JP2019218335A - Compound, resin, resist composition, and method for producing resist pattern - Google Patents

Abstract

To provide a compound, a resin, and a resist composition capable of producing a resist pattern having good line edge roughness (LER).SOLUTION: The compound is represented by formula (IA) or formula (IB), and the resin and the resist composition contain a structural unit derived from the compound. (Formula IA): CH=C(-R)-X-L(-OR)(-OR)(-0R). (Formula IB): CH=C(-R)-X-L(-X-C(-R)=CH)(-OR)(-0R). [Rand Reach represent H or a methyl group; Xand Xeach represent -C(=O)O- or the like; Lrepresents a substituted/unsubstituted C1-48 hydrocarbon group; and R, Rand Reach represent a C2-4 cyclic hydrocarbon group containing one O, which may have a saturated hydrocarbon group.]SELECTED DRAWING: None

Description

  The present invention relates to a compound, 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 compound.
Patent Document 2 discloses a resist composition containing a resin having a structural unit derived from the following compound.
Patent Document 3 discloses the following compound.
Patent Document 4 discloses a resist composition containing a resin having a structural unit derived from the following compound.

JP-A-55-060941 JP 2007-155851 A JP 09-258441 A JP 2017-095444 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 a resin having a structural unit derived from the above compound. .

The present invention includes the following inventions.
[1] A compound represented by the formula (IA) or the formula (IB).
[In the formulas (IA) and (IB),
R ¹ and R ² each independently represent a hydrogen atom or a methyl group.
X ¹ and ^{X 2} each independently represent a group represented by any one of formula ^(X 1 -1) ~ Formula ^(X 1 -7).
(In the formula ^(X 1 -1) ~ Formula ^(X 1 -7),
*, ** represents a binding site, ** represents the bonding site to ^{L 1.} )
L ¹ represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group is -O-, -S-, -CO- or —SO ₂ — may be substituted.
R ³ is a hydrocarbon group having 1 to 36 carbon atoms having a group represented by the formula (IC) (the hydrocarbon group may have a substituent, and —CH ₂ — contained in the hydrocarbon group is included). is, -O -, - S -, - CO- or -SO ₂ -. which may be substituted with) represents a.
R ⁴ and R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms which may have a group represented by the formula (IC) (the hydrocarbon group has a substituent; And —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO ₂ —.) ]
[In the formula (IC),
^RA represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
u1 represents an integer of 0 to 2, when u1 is 2, or a plurality of ^{R A} are the same, different.
s1 represents 1 or 2.
t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2.
* Represents a binding site. ]
[2] ^{L 1} is a group represented by the formula radical or formula represented by ^{(L 1 A) (L 1} B) [1] Compounds according.
[In the formulas (L ¹ A) and (L ¹ B),
L ⁴ and L ^{4 ′} each independently represent a single bond or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group is- O -, - S -, - CO- or -SO ₂ - may be replaced with.
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 an oxygen atom or X ² in -OR ^5, * c represents the binding site to the oxygen atoms in the -OR ^3, * d is -OR ⁴ represents a bonding site to an oxygen atom. ]
[3] L ⁴ and L ^{4 ′} each independently represent 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 base (the alkanediyl group composed of a combination of bets - -CH ₂ may be replaced by -O- or -CO-, contained in the alicyclic hydrocarbon group - is - O -, - S -, - CO- or -SO ₂ - is also be) have replaced, L ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms, L ³ is 1 to carbon atoms (4) The compound according to (2), wherein 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 compound according to the above.
[5] A resin containing a structural unit derived from the compound according to any one of [1] to [4].
[6] The resin according to [5], further comprising a structural unit having an acid labile group.
[7] The resin according to [6], wherein the structural unit having an acid labile group includes at least one of a structural unit represented by Formula (a1-1) and a structural unit represented by Formula (a1-2). .
[In the formulas (a1-1) and (a1-2),
L ^a1 and L ^a2 each independently, -O- or _{* -O- (CH 2) k1 -CO} -O- the stands, k1 represents an integer of 1-7, and * -CO- And represents a 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 an integer of any of 0 to 14.
n1 represents any integer of 0-10.
n1 ′ represents any integer of 0 to 3. ]
[8] A resist composition comprising the resin according to any one of [5] to [7] and an acid generator.
[9] The resist composition according to [8], 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 a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and-is included in the alicyclic hydrocarbon group. CH ₂ — may be replaced by —O—, —S (O) ₂ — or —CO—.
Z ⁺ represents an organic cation. ]
[10] The resist composition according to [8] or [9], further comprising a salt that generates an acid having a lower acidity than the acid generated from the acid generator.
[11] (1) a step of applying the resist composition according to any one of [8] to [10] on a substrate;
(2) drying the composition after application to form a composition layer;
(3) exposing the composition layer to light,
A method for producing a resist pattern, comprising: (4) a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

  By using a resist composition containing a resin having a structural unit derived from the compound of the present invention, a resist pattern can be manufactured with good CD uniformity (CDU).

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

[Compounds represented by Formula (IA) and Formula (IB)]
The compound of the present invention may be a compound represented by the formula (IA) (hereinafter, sometimes referred to as “compound (IA)”) and a compound represented by the formula (IB) (hereinafter, referred to as “compound (IB)”) ).
In formula (IA) and Formula (IB), ^{X 1} and ^{X 2} is a group represented by any one of formula ^(X 1 -1) ~ Formula ^(X 1 -7). Of these, ^{X 1} is the formula ^(X 1 -1), wherein ^(X 1 -3) or is preferably a group represented by any one of formulas ^(X 1 -4), formula ^(X 1 -1 ) or more preferably a group represented by any one of formulas (X 1 ^-4).
Examples of the hydrocarbon group having 1 to 48 carbon atoms of L ¹ include an aliphatic hydrocarbon group (a chain hydrocarbon group such as an alkanetetrayl group, an alkenetetrayl group, and an alkynetetrayl group; a monocyclic or polycyclic hydrocarbon group). Alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and the like, and a tetravalent hydrocarbon group (for example, a tetravalent aliphatic hydrocarbon group and a divalent hydrocarbon group) obtained by combining two or more of these groups. A tetravalent hydrocarbon group obtained by combining an alicyclic hydrocarbon group of the above, a tetravalent alicyclic hydrocarbon group or a tetravalent obtained by combining an aromatic hydrocarbon group with one or more divalent aliphatic hydrocarbon groups Hydrocarbon group, a trivalent or tetravalent alicyclic hydrocarbon group and / or a tetravalent hydrocarbon group obtained by combining an aromatic hydrocarbon group and an alkanediyl group).

Examples of the alkanetetrayl group include a methanetetrayl group, an ethanetetrayl group, a propanetetrayl group, a butanetetrayl group, a pentanetetrayl group, a hexanetetrayl group, a heptanetetrayl group, an octanetetrayl group, and a nonanetetrayl group. And linear or branched alkanetetrayl groups such as a group, a decanetetrayl group, an undecanetetrayl group, and a dodecanetetrayl group.
Examples of the alkenetetrayl group include an ethenetetrayl group, a propenetetrayl group, an isopropenetetrayl group, a butenetetrayl group, an isobutenetetrayl group, a tert-butenetetrayl group, a pentenetetrayl group, a hexenetetrayl group, Examples include a heptenetetrayl group, an octynetetrayl group, an isooctynetetrayl group, and a nonenetetrayl group.
Examples of the alkynetetrayl group include a propynetetrayl group, an isopropynetetrayl group, a butynetetrayl group, an isobutynetetrayl group, a tert-butynetetrayl group, a pentynetetrayl group, a hexynetetrayl group, and an octynetetrayl group. And an yl group and a nonintetrayl group.
Examples of the monocyclic alicyclic hydrocarbon group include a monocyclic cycloalkanetetrayl group such as a cyclobutanetetrayl group, a cyclopentanetetrayl group, a cyclohexanetetrayl group, a cyclohexenetetrayl group, and a cyclooctanetetrayl group. No.
Examples of the polycyclic alicyclic hydrocarbon group include a polycyclic cycloalkanetetrayl group such as a norbornanetetrayl group, a norbornanetetrayl group, a 5-norbornenetetrayl group, an adamantanetetrayl group, and an adamantanetetrayl group. No.
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 and an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group are combined, and specifically, alkanetetrayl A group obtained by combining a group with a monovalent alicyclic hydrocarbon group and / or an aromatic hydrocarbon group, wherein the methylene group contained in the alkanetetrayl group is a divalent alicyclic hydrocarbon group and / or a divalent alicyclic hydrocarbon group. Examples thereof include a group substituted by an aromatic hydrocarbon group, a trivalent or tetravalent alicyclic hydrocarbon group, and / or a group obtained by combining an aromatic hydrocarbon group with an alkanediyl group.

Examples of the substituent which 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 by —O—), a carboxy group (a —CH ₂ —CH ₂ — contained in an ethyl group is replaced by —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 the alkyl group of Formulas 4 to 15 is replaced by —O—CO—, an alkylcarbonyl group having 2 to 13 carbon atoms (an alkyl group having 3 to 14 carbon atoms) Is a group in which -CH ₂ -is replaced by -CO-), an alkylcarbonyloxy group having 2 to 13 carbon atoms (-CH ₂ -CH _2- included in an alkyl group having 4 to 15 carbon atoms is -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, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy. Group, dodecyloxy group and the like.
An alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms and an alkylcarbonyloxy group having 2 to 13 carbon atoms are the above-mentioned alkyl or alkoxy groups to which a carbonyl or carbonyloxy group is bonded. 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.
Tetravalent hydrocarbon group of 1 to 48 carbon atoms represented by L ¹ may have one substituent or more substituents.

-CH ₂ contained in the hydrocarbon group of 1 to 48 carbon atoms L ¹ - is, -O -, - S -, - CO- or -SO ₂ - may be replaced with.
Is -O - -, - -CH ₂ hydrocarbon group of 1 to 48 carbon atoms of L ¹ is contained in a case or the hydrocarbon group having a substituent S -, - CO- or -SO ₂ - in the replaced by In this case, the number of carbon atoms before replacement is the number of carbon atoms of the hydrocarbon group.

L ¹ is preferably a group represented by the formula (L ¹ A) or the formula (L ¹ B).
[In the formulas (IIA) and (IIB),
L ⁴ and L ^{4 ′} each independently represent a single bond or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group is- O -, - S -, - CO- or -SO ₂ - may be replaced with.
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 an oxygen atom or ^{X 2,} * c represents the binding site to the oxygen atoms in the -OR ^3, * d is the -OR ⁴ Represents a bonding site to an 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 group, alkenediyl group, and alkynediyl group, and monocyclic or polycyclic hydrocarbon groups). A divalent alicyclic hydrocarbon group), an aromatic hydrocarbon group, and the like, and a divalent hydrocarbon group obtained by combining two or more of these groups 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 A linear alkanediyl group such as a 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- Examples include a branched alkanediyl group such as a 1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group.
Examples of the alkenediyl group include an ethenediyl group, a propenediyl group, an isopropenediyl group, a butenediyl group, an isobutenediyl group, a tert-butenediyl group, a pentenediyl group, a hexenediyl group, a heptenediyl group, an octindiyl group, an isooctindiyl group, and a nonenediyl group. .
Examples of the alkynediyl group include an ethynediyl group, a propyndiyl group, an isopropyndiyl group, a butyndiyl group, an isobutyndiyl group, a tert-butyndiyl group, a pentyndiyl group, a hexynediyl group, an octindiyl group, and a nonindiyl group.
Examples of the monocyclic divalent alicyclic hydrocarbon group include cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclohexene-3,6- And monocyclic cycloalkanediyl groups such as a diyl group and a cyclooctane-1,5-diyl group.
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, and adamantane-1,5. And polycyclic cycloalkanediyl groups such as -diyl group and 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 which two or more kinds are combined include a group in which a chain hydrocarbon group and an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group are combined, and specifically, an alkanediyl group And a cycloaliphatic hydrocarbon group and / or an aromatic hydrocarbon group. -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 which the hydrocarbon group of L ⁴ and L ^{4 ′} may have include the same substituents as those 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 in L ⁴ and L ^{4 '-} is, -O -, - S -, - CO- or -SO ₂ - may be replaced with.
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 it is replaced by-, the number of carbon atoms before the replacement is defined as the number of carbon atoms of the hydrocarbon group.

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

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

The hydrocarbon group having a group represented by the formula (IC) in R ³ , R ⁴ and R ⁵ refers to a hydrocarbon group in which one or more groups represented by the formula (IC) are substituted as substituents. Means what you have. Hydrocarbon group here, -CH ₂ contained in the hydrocarbon group - is, -O -, - S -, - CO- or -SO ₂ - may be replaced, in the formula (IC) It may have one or more substituents other than the groups represented.
Examples of the hydrocarbon group for R ³ , R ⁴ and R ⁵ include an aliphatic hydrocarbon group (a chain hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group and an alicyclic hydrocarbon group), and an aromatic hydrocarbon group. And a combination thereof.
Examples of the alkyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a nonyl group. The carbon number of the alkyl group is preferably 1 to 9, more preferably 1 to 4.
Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octynyl group, an isooctynyl group, and a nonenyl group.
Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, an isobutynyl group, a tert-butynyl group, a pentynyl group, a hexynyl group, an octynyl group, a noninyl group, and the like.
The alicyclic hydrocarbon group may be monocyclic, polycyclic or spiro ring, and may be saturated or unsaturated. Examples of the alicyclic hydrocarbon group include a monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cyclododecyl group, a norbornyl group, and an adamantyl. And a polycyclic cycloalkyl group such as a group.
As the alicyclic hydrocarbon group represented by R ³ , R ⁴ and R ⁵ , groups represented by formulas (Y1) to (Y41) (* represents a bonding site) are preferable, and formula (Y1) And more preferably a group represented by any one of formulas (Y20), (Y26), (Y27), (Y30), (Y31), (Y39) to (Y41), It is a group represented by the formulas (Y3), (Y4), (Y9), (Y11), (Y14), (Y15), (Y16), (Y20), and (Y30). Is more preferable. The number of carbon atoms of the alicyclic hydrocarbon group is preferably 3 to 18, more preferably 3 to 16.
Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and a binaphthyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 14, and more preferably 6 to 10. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, as in the group described below, and may be an aromatic hydrocarbon group having a chain hydrocarbon group (tolyl group). Group, xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic hydrocarbon And an aromatic hydrocarbon group having a group (p-cyclohexylphenyl group, p-adamantylphenyl group, etc.).
The combined group is
A group obtained by combining an alicyclic hydrocarbon group and a chain hydrocarbon group (alkyl group, alkenyl group and / or alkynyl group) (the chain hydrocarbon group (alkyl group, alkenyl group, alkynyl group) and the alicyclic group); is, -O - - -CH ₂ included in the formula hydrocarbon group, - S -, - CO- or -SO ₂ - may be replaced by)
A group in which a chain hydrocarbon group (alkyl group, alkenyl group and / or alkynyl group) and an aromatic hydrocarbon group are combined (included in the chain hydrocarbon group (alkyl group, alkenyl group and / or alkynyl group)) —CH ₂ — may be replaced by —O—, —S—, —CO— or —SO ₂ —), and a group obtained by combining an alicyclic hydrocarbon group and an aromatic hydrocarbon group (the is, -O - - -CH ₂ contained in the alicyclic hydrocarbon group, - S -, - CO- or -SO ₂ - represents a may be replaced with). In the combination, two or more alicyclic hydrocarbon groups, chain hydrocarbon groups (alkyl group, alkenyl group, alkynyl) group and aromatic hydrocarbon group may be used in combination.
Specifically, as the combined group,
Adamantylmethyl group, an alicyclic hydrocarbon group such as a cyclohexylmethyl group - chain hydrocarbon group - * (-CH included in the chain hydrocarbon group and alicyclic hydrocarbon group ₂ -, -O- , -S -, - CO- or -SO ₂ - may be replaced by)
A chain hydrocarbon group such as a methyl adamantyl group-an alicyclic hydrocarbon group-* (-CH _2- contained in the chain hydrocarbon group and the alicyclic hydrocarbon group is -O-, -S- , -CO- or -SO ₂ - may be replaced by)
Tolyl, chain hydrocarbon groups such as a xylyl group - aromatic hydrocarbon radical - * (-CH ₂ contained in the chain hydrocarbon group - is, -O -, - S -, - CO- or -SO _2- may be replaced)
Alicyclic hydrocarbon groups such as a phenyl group - an aromatic hydrocarbon radical - * (-CH ₂ contained in the alicyclic hydrocarbon group - is, -O -, - S -, - CO- or -SO _2- may be replaced)
Chain hydrocarbon group such as a methyl cyclohexylmethyl group - alicyclic hydrocarbon group - chain hydrocarbon group - * (-CH included in the chain hydrocarbon group and alicyclic hydrocarbon group ₂ -, —O—, —S—, —CO— or —SO ₂ —).
Aromatic hydrocarbon group such as benzyl group-chain hydrocarbon group- * (-CH _2- contained in the chain hydrocarbon group is -O-, -S-, -CO- or -SO _2- May be replaced),
Chain hydrocarbon groups such as tolylmethyl group - aromatic hydrocarbon radical - chain hydrocarbon group - * (-CH included in the chain hydrocarbon group ₂ -, -O -, - S -, - CO- Or -SO _2- )
And the like. Here, * represents a bonding site with an oxygen atom.

The hydrocarbon group represented by R ³ is preferably an aliphatic hydrocarbon group having 1 to 36 carbon atoms which may have a substituent (provided that —CH ₂ — contained in the aliphatic hydrocarbon group is included). May be replaced by —O—, —S—, —CO— or —SO ₂ —, and at least one of the hydrogen atoms contained in the aliphatic hydrocarbon group is represented by the formula (IC) Substituted with a group.)
More preferably, an alkyl group (-CH _2- contained in the alkyl group may be replaced by -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is represented by the formula (IC )) Or a combination of an alicyclic hydrocarbon group and an alkyl group (-CH _2- contained in the alkyl group is replaced by -O- or -CO-. And at least one of the hydrogen atoms contained in the alkyl group is substituted with a group represented by the formula (IC).
More preferably, a * -alkyl group (-CH _2- contained in the alkyl group may be replaced by -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is represented by the formula: (IC represents a bonding site to an oxygen atom.) Or * -alkyl group-alicyclic hydrocarbon group-alkyl group (-CH contained in the alkyl group) _2- may be replaced by -O- or -CO-, and at least one of the hydrogen atoms contained in the alkyl group is replaced by a group represented by the formula (IC). Represents a bonding site with an atom).

As the hydrocarbon group represented by R ⁴ and R ⁵ , preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 36 carbon atoms which may have a substituent (provided that the aliphatic hydrocarbon group —CH ₂ — contained therein may be replaced by —O—, —S—, —CO— or —SO ₂ —, and at least one of the hydrogen atoms contained in the aliphatic hydrocarbon group is represented by the formula ( IC) may be substituted.)
More preferably, a hydrogen atom, an alkyl group (-CH _2- contained in the alkyl group may be replaced by -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is Substituted with a group represented by the formula (IC)) or a group obtained by combining an alicyclic hydrocarbon group with an alkyl group (-CH _2- contained in the alkyl group is -O- or -CO And at least one of the hydrogen atoms contained in the alkyl group may be substituted with a group represented by the formula (IC).
More preferably, a hydrogen atom, * -alkyl group (-CH _2- contained in the alkyl group may be replaced by -O- or -CO-, and at least one of the hydrogen atoms contained in the alkyl group Is substituted with a group represented by the formula (IC). * Represents a bonding site to an oxygen atom.) Or * -alkyl group-alicyclic hydrocarbon group-alkyl group (included in the alkyl group) —CH ₂ — may be replaced by —O— or —CO—, and at least one of the hydrogen atoms contained in the alkyl group may be substituted with a group represented by the formula (IC). * Represents a bonding site to an oxygen atom.)
Even more preferably, a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms which may have a substituent (provided that -CH _2- contained in the aliphatic hydrocarbon group is -O-,- S -, - CO- or -SO 2 _- may be replaced, at least one of the hydrogen atoms contained in the aliphatic hydrocarbon group is substituted with a group represented by the formula (IC). )
Even more preferably, a hydrogen atom, an alkyl group (-CH ₂ contained in the alkyl group - may be replaced by -O- or -CO-, at least one of the hydrogen atoms contained in the alkyl group , A group represented by the formula (IC)) or a combination of an alicyclic hydrocarbon group and an alkyl group (-CH _2- contained in the alkyl group is -O- or- CO-, and at least one of the hydrogen atoms contained in the alkyl group is substituted with a group represented by the formula (IC).
Particularly preferably, a hydrogen atom, * -alkyl group (-CH _2- contained in the alkyl group may be replaced by -O- or -CO-, and at least one hydrogen atom contained in the alkyl group is Is substituted with a group represented by the formula (IC). * Represents a bonding site to an oxygen atom.) Or * -alkyl group-alicyclic hydrocarbon group-alkyl group (included in the alkyl group) —CH ₂ — may be replaced by —O— or —CO—, and at least one of the hydrogen atoms contained in the alkyl group is substituted with a group represented by the formula (IC). * Represents a bonding site with an oxygen atom.)

The groups represented by the formula (IC) are as follows.
[In the formula (IC),
^RA represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
u1 represents an integer of 0 to 2, when u1 is 2, or a plurality of R ^A are the same, different.
s1 represents 1 or 2.
t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2.
* Represents a binding site. ]

s1 is preferably 1, t1 is preferably 1, the sum of s1 and t1 is preferably 1 or 2, and more preferably the sum of s1 and t1 is 2.
The group represented by the formula (IC) is preferably a group represented by the following.

When u1 is 1 in the group represented by the formula (IC), a group represented by the following formula is also included in the formula (IC).
Examples of the saturated hydrocarbon group for ^RA include an alkyl group, an alicyclic hydrocarbon group, and a combination thereof.
Examples of the alkyl group of ^RA include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, and a nonyl group. The carbon number of the alkyl group is preferably 1 to 9, more preferably 1 to 4.
The alicyclic hydrocarbon group may be any of a monocyclic, polycyclic and spiro ring. Examples of the alicyclic hydrocarbon group include a monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cyclododecyl group, a norbornyl group, and an adamantyl. And a polycyclic cycloalkyl group such as a group.

Examples of the substituent other than the group represented by the formula (IC) in the hydrocarbon group represented by R ³ , R ⁴ and R ⁵ include a halogen atom and a cyano group.
The halogen atom include the same ones as exemplified for L ^1.
Further, a group included by the substitution of —CH ₂ — in the hydrocarbon group, that is, a hydroxy group, a carboxy group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, and 2 to 13 carbon atoms alkylcarbonyl group, is the same as L ¹ for alkylcarbonyloxy group 2 to 13 carbon atoms.
When —CH ₂ — contained in the hydrocarbon group represented by R ³ , R ^4, and R ⁵ is replaced with —O—, —S—, —CO—, or —SO ₂ —, the number of carbon atoms before the replacement. Is the total carbon number of the hydrocarbon group. When a substituent such as Formula (IC) is bonded to the hydrocarbon group represented by R ³ , R ^4, and R ⁵ , the number of carbon atoms before substitution is defined as the total number of carbon atoms of the hydrocarbon group.

Examples of the compound (IA) include the following compounds.

In the compounds represented by the formulas (IA-1) to (IA-10), (IA-12), (IA-14), and (IA-16) to (IA-32), IA) In the compounds in which the methyl group corresponding to R ¹ in IA) has been replaced by a hydrogen atom, and the compounds represented by the formulas (IA-11), (IA-13) and (IA-15), Compounds in which the hydrogen atom corresponding to R ¹ has been replaced by a methyl group can also be mentioned as specific examples of compound (IA). Among them, the compounds represented by the formulas (IA-1) to (IA-12), (IA-17) to (IA-18), (IA-23) to (IA-26) preferable.

As the compound (IB), for example, the following compounds can be mentioned.

In the compounds represented by the formulas (IB-1) to (IB-10), (IB-12), (IB-14), (IB-16) to (IB-26), In a compound in which a methyl group corresponding to R ¹ and R ² in IB) is replaced by a hydrogen atom, and a compound represented by formula (IB-11), formula (IB-13) or formula (IB-15), Compounds in which the hydrogen atoms corresponding to R ¹ and R ² in IB) have been replaced with methyl groups can also be mentioned as specific examples of compound (IB). Among them, the compounds represented by the formulas (IB-1) to (IB-12), (IB-17) to (IB-18), (IB-23) to (IB-26) preferable.

<Method for producing compound (IA) or compound (IB)>
In the compound (IA),
A compound in which R ³ , R ⁴ and R ⁵ are each independently a group represented by the formula (ICI) (a compound represented by the formula (IA1));
A compound in which R ⁵ is a hydrogen atom, and R ³ and R ⁴ are each independently a group represented by the formula (ICI) (a compound represented by the formula (IA2));
A compound in which R ⁴ and R ⁵ are a hydrogen atom and R ³ is a group represented by the formula (ICI) (a compound represented by the formula (IA3)) is, for example, a compound represented by the formula (Ib) After reacting the compound to be reacted with carbonyldiimidazole in a solvent, the compound can be further reacted with a salt represented by the formula (IA-a).
In the compound (IB),
A compound in which R ³ and R ⁴ are each independently a group represented by the formula (ICI) (a compound represented by the formula (IB1));
The compound (compound represented by formula (IB2)) in which R ⁴ is a hydrogen atom and R ³ is a group represented by formula (ICI) is, for example, a compound represented by formula (Ib) And carbonyldiimidazole in a solvent, and further reacted with a salt represented by the formula (IB-a).
(In the formula (ICI), s1, t1, u1, and ^RA each have the same meaning as described above. L ^2I represents an optionally substituted hydrocarbon group having 1 to 34 carbon atoms; —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO ₂ — nn represents 0 or 1. * represents an oxygen atom Represents a binding site.)

(In the formula, all symbols represent the same meaning as described above.)
Examples of the solvent in this reaction include chloroform, acetonitrile, and the like.
When 1 mol of the compound represented by the formula (IA-a) is reacted with 2.6 mol or more (preferably 3.0 mol or more) of the compound represented by the formula (Ib), the compound represented by the formula (IA1) is obtained. Is obtained as the main product. 1.6 to 2.4 mol (preferably 1.8 to 2.2 mol) of the compound represented by the formula (Ib) per 1 mol of the compound represented by the formula (IA-a) When reacted, the compound represented by the formula (IA2) is obtained as a main product. The compound represented by the formula (Ib) is used in an amount of 0.6 to 1.4 mol (preferably 0.8 to 1.1 mol) per 1 mol of the compound represented by the formula (IA-a). When reacted, the compound represented by the formula (IA3) is obtained as a main product.
When 1 mol of the compound represented by the formula (IB-a) is reacted with 1.6 mol or more (preferably 2.0 mol or more) of the compound represented by the formula (Ib), the compound represented by the formula (IB1) Is obtained as the main product. The compound represented by the formula (Ib) is used in an amount of 0.6 to 1.4 mol (preferably 0.8 to 1.1 mol) per 1 mol of the compound represented by the formula (IB-a). ) When reacted, the compound represented by the formula (IB2) is obtained as a main product.
The reaction temperature is usually 5 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.
Examples of the compound represented by the formula (Ib) include a compound represented by the following formula, which can be easily obtained from the market.

In the compounds of the formula (IA-a), ^{X 1} is the formula ^(X 1 -1), a group represented by any one of formulas ^(X 1 -3) or Formula ^(X 1 -4) The compound (compound represented by the formula (I1A-a)) is obtained by reacting a compound represented by the formula (I1-c1) with carbonyldiimidazole in a solvent, and further reacting the compound represented by the formula (Id) The compound can be produced by reacting with the compound represented by the formula and treating with an acid.
In the compounds of the formula (IB-a), ^{X 1} and ^{X 2} are, each independently, formula ^(X 1 -1), any of the formulas ^(X 1 -3) or Formula ^(X 1 -4) (A compound represented by the formula (I1B-a)), a compound represented by the formula (I1-c1), a compound represented by the formula (I1-c2) and carbonyldiimidazole Is reacted in a solvent, and further reacted with a compound represented by the formula (Id), followed by treatment with an acid.
(Wherein, R ¹ , L ¹ , and R ² each have the same meaning as described above. X ^1A and X ^2A represent a single bond 1,4-phenylene group or —CO—O—Ar ¹ — * And Ar ¹ represents a 1,4-phenylene group. * Represents a bonding site to a carbon atom of a carbonyl group.)
Examples of the solvent include tetrahydrofuran, chloroform and acetonitrile.
Examples of the acid include p-toluenesulfonic acid, sulfuric acid, hydrochloric acid and the like.
The reaction temperature is usually 0 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.
Examples of the compounds represented by the formulas (I1-c1) and (I1-c2) include the compounds represented by the following formulas, which can be easily obtained from the market.
Examples of the compound represented by the formula (Id) include a compound represented by the following formula and the like, which can be easily obtained from the market, and can be easily produced by a known synthesis method.

In the compounds of the formula (IA-a), ^{X 1} is represented by the formula ^(X 1 -2) or compound is a group represented by the formula ^(X 1 -5) ^(formula (I2A-a) Is produced by reacting a compound represented by the formula (I2-c1) with a compound represented by the formula (Id) in a solvent in the presence of a base, followed by treatment with an acid. can do.
In the compounds of the formula (IB-a), ^{X 1} and ^{X 2} are, each independently, formula ^(X 1 -2) or compound is a group represented by the formula ^(X 1 -5) (formula ( The compound represented by I2B-a) is a compound represented by the formula (I2-c1), a compound represented by the formula (I2-c2) and a compound represented by the formula (Id): It can be produced by reacting in a solvent in the presence of a base and then treating with an acid.
(Wherein, R ¹ , L ¹ and R ² each have the same meaning as described above. X ^1B and X ^2B each represent -Ar ^1- * or -CO-O-Ar ^1- *. Ar represents 1 , 4-phenylene group. * Represents a bonding site to an oxygen atom.)
Examples of the solvent include tetrahydrofuran, chloroform and acetonitrile.
Examples of the base include potassium hydroxide.
Examples of the acid include p-toluenesulfonic acid, sulfuric acid, hydrochloric acid and the like.
The reaction temperature is usually 0 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.
Examples of the compounds represented by the formulas (I2-c1) and (I2-c2) include the compounds represented by the following formulas, and can be easily obtained from the market.

X ¹ has the formula ^(X 1 -6) or a compound of the formula group a is the formula represented by ^{(X 1 -7) (I3A-} a) is a compound represented by the formula (I2-c1) And carbonyldiimidazole in a solvent, and further reacted with a compound represented by the formula (Id), followed by treatment with an acid.
X ¹ and ^{X 2} are, each independently, formula ^(X 1 -6) or a compound of the formula group a is the formula represented by ^{(X 1 -7) (I3B-} a) has the formula (I2- After reacting the compound represented by c1) with the compound represented by the formula (I2-c2) and carbonyldiimidazole in a solvent, the compound was further reacted with the compound represented by the formula (Id). Thereafter, it can be produced by treating with an acid.
(In the formula, all symbols represent the same meaning as described above.)
Examples of the solvent include tetrahydrofuran, chloroform and acetonitrile.
Examples of the acid include p-toluenesulfonic acid, sulfuric acid, hydrochloric acid and the like.
The reaction temperature is usually 0 ° C to 80 ° C, and the reaction time is usually 0.5 hours to 24 hours.

〔resin〕
The resin of the present invention may be a resin containing a structural unit derived from the compound (IA) or the compound (IB) (hereinafter sometimes referred to as “structural unit (I)”) (hereinafter sometimes referred to as “resin (A)”). )). The resin (A) may be a homopolymer of the structural unit (I), a copolymer composed of only the structural unit (I), or include one or more structural units other than the structural unit (I). It may be a polymer.
Examples of the structural unit other than the structural unit (I) include a structural unit having an acid labile group (hereinafter, may be referred to as a “structural unit (a1)”) and a structural unit other than a structural unit having an acid labile group. A structural unit having a halogen atom (hereinafter sometimes referred to as “structural unit (a4)”), a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”), non-desorbed carbonized And a structural unit having a hydrogen group (hereinafter sometimes referred to as “structural unit (a5)”). Here, the acid labile group means a group that has a leaving group and forms a hydrophilic group (for example, a hydroxy group or a carboxy group) by leaving the leaving group upon contact with an acid.

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

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

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

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

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

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

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

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

R ^a01 , R ^a4 and R ^a5 are preferably a methyl group.
L ^a01 , L ^a1 and L ^a2 are preferably an oxygen atom or * —O— (CH ₂ ) _k01 —CO—O— (however, k01 is preferably an integer of 1 to 4, more preferably Is 1.), and more preferably an oxygen atom.
Examples of the alkyl group, alicyclic hydrocarbon group and the combination thereof in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 include the groups listed for R ^a1 , R ^a2 and R ^a3 in the formula (1). And the same groups as mentioned above.
R ^a02, R ^a03, and the carbon number of the alkyl group in R ^a04 is preferably 1 to 6, more preferably methyl group or ethyl group, more preferably a methyl group.
The carbon number of the alkyl group in ^Ra6 and ^Ra7 is preferably 1 to 6, more preferably a methyl group, an ethyl group or an isopropyl group, and further preferably an ethyl group or an isopropyl group.
The carbon number of the alicyclic hydrocarbon group of ^Ra02 , ^Ra03 and ^Ra04 is preferably 5 to 12, and more preferably 5 to 10.
The group obtained by combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less obtained by combining the alkyl group and the alicyclic hydrocarbon group.
^Ra02 and ^Ra03 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
^Ra04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.
R ^a6 and R ^a7 are preferably an alkyl group of 1 to 6, more preferably a methyl group, an ethyl group or an isopropyl group, and further preferably an ethyl group or an isopropyl group.
m1 is preferably an integer of any of 0 to 3, and more preferably 0 or 1.
n1 is preferably an integer of any of 0 to 3, and more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

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

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

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

When the resin (A) contains the structural unit (a1-0), its content is usually 1 to 50 mol%, preferably 3 to 40 mol%, based on all structural units of the resin (A). And more preferably 5 to 30 mol%.
When the resin (A) includes the structural unit (a1-1) and / or the structural unit (a1-2), the total content thereof is based on the total structural units of the resin (A).
Usually, it is 10 to 95 mol%, preferably 15 to 80 mol%, more preferably 15 to 75 mol%, still more preferably 20 to 70 mol%, and still more preferably 20 to 65 mol%. It is.

Examples of the structural unit having the group (2) in the structural unit (a1) include a structural unit represented by the formula (a1-4) (hereinafter, sometimes referred to as “structural unit (a1-4)”). .
[In the formula (a1-4),
^Ra32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl. Represents an oxy group or a methacryloyloxy group.
la represents any integer of 0-4. When la is 2 or more, a plurality of ^Ra33 may be the same or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 may represent a hydrocarbon group having 1 to 20 carbon atoms, R ^a35 and R ^a36 are bonded to each other To form a divalent hydrocarbon group having 2 to 20 carbon atoms together with -CO- to which they are bonded, and -CH _2- contained in the hydrocarbon group and the divalent hydrocarbon group is- It may be replaced by O- or -S-. ]

^Examples of the alkyl group for ^Ra32 and ^Ra33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
Examples of the halogen atom in R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl, perfluorohexyl, etc. No.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further preferable.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and the like.
As the hydrocarbon group for R ^a34, R ^a35 and R ^a36, an alkyl group, an alicyclic hydrocarbon group, aromatic hydrocarbon group and a group formed by combining these are exemplified, as the alkyl group and alicyclic hydrocarbon groups It ^{is, R a02, R a03, R} a04, include the same groups as the alkyl group and alicyclic hydrocarbon group for R ^a6 and R ^a7.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group.
Examples of the combined group include a group obtained by combining the above-described alkyl group and alicyclic hydrocarbon group, an aralkyl group such as a benzyl group, and an aromatic hydrocarbon group having an alkyl group (p-methylphenyl group, p-tert- An aromatic hydrocarbon group having a butylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, or an alicyclic hydrocarbon group ( p-cyclohexylphenyl group, p-adamantylphenyl group, etc., and aryl-cycloalkyl group (phenylcyclohexyl group, etc.). In particular, R ^a36 is an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. Is mentioned.

In the formula (a1-4), R ^a32 is preferably a hydrogen atom.
^Ra33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and further preferably a methoxy group.
As la, 0 or 1 is preferable, and 0 is more preferable.
^Ra34 is preferably a hydrogen atom.
^Ra35 is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, and more preferably a methyl group or an ethyl group.
The hydrocarbon group of ^Ra36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. It is a group formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group for R ^a36 are preferably unsubstituted. Aromatic hydrocarbon group for R ^a36 is an aromatic ring preferably has an aryloxy group having 6 to 10 carbon atoms.
^{-OC (R a34) (R a35} ) -O-R a36 in the structural unit (a1-4) is desorbed by contact with an acid (e.g. p- toluenesulfonic acid) to form a hydroxy group.

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

  When the resin (A) has the structural unit (a1-4), its content is preferably 5 to 60 mol%, and more preferably 5 to 50 mol%, based on the total of all the structural units of the resin (A). More preferably, it is 10 mol%, more preferably 10 mol% to 40 mol%.

Examples of the structural unit derived from the (meth) acrylic monomer having the group (2) also include a structural unit represented by the formula (a1-5) (hereinafter, may be referred to as “structural unit (a1-5)”). Can be
In the formula (a1-5),
R ^a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or _{* - (CH 2) h3 -CO} -L 54 - represents, h3 represents an integer of 1 to 4, * represents a binding site with L ^51.
L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent —O— or —S—.
s1 represents 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a fluoromethyl group and a trifluoromethyl group. Groups.
In the formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
Of L ⁵² and L ^53, one of -O-, and is preferably other is -S-.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 represents a single bond or * -CH ₂ -CO-O- are preferable.

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

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

The structural unit (a1) also includes, for example, a structural unit represented by the formula (a1-0X) (hereinafter, may be referred to as a structural unit (a1-0X)).
[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 of 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 either 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 for Ar ^X1 include an aryl group 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 has 6 to 18 carbon atoms, and still more preferably is 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 further preferably a phenyl group.
R ^X1 , R ^x2 and R ^x3 are each independently preferably a methyl group or an ethyl group, more preferably a methyl group.

Examples of the structural unit (a1-0X) include a structural unit described below and a compound in which a methyl group corresponding to R ^X1 in the structural unit (a1-0X) is replaced with a hydrogen atom. The structural unit (a1-0X) is preferably a structural unit (a1-0X-1) to a structural unit (a1-0X-3).

When the resin (A) has the structural unit (a1-0X), its content is preferably from 5 to 60 mol%, more preferably from 5 to 50 mol%, based on all monomers in the resin (A). More preferably, it is more preferably 10 to 40 mol%.
The resin (A) may contain two or more structural units (a1-0X).

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

  When the resin (A) contains the above structural unit, its content is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, and more preferably 10 to 40 mol%, based on all structural units of the resin (A). % Is more preferred.

<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. Structure having a hydroxy group and not having an acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or having a lactone ring and having no acid labile group Use of a resin having units (hereinafter sometimes referred to as “structural unit (a3)”) in the resist composition of the present invention can improve the resolution of a resist pattern and the adhesion to a substrate.

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

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

^Examples of the halogen atom for 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, , 1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3 , 3,4,4-octafluorobutyl, butyl, perfluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, pentyl, hexyl and perfluorohexyl Groups.
^Ra50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the alkyl group for ^Ra51 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
^Examples of the alkoxy group for ^Ra51 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group is even more preferred.
^Examples of the alkylcarbonyl group for ^Ra51 include an acetyl group, a propionyl group, and a butyryl group.
^Examples of the alkylcarbonyloxy group for ^Ra51 include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
^Ra51 is preferably a methyl group.

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

Examples of the alkanediyl group 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, a pentane-1,5-diyl group, a hexane- 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -Methylbutane-1,4-diyl group and the like.
A ^a52 is preferably a methylene group or an ethylene group.

A ^a50 is preferably a single bond, ^* -CO-O- or ^* -CO-O- ^Aa52- CO-O-, and a single bond, ^* -CO-O- or ^* -CO-O-CH It is more preferably _2- CO-O-, and even more preferably a single bond or ^* -CO-O-.

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

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

As the structural unit (a2-A), the structural units represented by formulas (a2-2-1) to (a2-2-6) and the formulas (a2-2-1) to (a2-2-2-) In the structural unit represented by 6), a structural unit in which a methyl group corresponding to ^Ra50 in the structural unit (a2-A) is replaced by a hydrogen atom is ^exemplified . The structural unit (a2-A) is a structural unit represented by the formula (a2-2-1), a structural unit represented by the formula (a2-2-3), or a structural unit represented by the formula (a2-2-6). In the structural unit represented by the formula (a2-2-1), the structural unit represented by the formula (a2-2-3) or the structural unit represented by the formula (a2-2-6), It is preferable that the methyl unit corresponding to ^Ra50 in the structural unit (a2-A) is a structural unit in which a hydrogen atom is replaced.

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

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

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

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

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

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

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

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group. Can be
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
^Examples of the alkyl group for ^Ra24 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. And more preferably a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom at ^Ra24 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluoropentyl group. Examples include a hexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

The alkanediyl group in ^La8 and ^La9 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, Examples include a 4-diyl group and a 2-methylbutane-1,4-diyl group.

In the formulas (a3-1) to (a3-3), L ^{a4 to} L ^a6 each independently preferably represent _{k3 in} —O— or * —O— (CH ₂ ) _k3 —CO—O—. group but is any integer of 1 to 4, more preferably -O- _{and, * - O-CH 2 -CO} -O-, more preferably an oxygen atom.
^{Ra18 to Ra21} are preferably a methyl group.
^Ra22 and ^Ra23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are each independently preferably an integer of any of 0 to 2, and more preferably 0 or 1.

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

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

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

<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, -CH ₂ contained in the saturated hydrocarbon group - may be replaced by -O- or -CO. ]
Examples of the saturated hydrocarbon group represented by R ⁴² include a chain hydrocarbon group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a group formed by combining these.

Examples of the chain hydrocarbon group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. No.
Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* Represents a binding site.) And a polycyclic alicyclic hydrocarbon group.
Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, and include -alkanediyl group- Alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, and the like.

As the structural unit (a4), at least one selected from the group consisting of the formulas (a4-0), (a4-1), (a4-2), (a4-3), and (a4-4) The 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 an alkanediyl group 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 alkanediyl group for L ^4a include a linear alkanediyl group such as a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, an ethane-1,1-diyl group, And branched alkanediyl groups such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group. Can be

^Examples of the perfluoroalkanediyl group for L ^3a include a difluoromethylene group, a perfluoroethylene group, a perfluoropropane-1,1-diyl group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, and a perfluoropropane group. -2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane -2,2-diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane -1,7-diyl group, perfluorohep -2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluoro An octane-3,3-diyl group, a perfluorooctane-4,4-diyl group and the like can be mentioned.
^Examples of the perfluorocycloalkanediyl group in L ^3a include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, a perfluoroadamantanediyl group, and the like.

L ^4a is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond or a methylene group.
L ^3a is preferably a C 1-6 perfluoroalkanediyl group, more preferably a C 1-3 perfluoroalkanediyl group.

Examples of the structural unit (a4-0) include a structural unit shown below, and a structural unit in which a methyl group corresponding to R ^5a in the structural unit (a4-0) in the following structural unit is replaced with a hydrogen atom.

[In the formula (a4-1),
^Ra41 represents a hydrogen atom or a methyl group.
R ^a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— or —CO—. You may.
A ^a41 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1). However, at least one of A ^a41 and R ^a42 has a halogen atom (preferably a fluorine atom) as a substituent.
[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
X ^a41 and X ^a42 each independently represent -O-, -CO-, ^-CO -O-, or -O-CO-.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less. ]
* Represents a binding site, and * on the right side represents a binding site to -O-CO- ^Ra42 . ]

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

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

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

^Examples of the aliphatic hydrocarbon group for A ^a45 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a pentadecyl group, a hexadecyl group, a 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 (* Represents a binding site.) And a polycyclic alicyclic hydrocarbon group.
Examples of the group formed by the combination include a group formed by combining one or more alkyl groups or one or more alkanediyl groups with one or more alicyclic hydrocarbon groups, and include -alkanediyl group- Alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group-alkyl group, and the like.

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

When R ^a42 is a saturated hydrocarbon group having a group represented by the formula (a-g3), R ^a42 is more preferably a group represented by the formula (a-g2).
[In the formula (a-g2),
A ^a46 represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom.
X ^a44 represents * ^-O -CO- or * -CO-O- (* represents a binding site to A ^a46 ).
A ^a47 represents 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 bonding site with a carbonyl group. ]

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

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

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

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

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

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

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, -CH ₂ contained in the alkanediyl group - may be replaced by -O- or -CO-.
R ^f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and a fluorine atom.
However, the upper limit of the total number of carbon atoms of L ⁴⁴ and R ^f6 are 21. ]

Alkanediyl group of L ⁴⁴ include the same groups as those exemplified with L ^4a.
As the saturated hydrocarbon group for R ^f6 , the same groups as those exemplified for R ^a42 can be mentioned.
The alkanediyl group in L ^44, preferably alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

Examples of the structural unit represented by the formula (a4-2) include structural units represented by formulas (a4-1-1) to (a4-1-11). A structural unit in which the methyl group corresponding to R ^f5 in the structural unit (a4-2) is replaced by 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.
And L ⁵ represents an alkanediyl group having 1 to 6 carbon atoms.
^Af13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom.
^Xf12 represents * -O-CO- or * -CO-O- (* represents a binding site to ^Af13 ).
^Af14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms 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. ]

The alkanediyl group in L ^5, include the same groups as those exemplified alkanediyl group L ^4a.

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

Or saturated hydrocarbon group which may have a saturated hydrocarbon group and a fluorine atom of A ^f14 include the same groups as those exemplified with R ^a42. Among them, trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, Fluorination of 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorooctyl group Alkyl group, cyclopropylmethyl group, cyclopropyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, Fluorocyclohexyl group, adamantyl group, adamantylmethyl group, adamantyl dimethyl group, norbornyl group, norbornylmethyl group, perfluoro adamantyl group, a perfluoroalkyl adamantylmethyl group and the like are preferable.

In the formula (a4-3), L ⁵ is preferably an ethylene group.
The divalent saturated hydrocarbon group 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 is preferably 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, ^Af14 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 the formula (a4-3) include structural units represented by the formulas (a4-1′-1) to (a4-1′-11). The structural unit in which the methyl group corresponding to R ^f7 in the structural unit (a4-3) is replaced with a hydrogen atom is also exemplified as the structural unit represented by the formula (a4-3).

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

^As the saturated hydrocarbon group for R ^f22 , the same as the saturated hydrocarbon group for R ^a42 can be mentioned. R ^f22 is preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom or an alicyclic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms having a fluorine atom. Preferably, an alkyl group having 1 to 6 carbon atoms having a fluorine atom is more preferable.

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

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. Structural units replaced with atoms.

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

<Structural unit (a5)>
Examples of the non-eliminated hydrocarbon group contained in the structural unit (a5) include groups having a linear, branched, or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1).
[In the formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. .
L ⁵⁵ represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, -CH ₂ contained in the saturated hydrocarbon group - may be replaced by -O- or -CO- . ]

The alicyclic hydrocarbon group for R ⁵² may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and 2 An alkyl group such as -ethylhexyl group.
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, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

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

-CH ₂ contained in the divalent saturated hydrocarbon group represented by L ⁵⁵ - is, the group replaced by -O- or -CO-, for example, by the formula (L1-1) ~ formula (L1-4) The group represented is mentioned. In the following formulas, * and ** each represent a binding site, and * represents a binding site to an oxygen atom.
In the formula (L1-1),
X ^x1 represents * -O-CO- or * -CO-O- (* represents a binding site to L ^x1 ).
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 15 carbon atoms.
However, the total carbon number of L ^x1 and L ^x2 is 16 or less.
In the formula (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
^Lx4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total carbon number of L ^x3 and L ^x4 is 17 or less.
In the formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent 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 the formula (L1-4),
L ^x8 and L ^{x9 each} 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 divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.
L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably 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.
^Lx8 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.
^Lx9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group.
W ^x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

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

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

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

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

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

The structural unit (a5-1), a methyl group corresponding to R ⁵¹ may be mentioned a structural unit replacing a hydrogen atom in the structural units in the structural units and the following structural units shown below (a5-1).

When the resin (A) has the structural unit (a5), its content is preferably from 1 to 30 mol%, more preferably from 2 to 20 mol%, based on all the structural units of the resin (A). ~ 15 mol% is more preferred.

<Structural unit (II)>
The resin (A) may further contain a structural unit that decomposes upon exposure to generate an acid (hereinafter, may be referred to as “structural unit (II)”). The structural unit described in JP-A-2006-79235 is mentioned, a structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain or a structural unit having a sulfonio group and an organic anion in the side chain. Preferably, there is.

The structural unit having a sulfonate group or a 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, -CH ₂ contained in the saturated hydrocarbon group - is -O -, - it is replaced in S- or -CO- The hydrogen atom contained in the saturated hydrocarbon group may be replaced by a halogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom or a hydroxy group.
A ^x1 represents an alkanediyl group having 1 to 8 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
RA ^- represents a sulfonate or carboxylate groups.
R ^III3 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
ZA ⁺ represents an organic cation. ]

Examples of the halogen atom represented by R ^III3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
As the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^III3, the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ^a8 The same is mentioned.
Examples of the alkanediyl group having 1 to 8 carbon atoms represented by A ^x1 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. Hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2, 4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like. No.
Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted by ^Ax1 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, and a perfluorotert-butyl group. -Butyl group, perfluoropentyl group, perfluorohexyl group and the like.
Examples of the divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by ^XIII3 include a linear or branched alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a combination of these.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 , 6-Diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group Alkanediyl groups such as, dodecane-1,12-diyl group; butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Alkanediyl groups such as pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group; cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1 , 4-diyl group, Cycloalkanediyl groups such as looctane-1,5-diyl group; norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group And other divalent polycyclic alicyclic saturated hydrocarbon groups.
Examples of the case where —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —S— or —CO— include divalent groups represented by Formulas (X1) to (X53). No. However, -CH ₂ contained in a saturated hydrocarbon group - is, -O -, - number of carbon atoms before replacing with S- or -CO- is respectively 17 or less. In the following formulas, * and ** represent the binding site, and * represents a binding site with A ^X1.

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

Examples of the organic cation represented by ZA ⁺ include an organic onium cation, for example, an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, an organic benzothiazolium cation and an organic phosphonium cation, and an organic sulfonium cation and an organic iodonium cation Is preferable, and an arylsulfonium cation is more preferable.
ZA ⁺ in the formula (II-2-A ′) is the same as the organic 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 any integer of 0 to 6.
R ^III2 and R ^III4 each independently represent a hydrogen atom, a fluorine atom or a C 1-6 perfluoroalkyl group, and when z is 2 or more, a plurality of R ^III2 and R ^III4 are the same as each other; Or different.
Q ^a and Q ^b are each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. ]
^Examples of the perfluoroalkyl group having 1 to 6 carbon atoms represented by R ^III2 , R ^III4 , Q ^a and Q ^b include the same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by Q ^b1 described below. .

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

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

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

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

As the structural unit containing a cation in the formula (II-1-1), a structural unit represented by the following and a group corresponding to a methyl group of R ^II4 have been replaced with a hydrogen atom, a fluorine atom, trifluoromethyl, or the like. And a structural unit.

Examples of the organic anion represented by A ⁻ include a sulfonate anion, a sulfonylimide anion, a sulfonylmethide anion, and a carboxylate anion. The organic anion represented by A ⁻ is preferably a sulfonic acid anion, and more preferably an anion contained in a salt represented by the formula (B1) described below.

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

Examples of the sulfonylmethide anion include the following.

Examples of the carboxylate anion include the following.

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

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

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

The resin (A) is preferably a resin comprising the structural unit (I) and an acid labile group, a resin comprising the structural unit (I) and the structural unit (a1), and a resin comprising the structural unit (I) and the structural unit (s). ), A resin comprising the structural unit (I), the structural unit (a1) and the structural unit (s), a resin comprising the structural unit (I), the structural unit (a1), the structural unit (s) and the structural unit (a4) ) And / or a resin composed only of the structural unit (a5), a resin composed solely of the structural unit (I), or a resin composed solely of the structural unit (I) and the structural unit (a4), more preferably a structural unit. A resin composed of (I), the structural unit (a1) and the structural unit (s), a resin composed of the structural unit (I) and the structural unit (s), or a resin composed of the structural unit (I) and the structural unit (a4) Resin consisting only of structural unit (a5), structural unit (I) and structural unit Resin comprising a4) and only a resin comprising structural units (I) and the structural unit (a4) and the structural unit (a1) alone.
The content of the structural unit (I) is usually 1 to 20 mol%, preferably 2 to 10 mol%, more preferably 2 to 6 mol%, based on all monomers in the resin (A). .
When the resin (A) contains a structural unit represented by the formula (a4) and / or (a5) (hereinafter sometimes referred to as “resin (AX)”), the structural unit in the resin (AX) of the present invention ( The content of I) is preferably 2 to 10 mol%, more preferably 2 to 6 mol%, based on the total of all the structural units of the resin (AX) of the present invention.

The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-0X), a structural unit (a1-1) and a structural unit (a1-2) (preferably a cyclohexyl group and a cyclopentyl group). At least one selected from the group consisting of the above structural units), more preferably the structural unit (a1-0), the structural unit (a1-0X), the structural unit (a1-1), and the structural unit (a1-2) (Preferably, the structural unit having a cyclohexyl group or a cyclopentyl group) is at least two selected from the group consisting of:
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). The structural unit (a3) is preferably a group consisting of a structural unit represented by the formula (a3-1), a structural unit represented by the formula (a3-2), and a structural unit represented by the formula (a3-4). At least one selected from

Each of the structural units constituting the resin (A) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, a radical polymerization method) using a monomer that leads to these structural units. be able to. The content of each structural unit of the resin (A) can be adjusted by the amount of the monomer used for polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, and further preferably 15,000 or less).
In the present specification, the weight average molecular weight is a value determined by gel permeation chromatography. Gel permeation chromatography can be measured under the analysis 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)”).
It is preferable that the resist composition of the present invention 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 the acid generated from the acid generator (hereinafter sometimes referred to as “quencher (C)”). And a solvent (hereinafter sometimes referred to as “solvent (E)”).

<Resins 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) is a resin not containing the structural unit (I). Examples of such a resin include a resin having a structural unit having an acid labile group, and a resin having the structural unit (I). Resin not containing (hereinafter sometimes referred to as “resin (A2)”), resin comprising only structural unit (a4), and resin comprising structural unit (a4) and structural unit (a5) (hereinafter referred to as structural unit (a4) ) Alone, and the resin consisting of the structural unit (a4) and the structural unit (a5) may be referred to as a resin (X) in some cases).

  In the resin (X), the content of the structural unit (a4) is preferably at least 30 mol%, more preferably at least 40 mol%, based on the total of all the structural units of the resin (X). , 45 mol% or more.

Each of the structural units constituting the resin (X) may be used alone or in combination of two or more, and is produced by a known polymerization method (for example, a radical polymerization method) using a monomer for deriving these structural units. can do. The content of each structural unit in the resin (X) can be adjusted by the amount of the monomer used for polymerization.
The weight average molecular weights of the resin (A2) and the resin (X) are each independently preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). is there. The means for measuring the weight average molecular weight of the resin (A2) and the resin (X) is the same as in the case of the resin (A).
When the resist composition of the present invention contains the resin (A2), the content is usually 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) with respect to 100 parts by mass of the resin (A). is there.
When the resist composition contains the resin (X), the content is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the resin (A). More preferably, it is 1 to 40 parts by mass, particularly preferably 1 to 30 parts by mass, particularly preferably 1 to 8 parts by mass.

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

<Acid generator (B)>
The acid generator (B) may be either nonionic or ionic. Examples of the nonionic acid generator include sulfonate esters (eg, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg, disulfone, Ketosulfone, sulfonyldiazomethane) and the like. Onium salts containing onium cations (eg, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) are typical examples of the ionic acid generator. 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, and JP-A-63-163452. JP-A-62-153853, JP-A-63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. 3,914,407, European Patent No. 126,712, etc. The compounds capable of generating an acid by the radiation described in (1) can be used. Further, a compound produced by a known method may be used. The acid generator (B) may be used in combination of two or more.

The acid generator (B) is preferably a fluorine-containing acid generator, and more preferably a salt represented by the formula (B1) (hereinafter sometimes referred to as “acid generator (B1)”).
[In the formula (B1),
Q ^b1 and Q ^b2 each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the 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 a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and-is included in the alicyclic hydrocarbon group. CH ₂ — may be replaced by —O—, —S (O) ₂ — or —CO—.
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 perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group and And perfluorohexyl groups.
Q ^b1 and Q ^b2 are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably both are fluorine atoms.

Examples of the divalent saturated hydrocarbon group for L ^b1 include a linear alkanediyl group, a branched alkanediyl group, and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group. It may be a group formed by combining two or more of the groups.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group Linear groups such as tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group Alkanediyl group;
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group; Divalent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbons such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group And the like.

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) And a group represented by any of the above. In the groups represented by the formulas (b1-1) to (b1-3) and the groups represented by the formulas (b1-4) to (b1-11), which are specific examples, * and * * Represents 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 a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group; —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—.
However, the total carbon number of L ^b2 and L ^b3 is 22 or less.
In the formula (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group; —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—.
However, the total carbon number of L ^b4 and L ^b5 is 22 or less.
In the formula (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group; —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—.
However, the total carbon number of L ^b6 and L ^b7 is 23 or less. ]

In the groups represented by the formulas (b1-1) to (b1-3), when —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O— or —CO—, the carbon before replacement is The number is defined as the number of carbon atoms of the saturated hydrocarbon group.
Examples of the divalent saturated hydrocarbon group include the same as the divalent saturated hydrocarbon group for L ^b1 .
L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—.
Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group represented by L ¹ is replaced by —O— or —CO— include those represented by Formula (b1-1) or Formula (b1-3). Are preferred.

Examples of the group represented by the formula (b1-1) include groups represented by the formulas (b1-4) to (b1-8).
[In the formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In the formula (b1-5),
L ^b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In the formula (b1-6),
L ^b11 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In the formula (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and -CH _2- contained in the divalent saturated hydrocarbon group is replaced by -O- or -CO-. Is also good.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group .
However, the total number of carbon atoms of L ^b13 ~L ^b15 is 19 or less.
In the formula (b1-8),
L ^b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and —CH ₂ — contained in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—.
L ^b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group .
However, the total carbon number of L ^{b16 to} L ^b18 is 19 or less. ]
L ^b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.
L ^b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.
L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

Examples of the group represented by the formula (b1-3) include groups represented by the formulas (b1-9) to (b1-11).
In the formula (b1-9),
L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Is also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced by —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be replaced by a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In the formula (b1-10),
L ^b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Is also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced by —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be replaced by a hydroxy group.
However, the total carbon number of L ^b21 , L ^b22 and L ^b23 is 21 or less.
In the formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. Is also good. —CH ₂ — contained in the alkylcarbonyloxy group may be replaced by —O— or —CO—, and a hydrogen atom contained in the alkylcarbonyloxy group may be replaced by 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) from the group represented by the formula (b1-9), when the hydrogen atom contained in the saturated hydrocarbon group is substituted by an alkylcarbonyloxy group, the group is replaced. The previous carbon number is 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 (Y36) to (Y38).
When —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y is replaced with —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 formulas (Y12) to (Y35) and formulas (Y39) to (Y41).

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

Examples of the substituent of the methyl group represented by Y 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 (where R ^b1 is an alkyl group having 1 to 16 carbon atoms, Represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof; ja represents an integer of any of 0 to 4. an alkyl group having 1 to 16 carbon atoms; And —CH ₂ — contained in the alicyclic hydrocarbon group having 3 to 16 carbon atoms may be replaced with —O—, —S (O) ₂ —, or —CO—.
Examples of the substituent of the alicyclic hydrocarbon group represented by Y 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 (where R ^b1 is an alkyl group having 1 to 16 carbon atoms, Represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof; ja represents an integer of any of 0 to 4. an alkyl group having 1 to 16 carbon atoms; and -CH ₂ - contained in the alicyclic hydrocarbon group having 3 to 16 carbon atoms - are _{-O -, - S (O)} 2 -. Or -CO- in may be replaced), and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, and the like.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and a phenanthryl group. The aromatic hydrocarbon group may have a chain hydrocarbon group or an alicyclic hydrocarbon group, 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, etc.) 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 a hydroxyalkyl group such as a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

Examples of Y include the following.

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

As the 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 referred to as an anion (B1-A -1) ". ] Are preferable, and the formulas (B1-A-1) to (B1-A-4), the formula (B1-A-9), the formula (B1-A-10), and the formulas (B1-A-24) to (B1-A-33), Formula (B1-A-36) to Formula (B1-A-40), or Formula (B1-A-47) to Formula (B1-A-55). Anions are more preferred.

Here, R ^{i2 to} R ⁱ⁷ are each independently, 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. And 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 anions described in JP-A-2010-204646.

Preferred anions in the salt represented by formula (B1) include anions represented by formulas (B1a-1) to (B1a-34).

  Among them, Formulas (B1a-1) to (B1a-3) and Formulas (B1a-7) to (B1a-16), Formula (B1a-18), Formula (B1a-19), and Formula (B1a-22) ) To (B1a-34) are preferred.

Examples of the organic cation for 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 aryl sulfonium cation is more preferable. Specifically, a cation represented by any of formulas (b2-1) to (b2-4) (hereinafter, may be referred to as “cation (b2-1)” or the like depending on the formula number). No.

In the formulas (b2-1) to (b2-4),
R ^{b4 to} R ^b6 each independently represent 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 be bonded to each other to form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring is -O-, -S- or -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 represent an integer of 0 to 5;
When m2 is 2 or more, a plurality of R ^b7 may be the same or different, and when n2 is 2 or more, a plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent 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 to each other to form a ring together with the sulfur atom to which they are bonded, and -CH _2- contained in the ring is -O-, -S- or -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. May be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be an alkoxy group having 1 to 12 carbon atoms or a carbon atom having 1 to 12 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may be bonded to each other to form a ring including —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring includes —O— and —S -Or -CO-.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b31 represents a sulfur atom or an oxygen atom.
o2, p2, s2, and t2 each independently represent any integer from 0 to 5.
q2 and r2 each independently represent any integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, a plurality of R ^b13 are the same or different. When p2 is 2 or more, a plurality of R ^b14 are the same or different. When q2 is 2 or more, a plurality of R ^b15 are the same or different. , When r2 is 2 or more, a plurality of R ^b16 are the same or different; when s2 is 2 or more, a plurality of R ^b17 are the same or different; when t2 is 2 or more, a plurality of R ^b18 are the same or different. different.
The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.
Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and an alkyl group of a 2-ethylhexyl group. No.
In particular, the chain hydrocarbon group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, Cycloalkyl groups such as a heptyl group, a cyclooctyl group and a cyclodecyl group are exemplified. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups.
In particular, the alicyclic hydrocarbon group of R ^{b9 to} R ^b12 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

  Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group and a 2-ethyladamantan-2-yl group. , 2-isopropyladamantan-2-yl group, methylnorbornyl group, isobornyl group and the like. In the alicyclic hydrocarbon group in which a hydrogen atom 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 an alicyclic ring having 3 to 18 carbon atoms. An aromatic hydrocarbon group having a formula hydrocarbon group (p-adamantylphenyl group, p-cyclohexylphenyl group, etc.) is preferred. Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.
Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, trityl group, naphthylmethyl group, and naphthylethyl group.

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

The ring formed by R ^b4 and R ^b5 bonded together with the sulfur atom to which they are bonded may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated. May be a ring. The ring includes a ring having 3 to 18 carbon atoms, and is preferably a ring having 4 to 18 carbon atoms. Further, the ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring, for example, the following rings. * Represents a binding site.

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

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

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

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

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

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

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

  In the resist composition of the present invention, the content of the acid generator is preferably from 1 part by mass to 40 parts by mass, more preferably from 3 parts by mass to 35 parts by mass, per 100 parts by mass of the resin (A). And more preferably 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.

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

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

  The content of the salt that generates an acid having a lower acidity than the acid generated from the acid generator contained in the resist composition is usually 0.01 to 5% by mass in the solid content of the resist composition, and is preferably Is 0.01 to 3% by mass.

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

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

<Other ingredients>
The resist composition of the present invention may contain components other than the above components (hereinafter, sometimes referred to as “other components (F)”) as necessary. The other component (F) is not particularly limited, and additives known in the resist field, for example, sensitizers, dissolution inhibitors, surfactants, stabilizers, dyes, and the like can be used.

<Preparation of resist composition>
The resist composition of the present invention comprises a resin (A) of the present invention, an acid generator (B), a salt that generates an acid having a lower acidity than the acid generated from the acid generator, and, if necessary, a resin. It can be prepared by mixing (A2), resin (X), quencher (C), solvent (E) and other components (F). The mixing order is arbitrary, and is not particularly limited. An appropriate temperature can be selected from 10 to 40 ° C. depending on the type of the resin or the like and the solubility of the resin or the like in the solvent (E). An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to perform filtration using a filter having a pore size of about 0.003 to 0.2 μm.

<Resist pattern manufacturing method>
The method of manufacturing a resist pattern according to the present invention includes:
(1) a step of applying the resist composition of the present invention on a substrate,
(2) drying the composition after application to form a composition layer;
(3) exposing the composition layer to light,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.
The application of the resist composition onto the substrate can be carried out by a commonly used apparatus such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.
By drying the composition after application, the solvent is removed to form a composition layer. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called prebaking), or using a decompression device. The heating temperature is preferably from 50 to 200 ° C., and the heating time is preferably from 10 to 180 seconds. The pressure at the time of drying under reduced pressure is preferably about 1 to 1.0 × 10 ⁵ Pa.
The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. The exposure light source, which emits laser light in a UV-region such as a KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser source (YAG or semiconductor laser And others that emit laser beams of higher harmonics in the far ultraviolet or vacuum ultraviolet region by converting the wavelength of the laser light from E.g. Can be. In this specification, irradiating these radiations may be collectively referred to as “exposure”. At the time of exposure, the exposure is usually performed through a mask corresponding to 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 a heat treatment (so-called post-exposure bake) in order to promote a deprotection reaction at the acid labile group. The heating temperature is usually about 50 to 200C, preferably about 70 to 150C.
The heated composition layer is usually developed using a developing solution using a developing device. Examples of the developing method include a dip method, a paddle method, a spray method, and a dynamic dispense method. The development temperature is preferably, for example, 5 to 60 ° C., and the development time is, for example, preferably 5 to 300 seconds. By selecting the type of the developer as follows, a positive resist pattern or a negative resist pattern can be produced.
When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as a developer. The alkaline developer may be any of various alkaline aqueous solutions used in this field. For example, aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline) can be mentioned. The alkaline developer may contain a surfactant.
After the development, it is preferable to wash the resist pattern with ultrapure water, and then remove water remaining on the substrate and the pattern.
When a negative resist pattern is produced from the resist composition of the present invention, a developer containing an organic solvent (hereinafter sometimes referred to as “organic developer”) is used as a developer.
Examples of the organic solvent contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether. Ether solvents; amide solvents such as N, N-dimethylacetamide; and aromatic hydrocarbon solvents such as anisole.
The content of the organic solvent in the organic developer is preferably from 90% by mass to 100% by mass, more preferably from 95% by mass to 100% by mass, and further preferably substantially only the organic solvent.
Above all, as the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. The total content of butyl acetate and 2-heptanone in the organic developer is preferably from 50% by mass to 100% by mass, more preferably from 90% by mass to 100% by mass, and substantially butyl acetate and / or 2% by mass. More preferably it is only heptanone.
The organic developer may contain a surfactant. Further, the organic developer may contain a small amount of water.
At the time of development, the development may be stopped by substituting a solvent of a type different from the organic developer.
It is preferable to wash the developed resist pattern with a rinse solution. The rinsing 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 is preferably an alcohol solvent or an ester solvent.
After the cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

<Applications>
The resist composition of the present invention 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.

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

Example 1: Synthesis of compound represented by formula (IB-1)
After mixing 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, and stirring at 70 ° C. for 10 hours, Cooled to 23 ° C. The obtained mixture was mixed with 300 parts of chloroform and 130 parts of a 5% aqueous sodium hydrogen carbonate solution, stirred at 23 ° C. for 30 minutes, and separated to separate an organic layer. 100 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated residue was fractionated using a column (silica gel 60N (spherical, neutral) 100 to 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 mixing 0.65 part of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile and stirring the mixture at 23 ° C. for 30 minutes, 1.34 of the compound represented by the formula (I-1-e) is mixed. Then, the mixture was heated to 50 ° C., and then stirred at 50 ° C. for 2 hours. To the obtained mixture, 0.66 parts of the compound represented by the formula (I-1-c) was added, and the mixture was stirred at 50 ° C for 2 hours. After the obtained mixture was cooled to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.52 parts of a compound represented by the formula (IB-1-f) was obtained. 0.52 parts of the obtained compound represented by the formula (IB-1-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23 ° C. for 6 hours. The obtained mixture was concentrated to obtain 0.41 part of a compound represented by the formula (IB-1-g).
0.29 parts of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.39 parts of a compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.33 part of a compound represented by the formula (IB-1-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the obtained reaction mixture, 50 parts of chloroform and 30 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After 30 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23 ° C. for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.35 part of a compound represented by the formula (IB-1) was obtained.
MASS: 557.3 [M + H] ⁺

Example 2: Synthesis of compound represented by formula (IA-1)
After mixing 0.65 part of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile and stirring the mixture at 23 ° C. for 30 minutes, 1.34 of the compound represented by the formula (I-1-e) is mixed. Then, the mixture was heated to 50 ° C., and then stirred at 50 ° C. for 2 hours. 1.32 parts of a compound represented by the formula (I-1-c) was added to the obtained mixture, and the mixture was stirred at 50 ° C for 2 hours. After the obtained mixture was cooled to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/2). By fractionation, 0.68 part of a compound represented by the formula (IA-1-f) was obtained. 0.68 part of the obtained compound represented by the formula (IA-1-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23 ° C. for 6 hours. The resulting mixture was concentrated to obtain 0.52 parts of a compound represented by the formula (IA-1-g).
0.44 parts of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.59 parts of the compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.25 part of a compound represented by the formula (IA-1-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the obtained reaction mixture, 50 parts of chloroform and 30 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After 30 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23 ° C. for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.42 parts of a compound represented by the formula (IA-1) was obtained.
MASS: 631.3 [M + H] ⁺

Example 3: Synthesis of compound represented by formula (IB-6)
After mixing 1.79 parts of the compound represented by the formula (I-6-d) and 20 parts of acetonitrile and stirring the mixture at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Then, the mixture was heated to 50 ° C. and then stirred 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 the mixture was stirred at 50 ° C for 2 hours. After the obtained mixture was cooled to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 1.09 parts of a compound represented by the formula (IB-6-f) were obtained. 1.05 part of the obtained compound represented by the formula (IB-6-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23 ° C for 6 hours. The obtained mixture was concentrated to obtain 0.92 parts of a compound represented by the formula (IB-6-g).
0.29 parts of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.39 parts of a compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.80 part of a compound represented by the formula (IB-6-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the obtained reaction mixture, 50 parts of chloroform and 30 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After 30 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23 ° C. for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.65 part of a compound represented by the formula (IB-6) was obtained.
MASS: 945.4 [M + H] ⁺

Example 4: Synthesis of compound represented by formula (IA-6)
After mixing 1.79 parts of the compound represented by the formula (I-6-d) and 20 parts of acetonitrile and stirring the mixture at 23 ° C. for 30 minutes, the compound 1.34 represented by the formula (I-1-e) is mixed. Then, the mixture was heated to 50 ° C. and then stirred at 50 ° C. for 2 hours. To the resulting mixture, 2.48 parts of the compound represented by the formula (I-1-c) was added, and the mixture was stirred at 50 ° C for 2 hours. After the obtained mixture was cooled to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/2). By fractionation, 2.21 parts of a compound represented by the formula (IA-6-f) was obtained. 1.50 parts of the obtained compound represented by the formula (IA-6-f), 0.01 parts of sulfuric acid and 20 parts of acetonitrile were mixed, and the mixture was stirred at 23 ° C. for 6 hours. The obtained mixture was concentrated to obtain 1.22 parts of a compound represented by the formula (IA-6-g).
0.44 parts of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.59 parts of the compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.49 part of a compound represented by the formula (IA-6-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the obtained reaction mixture, 50 parts of chloroform and 30 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After 30 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23 ° C. for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.62 parts of a compound represented by the formula (IA-6) was obtained.
MASS: 825.4 [M + H] ⁺

Example 5: Synthesis of compound represented by formula (IB-12)
After mixing 1.56 parts of the compound represented by the formula (I-12-d) and 20 parts of acetonitrile, stirring the mixture at 23 ° C. for 30 minutes, 1.34 of the compound represented by the formula (I-1-e) is mixed. Then, the mixture was heated to 50 ° C., and then stirred 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 the obtained mixture was cooled to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.28 part of a compound represented by the formula (IB-12-f) was obtained. 0.27 part of the obtained compound represented by the formula (IB-12-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23 ° C for 6 hours. By concentrating the obtained mixture, 0.24 parts of a compound represented by the formula (IB-12-g) was obtained.
0.10 part of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.13 part of a compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.21 part of a compound represented by the formula (IB-12-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the resulting reaction mixture, 50 parts of chloroform and 20 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, liquid separation was performed to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.24 part of a compound represented by the formula (IB-12) was obtained.
MASS: 797.3 [M + H] ⁺

Example 6: Synthesis of compound represented by formula (IA-12)
After mixing 1.56 parts of the compound represented by the formula (I-12-d) and 20 parts of acetonitrile, stirring the mixture at 23 ° C. for 30 minutes, 1.34 of the compound represented by the formula (I-1-e) is mixed. Then, the mixture was heated to 50 ° C., and then stirred at 50 ° C. for 2 hours. 0.70 parts of the compound represented by the formula (I-1-c) was added to the obtained mixture, and the mixture was stirred at 50 ° C for 2 hours. After the obtained mixture was cooled to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/2). By fractionation, 0.39 part of a compound represented by the formula (IA-12-f) was obtained. 0.27 part of the obtained compound represented by the formula (IA-12-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23 ° C for 6 hours. The obtained mixture was concentrated to obtain 0.28 parts of a compound represented by the formula (IA-12-g).
0.22 parts of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.30 part of a compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.20 part of a compound represented by the formula (IA-12-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the resulting reaction mixture, 50 parts of chloroform and 20 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After adding 20 parts of ion-exchanged water to the obtained organic layer and stirring at 23 ° C. for 30 minutes, liquid separation was performed to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.22 parts of a compound represented by the formula (IA-12) was obtained.
MASS: 751.3 [M + H] ⁺

Example 7: Synthesis of compound represented by formula (IB-17)
After mixing 0.65 part of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile and stirring the mixture at 23 ° C. for 30 minutes, 1.34 of the compound represented by the formula (I-1-e) is mixed. Then, the mixture was heated to 50 ° C., and then stirred at 50 ° C. for 2 hours. To the obtained mixture, 0.61 part of a compound represented by the formula (I-17-c) was added, and the mixture was stirred at 50 ° C for 2 hours. After the obtained mixture was cooled to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.48 part of a compound represented by the formula (IB-17-f) was obtained. 0.48 part of the obtained compound represented by the formula (IB-17-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23 ° C for 6 hours. The obtained mixture was concentrated to obtain 0.39 parts of a compound represented by the formula (IB-17-g).
0.29 parts of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.39 parts of a compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.31 part of a compound represented by the formula (IB-17-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the obtained reaction mixture, 50 parts of chloroform and 30 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After 30 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23 ° C. for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.29 part of a compound represented by the formula (IB-17) was obtained.
MASS: 543.2 [M + H] ⁺

Example 8: Synthesis of compound represented by formula (IA-17)
After mixing 0.65 part of the compound represented by the formula (I-1-d) and 20 parts of acetonitrile and stirring the mixture at 23 ° C. for 30 minutes, 1.34 of the compound represented by the formula (I-1-e) is mixed. Then, the mixture was heated to 50 ° C., and then stirred at 50 ° C. for 2 hours. To the obtained mixture, 1.22 parts of a compound represented by the formula (I-17-c) was added, and the mixture was stirred at 50 ° C for 2 hours. After the obtained mixture was cooled to 23 ° C., 50 parts of chloroform and 20 parts of ion-exchanged water were added, and the mixture was stirred at 23 ° C. for 30 minutes. 20 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, and then separated to take out the organic layer. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/2). By fractionation, 0.57 part of a compound represented by the formula (IA-17-f) was obtained. 0.57 part of the obtained compound represented by the formula (IA-17-f), 0.01 part of sulfuric acid and 20 parts of acetonitrile were mixed and stirred at 23 ° C. for 6 hours. The obtained mixture was concentrated to obtain 0.46 parts of a compound represented by the formula (IA-17-g).
0.44 parts of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.59 parts of the compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.23 part of a compound represented by the formula (IA-17-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the obtained reaction mixture, 50 parts of chloroform and 30 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After 30 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23 ° C. for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.34 part of a compound represented by the formula (IA-17) was obtained.
MASS: 617.3 [M + H] ⁺

Example 9: Synthesis of compound represented by formula (IA-2)
0.29 parts of the compound represented by the formula (I-1-h) and 30 parts of acetonitrile were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, 0.59 parts of the compound represented by the formula (I-1-e) was added, and the mixture was further stirred at 50 ° C for 2 hours. To the obtained reaction mixture, 0.25 part of a compound represented by the formula (IA-1-g) was added, and the mixture was further stirred at 50 ° C for 4 hours, and then cooled to 23 ° C. To the obtained reaction mixture, 50 parts of chloroform and 30 parts of a 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23 ° C. for 30 minutes. After 30 parts of ion-exchanged water was added to the obtained organic layer and the mixture was stirred at 23 ° C. for 30 minutes, the layers were separated and the organic layer was taken out. This washing operation was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was subjected to column chromatography (silica gel 60N (spherical, neutral) 100 to 210 μm; manufactured by Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate = 1/1). By fractionation, 0.21 part of a compound represented by the formula (IA-2) was obtained.
MASS: 489.2 [M + H] ⁺

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

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

Example 10 [Synthesis of Resin A1]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IB-1) were used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IB-1)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in an amount of 1.5 mol% and 4.5 mol% with respect to the total amount of the monomers, respectively. Heat for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin A1 having a molecular weight of 7.7 × 10 ³ was obtained with a yield of 60%. This resin A1 has the following structural units.

Example 11 [Synthesis of resin A2]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IA-1) were used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IA-1)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators based on the total amount of the monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin A2 having a molecular weight of 7.9 × 10 ³ was obtained with a yield of 58%. This resin A2 has the following structural units.

Example 12 [Synthesis of Resin A3]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-5), a monomer (a2-1-1), a monomer (a3-4-2), and a monomer (IB-6) are used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IB-6)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in an amount of 1.5 mol% and 4.5 mol% with respect to the total amount of the monomers, respectively. Heat for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin A3 having a molecular weight of 8.0 × 10 ³ was obtained with a yield of 62%. This resin A3 has the following structural units.

Example 13 [Synthesis of Resin A4]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-5), a monomer (a2-1-1), a monomer (a3-4-2), and a monomer (IA-6) were used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IA-6)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators based on the total amount of the monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin A4 having a molecular weight of 7.9 × 10 ³ was obtained with a yield of 62%. This resin A4 has the following structural units.

Example 14 [Synthesis of Resin A5]
Monomers (a1-1-1), monomers (a1-0-1), monomers (a3-2-1) and monomers (IB-1) were used as monomers, and their molar ratios were [monomer (a1-1-1) ): Monomer (a1-0-1): Monomer (a3-2-1): Monomer (IB-1)] was mixed so as to be 46: 11: 34: 9, and 1.5 mass of the total monomer amount. Double the amount of propylene glycol monomethyl ether acetate was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in an amount of 1.5 mol% and 4.5 mol% with respect to the total amount of the monomers, respectively. Heat for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin A5 having a molecular weight of 7.8 × 10 ³ was obtained at a yield of 85%. This resin A5 has the following structural units.

Example 15 [Synthesis of resin A9]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-5), a monomer (a2-1-1), a monomer (a3-4-2), and a monomer (IB-17) are used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IB-17)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in an amount of 1.5 mol% and 4.5 mol% with respect to the total amount of the monomers, respectively. Heat for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin A9 having a molecular weight of 7.4 × 10 ³ was obtained with a yield of 62%. This resin A9 has the following structural units.

Example 16 [Synthesis of Resin A10]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IA-17) were used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IA-17)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators based on the total amount of the monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin A10 having a molecular weight of 7.7 × 10 ³ was obtained with a yield of 61%. This resin A10 has the following structural units.

Example 17 [Synthesis of Resin A11]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-5), a monomer (a2-1-1), a monomer (a3-4-2), and a monomer (IA-2) were used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IA-2)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators based on the total amount of the monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin A11 having a molecular weight of 7.8 × 10 ³ was obtained at a yield of 60%. This resin A11 has the following structural units.

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

Synthesis Example 2 [Synthesis of resin AX2]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IX-1) were used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IX-1)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in an amount of 1.5 mol% and 4.5 mol% with respect to the total amount of the monomers, respectively. Heat for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin AX2 having a molecular weight of 7.9 × 10 ³ was obtained with a yield of 60%. This resin AX2 has the following structural units.

Synthesis Example 3 [Synthesis of resin AX3]
Monomers (a1-1-3), monomers (a1-2-5), monomers (a2-1-1), monomers (a3-4-2) and monomers (IX-2) were used as monomers, The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IX-2)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators in an amount of 1.5 mol% and 4.5 mol% with respect to the total amount of the monomers, respectively. Heat for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin AX3 having a molecular weight of 7.8 × 10 ³ was obtained with a yield of 64%. This resin AX3 has the following structural units.

Synthesis Example 4 [Synthesis of resin AX4]
As the monomer, a monomer (a1-1-3), a monomer (a1-2-5), a monomer (a2-1-1), a monomer (a3-4-2), and a monomer (IX-3) were used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IX-3)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators based on the total amount of the monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. A resin AX4 having a molecular weight of 8.0 × 10 ³ was obtained with a yield of 60%. This resin AX4 has the following structural units.

Synthesis Example 5 [Synthesis of resin AX5]
As monomers, monomer (a1-1-3), monomer (a1-2-5), monomer (a2-1-1), monomer (a3-4-2) and monomer (IX-4) were used. The ratio [monomer (a1-1-3): monomer (a1-2-5): monomer (a2-1-3): monomer (a3-4-2): monomer (IX-4)] is 45:14: The mixture was mixed at a ratio of 4: 34: 3, and propylene glycol monomethyl ether acetate 1.5 times by mass of the total amount of the monomers was added to form a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) were added as initiators based on the total amount of the monomers, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol / water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution is poured into a mixed solvent of methanol / water to precipitate the resin. Resin AX5 having a molecular weight of 7.6 × 10 ³ was obtained with a yield of 55%. This resin AX5 has the following structural units.

Example 18 [Synthesis of Resin A6]
As the monomers, a monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (IB-12) were used, and their molar ratios [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IB-12)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 parts by mass of methyl isobutyl ketone based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain a resin A6 having a weight average molecular weight of about 5.6 × 10 ³ in a yield of 55%. This resin A6 has the following structural units.

Example 19 [Synthesis of Resin A7]
As the monomer, a monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6), and a monomer (IA-12) were used, and the molar ratio thereof was [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IA-12)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 mass times of methyl isobutyl ketone based on the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, followed by filtration and recovery, whereby a resin A7 having a weight average molecular weight of about 5.9 × 10 ³ was obtained at a yield of 59%. This resin A7 has the following structural units.

Example 20 [Synthesis of resin A8]
As the monomers, a monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (IB-1) were used, and their molar ratios [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IB-1)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 parts by mass of methyl isobutyl ketone based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, and the resin was filtered and collected to obtain a resin A8 having a weight average molecular weight of about 5.9 × 10 ³ in a yield of 48%. This resin A8 has the following structural units.

Example 21 [Synthesis of Resin A12]
As the monomers, a monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (IA-1) were used, and their molar ratios [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IA-1)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 parts by mass of methyl isobutyl ketone based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, and the resin was filtered and collected to obtain a resin A12 having a weight average molecular weight of about 5.6 × 10 ³ in a yield of 64%. This resin A12 has the following structural units.

Example 22 [Synthesis of Resin A13]
As the monomer, a monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (IB-17) were used, and the molar ratio thereof was [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IB-17)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 mass times of methyl isobutyl ketone based on the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected, whereby a resin A13 having a weight average molecular weight of about 5.5 × 10 ³ was obtained at a yield of 54%. This resin A13 has the following structural units.

Example 23 [Synthesis of Resin A14]
Monomers (a1-4-2), monomers (a1-1-3), monomers (a1-2-6) and monomers (IA-17) were used as the monomers, and the molar ratio thereof was [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IA-17)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 parts by mass of methyl isobutyl ketone based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, and the resin was filtered and collected to obtain a resin A14 having a weight average molecular weight of about 5.4 × 10 ³ in a yield of 62%. This resin A14 has the following structural units.

Example 24 [Synthesis of Resin A15]
Monomers (a1-4-2), monomers (a1-1-3), monomers (a1-2-6) and monomers (IA-2) were used as the monomers, and the molar ratio thereof was [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IA-2)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 parts by mass of methyl isobutyl ketone based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected, whereby a resin A15 having a weight average molecular weight of about 5.5 × 10 ³ was obtained in a yield of 65%. This resin A15 has the following structural units.

Synthesis Example 6 [Synthesis of resin AX6]
Monomers (a1-4-2), monomers (a1-1-3), monomers (a1-2-6) and monomers (IX-1) were used as the monomers, and the molar ratio thereof was [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IX-1)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 parts by mass of methyl isobutyl ketone based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected, whereby a resin AX6 having a weight average molecular weight of about 5.7 × 10 ³ was obtained at a yield of 50%. This resin AX6 has the following structural units.

Synthesis Example 7 [Synthesis of resin AX7]
Monomers (a1-4-2), monomers (a1-1-3), monomers (a1-2-6), and monomers (IX-2) were used as the monomers, and the molar ratio of the monomers (monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IX-2)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 parts by mass of methyl isobutyl ketone based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 12 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, which was filtered and collected to obtain a resin AX7 having a weight average molecular weight of about 5.8 × 10 ³ in a yield of 53%. This resin AX7 has the following structural units.

Synthesis Example 8 [Synthesis of resin AX8]
Monomers (a1-4-2), monomers (a1-1-3), monomers (a1-2-6) and monomers (IX-3) were used as the monomers, and the molar ratio thereof was [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IX-3)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 parts by mass of methyl isobutyl ketone based on the total mass of all the monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, and the resin was filtered and collected to obtain a resin AX8 having a weight average molecular weight of about 5.7 × 10 ³ in a yield of 50%. This resin AX8 has the following structural units.

Synthesis Example 9 [Synthesis of resin AX9]
As the monomers, a monomer (a1-4-2), a monomer (a1-1-3), a monomer (a1-2-6) and a monomer (IX-4) were used, and their molar ratio [monomer (a1-4-2) ): Monomer (a1-1-3): Monomer (a1-2-6): Monomer (IX-4)], and mixed at a ratio of 38: 29: 30: 3. Was mixed with 1.5 mass times of methyl isobutyl ketone based on the total mass of all monomers. To the obtained mixture, azobisisobutyronitrile as an initiator was added in an amount of 7 mol% based on the total number of moles of all monomers, and the mixture was heated at 85 ° C. for about 5 hours to perform polymerization. Was. Thereafter, an aqueous solution of p-toluenesulfonic acid was added to the polymerization reaction solution, stirred for 6 hours, and then separated. The obtained organic layer was poured into a large amount of n-heptane to precipitate a resin, and the resin was filtered and collected, whereby a resin AX9 having a weight average molecular weight of about 5.9 × 10 ³ was obtained at a yield of 55%. This resin AX9 has the following structural units.

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

<Preparation of resist composition>
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 A15, AX1 to AX9, X1: resin A1 to resin A15, resin AX1 to resin AX9, resin X1
<Acid generator (B)>
B1-21: A salt represented by the formula (B1-21) (synthesized according to the examples of JP-A-2012-246611)
B1-22: Salt represented by the formula (B1-22) (synthesized according to the example of JP-A-2012-246611)
B1-43: Salt represented by formula (B1-43) (synthesized according to the examples in JP-A-2016-47815)
<Quencher (C)>
(Salt that generates an acid whose acidity is weaker than the acid generated from the acid generator)
D1: synthesized by the method described in JP-A-2011-39502
D2: (Tokyo Chemical Industry Co., Ltd.)
<Solvent: composition 1-5, 9-11, comparative composition 1-5>
Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts <Solvent: compositions 6 to 8, 12 to 15, comparative compositions 6 to 9>
Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 150 parts γ-butyrolactone 5 parts

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

<CD uniformity (CDU) evaluation>
In the effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 55 nm was measured 24 times for each hole, and the average value was defined as the average hole diameter of one hole. The standard deviation was determined using a population obtained by measuring 400 average hole diameters of a pattern formed with a mask having a hole diameter of 55 nm in the same wafer.
Table 2 shows the results. The values in parentheses indicate the standard deviation (nm).

Standard deviations of compositions 1 to 5 and 9 to 11 were smaller than those of comparative compositions 1 to 5, and the evaluation of CD uniformity (CDU) was good.

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

<CD uniformity (CDU) evaluation>
In the effective sensitivity, the hole diameter of a pattern formed with a mask having a hole diameter of 17 nm was measured 24 times for each hole, and the average value was defined as the average hole diameter of one hole. The standard deviation was determined using a population obtained by measuring 400 average hole diameters of a pattern formed with a mask having a hole diameter of 55 nm in the same wafer.
Table 3 shows the results. The values in parentheses indicate the standard deviation (nm).

Standard deviations of compositions 6 to 8 and 12 to 15 were smaller than those of comparative compositions 6 to 9, 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 fine processing of semiconductors and is extremely useful in industry.

Claims (11)

A compound represented by the formula (IA) or (IB).
[In the formulas (IA) and (IB),
R ¹ and R ² each independently represent a hydrogen atom or a methyl group.
X ¹ and ^{X 2} each independently represent a group represented by any one of formula ^(X 1 -1) ~ Formula ^(X 1 -7).
(In the formula ^(X 1 -1) ~ Formula ^(X 1 -7),
*, ** represents a binding site, ** represents the bonding site to ^{L 1.} )
L ¹ represents a hydrocarbon group having 1 to 48 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group is -O-, -S-, -CO- or —SO ₂ — may be substituted.
R ³ is a hydrocarbon group having 1 to 36 carbon atoms having a group represented by the formula (IC) (the hydrocarbon group may have a substituent, and —CH ₂ — contained in the hydrocarbon group is included). is, -O -, - S -, - CO- or -SO ₂ -. which may be substituted with) represents a.
R ⁴ and R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 36 carbon atoms which may have a group represented by the formula (IC) (the hydrocarbon group has a substituent; And —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO ₂ —.) ]
[In the formula (IC),
^RA represents a saturated hydrocarbon group having 1 to 12 carbon atoms.
u1 represents an integer of 0 to 2, when u1 is 2, or a plurality of ^{R A} are the same, different.
s1 represents 1 or 2.
t1 represents 0 or 1. However, the sum of s1 and t1 is 1 or 2.
* Represents a binding site. ] L ¹ is The compound of claim 1, wherein a group represented by the formula radical or formula represented by ^{(L 1 A) (L 1} B).
[In the formulas (L ¹ A) and (L ¹ B),
L ⁴ and L ^{4 ′} each independently represent a single bond or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and -CH _2- contained in the hydrocarbon group is- O -, - S -, - CO- or -SO ₂ - may be replaced with.
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 an oxygen atom or X ² in -OR ^5, * c represents the binding site to the oxygen atoms in the -OR ^3, * d is -OR ⁴ represents a bonding site to an 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. groups (-CH ₂ contained in the alkanediyl group - may be replaced by -O- or -CO-, -CH ₂ contained in the alicyclic hydrocarbon group - is -O-, —S—, —CO— or —SO ₂ —), L ² is a single bond or an alkanediyl group having 1 to 4 carbon atoms, and L ³ is an alkane having 1 to 4 carbon atoms. The compound according to claim 2, wherein the compound is a diyl group, and L3 ^' is an alkanetriyl group having 1 to 4 carbon atoms. X ¹ has the formula ^(X 1 -1), wherein ^(X 1 -3) or compound according to claim 1 is a group represented by any one of formulas ^(X 1 -4).   A resin containing a structural unit derived from the compound according to claim 1.   The resin according to claim 5, further comprising a structural unit having an acid labile group. The resin according to claim 6, wherein the structural unit having an acid labile group includes at least one of a structural unit represented by the formula (a1-1) and a structural unit represented by the formula (a1-2).
[In the formulas (a1-1) and (a1-2),
L ^a1 and L ^a2 each independently, -O- or _{* -O- (CH 2) k1 -CO} -O- the stands, k1 represents an integer of 1-7, and * -CO- And represents a 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 an integer of any of 0 to 14.
n1 represents any integer of 0-10.
n1 ′ represents any integer of 0 to 3. ]   A resist composition comprising the resin according to claim 5 and an acid generator. The resist composition according to claim 8, 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 a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and-is included in the alicyclic hydrocarbon group. CH ₂ — may be replaced by —O—, —S (O) ₂ — or —CO—.
Z ⁺ represents an organic cation. ]   10. The resist composition according to claim 8, further comprising a salt that generates an acid having a lower acidity than the acid generated from the acid generator. (1) a step of applying the resist composition according to any one of claims 8 to 10 on a substrate;
(2) drying the composition after application to form a composition layer;
(3) exposing the composition layer to light,
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.
A method for producing a resist pattern comprising: