to 4. When mb is any integer of 2 or more, the plurality of ^Ra51s may be the same as or different from each other. ]

^Examples of the halogen atom for R ^a50 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 in 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 group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group and perfluoro A hexyl group is mentioned.
R ^a50 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 even more preferably a hydrogen atom or a methyl group.
^Examples of the alkyl group for R ^a51 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 R ^a51 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. A C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is more preferable.
^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 R ^a51 include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
R ^a51 is preferably a methyl group.

^* -X ^a51- (A ^a52 -X ^a52 ) _nb- includes ^* -O-, ^* -CO-O-, ^* -O-CO-, ^* -CO-O-A ^a52 -CO-O-, ^* —O—CO—A ^a52 —O—, ^* —O—A ^a52 —CO—O—, ^* —CO—O—A ^a52 —O—CO—, ^* —O—CO—A ^a52 —O—CO -. Of these, ^* —CO—O—, ^* —CO—O—A ^a52 —CO—O— or ^* —O—A ^a52 —CO—O— is preferable.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -Methylbutane-1,4-diyl group etc. are mentioned.
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 is preferably a single bond, ^* —CO—O— or ^* —CO—O—CH. _2- CO-O- is more preferable, and a single bond or ^* -CO-O- is more preferable.

mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0.
The hydroxy group is preferably bonded to the o-position or p-position of the benzene ring, and more preferably bonded to the p-position.

  Examples of the structural unit (a2-A) include structural units derived from monomers described in JP2010-204634A and JP2012-12577A.

As the structural unit (a2-A), structural units represented by formula (a2-2-1) to formula (a2-2-6) and formula (a2-2-1) to formula (a2-2-2) In the structural unit represented by 6), a structural unit in which a methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom can be mentioned. The structural unit (a2-A) is represented by the structural unit represented by the formula (a2-2-1), the structural unit represented by the formula (a2-2-3), and the formula (a2-2-6). A structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3) or a structural unit represented by formula (a2-2-6), The structural unit is preferably a structural unit in which a methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom.

When the structural unit (a2-A) is contained in the resin (A), the content of the structural unit (a2-A) is preferably 5 to 80 mol%, more preferably based on all structural units. It is 10-70 mol%, More preferably, it is 15-65 mol%, More preferably, it is 20-65 mol%.
The structural unit (a2-A) can be included in the resin (A) by treating, for example, a resin containing the structural unit (a1-4) with an acid such as p-toluenesulfonic acid. Moreover, after superposing | polymerizing using acetoxy styrene etc., a structural unit (a2-A) can be included in resin (A) by processing with alkalis, such as a 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 formula (a2-1),
L ^a3 represents —O— or ^* —O— (CH ₂ ) _k2 —CO—O—,
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 represents a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10.

In the formula (a2-1), L ^a3 is preferably —O—, —O— (CH ₂ ) _f1 —CO—O— (wherein f1 represents an integer of 1 to 4). More preferably, it is —O—.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

Examples of the structural unit (a2-1) include structural units derived from monomers described in JP2010-204646A. A structural unit represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferred, and any one of formula (a2-1-1) to formula (a2-1-4) The structural unit represented is more preferable, and the structural unit represented by the formula (a2-1-1) or the formula (a2-1-3) is more preferable.

  When resin (A) contains a structural unit (a2-1), the content rate is 1-45 mol% normally with respect to all the structural units of resin (A), Preferably it is 1-40 mol%. Yes, more preferably 1 to 35 mol%, still more preferably 1 to 20 mol%, and even more preferably 1 to 10 mol%.

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

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 Formula (a3-1), Formula (a3-2), Formula (a3-3) and Formula (a3-4),
L ^a4 , L ^a5 and L ^a6 are each independently represented by —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents an integer of 1 to 7). 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 ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents a binding site with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently represents 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.
R ^a21 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 any integer 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 0 to 8.
When p1, q1, r1 and / or w1 is 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same as or different from each other. ]

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl groups. It is done.
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 R ^a24 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 for R ^a24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.

^Examples of the alkanediyl group in ^La8 and ^La9 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and 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, 4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned.

In the formula (a3-1) to the formula (a3-3), L ^{a4 to} L ^a6 are each independently, preferably —O— or * —O— (CH ₂ ) _k3 —CO—O—, Is a group of any one of 1 to 4, more preferably —O— and * —O—CH ₂ —CO—O—, still more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 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 0 to 2, more preferably 0 or 1.

In 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 still more preferably a hydrogen atom or a methyl group. It is.
R ^a25 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 —O—, —O—CH ₂ —CO—O— or —O—C ₂ H ₄ —. CO-O-.
w1 is preferably an integer of 0 to 2, and more preferably 0 or 1.
In particular, the formula (a3-4) is preferably the formula (a3-4) ′.
(In the formula, R ^a24 and L ^a7 represent the same meaning as described above.)

As the structural unit (a3), a monomer derived from JP2010-204646, a monomer described in JP2000-122294A, a structure derived from a monomer described in JP2012-41274A Units are listed. 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) 1), a structural unit represented by any one of formula (a3-3-2) and formula (a3-4-1) to formula (a3-4-12), and the structural unit represented by formula (a3-1) ) To a structural unit in which a methyl group corresponding to R ^a18 , R ^a19 , R ^a20 and R ^a24 in formula (a3-4) is replaced with a hydrogen atom.

When the resin (A) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A). More preferably, it is 10-60 mol%.
Moreover, the content rate of a structural unit (a3-1), a structural unit (a3-2), a structural unit (a3-3), or a structural unit (a3-4) is respectively with respect to all the structural units of resin (A). 5 to 60 mol% is preferable, 5 to 50 mol% is more preferable, and 10 to 50 mol% is more 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 fluorine atom having 1 to 24 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —CO. ]
Saturated hydrocarbon groups represented by R ⁴² is a chain hydrocarbon group and monocyclic or polycyclic alicyclic hydrocarbon group, and, and a group formed by combining these.

The chain hydrocarbon group includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Can be mentioned.
Examples of monocyclic or polycyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; decahydronaphthyl, adamantyl, norbornyl, and the following groups And polycyclic alicyclic hydrocarbon groups such as (* 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 and one or more alicyclic hydrocarbon groups, -alkanediyl group- An alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like can be mentioned.

The structural unit (a4) is at least selected from the group consisting of formula (a4-0), formula (a4-1), formula (a4-2), formula (a4-3), and formula (a4-4). A structural unit represented by one is mentioned.
[In the formula (a4-0),
R ^5a represents a hydrogen atom or a methyl group.
L ^4a represents a single bond or a divalent alkanediyl having 1 to 4 carbon atoms.
L ^3a represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
R ^6a represents a hydrogen atom or a fluorine atom. ]

^Examples of the divalent alkanediyl group in L ^4a include linear alkanediyl groups such as methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, and ethane-1,1- Branched alkanediyl such as diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group Groups.

As the perfluoroalkanediyl group in L ^3a , difluoromethylene group, perfluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane -2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane -2,2-diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane -1,7-diyl group, perfluorohe Tan-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 Examples include an octane-3,3-diyl group and a perfluorooctane-4,4-diyl group.
^Examples of the perfluorocycloalkanediyl group in L ^3a include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, and a perfluoroadamantanediyl group.

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 C 1-6 perfluoroalkanediyl group, and more preferably a C 1-3 C perfluoroalkanediyl group.

As the structural unit (a4-0), a structural unit in which the methyl group corresponding to R ^5a in the structural unit shown below and the structural unit (a4-0) in the structural unit shown below is replaced with a hydrogen atom can be mentioned.

[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a C1-C20 saturated hydrocarbon group which may have a substituent, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— or —CO—. May be.
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 ^C 1-5 divalent saturated hydrocarbon group which may have a substituent.
A ^a43 represents a ^C1-C5 divalent aliphatic hydrocarbon group which may have a single bond or 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. ]
* ^Represents a binding site, and * on the right side is a binding site to —O—CO—R ^a42 . ]

^Examples of the saturated hydrocarbon group for R ^a42 include a chain saturated hydrocarbon group, a monocyclic or polycyclic alicyclic saturated hydrocarbon group, and a group formed by combining these.
The chain saturated hydrocarbon group includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Is mentioned. Examples of monocyclic or polycyclic alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; decahydronaphthyl, adamantyl, norbornyl, and the following groups And polycyclic alicyclic saturated hydrocarbon groups such as (* 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 and one or more saturated alicyclic hydrocarbon groups, and -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 R ^a42 may have include at least one selected from the group consisting of a halogen atom and a group represented by the formula (a-g3). As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably it is a fluorine atom.
[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, * ^—O —CO— or * —CO—O— (* represents a bonding site with R ^a42 ).
A ^a45 represents an aliphatic 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 does not have a halogen atom, A ^a45 represents a C ^1-17 aliphatic hydrocarbon group having at least one halogen atom.

^Examples of the aliphatic hydrocarbon group for A ^a45 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and Alkyl groups such as octadecyl group; monocyclic alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; and decahydronaphthyl group, adamantyl group, norbornyl group and the following groups: And polycyclic alicyclic hydrocarbon groups such as (* 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 and one or more alicyclic hydrocarbon groups, -alkanediyl group- An alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group and the like can be mentioned.

R ^a42 is preferably a saturated hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or a saturated hydrocarbon group having a group represented by 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, still more preferably 1 to 1 carbon atoms. 6 perfluoroalkyl group, 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 R ^a42 is a saturated hydrocarbon group having a group represented by the formula (a-g3), including the number of carbons contained in the group represented by the formula (a-g3), the total carbon of R ^a42 The number is preferably 15 or less, and more preferably 12 or less. When it has a group represented by the formula (a-g3) as a substituent, the number is preferably 1.

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 C ^1-17 divalent saturated hydrocarbon group which may have a halogen atom.
X ^a44 represents * ^—O —CO— or * —CO—O— (* represents a binding site with A ^a46 ).
A ^a47 represents an aliphatic 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 binding site with a carbonyl group. ]

1-6 are preferable and, as for carbon number of the saturated hydrocarbon group of ^Aa46 , 1-3 are more preferable.
4-15 are preferable, as for carbon number of the aliphatic hydrocarbon group of A ^<a47> , 5-12 are more preferable, and A ^<a47> is further more preferably a cyclohexyl group or an adamantyl group.

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

As the alkanediyl group in ^Aa41 , a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group Linear alkanediyl group 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 thereof include branched alkanediyl groups such as 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.

The divalent saturated hydrocarbon group represented by A ^a42 , A ^a43 and A ^{a44 in} the group represented by the formula (a-g1) includes a linear or branched alkanediyl group and a monocyclic or polycyclic divalent divalent hydrocarbon group. Examples thereof include an alicyclic hydrocarbon group and a group formed by combining an alkanediyl group and a divalent alicyclic hydrocarbon group. Specifically, a methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, Examples include 2-methylpropane-1,3-diyl group and 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 with —O—CO—R ^a42 .

As the structural unit represented by the formula (a4-1), a methyl group corresponding to R ^a41 in the structural unit shown below and the structural unit represented by the formula (a4-1) in the following structural unit is a hydrogen atom. Examples include structural units that have been replaced.

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

Alkanediyl group of L ⁴⁴ include the same groups as those exemplified with L ^4a.
Examples of the saturated hydrocarbon group for R ^f6 include the same groups as those exemplified for R ⁴² .
The alkanediyl group for L ⁴⁴ is preferably an 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 formula (a4-1-1) to formula (a4-1-11), respectively. A structural unit in which a 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 C 1-18 divalent saturated hydrocarbon group which may have a fluorine atom.
X ^f12 represents * —O—CO— or * —CO—O— (* represents a binding site with A ^f13 ).
A ^f14 represents a C ^1-17 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 in L ⁵ include the same groups as those exemplified for the alkanediyl group of L ^4a .

The divalent saturated hydrocarbon group which may have a fluorine atom in A ^f13 preferably has a divalent chain saturated hydrocarbon group which may have a fluorine atom and a fluorine atom. A divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanediyl group.
Examples of the divalent chain hydrocarbon group which may have a fluorine atom include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; difluoromethylene group, perfluoroethylene group, perfluoro Examples thereof include perfluoroalkanediyl groups such as propanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.
The divalent alicyclic hydrocarbon group which may have a fluorine atom may be 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, and a perfluoroadamantanediyl group.

As the saturated hydrocarbon group for A ^{f14 and} the saturated hydrocarbon group which may have a fluorine atom, the same groups as those exemplified for R ⁴² can be mentioned. 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, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3 , 3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl Group, heptyl group, perfluoroheptyl group, octyl group, perfluorooctyl group and other fluorinated alkyl groups, cyclopropylmethyl group, cyclopropyl group, cyclobutyl group Rumechiru group, a cyclopentyl group, a cyclohexyl group, perfluorocyclohexyl group, an adamantyl group, adamantylmethyl group, adamantyl dimethyl group, norbornyl group, norbornylmethyl group, perfluoro adamantyl group, a perfluoroalkyl adamantylmethyl group and the like are preferable.

In formula (a4-3), L ⁵ is preferably an ethylene group.
The divalent saturated hydrocarbon group for A ^f13 is preferably a group containing a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms. 2-3 divalent chain hydrocarbon groups are more preferred.
The saturated hydrocarbon group for A ^f14 is preferably a group containing a chain hydrocarbon group having 3 to 12 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a chain hydrocarbon group having 3 to 10 carbon atoms. And a group containing an alicyclic hydrocarbon group having 3 to 10 carbon atoms is more preferable. Among them, A ^f14 is preferably a group containing an alicyclic 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 formula (a4-3) include structural units represented by formula (a4-1′-1) to formula (a4-1′-11), respectively. A structural unit in which a 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) include a structural unit represented by the formula (a4-4).
[In the formula (a4-4),
R ^f21 represents a hydrogen atom or a methyl group.
A ^f21 represents — (CH ₂ ) _j1 —, — (CH ₂ ) _j2 —O— (CH ₂ ) _j3 — or — (CH ₂ ) _j4 —CO—O— (CH ₂ ) _j5 —.
j1 to j5 each independently represents an integer of 1 to 6.
R ^f22 represents a C 1-10 saturated hydrocarbon group having a fluorine atom. ]

^Examples of the saturated hydrocarbon group for R ^f22 include the same saturated hydrocarbon group represented by R ^a42 . R ^f22 is preferably a ^C 1-10 alkyl group having a fluorine atom or a C 1-10 alicyclic hydrocarbon group having a fluorine atom, more preferably a C 1-10 alkyl group having a fluorine atom. Preferably, the C1-C6 alkyl group which has a fluorine atom is further more preferable.

In Formula (a4-4), A ^f21 is preferably — (CH ₂ ) _j1 —, more preferably an ethylene group or a methylene group, and still more preferably a methylene group.

As the structural unit represented by the formula (a4-4), for example, in the following structural unit and the structural unit represented by the following formula, a methyl group corresponding to R ^f21 in the structural unit (a4-4) is hydrogen. Examples include structural units replaced by atoms.

  When the resin (A) has a structural unit (a4), the content is preferably 1 to 20 mol%, more preferably 2 to 15 mol%, based on all structural units of the resin (A). More preferably, it is 10 mol%.

<Structural unit (a5)>
Examples of the non-elimination hydrocarbon group that the structural unit (a5) has include a group having a linear, branched, or cyclic hydrocarbon group. Among these, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.
As a structural unit (a5), the structural unit represented by a formula (a5-1) is mentioned, for example.
[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 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.
Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and 2 -Alkyl groups, such as an ethylhexyl group, are mentioned.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and 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, 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 cycloalkanediyl groups such as cyclopentanediyl group and cyclohexanediyl group. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adamantanediyl group and a norbornanediyl group.

Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ⁵⁵ is replaced by —O— or —CO— include those represented by formulas (L1-1) to (L1-4): And the group represented. In the following formula, * and ** each represent a binding site, and * represents a binding site with an oxygen atom.
In formula (L1-1),
X ^x1 represents * —O—CO— or * —CO—O— (* represents a binding site with 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 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 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 aliphatic saturated 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 formula (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of L ^x8 , L ^x9 and W ^x1 is 15 or less.

L ^x1 is preferably a C 1-8 divalent aliphatic saturated hydrocarbon group, 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, more preferably a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x5 is preferably a C 1-8 divalent aliphatic saturated hydrocarbon group, more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.
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 C 3-10 divalent alicyclic saturated hydrocarbon group, more preferably a cyclohexanediyl group or an adamantanediyl group.

As group represented by a formula (L1-1), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-2), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-3), the bivalent group shown below is mentioned, for example.

As group represented by a formula (L1-4), the bivalent group shown below is mentioned, for example.

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

Examples of the structural unit (a5-1) include structural units in which the methyl group corresponding to R ⁵¹ in the structural unit shown below and the structural unit (a5-1) in the structural unit shown below is replaced with a hydrogen atom.
When the resin (A) has the structural unit (a5), the content is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, based on all structural units of the resin (A). More preferred is ˜15 mol%.

<Structural unit (II)>
The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter sometimes referred to as “structural unit (II)”. As the structural unit (II), Specifically, the structural unit described in JP-A-2016-79235 can be mentioned, and the structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain, or the structural unit having a sulfonio group and an organic anion in the side chain It is preferable that

The structural unit having a sulfonate group or carboxylate group and an organic cation in the side chain 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 with 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 , an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 ; The same can be 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, etc. Can be mentioned.
Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted with A ^x1 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoro sec-butyl group, perfluoro tert -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, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. Or a combination thereof.
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 Branched 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 group 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 Bivalent polycyclic alicyclic saturated hydrocarbon groups and the like.
Examples of the group in which —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —S—, or —CO— include divalent groups represented by formula (X1) to formula (X53), for example. Can be mentioned. However, the number of carbon atoms before —CH ₂ — contained in the saturated hydrocarbon group is replaced with —O—, —S—, or —CO— is 17 or less. In the following formula, * and ** represent a 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 organic onium cations such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, organic benzothiazolium cation, and organic phosphonium cation, and organic sulfonium cation and organic iodonium cation. Are preferred, and arylsulfonium cations are more preferred.
Examples of ZA ^{+ in} formula (II-2-A ′) include the same as cation Z ⁺ in the acid generator (B1) described later.

The structural unit represented by the formula (II-2-A ′) is preferably a structural unit represented by the formula (II-2-A).
[In Formula (II-2-A), R ^III3 , X ^III3 and ZA ⁺ represent the same meaning as described above.
z2A represents an 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, the plurality of R ^III2 and R ^III4 are the same as each other It may be different or different.
Q ^a and Q ^b each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. ]
^{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 later. .

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 0 to 6.
X ^I2 represents a divalent saturated hydrocarbon group having 1 to 11 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 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 methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Examples thereof include linear or branched alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
Examples of the divalent saturated hydrocarbon group represented by X ^I2 include the same divalent saturated hydrocarbon groups 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 International Publication No. 2012/050015. ZA ⁺ represents the same meaning as described above.

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 thereof 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 , an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 ; The same can be 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: -O-, -S- or -CO- may be substituted. Specifically, the same thing as a C1-C18 bivalent saturated hydrocarbon group represented by ^XIII3 is mentioned.

As the structural unit containing a cation in formula (II-1-1), the structural unit represented below and the group corresponding to the methyl group of R ^II4 were replaced with a hydrogen atom, a fluorine atom, trifluoromethyl, or the like. Examples include structural units.

A ^- The organic anion represented by a sulfonic acid anion, sulfonyl imide anion, methide anion and a carboxylate anion, and the like. A ^- organic anion represented by the sulfonate anion are preferable, and as a sulfonate anion, more preferably an anion contained in the salt represented by the formula (B1) to be described later.

A ^- The sulfonyl imide anions represented by, the following may be mentioned.

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 structural units represented below.

  When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is preferably 1 to 20 mol% with respect to the total structural units of the resin (A). Preferably it is 2-15 mol%, More preferably, it is 3-10 mol%.

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

  The resin (A) includes at least one selected from the group consisting of the structural unit (IA) and the structural unit (IB), and a structural unit represented by the structural unit (a1-1) and the structural unit (a1-2). Although it may be a resin composed of at least one selected from the group, preferably, at least one selected from the group consisting of the structural unit (IA) and the structural unit (IB), the structural unit (a1-1) and At least one selected from the group consisting of structural units represented by the structural unit (a1-2) and a resin consisting of the structural unit (s), a structural unit (IA), and a structural unit (IB). At least one, at least one selected from the group consisting of structural units represented by structural unit (a1-1) and structural unit (a1-2), structural unit (a1-0), and structural unit (s) Kara At least one selected from the group consisting of resin, structural unit (IA) and structural unit (IB), and selected from the group consisting of structural units represented by structural unit (a1-1) and structural unit (a1-2) Resin comprising at least one, structural unit (s), structural unit (a4) and / or structural unit (a5), more preferably selected from the group consisting of structural unit (IA) and structural unit (IB) A resin comprising at least one and at least one selected from the group consisting of structural units represented by structural unit (a1-1) and structural unit (a1-2), and structural unit (s), structural unit (IA) And at least one selected from the group consisting of structural units (IB), at least one selected from the group consisting of structural units represented by structural units (a1-1) and (a1-2), The unit (a1-0), a resin consisting of a structural unit (s).

  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 represented by the formula (a2-A) or a structural unit represented by the formula (a2-1). 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). Is at least one selected from

Each structural unit 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, radical polymerization method) using a monomer that derives these structural units. be able to. The content rate of each structural unit which resin (A) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, more preferably 15,000 or less).
In this specification, the weight average molecular weight is a value determined by gel permeation chromatography. Gel permeation chromatography can be measured by the analytical conditions described in the examples.

[Resist composition]
The resist composition of the present invention preferably contains a resin (A) and an acid generator known in the resist field (hereinafter sometimes referred to as “acid generator (B)”).
The resist composition of the present invention preferably further contains a resin other than the resin (A).
The resist composition of the present invention preferably contains a quencher such as a salt that generates an acid having a lower acidity than an acid generated from an acid generator (hereinafter sometimes referred to as “quencher (C)”). And a solvent (hereinafter sometimes referred to as “solvent (E)”).

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). The resin other than the resin (A) may be any resin that does not contain the structural unit (IA) and the structural unit (IB), or the structural unit (a1-1) and the structural unit (a1-2). Examples of such a resin include a resin obtained by removing the structural unit (IA) and the structural unit (IB) from the resin (A) (hereinafter sometimes referred to as “resin (A2)”), and a structural unit from the resin (A). Resin excluding (a1-1) and the structural unit (a1-2) (hereinafter sometimes referred to as “resin (A3)”), a resin consisting only of the structural unit (a4) and the structural unit (a5) (hereinafter referred to as “resin (A3)”) Resin (X) in some cases).

As the resin (X), a resin containing the structural unit (a4) (however, the structural unit (IA) and the structural unit (IB) are not included) is preferable.
In the resin (X), the content of the structural unit (a4) is preferably 30 mol% or more, more preferably 40 mol% or more with respect to the total of all the structural units of the resin (X). More preferably, it is 45 mol% or more.
Examples of the structural unit that the resin (X) may further include a structural unit derived from the structural unit (a2), the structural unit (a3), and other known monomers. Especially, it is preferable that resin (X) is resin which consists only of a structural unit (a4) and / or a structural unit (a5).

Each structural unit 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, radical polymerization method) using a monomer that derives these structural units. can do. The content rate of each structural unit which resin (X) has can be adjusted with the usage-amount of the monomer used for superposition | polymerization.
The weight average molecular weights of the resin (A2), the resin (A3), and the resin (X) are each independently preferably 6,000 or more (more preferably 7,000 or more), 80,000 or less (more preferably 60). , 000 or less). The means for measuring the weight average molecular weight of the resin (A2), the resin (A3) and the resin (X) is the same as in the case of the resin (A).
When the resist composition of this invention contains resin (A2) and / or resin (A3), the total content is 1-2500 mass parts (more preferably) with respect to 100 mass parts of resin (A). Is 10 to 1000 parts by mass).
Moreover, when a resist composition contains resin (X), the content becomes like this. Preferably it is 1-60 mass parts with respect to 100 mass parts of resin (A), More preferably, it is 1-50 mass parts. More preferably, it is 1-40 mass parts, Most preferably, it is 1-30 mass parts, Most preferably, it is 1-8 mass parts.

  In the resist composition of the present invention, the resin (A) is preferably used in combination with a resin other than the resin (A), and includes a resin containing a structural unit having an acid labile group and / or a resin containing a structural unit having a fluorine atom. Is more preferable, and it is more preferable to use the resin (A2), the resin (A3) and / or the resin (X) in combination.

  The content of the resin (A) in the resist composition is preferably 80% by mass or more and 99% by mass or less, and more preferably 90-99% by mass with respect to the solid content of the resist composition. Moreover, when resin other than resin (A) is included, the total content rate of resin other than resin (A) and resin (A) is 80 mass% or more and 99 mass% with respect to solid content of a resist composition. The following is preferable, and 90 to 99% by mass is more preferable. The solid content of the resist composition and the resin content relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<Acid generator (B)>
The acid generator (B) may be either nonionic or ionic. Examples of the nonionic acid generator include sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (for example, disulfone, Ketosulfone, sulfonyldiazomethane) and the like. Typical examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts). Examples of the anion of the onium salt include a sulfonate 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, JP-A-63-163452, Kaisho 62-153853, JP 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat.No. 3,849,137, German Patent 3914407, European Patent 126,712, etc. The compound which generate | occur | produces an acid by the radiation as described in 1 can be used. Moreover, you may use the compound manufactured by the well-known method. Two or more acid generators (B) may be used in combination.

The acid generator (B) is preferably a fluorine-containing acid generator, 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 divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — may be replaced by —O—, —S (O) ₂ —, or —CO—.
Z ⁺ represents an organic cation. ]

^Examples of the perfluoroalkyl group represented by Q ^b1 and Q ^b2 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro sec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and A perfluorohexyl group etc. are mentioned.
Q ^b1 and Q ^b2 are preferably each independently a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom.

Examples of the divalent saturated hydrocarbon group for L ^b1 include a linear alkanediyl group, a branched alkanediyl group, 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 , 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 cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Groups and the like.

Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ^b1 is replaced by —O— or —CO— include, for example, formulas (b1-1) to (b1-3) Or a group represented by any of the above. In the groups represented by formula (b1-1) to formula (b1-3) and the groups represented by formula (b1-4) to formula (b1-11) as specific examples thereof, * and * * Represents a binding site, and * represents a binding site to -Y.

[In the formula (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the 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 the 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 with —O— or —CO—.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In formula (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the 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 the 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 with —O— or —CO—.
However, the total carbon number of L ^b4 and L ^b5 is 22 or less.
In formula (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the 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 the 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 with —O— or —CO—.
However, the total carbon number of L ^b6 and L ^b7 is 23 or less. ]

In the groups represented by formula (b1-1) to formula (b1-3), when —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— or —CO—, the carbon before the replacement The number is the carbon number of the saturated hydrocarbon group.
Examples of the divalent saturated hydrocarbon group include the same divalent saturated hydrocarbon groups as those represented by 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 the 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 the 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—.
The group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ¹ is replaced by —O— or —CO— is represented by the formula (b1-1) or the formula (b1-3). Preferred are the groups

Examples of the group represented by the formula (b1-1) include groups represented by the formula (b1-4) to the formula (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 the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In 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 the 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 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 the 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 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, and —CH ₂ — contained in the divalent saturated hydrocarbon group is replaced by —O— or —CO—. Also good.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the 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 ^{b13 to} L ^b15 is 19 or less.
In formula (b1-8),
L ^b16 represents a C 1-18 divalent saturated hydrocarbon group, 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 the 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, 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 formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11), respectively.
In formula (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the 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 the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In formula (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and the 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 the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b21 , L ^b22 and L ^b23 is 21 or less.
In formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the 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 the hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced with —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxy group.
However, L ^b24, the total number of carbon atoms of L ^b25 and L ^b26 is 21 or less.

  In addition, in the group represented by the formula (b1-11) to the group represented by the formula (b1-9), when the hydrogen atom contained in the saturated hydrocarbon group is substituted with an alkylcarbonyloxy group, the group is replaced. The previous carbon number is defined as the carbon number of the saturated hydrocarbon group.

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

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 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 is replaced by —O—, —S (O) ₂ — or —CO—, the number may be one, or two or more. Good. Examples of such a group include groups represented by formula (Y12) to formula (Y35) and formula (Y39) to formula (Y41).

The alicyclic hydrocarbon group represented by Y is preferably formula (Y1) to formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39). To a group represented by any one of formula (Y41), more preferably formula (Y11), formula (Y15), formula (Y16), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) or group represented by formula (Y40), more preferably formula (Y11), formula (Y15), formula (Y20), formula (Y30), formula (Y39) or a group represented by the formula (Y40).
When the alicyclic hydrocarbon group represented by Y is a spiro ring such as formula (Y28) to formula (Y35), formula (Y39) to formula (Y40), etc., an alkanediyl group between two oxygen atoms Preferably has one or more fluorine atoms. Of the alkanediyl groups contained in the ketal structure, the methylene group adjacent to the oxygen atom is preferably not substituted with a fluorine atom.

Examples of the substituent of the methyl group represented by Y 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,-( CH ₂ ) _ja —CO—O—R ^b1 group or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms and 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 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 by —O—, —S (O) ₂ —, or —CO—).
Examples of the substituent for the alicyclic hydrocarbon group represented by Y 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. A hydrocarbon group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, a glycidyloxy group,-( CH ₂ ) _ja —CO—O—R ^b1 group or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms and 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 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 aryl groups 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, and an 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) and an aromatic hydrocarbon group having an alicyclic hydrocarbon group ( p-cyclohexylphenyl group, p-adamantylphenyl group, etc.).
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 hydroxyalkyl groups such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and 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.

Examples of Y include the following.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and the alicyclic carbonization —CH ₂ — constituting the hydrogen group or adamantyl group may be replaced by —CO—, —S (O) ₂ — or —CO—. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group represented by the following.

As the sulfonate anion in the salt represented by the formula (B1), an anion represented by the formula (B1-A-1) to the formula (B1-A-55) [hereinafter, “anion (B1 -A-1) "or the like. ] Are preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula (B1-A-33), Formula (B1-A-36) to Formula (B1-A-40), Formula (B1-A-47) to Formula (B1-A-55) An anion is more preferable.

Here, R ^{i2 to} R ⁱ⁷ are independently of each other, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ⁱ⁸ is formed by, for example, an aliphatic 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. More preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. L ^A41 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 sulfonate anion in the salt represented by the formula (B1) include the anions described in JP 2010-204646 A.

Examples of the sulfonate anion in the salt represented by the preferred formula (B1) include anions represented by formulas (B1a-1) to (B1a-34), respectively.

  Especially, Formula (B1a-1)-Formula (B1a-3) and Formula (B1a-7)-Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) ) To (B1a-34) are preferable.

Examples of the organic cation of Z ⁺ 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 arylsulfonium cation is more preferable. Specifically, a cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter sometimes referred to as “cation (b2-1)” depending on the formula number). Can be mentioned.

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represent a chain 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 chain 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 combine with 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 -CO- may be substituted.
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 represents an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7 may be the same or different, and when n2 is 2 or more, the plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent a chain 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 together 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 -CO- may be substituted.
R ^b11 represents a hydrogen atom, a chain 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 a chain 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 chain hydrocarbon. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is an alkoxy group having 1 to 12 carbon atoms or 1 to 1 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 is —O—, —S -Or -CO- may be substituted.
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 represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 are the same or different, when p2 is 2 or more, the plurality of R ^b14 are the same or different, and when q2 is 2 or more, the 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, and when t2 is 2 or more, a plurality of R ^b18 are the same or different Different.

An aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
Examples of chain hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl and 2-ethylhexyl alkyl groups. Can be mentioned.
In particular, the chain 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, a cyclo group. Examples thereof include cycloalkyl groups such as heptyl group, cyclooctyl group and cyclodecyl group. 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 is substituted with an aliphatic hydrocarbon group, the total number of carbon atoms 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 biphenylyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group having 1 to 18 carbon atoms (tolyl group, xylyl group). Group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and alicyclic ring having 3 to 18 carbon atoms Aromatic hydrocarbon groups having a general hydrocarbon group (p-adamantylphenyl group, p-cyclohexylphenyl group, etc.) are 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 chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and 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.
As the alkylcarbonyloxy group, methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, pentylcarbonyloxy group Hexylcarbonyloxy group, octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group and the like.

The ring formed by combining R ^b4 and R ^b5 together with the sulfur atom to which they are bonded is monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. The ring may be Examples of the ring include a ring having 3 to 18 carbon atoms, and a ring having 4 to 18 carbon atoms is preferable. Moreover, the ring containing a sulfur atom includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring, and examples thereof include the following rings. * Represents a binding site.

The ring formed by combining R ^b9 and R ^b10 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. Examples thereof include a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and a 1,4-oxathian-4-ium ring.
The ring formed by ^combining R ^b11 and R ^b12 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. This ring includes a 3-membered ring to a 12-membered ring, preferably a 3-membered ring to a 7-membered ring. Examples include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

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

Preferred examples of the acid generator (B) include those represented by formulas (B1-1) to (B1-48). Among them, those containing an arylsulfonium cation are preferred, and the formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~ Formula (B1-14), Formula (B1-17), Formula (B1-20) ~ The compounds represented by formula (B1-26), formula (B1-29), formula (B1-31) to formula (B1-48) are particularly preferable.

  In the resist composition of the present invention, the content of the acid generator is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin (A). More preferably, it is 10 parts by mass or more and 35 parts by mass or less. The resist composition of the present invention may contain one kind of acid generator (B) alone or may contain plural kinds.

<Solvent (E)>
The content of the solvent (E) is usually 90% by mass or more and 99.9% by mass or less, preferably 92% by mass or more and 99% by mass or less, more preferably 94% by mass or more and 99% by mass in the resist composition. % Or less. The content rate of a solvent (E) can be measured with well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.
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. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines 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, tri 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, 4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipicolylamine, bipyridine and the like are preferable, and aromatic amines such as diisopropylaniline are preferable, and 2,6-diisopropyl is more preferable. Aniline is mentioned.
Examples of ammonium salts 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 can be mentioned.

The acidity in 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 in which the acid dissociation constant of the acid generated from the salt is usually −3 <pKa, preferably −1 < A salt having a pKa <7, more preferably a salt having a 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 also referred to as “weak acid inner salt (D)”), JP 2012-229206 A, JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A. And salts described in JP-A-2011-191745. The salt that generates an acid having a weaker 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 in the solid content of the resist composition, preferably 0.01 to 3% by mass.

<Other ingredients>
The resist composition of the present invention may contain components other than the above-described components (hereinafter may be referred to as “other components (F)”) as necessary. The other component (F) is not particularly limited, and additives known in the resist field such as 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 the resin (A) and the acid generator (B) of the present invention, and if necessary, the resin (A2), the resin (X), the quencher (C), and the solvent (E). And other components (F) can be mixed. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature from 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (E), such as resin. 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 filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) The process of apply | coating the resist composition of this invention on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.
The resist composition can be applied onto the substrate 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 coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. Moreover, it is preferable that the pressure at the time of drying under reduced pressure is about 1-1.0 * 10 < ⁵ > Pa.
The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) Using various lasers such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do. In this specification, the irradiation of these radiations may be collectively referred to as “exposure”. At the time of exposure, exposure is usually performed through a mask corresponding to a 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 exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection reaction in the acid labile group. The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C.
The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., for example, and the development time is preferably 5 to 300 seconds, for example. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.
When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly called choline). The alkali developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern.
In the case of producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents 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 Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent 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 still more preferably only the organic solvent.
Among them, the organic developer is preferably a developer containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass to 100% by mass, more preferably 90% by mass to 100% by mass, and substantially butyl acetate and / or 2 -More preferred is heptanone alone.
The organic developer may contain a surfactant. 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 different type from the organic developer.
It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid 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 an alcohol solvent or an ester solvent is preferable.
After the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

<Application>
The resist composition of the present invention is suitable as 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. Yes, it is more suitable as a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, and is useful for fine processing of semiconductors.

[Compounds Represented by Formula (IA1) and Formula (IB1)]
The compound of the present invention includes a compound represented by the formula (IA1) (hereinafter sometimes referred to as “compound (IA1)”) and a compound represented by the formula (IB1) (hereinafter sometimes referred to as “compound (IB1)”). )
In Formula (IA1) and Formula (IB1), X ¹¹ and X ²¹ are groups represented by any of Formula (X ¹ -2) to Formula (X ¹ -7).
L ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , L ⁴ , L ^{4 ′} , L ² , L ³ and L ^{3 ′} are the same as above. Is mentioned.
In the compound represented by the formula (IA1) and the formula (IB1), among the structural unit represented by the formula (IA) and the structural unit represented by the formula (IB), X ¹ and X ² are represented by the formula It is a compound that leads to a structural unit that is a group represented by any one of (X ¹ -2) to formula (X ¹ -7).

As the compound (IA1), the following compounds can be mentioned.

As the compound (IB1), the following compounds can be mentioned.

In the compounds represented by formula (IA1-13), formula (IA1-15) and formula (IA1-17), a compound in which the methyl group corresponding to R ¹ in formula (IA1) is replaced by a hydrogen atom, and In the compounds represented by IA1-14) and formula (IA1-16), a compound in which a hydrogen atom corresponding to R ¹ in formula (IA1) is replaced with a methyl group may also be mentioned as specific examples of compound (IA1). it can.
In the compounds represented by formula (IB1-13), formula (IB1-15) and formula (IB1-17), a compound in which the methyl group corresponding to R ¹ in formula (IB1) is replaced with a hydrogen atom, and In the compounds represented by IB1-14) and formula (IB1-16), a compound in which the hydrogen atom corresponding to R ¹ in formula (IB1) is replaced with a methyl group may also be mentioned as specific examples of compound (IB1). it can.

The present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -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)
Moreover, the structure of the compound was confirmed by measuring a molecular ion peak using mass spectrometry (LC: Model 1100 manufactured by Agilent, and MASS: LC / MSD manufactured by Agilent). In the following examples, the value of this molecular ion peak is indicated by “MASS”.

Synthesis Example 1: Synthesis of compound represented by formula (IB-1)
20 parts of the compound represented by the formula (I-1-a), 140 parts of the compound represented by the formula (I-1-b) and 0.74 part of sulfuric acid were mixed and stirred at 70 ° C. for 10 hours. Cooled to 23 ° C. To the obtained mixture, 300 parts of chloroform and 130 parts of 5% aqueous sodium hydrogen carbonate solution were mixed, stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. To the obtained organic layer, 100 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to obtain the formula ( 10.22 parts of the compound represented by I-1-c) were obtained.
After 0.65 parts of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile are mixed and stirred at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 0.66 part of a compound represented by the formula (I-1-c) was added and stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 0.52 parts of a compound represented by the formula (IB-1) was obtained.
MASS: 313.2 [M + H] ⁺

Synthesis Example 2: Synthesis of compound represented by formula (IA-1)
After 0.65 parts of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile are mixed and stirred at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 1.32 parts of a compound represented by the formula (I-1-c) was added and stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/2). As a result, 0.68 part of a compound represented by the formula (IA-1) was obtained.
MASS: 245.1 [M + H] ⁺

Synthesis Example 3: Synthesis of compound represented by formula (IB-18)
After 0.65 parts of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile are mixed and stirred at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 0.61 part of a compound represented by the formula (I-18-c) was added and stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 0.48 parts of a compound represented by the formula (IB-18) was obtained.
MASS: 299.1 [M + H] ⁺

Synthesis Example 4: Synthesis of compound represented by formula (IA-18)
After 0.65 parts of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile are mixed and stirred at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 1.22 parts of the compound represented by the formula (I-18-c) was added, and the mixture was stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/2). As a result, 0.57 parts of a compound represented by the formula (IA-18) was obtained.
MASS: 231.1 [M + H] ⁺

Synthesis Example 5: Synthesis of compound represented by formula (IB-6)
1.79 parts of the compound represented by the formula (I-6-d) and 20 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then compound 1.34 represented by the formula (I-1-e). Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 1.24 parts of the compound represented by the formula (I-1-c) was added and stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 1.09 parts of a compound represented by the formula (IB-6) were obtained.
MASS: 701.4 [M + H] ⁺

Synthesis Example 6: Synthesis of compound represented by formula (IA-6)
1.79 parts of the compound represented by the formula (I-6-d) and 20 parts of acetonitrile were mixed, stirred at 23 ° C. for 30 minutes, and then compound 1.34 represented by the formula (I-1-e). Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 2.48 parts of a compound represented by the formula (I-1-c) was added and stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/2). This gave 2.21 parts of the compound represented by the formula (IA-6).
MASS: 439.2 [M + H] ⁺

Synthesis Example 7: Synthesis of compound represented by formula (IB-13)
After 1.56 parts of the compound represented by the formula (I-13-d) and 20 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) was mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 0.35 part of a compound represented by the formula (I-1-c) was added, and the mixture was stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 0.28 parts of a compound represented by the formula (IB-13) was obtained.
MASS: 553.2 [M + H] ⁺

Synthesis Example 8: Synthesis of compound represented by formula (IA-13)
After 1.56 parts of the compound represented by the formula (I-13-d) and 20 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) was mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 0.70 part of a compound represented by the formula (I-1-c) was added, and the mixture was stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/2). As a result, 0.39 parts of a compound represented by the formula (IA-13) was obtained.
MASS: 365.2 [M + H] ⁺

Synthesis Example 9: Synthesis of compound represented by formula (IB-2A)
20 parts of the compound represented by the formula (I-1-a), 140 parts of the compound represented by the formula (I-2-b) and 0.74 part of sulfuric acid were mixed and stirred at 70 ° C. for 10 hours. Cooled to 23 ° C. To the obtained mixture, 300 parts of chloroform and 130 parts of 5% aqueous sodium hydrogen carbonate solution were mixed, stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. To the obtained organic layer, 100 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated residue was fractionated using a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to obtain the formula ( 14.19 parts of the compound represented by I-2-c) were obtained.
After mixing 0.54 part of the compound represented by the formula (I-1A-d) and 20 parts of acetonitrile and stirring at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 0.81 part of a compound represented by the formula (I-2-c) was added and stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 0.32 parts of a compound represented by the formula (IB-2A) was obtained.
MASS: 325.2 [M + H] ⁺

Synthesis Example 10: Synthesis of compound represented by formula (IB-2)
After 0.65 parts of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile are mixed and stirred at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 0.81 part of a compound represented by the formula (I-2-c) was added and stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 0.38 parts of a compound represented by the formula (IB-2) was obtained.
MASS: 353.2 [M + H] ⁺

Synthesis Example 11 Synthesis of Compound Represented by Formula (IB-21)
20 parts of the compound represented by the formula (I-1-a), 26.50 parts of the compound represented by the formula (I-21-b), 100 parts of acetonitrile and 0.74 part of sulfuric acid were mixed, and 70 ° C. After stirring for 10 hours, the mixture was cooled to 23 ° C. To the obtained reaction mixture, 300 parts of chloroform and 130 parts of 5% aqueous sodium hydrogen carbonate solution were mixed, stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. To the obtained organic layer, 100 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer was concentrated, and the concentrated mass was separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: ethyl acetate) to give the formula (I-21 2.68 parts of the compound represented by -c) were obtained.
After 0.65 parts of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile are mixed and stirred at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Part was added, and the temperature was raised to 50 ° C., followed by stirring at 50 ° C. for 2 hours. To the obtained mixture, 1.38 parts of a compound represented by the formula (I-21-c) was added and stirred at 50 ° C. for 2 hours. After cooling the obtained mixture to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added and stirred at 23 ° C. for 30 minutes, followed by liquid separation and taking out the organic layer. To the collected organic layer, 20 parts of ion-exchanged water was added and stirred at 23 ° C. for 30 minutes, followed by liquid separation to take out the organic layer. This washing operation was repeated 5 times. The obtained organic layer is concentrated, and the concentrated mixture is fractionated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 1/1). As a result, 0.44 parts of a compound represented by the formula (IB-21) was obtained.
MASS: 405.2 [M + H] ⁺

Resin Synthesis The compounds (monomers) used in the resin synthesis are shown below.

Hereinafter, these monomers are referred to as “monomer (a1-1-3)” or the like according to the formula number.

Example 1 [Synthesis of Resin A1]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-5), the monomer (a2-1-1), the monomer (a3-4-2) and the monomer (IB-1) The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IB-1)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A1 having a molecular weight of 7.8 × 10 ³ was obtained with a yield of 55%. This resin A1 has the following structural units.

Example 2 [Synthesis of Resin A2]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-5), the monomer (a2-1-1), the monomer (a3-4-2) and the monomer (IA-1) The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IA-1)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A2 having a molecular weight of 7.6 × 10 ³ was obtained in a yield of 60%. This resin A2 has the following structural units.

Example 3 [Synthesis of Resin A3]
As the monomer, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IB-18) were used, The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IB-18)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A3 having a molecular weight of 8.2 × 10 ³ was obtained in a yield of 58%. This resin A3 has the following structural units.

Example 4 [Synthesis of Resin A4]
As the monomer, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IA-18) were used, The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IA-18)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A4 having a molecular weight of 7.9 × 10 ³ was obtained in a yield of 62%. This resin A4 has the following structural units.

Example 5 [Synthesis of Resin A5]
As the monomer, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IB-6) were used, The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IB-6)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A5 having a molecular weight of 8.8 × 10 ³ was obtained in a yield of 60%. This resin A5 has the following structural units.

Example 6 [Synthesis of Resin A6]
As the monomer, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IA-6) were used, The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IA-6)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A6 having a molecular weight of 8.1 × 10 ³ was obtained in a yield of 64%. This resin A6 has the following structural units.

Example 7 [Synthesis of Resin A7]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-5), the monomer (a2-1-1), the monomer (a3-4-2) and the monomer (IB-2A) The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IB-2A)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A7 having a molecular weight of 7.5 × 10 ³ was obtained in a yield of 53%. This resin A7 has the following structural units.

Example 8 [Synthesis of Resin A8]
As the monomer, monomer (a1-1-1), monomer (a1-0-1), monomer (a3-2-1) and monomer (IB-1) were used, and the molar ratio [monomer (a1-1-1) ): Monomer (a1-0-1): monomer (a3-2-1): monomer (IB-1)] is 46: 11: 34: 9, and the total monomer amount is 1.5 mass. Doubled propylene glycol monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A8 having a molecular weight of 7.9 × 10 ³ was obtained in a yield of 84%. This resin A8 has the following structural units.

Example 9 [Synthesis of Resin A13]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-5), the monomer (a2-1-1), the monomer (a3-4-2) and the monomer (IB-2) The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IB-2)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A13 having a molecular weight of 7.8 × 10 ³ was obtained in a yield of 59%. This resin A13 has the following structural units.

Example 10 [Synthesis of Resin A14]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-5), the monomer (a2-1-1), the monomer (a3-4-2) and the monomer (IB-21) are used and their moles are used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IB-21)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin A14 having a molecular weight of 7.7 × 10 ³ was obtained in a yield of 55%. This resin A14 has the following structural units.

Synthesis Example 12 [Synthesis of Resin AX1]
As the monomer, monomer (a1-1-1), monomer (a1-0-1), monomer (a3-2-1) and monomer (IX-1) were used, and the molar ratio [monomer (a1-1-1) ): Monomer (a1-0-1): monomer (a3-2-1): monomer (IX-1)] is 46: 11: 34: 9, and the total amount of monomers is 1.5 mass. Doubled propylene glycol monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, followed by reprecipitation operation of filtering the resin twice. Resin AX1 having a molecular weight of 7.8 × 10 ³ was obtained in a yield of 85%. This resin AX1 has the following structural units.

Synthesis Example 13 [Synthesis of Resin AX2]
As the monomer, the monomer (a1-1-3), the monomer (a1-2-5), the monomer (a2-1-1), the monomer (a3-4-2) and the monomer (IX-2) The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-1): monomer (a3-4-2): monomer (IX-2)] is 45:14: The mixture was mixed so that the ratio was 4: 34: 3, and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to obtain a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol / water mixed solvent to precipitate the resin, and this resin was filtered twice. Resin AX2 having a molecular weight of 7.7 × 10 ³ was obtained in a yield of 63%. This resin AX2 has the following structural units.

Example 11 [Synthesis of Resin A9]
As the monomer, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (IB-13) were used, and their molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (A1-2-6): monomer (IB-13)] is mixed at a ratio of 38: 29: 30: 3, and this monomer mixture is further mixed with 1 to the total mass of all monomers. .5 mass times of methyl isobutyl ketone was mixed. Polymerization was performed by adding azobisisobutyronitrile as an initiator to the obtained mixture so as to be 12 mol% with respect to the total number of moles of all monomers, and heating this at 85 ° C. for about 5 hours. It was. Thereafter, a 25% tetramethylammonium hydroxide aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours, followed by liquid separation. The recovered organic layer was poured into a large amount of n-heptane to precipitate a resin, which was filtered and recovered to obtain a resin A9 having a weight average molecular weight of about 5.5 × 10 ³ in a yield of 52%. This resin A9 has the following structural units.

Example 12 [Synthesis of Resin A10]
As the monomer, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (IA-13) were used, and the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (A1-2-6): monomer (IA-13)] is mixed at a ratio of 38: 29: 30: 3, and this monomer mixture is further mixed with 1 to the total mass of all monomers. .5 mass times of methyl isobutyl ketone was mixed. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% based on the total number of moles of all monomers, and this was heated at 85 ° C. for about 5 hours for polymerization. It was. Thereafter, a 25% tetramethylammonium hydroxide aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours, followed by liquid separation. The collected organic layer was poured into a large amount of n-heptane to precipitate a resin, and filtered and collected to obtain Resin A10 having a weight average molecular weight of about 5.8 × 10 ³ in a yield of 58%. This resin A10 has the following structural units.

Example 13 [Synthesis of Resin A11]
As the monomer, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (IB-1) were used, and their molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (A1-2-6): monomer (IB-1)] is mixed so as to have a ratio of 38: 29: 30: 3, and this monomer mixture is further mixed with 1 to the total mass of all monomers. .5 mass times of methyl isobutyl ketone was mixed. Polymerization was performed by adding azobisisobutyronitrile as an initiator to the obtained mixture so as to be 12 mol% with respect to the total number of moles of all monomers, and heating this at 85 ° C. for about 5 hours. It was. Thereafter, a 25% tetramethylammonium hydroxide aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours, followed by liquid separation. The recovered organic layer was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain Resin A11 having a weight average molecular weight of about 5.9 × 10 ³ in a yield of 48%. This resin A11 has the following structural units.

Example 14 [Synthesis of Resin A12]
As the monomer, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (IA-1) were used, and the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (A1-2-6): monomer (IA-1)] is mixed in a ratio of 38: 29: 30: 3, and this monomer mixture is further mixed with 1 to the total mass of all monomers. .5 mass times of methyl isobutyl ketone was mixed. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% based on the total number of moles of all monomers, and this was heated at 85 ° C. for about 5 hours for polymerization. It was. Thereafter, a 25% tetramethylammonium hydroxide aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours, followed by liquid separation. The recovered organic layer was poured into a large amount of n-heptane to precipitate a resin, which was filtered and recovered to obtain Resin A12 having a weight average molecular weight of about 6.1 × 10 ³ in a yield of 53%. This resin A12 has the following structural units.

Example 15 [Synthesis of Resin A15]
As the monomer, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (IB-2) were used, and the molar ratio thereof [acetoxystyrene: monomer (a1-1-3): monomer (A1-2-6): monomer (IB-2)] is mixed at a ratio of 38: 29: 30: 3, and this monomer mixture is further mixed with a total mass of all monomers of 1 .5 mass times of methyl isobutyl ketone was mixed. Polymerization was performed by adding azobisisobutyronitrile as an initiator to the obtained mixture so as to be 12 mol% with respect to the total number of moles of all monomers, and heating this at 85 ° C. for about 5 hours. It was. Thereafter, a 25% tetramethylammonium hydroxide aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours, followed by liquid separation. The recovered organic layer was poured into a large amount of n-heptane to precipitate a resin, which was filtered and recovered to obtain Resin A15 having a weight average molecular weight of about 5.6 × 10 ³ in a yield of 56%. This resin A15 has the following structural units.

Example 16 [Synthesis of Resin A16]
As the monomer, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (IB-21) were used, and the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (A1-2-6): monomer (IB-21)] is mixed at a ratio of 38: 29: 30: 3, and this monomer mixture is further mixed with the total mass of all monomers of 1 .5 mass times of methyl isobutyl ketone was mixed. Polymerization was performed by adding azobisisobutyronitrile as an initiator to the obtained mixture so as to be 12 mol% with respect to the total number of moles of all monomers, and heating this at 85 ° C. for about 5 hours. It was. Thereafter, a 25% tetramethylammonium hydroxide aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours, followed by liquid separation. The recovered organic layer was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain Resin A16 having a weight average molecular weight of about 5.4 × 10 ³ with a yield of 49%. This resin A16 has the following structural units.

Synthesis Example 14 [Synthesis of Resin AX3]
As the monomer, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (IX-1) were used, and the molar ratio thereof [acetoxystyrene: monomer (a1-1-3): monomer (A1-2-6): monomer (IX-1)] is mixed so as to have a ratio of 38: 29: 30: 3, and this monomer mixture is further mixed with 1 to the total mass of all monomers. .5 mass times of methyl isobutyl ketone was mixed. Polymerization was performed by adding azobisisobutyronitrile as an initiator to the obtained mixture so as to be 12 mol% with respect to the total number of moles of all monomers, and heating this at 85 ° C. for about 5 hours. It was. Thereafter, a 25% tetramethylammonium hydroxide aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours, followed by liquid separation. The recovered organic layer was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain Resin AX3 having a weight average molecular weight of about 6.0 × 10 ³ in a yield of 51%. This resin AX3 has the following structural units.

Synthesis Example 15 [Synthesis of Resin AX4]
As the monomer, acetoxystyrene, monomer (a1-1-3), monomer (a1-2-6) and monomer (IX-2) were used, and the molar ratio [acetoxystyrene: monomer (a1-1-3): monomer (A1-2-6): monomer (IX-2)] is mixed so as to have a ratio of 38: 29: 30: 3, and is further added to this monomer mixture with respect to the total mass of all monomers. .5 mass times of methyl isobutyl ketone was mixed. To the obtained mixture, azobisisobutyronitrile was added as an initiator so as to be 7 mol% based on the total number of moles of all monomers, and this was heated at 85 ° C. for about 5 hours for polymerization. It was. Thereafter, a 25% tetramethylammonium hydroxide aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 12 hours, followed by liquid separation. The recovered organic layer was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery to obtain Resin AX4 having a weight average molecular weight of about 6.1 × 10 ³ in a yield of 55%. This resin AX4 has the following structural units.

Synthesis Example 16: Synthesis of Resin X1 As monomer, monomer (a5-1-1) and monomer (a4-0-12) were used, and the molar ratio [monomer (a5-1-1): monomer (a4-0-) 12)] is 50:50, and methyl isobutyl ketone 1.2 mass times the total monomer amount is added to obtain a solution. To this solution, 3 mol% of azobis (2,4-dimethylvaleronitrile) as an initiator was added based on the total amount of monomers, and heated at 70 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent 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>
A mixture obtained by mixing and dissolving the components shown in Table 1 was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

<Resin>
A1 to A16, AX1 to AX4: Resin A1 to Resin A16, Resin AX1 to Resin AX4
<Acid generator (B)>
B1-21: a salt represented by the formula (B1-21) (synthesized according to Examples in JP 2012-224611 A)
B1-22: a salt represented by the formula (B1-22) (synthesized according to Examples in JP 2012-224611 A)
B1-43: a salt represented by the formula (B1-43) (synthesized according to Examples in JP-A-2016-47815)
<Quencher (C)>
(Salts that generate acids with lower acidity than acids generated from acid generators)
D1: synthesized by the method described in JP2011-39502A
D2: (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Solvent: Compositions 1-8, Comparative Compositions 1, 2>
Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts <Solvent: Compositions 9-12, Comparative compositions 3, 4>
Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 150 parts γ-butyrolactone 5 parts

(ArF exposure evaluation of resist composition)
An organic antireflective coating composition (ARC-29; manufactured by Nissan Chemical Co., Ltd.) is applied to a silicon wafer and baked at 205 ° C. for 60 seconds to form an organic reflective film having a thickness of 78 nm on the wafer. A prevention film was formed. Next, the resist composition was applied (spin coated) on the organic antireflection film so that the film thickness after drying was 85 nm. After coating, the silicon wafer was pre-baked on a direct hot plate at the temperature described in the “PB” column of Table 1 for 60 seconds to form a composition layer. ArF excimer stepper for immersion exposure (XT: 1900Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light) on a silicon wafer on which the composition layer is formed, and a contact hole pattern (hole pitch 90 nm) Using a mask for forming a hole diameter of 55 nm), exposure was performed by changing the exposure amount stepwise. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 1. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.
In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask was 45 nm was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In terms of effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 55 nm was measured 24 times per hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was determined using a population of measurements of the average hole diameter of 400 patterns formed with a mask having a hole diameter of 55 nm in the same wafer.
The results are shown in Table 2. Numerical values in parentheses indicate standard deviation (nm).

Compared with the comparative compositions 1 and 2, the standard deviations in the compositions 1 to 8, 13 and 14 were small, and the CD uniformity (CDU) evaluation was good.

(Electron beam exposure evaluation of resist composition)
A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds. This silicon wafer was spin-coated with a resist composition so that the film thickness of the composition layer was 0.04 μm. Then, it prebaked on the direct hot plate for 60 second at the temperature shown in the "PB" column of Table 1, and formed the composition layer. The composition layer formed on the wafer was subjected to an electron beam lithography machine (“ELS-F125 125 keV” manufactured by Elionix Co., Ltd.), and the exposure amount was changed stepwise to form a contact hole pattern (hole pitch 40 nm / hole (Diameter 17 nm) was directly drawn.
After the exposure, post exposure baking is performed for 60 seconds on the hot plate at the temperature shown in the “PEB” column of Table 1, and further, paddle development is performed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. A resist pattern was obtained.
In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask becomes 17 nm was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In terms of effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 17 nm was measured 24 times per hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was determined using a population of measurements of the average hole diameter of 400 patterns formed with a mask having a hole diameter of 55 nm in the same wafer.
The results are shown in Table 3. Numerical values in parentheses indicate standard deviation (nm).

Compared with the comparative compositions 3 and 4, the standard deviation in the compositions 9 to 12, 15, and 16 was small, and the CD uniformity (CDU) evaluation was good.

  Since the resist composition of the present invention can obtain a resist pattern having good CD uniformity (CDU), it is suitable for semiconductor microfabrication and is extremely useful industrially.

Claims (11)

At least one selected from the group consisting of a structural unit represented by formula (IA) and a structural unit represented by formula (IB), and a structural unit represented by formula (a1-1) and formula (a1-2) A resin comprising at least one selected from the group consisting of structural units represented by:
[In Formula (IA) and Formula (IB),
R ¹ and R ² each independently represents a hydrogen atom or a methyl group.
X ¹ and X ² each independently represent a group represented by any one of formulas (X ¹ -1) to (X ¹ -7).
(In the formula (X ¹ -1) to the formula (X ¹ -7),
*, ** represents a binding site, ** represents the bonding site to ^{L 1.} )
L ¹ represents an optionally substituted hydrocarbon group having 1 to 48 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or It may be replaced by —SO ₂ —.
R ³ and R ⁴ each independently represent a group represented by the formula (Aa) or a group represented by the formula (Ab), or R ³ and R ⁴ are bonded to each other and bonded to an oxygen atom Together with this, an acid labile ring is formed. ]
[In Formula (Aa), R ⁵ , R ⁶ and R ⁷ 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 ⁵ and R ⁶ are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
n represents 0 or 1.
* Represents a binding site. ]
[In Formula (Ab), R ⁸ and R ⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, R ⁹ and R ¹⁰ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and ^Xb , and —CH ₂ — contained in the hydrocarbon group and the heterocycle is — O- or -S- may be substituted.
^Xb represents an oxygen atom or a sulfur atom.
* Represents a binding site. ]
[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or * —O— (CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents —CO—. Represents the binding site.
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 0-14.
n1 represents an integer of 0 to 10.
n1 ′ represents any integer of 0 to 3. ] The resin according to claim 1, wherein L ¹ is a group represented by the formula (IIA) or a group represented by the formula (IIB).
[In Formula (IIA) and Formula (IIB),
L ⁴ and L ^{4 ′} each independently represent a C 1-24 hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the hydrocarbon group is — O—, —S—, —CO— or —SO ₂ — may be substituted.
L ² and L ³ each independently represent a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^{3 ′} represents an alkanetriyl group having 1 to 4 carbon atoms.
* A represents a bonding site with X ¹ , * b represents a bonding site with oxygen atom or X ² , * c represents a bonding site with oxygen atom in -OR ³ , * d represents in -OR ⁴ Represents the bonding site with the oxygen atom. ] L ⁴ and L ^{4 ′} are each independently a single bond, an alkanediyl group having 1 to 6 carbon atoms or an alkanediyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. Group (—CH ₂ — contained in the alkanediyl group may be replaced by —O— or —CO—, and —CH ₂ — contained in the alicyclic hydrocarbon group is —O—, — S—, —CO— or —SO ₂ — may be substituted), L ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms, and L ³ is 1 to 4 carbon atoms. The resin according to claim 1 or 2, which is an alkanediyl group and L ^{3 '} is an alkanetriyl group having 1 to 4 carbon atoms. The resin according to any one of claims 1 to 3, wherein X ¹ is a group represented by any ^one of the formula (X ¹ -1), the formula (X ¹ -3), and the formula (X ¹ -4).   The resist composition containing the resin and acid generator in any one of Claims 1-4. The resist composition according to claim 5, wherein the acid generator contains a salt represented by the formula (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 divalent saturated hydrocarbon group may be replaced by —O— or —CO—. The hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents an optionally substituted methyl group or an optionally substituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, and is included in the alicyclic hydrocarbon group − CH ₂ — may be replaced by —O—, —S (O) ₂ — or —CO—.
Z ⁺ represents an organic cation. ]   The resist composition according to claim 5 or 6, further comprising a salt that generates an acid having a lower acidity than an acid generated from the acid generator.   Furthermore, the resist composition in any one of Claims 5-7 containing resin containing the structural unit which has a fluorine atom. (1) The process of apply | coating the resist composition in any one of Claims 5-8 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(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 including: A compound represented by formula (IA1) or formula (IB1).
[In Formula (IA1) and Formula (IB1),
R ¹ and R ² each independently represents a hydrogen atom or a methyl group.
X ¹¹ and X ²¹ each independently represent a group represented by any one of formula (X ¹ -2) to formula (X ¹ -7).
(In the formula (X ¹ -2) to the formula (X ¹ -7),
*, ** represents a binding site, ** represents the bonding site to ^{L 1.} )
L ¹ represents an optionally substituted hydrocarbon group having 1 to 48 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, —CO— or It may be replaced by —SO ₂ —.
R ³ and R ⁴ each independently represent a group represented by the formula (Aa) or a group represented by the formula (Ab), or R ³ and R ⁴ are bonded to each other and bonded to an oxygen atom Together with this, an acid labile ring is formed. ]
[In Formula (Aa), R ⁵ , R ⁶ and R ⁷ 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 ⁵ and R ⁶ are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
n represents 0 or 1.
* Represents a binding site. ]
[In Formula (Ab), R ⁸ and R ⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, R ⁹ and R ¹⁰ are bonded to each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom to which they are bonded and ^Xb , and —CH ₂ — contained in the hydrocarbon group and the heterocycle is — O- or -S- may be substituted.
^Xb represents an oxygen atom or a sulfur atom.
* Represents a binding site. ] The compound according to claim 10, wherein L ¹ is a group represented by the formula (IIA) or a group represented by the formula (IIB).
[In Formula (IIA) and Formula (IIB),
L ⁴ and L ^{4 ′} each independently represent a C 1-24 hydrocarbon group which may have a single bond or a substituent, and —CH ₂ — contained in the hydrocarbon group is — O—, —S—, —CO— or —SO ₂ — may be substituted.
L ² and L ³ each independently represent a single bond or an alkanediyl group having 1 to 4 carbon atoms.
L ^{3 ′} represents an alkanetriyl group having 1 to 4 carbon atoms.
* A represents a bonding site with X ¹ , * b represents a bonding site with oxygen atom or X ² , * c represents a bonding site with oxygen atom in -OR ³ , * d represents in -OR ⁴ Represents the bonding site with the oxygen atom. ]