JP2018002708A - Compound, acid generator, polymer, resist composition, and method for producing resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound capable of producing a resist pattern with good line edge roughness, an acid generator, a polymer, and a resist composition.SOLUTION: The compound is represented by formula (I) [where Qand Qeach independently represent a perfluoroalkyl group or the like; Rand Reach independently represent a perfluoroalkyl group or the like; z represents an integer of 0-6; Xrepresents *1-CO-O-, *1-O-CO-, -O-CO-O-, or -O-; Arepresents a hydrocarbon group which may have a substituent; Xrepresents *2-CO-O-, -O-CO-O-, or -O-; Rand Reach independently represent a saturated hydrocarbon group or the like; Xrepresents a specific group; Rrepresents an alkyl group which may have a halogen atom, or the like; and Zrepresents an organic cation].SELECTED DRAWING: None

Description

  The present invention relates to a compound, an acid generator, a polymer, a resist composition, a method for producing a resist pattern using the resist composition, and the like.

Patent Document 1 describes a resist composition containing a resin having a structural unit derived from the following compound.
Patent Document 2 describes a resist composition containing a resin having a structural unit derived from the following compound.

JP 2007-197718 A JP 2014-197168 A

The present invention includes the following inventions.
[1] A compound represented by the formula (I).
[In the formula (I),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * 1-CO—O—, * 1-O—CO—, —O—CO—O— or —O—, and * 1 represents C (R ¹ ) (R ² ) or C ( Q ¹ ) represents a binding site with (Q ² ).
A ¹ represents an optionally substituted divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, — CO— or —SO ₂ — may be substituted.
X ² represents * 2-CO—O—, —O—CO—O— or —O—, and * 2 represents a binding site with A ¹ .
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
X ³ represents a group represented by any one of formula (X ³ -1) to formula (X ³ -8).
(In the formula (X ³ -1) to the formula (X ³ -8),
* Represents a binding site with C (R ³ ) (R ⁴ ). )
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ⁺ represents an organic cation. ]
[2] The compound according to [1], wherein X ¹ is * 1-CO—O—.
[3] The compound according to [1] or [2], wherein A ¹ is an optionally substituted alkanediyl group having 2 to 6 carbon atoms or an adamantanediyl group optionally having a substituent. .
[4] The compound according to any one of [1] to [3], wherein X ² is —O—.
[5] ^{X 3} is A compound according to any one of a group represented by the formula radical or formula represented by ^{(X 3 -1) (X 3} -7) [1] to [4].
[6] An acid generator containing the compound according to any one of [1] to [5].
[7] A polymer having a structural unit derived from the compound according to any one of [1] to [5].
[8] The polymer according to [7], further comprising a structural unit having an acid labile group.
[9] A resist composition comprising the compound according to any one of [1] to [5] and a resin.
[10] A resist composition comprising the polymer according to [7] or [8] and an acid generator.
[11] The resist composition according to [10], wherein the acid generator includes a compound represented by the formula (I).
[12] (1) A step of applying the resist composition according to any one of [9] to [11] on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.
[13] A compound represented by the formula (I ′) obtained by reacting a compound represented by the formula (Ia) with a compound represented by the formula (Ib) in a solvent in the presence of an acid catalyst. The manufacturing method of the compound represented by this.
[Where:
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * —CO—O—, * —O—CO—, —O—CO—O— or —O—, and * represents C (R ¹ ) (R ² ) or C (Q ¹ ). It represents a binding site with (Q ² ).
A ¹ represents a divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ —. The hydrogen atom contained in the hydrocarbon group may be a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 13 carbon atoms, an acyloxy group having 2 to 13 carbon atoms, a cyano group, or a carboxyl group. It may be substituted with one or more groups selected from the group consisting of groups.
X ² represents * —CO—O—, —O—CO—O— or —O—, and * represents a binding site to A ¹ .
R ³ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ^{4 ′} represents a group obtained by removing one hydrogen atom from a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ^{4 ″} represents a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
X ³ represents a group represented by any one of formula (X ³ -1) to formula (X ³ -8).
(In the formula (X ³ -1) to the formula (X ³ -8),
* Represents a binding site with C (R ³ ) (R ⁴ ). )
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ⁺ represents an organic cation. ]
[14] A compound represented by formula (Ia).
[In the formula (Ia),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * —CO—O—, * —O—CO—, —O—CO—O— or —O—, and * represents C (R ¹ ) (R ² ) or C (Q ¹ ). It represents a binding site with (Q ² ).
A ¹ represents a divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ —. The hydrogen atom contained in the hydrocarbon group may be a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 13 carbon atoms, an acyloxy group having 2 to 13 carbon atoms, a cyano group, or a carboxyl group. It may be substituted with a group or a combination thereof.
X ² represents * —CO—O—, —O—CO—O— or —O—, and * represents a binding site to A ¹ .
R ³ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ^{4 ′} represents a group obtained by removing one hydrogen atom from a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
Z ⁺ represents an organic cation. ]

In the present specification, “(meth) acrylate” means “at least one of acrylate and methacrylate”. Notations such as “(meth) acrylic acid” and “(meth) acryloyl” have the same meaning.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described later from the total amount of the resist composition.

<Compound represented by formula (I) (hereinafter sometimes referred to as compound (I))>
[In the formula (I),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * 1-CO—O—, * 1-O—CO—, —O—CO—O— or —O—, and * 1 represents C (R ¹ ) (R ² ) or C ( Q ¹ ) represents a binding site with (Q ² ).
A ¹ represents an optionally substituted divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, — CO— or —SO ₂ — may be substituted.
X ² represents * 2-CO—O—, —O—CO—O— or —O—, and * 2 represents a binding site with A ¹ .
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
X ³ represents a group represented by any one of formula (X ³ -1) to formula (X ³ -8).
(In the formula (X ³ -1) to the formula (X ³ -8),
* Represents a binding site with C (R ³ ) (R ⁴ ). )
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ⁺ represents an organic cation. ]

As the perfluoroalkyl group for Q ¹ , Q ² , R ¹ and R ² , a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group , Perfluoropentyl group, perfluorohexyl group and the like.
Q ¹ and Q ² are independently of each other preferably a trifluoromethyl group or a fluorine atom, and more preferably a fluorine atom.
R ¹ and R ² are independently of each other preferably a hydrogen atom or a fluorine atom.
z is preferably 0.

X ¹ is preferably * 1-CO—O— (* 1 represents a binding site with C (R ¹ ) (R ² ) or C (Q ¹ ) (Q ² )).

Examples of the divalent hydrocarbon group represented by A ¹ include alkanediyl groups, monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, aromatic hydrocarbon groups, and the like. A combination of two or more of the groups may be used.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 , 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group Linear alkanediyl groups such as
Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- Branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group;
Monocyclic 2 which is a cycloalkanediyl group such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group Valent alicyclic saturated hydrocarbon group;
Polycyclic divalent alicyclic saturated hydrocarbon such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group, etc. Group;
Phenylene group, naphthylene group, anthrylene group, p-methylphenylene group, p-tert-butylphenylene group, p-adamantylphenylene group, tolyl group, xylylene group, cumenylene group, mesitylene group, biphenylene group, phenanthrylene group, 2,6 -Aromatic hydrocarbon groups such as diethylphenylene group and 2-methyl-6-ethylphenylene group.

The divalent hydrocarbon group represented by A ¹ may have a substituent, and examples of the substituent include a hydroxy group, a cyano group, a carboxyl group having 1 to 12 carbon atoms, and a carbon number of 2 ˜13 acyl groups and C 2-13 acyloxy groups.
Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Examples of the acyl group having 2 to 13 carbon atoms include an acetyl group, a propionyl group, and a butyryl group.
Examples of the acyloxy group having 2 to 13 carbon atoms include acetyloxy group, propionyloxy group, and butyryloxy group.
The hydrocarbon group represented by A ¹ may have one substituent or a plurality of substituents.

A ¹ is preferably an alkanediyl group having 2 to 6 carbon atoms which may have a substituent and an adamantanediyl group which may have a substituent, and an alkanediyl group and an adamantanediyl group having 2 to 6 carbon atoms. Is more preferable.
X ² is preferably —O—.

Examples of the monovalent saturated hydrocarbon group represented by R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. An cycloalkyl group such as a cyclopentyl group and a cyclohexyl group;
At least one of R ³ and R ⁴ is preferably a saturated hydrocarbon group having 1 to 6 carbon atoms.
R ³ and R ⁴ are each independently preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, and one is a hydrogen atom and the other is a methyl group. Further preferred.
X ³ includes formula (X ³ -1), formula (X ³ -4), formula (X ³ -5), formula (X ³ -6), formula (X ³ -7) and formula (X ^3- 8) is preferably a group represented by any one of formula (X ³ -1), formula (X ³ -6), formula (X ³ -7) and formula (X ³ -8). The group represented by formula (X ³ -1) or the group represented by formula (X ³ -7) is more preferred.

Examples of the alkyl group for R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. , Preferably, a C1-C4 alkyl group is mentioned, More preferably, a methyl group and an ethyl group are mentioned.
Examples of the halogen atom for R ⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having a halogen atom of R ⁵ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro group. A hexyl group, a perchloromethyl group, a perbromomethyl group, a periododomethyl group, etc. are mentioned.
R ⁵ is preferably a hydrogen atom or a methyl group.

Examples of the anion in compound (I) include the following anions. Especially, the anion represented by a formula (Ia-1)-a formula (Ia-18) is preferable, and the anion represented by a formula (Ia-1)-a formula (Ia-12) is more preferable.

The cation Z ⁺ in the compound (I) is preferably an organic onium cation.
Examples of the organic onium cation include an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation, preferably an organic sulfonium cation or an organic iodonium cation, and more preferably an arylsulfonium cation. It is.
Among these, a cation represented by any one of the formulas (b2-1) to (b2-4) (hereinafter may be referred to as “cation (b2-1)” or the like depending on the formula number) is preferable.
[In Formula (b2-1)-Formula (b2-4),
R ^{b4 to} R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 36 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group is a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an acyl 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 form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b7 and R ^b8 each independently represent a hydroxy group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5.
When m2 is 2 or more, the plurality of R ^b7 may be the same or different, and when n2 is 2 or more, the plurality of R ^b8 may be the same or different.
R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.
R ^b9 and R ^b10 may form a ring together with the sulfur atom to which they are bonded, and —CH ₂ — contained in the ring may be replaced with —O—, —SO— or —CO—. .
R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and is included in the aliphatic hydrocarbon. The hydrogen atom may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is an alkoxy group having 1 to 12 carbon atoms or 1 to 1 carbon atoms. It may be substituted with 12 alkylcarbonyloxy groups.
R ^b11 and R ^b12 may together form a ring containing —CH—CO— to which they are bonded, and —CH ₂ — contained in the ring is —O—, —SO—. Alternatively, it may be replaced by -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 -S- or -O-.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more The plurality of R ^b15 may be the same or different. When r2 is 2 or more, the plurality of R ^b16 may be the same or different. When s2 is 2 or more, the plurality of R ^b17 is ^They may be the same or different, and when t2 is 2 or more, the plurality of R ^b18 may be the same or different. ]

  Specific examples of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, acyl group, halogen atom, alkylcarbonyloxy group, ring that two substituents can form together Examples include the same groups as exemplified in the substituents in the present application and examples of cations similar to the above formula in JP-A No. 2006-102163.

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

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

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

Examples of the cation (b2-4) include the following cations.
Among them, the formulas (b2-c-1), (b2-c-10), (b2-c-12), (b2-c-14), (b2-c-27), (b2-c-30) And cations represented by (b2-c-31) are preferred.

  Compound (I) is a combination of the above-mentioned anions and organic cations. These anions and cations can be arbitrarily combined. Specific examples of compound (I) are shown in Table 1.

In Table 1, each anion and each organic cation are indicated by a sign of a formula representing them. For example, the compound (I-1) is a compound composed of an anion represented by the formula (Ia-1) and an organic cation represented by the formula (b2-c-1), and is a compound shown below.

  Especially, compound (I) is compound (I-1), compound (I-2), compound (I-5), compound (I-6), compound (I-19), compound (I-20). , Compound (I-23), Compound (I-24), Compound (I-37), Compound (I-38), Compound (I-41), Compound (I-42), Compound (I-55), Compound (I-56), Compound (I-59), Compound (I-60), Compound (I-73), Compound (I-74), Compound (I-77), Compound (I-78), Compound (I-91), Compound (I-92), Compound (I-95), Compound (I-96), Compound (I-109), Compound (I-110), Compound (I-113), Compound ( I-114), compound (I-127), compound (I-128), compound (I-131), compound (I-1 2), Compound (I-135), Compound (I-136), Compound (I-139), Compound (I-140), Compound (I-143), Compound (I-144), Compound (I-147) ), Compound (I-148), compound (I-151) and compound (I-152) are preferred.

<Method for Producing Compound (I)>
The compound represented by the formula (I ′) in which R ⁴ is a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms includes, for example, a salt represented by the formula (Ia), a formula (I— It can also be obtained by reacting the compound represented by b) in a solvent in the presence of an acid catalyst.
[Wherein, R ^{4 ′} represents an alkylidene group obtained by removing one hydrogen atom from the alkyl group represented by R ⁴ . The other symbols have the same meaning as described above.
R ^{4 ″} represents a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms. ]
The reaction is preferably performed in the temperature range of −5 ° C. to 80 ° C. for 0.5 to 24 hours.
Examples of the acid catalyst include camphorsulfonic acid.
Examples of the solvent include chloroform.

Examples of the compound represented by the formula (Ib) include compounds represented by the following.
The salt represented by the formula (Ia) is obtained by combining a compound represented by the formula (Ic) and a compound represented by the formula (Id) in a solvent in the presence of a base catalyst. It can be obtained by reacting.
[Wherein each symbol represents the same meaning as described above. ]
The reaction is preferably performed in a temperature range of 5 ° C to 80 ° C for 0.5 to 24 hours.
Examples of the base catalyst include potassium carbonate, potassium iodide, triethylamine, pyridine and the like.
Examples of the solvent include dimethylformamide, chloroform, tetrahydrofuran and the like.
Examples of the compound represented by the formula (I1-c) include a compound represented by the following formula.
Examples of the compound represented by the formula (Id) include compounds represented by the following formula.

The salt represented by the formula (I1) in which R ⁴ is a hydrogen atom includes, for example, a salt represented by the formula (I1-a) and a compound represented by the formula (I1-b) as a base catalyst. Can also be obtained by reacting in a solvent in the presence of.
[Wherein all symbols have the same meaning as described above. ]
The reaction is preferably performed in the temperature range of −5 ° C. to 80 ° C. for 0.5 to 24 hours.
Examples of the base catalyst include sodium hydride, potassium carbonate, potassium iodide, triethylamine, pyridine and the like.
Examples of the solvent include dimethylformamide, chloroform, tetrahydrofuran and the like.
Examples of the compound represented by the formula (I1-a) include a compound represented by the following formula.
Examples of the compound represented by the formula (I1-b) include a compound represented by the following formula.

<Acid Generator Containing Compound Represented by Formula (I)>
The acid generator of the present invention contains compound (I). In the acid generator, compound (I) may be used alone or in combination of two or more.
The acid generator of the present invention may contain, in addition to the compound (I), an acid generator known in the resist field (hereinafter sometimes referred to as “acid generator (B)”). The acid generator (B) will be described later.
When the compound (I) and the acid generator (B) are contained as the acid generator, the ratio of the content of the compound (I) and the acid generator (B) (mass ratio, compound (I): acid generator ( B)) is usually 1:99 to 99: 1, preferably 2:98 to 98: 2, more preferably 5:95 to 95: 5, and even more preferably 10:90 to 40:60. .

<Polymer having structural unit derived from compound represented by formula (I)>
The polymer of the present invention is a polymer having a structural unit derived from the compound represented by formula (I) (hereinafter sometimes referred to as “structural unit (I)”) (hereinafter referred to as “resin (A)”). There is.)
The resin (A) may be a homopolymer having one type of structural unit (I) or a copolymer having two or more types of structural units (I).
Content of structural unit (I) is 0.1-100 mol% normally with respect to the whole quantity of resin (A), Preferably it is 0.5-50 mol%, More preferably, it is 0.8- It is 30 mol%, More preferably, it is 1-10 mol%.

In addition to the structural unit (I), the resin (A) further has a structural unit having an acid labile group other than the structural unit (I) (hereinafter sometimes referred to as “structural unit (a1)”). May be. Here, the “acid labile group” has a leaving group, the leaving group is eliminated by contact with an acid, and the structural unit has a hydrophilic group (for example, a hydroxy group or a carboxy group). Means a group that converts to
The resin (A) preferably further has a structural unit other than the structural unit (a1). Examples of the structural unit other than the structural unit (a1) include structural units known in the art such as a structural unit having no acid labile group (hereinafter sometimes referred to as “structural unit (s)”).

<Structural unit (a1)>
The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”).

The acid labile group contained in the resin (A) is preferably a group represented by the formula (1) and / or a group represented by the formula (2).
[In Formula (1), R ^<a1 > -R < ^a3 > represents a C1-C8 alkyl group, a C3-C20 alicyclic hydrocarbon group, or the group which combined these independently each other, or R ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
na represents 0 or 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. R ^{a2 ′} and R ^{a3 ′} are bonded to each other to form a divalent heterocyclic group having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and the hydrocarbon group and the divalent heterocyclic group. —CH ₂ — contained in the ring group may be replaced by —O— or —S—.
X represents an oxygen atom or a sulfur atom.
* Represents a binding site. ]

^Examples of the alkyl group of R ^{a1 to} R ^a3 include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a binding site). The alicyclic hydrocarbon group of R ^{a1 to} R ^a3 is preferably an alicyclic hydrocarbon group having 3 to 16 carbon atoms.

Examples of the group that combines an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, and a norbornylethyl group. Etc.
na is preferably 0.

Examples of —C (R ^a1 ) (R ^a2 ) (R ^a3 ) in the case where R ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group include the following groups. The divalent alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * Represents a binding site to -O-.

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (a group in which R ^{a1 to} R ^a3 are alkyl groups in the formula (1), preferably a tert-butoxycarbonyl group), 2- An alkyladamantan-2-yloxycarbonyl group (in formula (1), wherein R ^a1 , R ^a2 and the carbon atom to which they are bonded form an adamantyl group, and R ^a3 is an alkyl group) and 1- (adamantane- 1-yl) -1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is an adamantyl group).

Examples of the hydrocarbon group of R ^{a1 ′ to} 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 alicyclic hydrocarbon group are the same as those described above.
The aromatic hydrocarbon group includes phenyl, naphthyl, anthryl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumenyl, mesityl, biphenyl. Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.
^{Examples of the} divalent heterocyclic group formed together with the carbon atom to which R ^{a2 ′} and R ^{a3 ′} are bonded to each other and X, and X include the following groups. * Represents a binding site.
Of R ^{a1 ′} and R ^{a2 ′} , at least one is preferably a hydrogen atom.

Specific examples of the group represented by the formula (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. If the resin (A) having a structural unit derived from the monomer (a1) having a bulky structure such as an alicyclic hydrocarbon group is used in the resist composition, the resolution of the resist pattern can be improved.

As a structural unit derived from a (meth) acrylic monomer having a group represented by the formula (1), a structural unit represented by the formula (a1-0) is preferably represented by the formula (a1-1). The structural unit represented by a structural unit or a formula (a1-2) is mentioned. These may be used alone or in combination of two or more. In this specification, the structural unit represented by formula (a1-0), the structural unit represented by formula (a1-1), and the structural unit represented by formula (a1-2) are each represented by structural unit (a1). -0), structural unit (a1-1), and structural unit (a1-2).
[In Formula (a1-0), Formula (a1-1) and Formula (a1-2),
L ^a01 , L ^a1 and L ^a2 each independently represent —O— or ^* —O— (CH ₂ ) _k1 —CO—O—, k1 represents any integer of 1 to 7, and * represents It 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 0 to 14.
n1 represents any integer of 0 to 10.
n1 ′ represents any integer of 0 to 3. ]

L ^a01 , L ^a1 and L ^a2 are preferably an oxygen atom or * —O— (CH ₂ ) _k01 —CO—O— (where k01 is preferably an integer of 1 to 4, more preferably Is 1.), more preferably an oxygen atom.
R ^a01 , R ^a4 and R ^a5 are preferably methyl groups.
Examples of the alkyl group of R ^{a02 to} R ^a04 , R ^a6, and R ^a7 , the alicyclic hydrocarbon group, and the combination thereof include the same groups as those ^exemplified for R ^{a1 to} R ^a3 of formula (1). It is done.
Carbon number of the alkyl group of R ^{< a02>} -R ^<a04> , R ^<a6> and R ^<a7> becomes like this. Preferably it is 1-6, More preferably, it is a methyl group or an ethyl group.
Carbon number of the alicyclic hydrocarbon group of R ^{a02 to} R ^a04 , R ^a6 and R ^a7 is preferably 3 to 8, and more preferably 3 to 6.
The group in which the alkyl group and the alicyclic hydrocarbon group are combined preferably has a total carbon number of 18 or less in combination of the alkyl group and the alicyclic hydrocarbon group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

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

As a structural unit (a1-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example.
As the structural unit (a1-1), for example, a structural unit represented by any one of the formulas (a1-1-1) to (a1-1-4) and R ^a4 in the structural unit (a1-1) Examples include a structural unit in which a corresponding methyl group is replaced with a hydrogen atom, and a structural unit represented by any one of formulas (a1-1-1) to (a1-1-3) is preferable.

The structural unit (a1-2) corresponds to the structural unit represented by any one of the formulas (a1-2-1) to (a1-2-6) and R ^a5 in the structural unit (a1-2). And a structural unit in which a methyl group is replaced by a hydrogen atom. In formula (a1-2-2), formula (a1-2-3), formula (a1-2-5) and formula (a1-2-6) The structural unit represented is preferable, and the structural unit represented by Formula (a1-2-2) and Formula (a1-2-5) is more preferable.

  When the resin (A) includes at least one structural unit selected from the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2), the total content thereof is the resin ( It is 10-95 mol% normally with respect to the sum total of all the structural units of A), Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

As a structural unit derived from a (meth) acrylic monomer having a group represented by the formula (2), a structural unit represented by the formula (a1-5) (hereinafter referred to as “structural unit (a1-5)”) Is also included).
[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 ) _{h 3} —CO—L ⁵⁴ —, h 3 represents an integer of 1 to 4, and * represents a binding site to L ⁵¹ .
L ^{51 to} L ⁵⁴ each independently represent —O— or —S—.
s1 represents any integer of 1 to 3.
s1 ′ represents any integer of 0 to 3. ]

As a halogen atom, a fluorine atom and a chlorine atom are mentioned, Preferably a fluorine atom is mentioned. 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 formula (a1-5), R ^a8 is preferably a hydrogen atom, a methyl group, or a trifluoromethyl group.
L ⁵¹ is preferably an oxygen atom.
One of L ⁵² and L ⁵³ is preferably —O—, and the other is preferably —S—.
s1 is preferably 1.
s1 ′ is preferably an integer of 0 to 2.
Z ^a1 is preferably a single bond or * —CH ₂ —CO—O—.

As a monomer which introduce | transduces structural unit (a1-5), the monomer described in Unexamined-Japanese-Patent No. 2010-61117 is mentioned, for example. As the structural unit (a1-5), structural units each represented by formula (a1-5-1) to formula (a1-5-4) are preferable. Formula (a1-5-1) or formula (a1- The structural unit represented by 5-2) is more preferable.

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

Furthermore, examples of the structural unit (a1) include structural units represented by the following formulas (a1-3-1) to (a1-3-7).

As the structural unit having an acid labile group other than the structural unit (a1-1) and the structural unit (a1-2), a structural unit represented by the formula (a1-4) (hereinafter referred to as “structural unit (a1- 4) ”may also be mentioned.
[In the formula (a1-4),
R ^a32 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl An oxy group or a methacryloyloxy group is represented.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ^a33 may be the same as or different from each other.
R ^a34 and R ^a35 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^a36 may represent a hydrocarbon group having 1 to 20 carbon atoms, R ^a35 and R ^a36 are bonded to each other Together with —C—O— to which they are bonded to form a divalent hydrocarbon group having 2 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent hydrocarbon group is — O- or -S- may be substituted. ]

^Examples of the alkyl group in R ^a32 and R ^a33 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
Examples of the halogen atom 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 trifluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 1,1,1-trifluoroethyl group, 1,1 , 2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3 , 4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group, perfluorohexyl group, etc. Is mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. Especially, a C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further more preferable.
Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.
Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
As the hydrocarbon group for R ^a34, R ^a35 and R ^a36, an alkyl group, an alicyclic hydrocarbon group include aromatic hydrocarbon groups, the same groups as R ^{a1 'and} R ^a2' of formula (2) Is mentioned. In particular, as R ^a36 , an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these Is mentioned.

In formula (a1-4), R ^a32 is preferably a hydrogen atom.
R ^a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
As la, 0 or 1 is preferable, and 0 is more preferable.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably an alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group, more preferably a methyl group or an ethyl group.
The hydrocarbon group for R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. A group to be formed, more preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. The alkyl group and the alicyclic hydrocarbon group in R ^a36 are preferably unsubstituted. The aromatic hydrocarbon group for R ^a36 is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms.

As the structural unit (a1-4), a hydrogen atom bonded to a structural unit represented by the formula (a1-4-4) to the formula (a1-4-8) and a main chain of these structural units is a methyl group. For example, the replaced structural unit.

  When resin (A) has the said structural unit, it is preferable that the content rate is 10-95 mol% with respect to the sum total of all the structural units of resin (A), and is 15-90 mol%. It is more preferable, and it is still more preferable that it is 20-85 mol%.

  The structural unit (a1) in the resin (A) is preferably at least one selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2). More than the kind is more preferable, the combination of the structural unit (a1-1) and the structural unit (a1-2), the combination of the structural unit (a1-1) and the structural unit (a1-0), the structural unit (a1-2) and A combination of the structural unit (a1-0), a combination of the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2) is more preferable, and the structural unit (a1-1) and the structural unit The combination of (a1-2) is even more preferable.

<Structural unit (s)>
The structural unit (s) which may be contained in the resin (A) of the present invention is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “monomer (s)”). As the monomer for deriving the structural unit (s), a monomer having no acid labile group known in the resist field can be used.
As the structural unit (s), a structural unit having a hydroxy group or a lactone ring and having no acid labile group is preferable. A structure having a hydroxy group and having no acid labile group (hereinafter sometimes referred to as “structural unit (a2)”) and / or a lactone ring and having no acid labile group If a resin having a unit (hereinafter sometimes referred to as “structural unit (a3)”) is used in the resist composition of the present invention, the resolution of the resist pattern and the adhesion to the substrate can be improved.

<Structural unit (a2)>
The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group.
When a resist pattern is produced from the resist composition of the present invention, when a high energy beam such as a KrF excimer laser (248 nm), an electron beam or EUV (ultra-ultraviolet light) is used as an exposure light source, the structural unit (a2) It is preferable to use the structural unit (a2) having a phenolic hydroxy group. Further, when an ArF excimer laser (193 nm) or the like is used, the structural unit (a2) having an alcoholic hydroxy group is preferable as the structural unit (a2). As a structural unit (a2), 1 type may be included independently and 2 or more types may be included.

Examples of the structural unit having a phenolic hydroxy group in the structural unit (a2) include a structural unit represented by the formula (a2-A) (hereinafter sometimes referred to as “structural unit (a2-A)”).
[In the formula (a2-A),
R ^a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a51 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, acryloyl An oxy group or a methacryloyloxy group is represented.
A ^a50 represents a single bond or ^* —X ^a51 — (A ^a52 —X ^a52 ) _na —, and * represents a bond to the carbon atom to which —R ^a50 is bonded.
A ^a52 each independently represents an alkanediyl group having 1 to 6 carbon atoms.
X ^a51 and X ^a52 each independently represent —O—, ^—CO —O— or —O—CO—.
na represents 0 or 1.
mb represents an integer of 0 to 4. When mb is any integer of 2 or more, the plurality of ^Ra51s may be the same as or different from each other. ]

^Examples of the halogen atom for R ^a50 include a fluorine atom, a chlorine atom and a bromine atom.
^Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom in R ^a50 include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, 1 , 1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3 , 3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, pentyl group, hexyl group and perfluorohexyl Groups.
R ^a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom or a methyl group.
^Examples of the alkyl group for R ^a51 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
^Examples of the alkoxy group for R ^a51 include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. A C1-C4 alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is more preferable.
^Examples of the alkylcarbonyl group for R ^a51 include an acetyl group, a propionyl group, and a butyryl group.
^Examples of the alkylcarbonyloxy group for R ^a51 include an acetyloxy group, a propionyloxy group, and a butyryloxy group.
R ^a51 is preferably a methyl group.

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

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- 1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and 2 -Methylbutane-1,4-diyl group etc. are mentioned.
A ^a52 is preferably a methylene group or an ethylene group.

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

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

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

As the structural unit (a2-A), structural units represented by formula (a2-2-1) to formula (a2-2-4) and formula (a2-2-1) to formula (a2-2-2) In the structural unit represented by 4), a structural unit in which a methyl group corresponding to R ^a50 in the structural unit (a2-A) is replaced with a hydrogen atom can be mentioned. The structural unit (a2-A) is represented by the structural unit represented by the formula (a2-2-1), the structural unit represented by the formula (a2-2-3), and the formula (a2-2-1). In the structural unit represented by formula (a2-2-3), the methyl group corresponding to R ^a50 in the structural unit (a2-A) is preferably 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 5 to 95 mol%, more preferably based on all structural units. It is 10-80 mol%, More preferably, it is 15-80 mol%, More preferably, it is 20-65 mol%.

Examples of the structural unit (a2) having an alcoholic hydroxy group include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).
[In the formula (a2-1),
L ^a3 represents —O— or * —O— (CH ₂ ) _k2 —CO—O—,
k2 represents any integer of 1 to 7. * Represents a binding site to -CO-.
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10. ]

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

As a structural unit (a2-1), the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. A structural unit represented by any one of formula (a2-1-1) to formula (a2-1-6) is preferred, and any one of formula (a2-1-1) to formula (a2-1-4) The structural unit represented is more preferable, and the structural unit represented by the formula (a2-1-1) or the formula (a2-1-3) is more preferable.

  When the resin (A) contains the structural unit (a2-1), the content is usually 1 to 45 mol%, preferably 1 to 40 mol, based on the total of all the structural units of the resin (A). %, More preferably 1 to 35 mol%, and still more preferably 2 to 20 mol%.

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

The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or the formula (a3-4). These 1 type may be contained independently and 2 or more types may be contained.
[In Formula (a3-1), Formula (a3-2), Formula (a3-3) and Formula (a3-4),
L ^a4 , L ^a5 and L ^a6 are each independently represented by —O— or ^* —O— (CH ₂ ) _k3 —CO—O— (k3 represents any integer of 1 to 7). Represents a group.
L ^a7 is —O—, ^* —O—L ^a8 —O—, ^* —O—L ^a8 —CO—O—, ^* —O—L ^a8 —CO—O—L ^a9 —CO—O— or ^* —O—L ^a8 —O—CO—L ^a9 —O— is represented.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
* Represents a binding site with a carbonyl group.
R ^a18 , R ^a19 and R ^a20 each independently 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.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
R ^a22 , R ^a23 and R ^a25 each independently represent a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents any integer of 0 to 5.
q1 represents any integer of 0 to 3.
r1 represents any integer of 0 to 3.
w1 represents an integer of 0 to 8.
When p1, q1, r1, and / or w1 is 2 or more, a plurality of R ^a21 , R ^a22 , R ^a23 and / or R ^a25 may be the same as or different from each other. ]

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and sec-butyl group. .
Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
^Examples of the alkyl group for R ^a24 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
Examples of the alkyl group having a halogen atom of Ra ²⁴ include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluoro A hexyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, etc. are mentioned.

^Examples of the alkanediyl group of L ^a8 and L ^a9 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -Diyl group, hexane-1,6-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1, 4-diyl group, 2-methylbutane-1,4-diyl group, etc. are mentioned.

In formula (a3-1) to formula (a3-4), L ^{a4 to} L ^a6 are preferably each independently —O— or k— is an integer of 1 to 4 —O— ( CH ₂ ) _{k 3} —CO—O—, more preferably —O— and * —O—CH ₂ —CO—O—, and still more preferably an oxygen atom.
L ^a7 is preferably —O— or ^* —O—L ^a8 —CO—O—, more preferably —O—, —O—CH ₂ —CO—O— or —O—C ₂ H ₄ —. CO-O-.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and still more preferably a hydrogen atom or a methyl group.
R ^a22 , R ^a23 and R ^a25 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1, r1 and w1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.
In formula (a3-4), formula (a3-4) ′ is particularly preferred.
(Wherein R ^a24 and L ^a7 represent the same meaning as described above.)

The structural unit (a3) includes a monomer described in JP2010-204646, a monomer described in JP2000-122294, and a structure derived from the monomer described in JP2012-41274. Units are listed. As the structural unit (a3), structural units represented by any of the following are preferable, and are represented by the formula (a3-1-1), the formula (a3-2-2) and the formula (a3-4-1) to the formula ( The structural unit represented by any one of a3-4-6) is more preferred, and the structure represented by the formula (a3-1-1), the formula (a3-2-3) or the formula (a3-4-2) Units are more preferred.

In the structural unit, R ^a18 , R ^a19 , R ^a20 and R ^{a24 in} the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3), or the structural unit (a3-4). A compound in which a methyl group corresponding to is replaced by a hydrogen atom is also a specific example of the structural unit (a3).

When the resin (A) contains the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on the total of all the structural units of the resin (A). More preferably, it is 10-60 mol%.
In addition, the content of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3), and the structural unit (a3-4) is, independently of each other, all structural units of the resin (A). It is preferable that it is 5-60 mol% with respect to the sum total of, It is more preferable that it is 5-50 mol%, It is further more preferable that it is 10-50 mol%.

<Structural unit (t)>
The resin (A) of the present invention comprises a structural unit other than the structural unit (a1), the structural unit (a2), and the structural unit (a3) (hereinafter, the structural unit is referred to as “structural unit (t)”). May be included.
As the structural unit (t), in addition to the structural unit (a2) and the structural unit (a3), a structural unit which may have a halogen atom (hereinafter sometimes referred to as “structural unit (a4)”) and non-depletion. And a structural unit having a hydrocarbon-separated hydrocarbon group (hereinafter sometimes referred to as “structural unit (a5)”).
As the structural unit (a4), a structural unit represented by formula (a4-0) can be given.
[In the formula (a4-0),
R ^5a represents a hydrogen atom or a methyl group.
L ⁵ represents a single bond or an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 3 to 12 carbon atoms.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

Examples of the aliphatic saturated hydrocarbon group for L ⁵ include an alkanediyl group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group. Having a side chain of an alkyl group (particularly, methyl group, ethyl group, etc.), ethane-1,1-diyl group, propane-1, Examples thereof include branched alkanediyl groups such as 2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.

As the perfluoroalkanediyl group of L ³ , a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, a perfluoropropane-1,2-diyl group, a perfluoropropane-2,2 -Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2 -Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -Diyl group, perfluoroheptane-2 , 2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3 , 3-diyl group, perfluorooctane-4,4-diyl group, and the like.
Examples of the L ³ perfluorocycloalkanediyl group include a perfluorocyclohexanediyl group, a perfluorocyclopentanediyl group, a perfluorocycloheptanediyl group, and a perfluoroadamantanediyl group.

L ⁵ is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group.
L ³ is preferably a C 1-6 perfluoroalkanediyl group, and more preferably a C ^1-3 C perfluoroalkanediyl group.

Examples of the structural unit (a4-0) include the structural units shown below.

In the structural unit, a structural unit in which a methyl group corresponding to R ^5a in the structural unit (a4-0) is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a4-0).

As the structural unit (a4), a structural unit represented by formula (a4-1) can be given.
[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced by —O— or —CO—. Good.
A ^a41 represents a ^C1-C6 alkanediyl group which may have a substituent or a group represented by the formula (a-g1). However, at least one of A ^a41 and R ^a42 has a halogen atom (preferably a fluorine atom) as a substituent. ]
[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent a ^C 1-5 divalent aliphatic hydrocarbon group which may have a substituent.
A ^a43 represents a ^C1-C5 divalent aliphatic hydrocarbon group which may have a single bond or a substituent.
X ^a41 and X ^a42 each independently represent —O—, —CO—, ^—CO —O— or —O—CO—.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41 and X ^a42 is 7 or less.
Of the two binding sites represented by *, the * on the right side is the binding site with -O-CO-R ^a42 . ]

^Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these.
The chain and cyclic aliphatic hydrocarbon groups may have carbon-carbon unsaturated bonds, but are formed by chain and cyclic aliphatic saturated hydrocarbon groups and combinations thereof. Groups are preferred. The aliphatic saturated hydrocarbon group includes a straight chain or branched alkyl group and a monocyclic or polycyclic alicyclic hydrocarbon group, and an aliphatic group formed by combining an alkyl group and an alicyclic hydrocarbon group. Group hydrocarbon group and the like.

Examples of chain aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl. Group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Cyclic aliphatic hydrocarbon groups include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other cycloalkyl groups; decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* is a bond) And a polycyclic alicyclic hydrocarbon group such as a moiety).
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthryl group, and a fluorenyl group.

^Examples of the substituent for R ^a42 include a halogen atom or a group represented by the formula (a-g3). As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom is mentioned.
[In the formula (a-g3),
^Xa43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents a C ^1-17 aliphatic hydrocarbon group having at least one halogen atom.
* Represents a binding site. ]

^Examples of the aliphatic hydrocarbon group for A ^{a45 include} the same groups as those exemplified for R ^a42 .
R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and / or an aliphatic hydrocarbon group having a group represented by the formula (a-g3). .
When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, and still more preferably a carbon number. It is a 1-6 perfluoroalkyl group, Most preferably, it is a C1-C3 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), including the number of carbons contained in the group represented by the formula (a-g3), the aliphatic hydrocarbon The total carbon number of the group 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 1.

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

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

A more preferable structure represented by * -A ^a46 -X ^a44 -A ^a47 is the following structure.

^As the alkanediyl group of ^Aa41 , a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group Linear alkanediyl group such as propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, Examples include branched alkanediyl groups such as 2-methylbutane-1,4-diyl group.
^Examples of the substituent in the alkanediyl group of ^Aa41 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

The aliphatic hydrocarbon group of A ^{a42 to} A ^a44 in the group (a-g1) may have a carbon-carbon unsaturated bond, but an aliphatic saturated hydrocarbon group is preferable. As the aliphatic saturated hydrocarbon group, an alkyl group (the alkyl group may be linear or branched), an alicyclic hydrocarbon group, and an alkyl group and an alicyclic hydrocarbon group are combined. An aliphatic hydrocarbon group formed by the above. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, Examples include 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
^Examples of the substituent for the aliphatic hydrocarbon group of A ^{a42 to} A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

^Examples of the group (a-g1) in which X ^a42 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group include the following groups. In the following examples, * and ** each represent a binding site, and ** is a binding site with —O—CO—R ^a42 .

As the structural unit represented by the formula (a4-1), a structural unit represented by the formula (a4-2) is preferable.
[In the formula (a4-2),
R ^f1 represents a hydrogen atom or a methyl group.
A ^f1 represents an alkanediyl group having 1 to 6 carbon atoms.
R ^f2 represents a C 1-10 hydrocarbon group having a fluorine atom. ]

As the alkanediyl group of A ^f1 , 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 straight-chain alkanediyl group such as hexane-1,6-diyl group; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2 -Branched alkanediyl groups such as a diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group.

Examples of the hydrocarbon group for R ^f2 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these. As the aliphatic hydrocarbon group, an alkyl group (straight or branched) and an alicyclic hydrocarbon group are preferable.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group and 2 -An ethylhexyl group is mentioned.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, and cyclodecyl group. A cycloalkyl group is mentioned. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, norbornyl group, A methyl norbornyl group and an isobornyl group are mentioned.

Examples of the hydrocarbon group having a fluorine atom for R ^f2 include an alkyl group having a fluorine atom and an alicyclic hydrocarbon group having a fluorine atom.
Examples of the alkyl group having a fluorine atom include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, 1 , 1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2,2,2- Tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3 , 3-hexafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl 2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2 , 2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluoro Butyl) ethyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5 Fluorinated alkyl groups such as 6,6-dodecafluorohexyl group, perfluoropentylmethyl group and perfluorohexyl group can be mentioned.
Examples of the alicyclic hydrocarbon group having a fluorine atom include fluorinated cycloalkyl groups such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

As A ^f1 in Formula (a4-2), an alkanediyl group having 2 to 4 carbon atoms is preferable, and an ethylene group is more preferable.
R ^f1 is preferably a fluorinated alkyl group having 1 to 6 carbon atoms.

As the structural unit represented by the formula (a4-2), a structural unit represented by the formula (a4-1-1) to the formula (a4-1-11) and a methyl group corresponding to R ^f1 can be a hydrogen atom. Examples include structural units that have been replaced.

Examples of the structural unit (a4) include the following structural units and structural units in which a methyl group corresponding to R ^f11 in the structural unit (a4) is replaced with a hydrogen atom.

Examples of the structural unit (a4) include the following structural units and structural units in which a methyl group corresponding to R ^f21 in the structural unit (a4) is replaced with a hydrogen atom.

  When resin (A) has a structural unit (a4), it is preferable that the content rate is 1-20 mol% with respect to the sum total of all the structural units of resin (A), and 2-15 mol% It is more preferable that it is 3 to 10 mol%.

<Structural unit (a5)>
Examples of the non-leaving hydrocarbon group that the structural unit (a5) has include a linear, branched, or cyclic hydrocarbon group. Especially, it is preferable that a structural unit (a5) is group which has an alicyclic hydrocarbon group.
As a structural unit (a5), the structural unit represented by a formula (a5-1) is mentioned, for example.
[In the formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms. .
However, the hydrogen atom bonded to the carbon atom at the coupling position with the L ⁵⁵ is not 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, a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a carbonyl group. ]

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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group and octyl group. And alkyl groups such as 2-ethylhexyl group.
Examples of the alicyclic hydrocarbon group having a substituent include a 3-hydroxyadamantyl group and a 3-methyladamantyl group.
R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group, or a cyclohexyl group.

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

Examples of the group in which the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group include the groups described below. * Represents a bonding site with an oxygen atom.

Examples of the non-elimination hydrocarbon group of the structural unit (a5) include the following structural units and structural units in which a methyl group corresponding to R ⁵¹ of the structural unit (a5) is replaced with a hydrogen atom.

  When resin (A) has a structural unit (a5), it is preferable that the content rate is 1-30 mol% with respect to the sum total of all the structural units of resin (A), and 2-20 mol% It is more preferable that it is 3-15 mol%.

The resin (A) is preferably a resin composed of the structural unit (I), the structural unit (a1), and the structural unit (s), that is, a copolymer of the compound (I), the monomer (a1), and the monomer (s). It is a polymer.
The structural unit (s) is preferably at least one of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably a structural unit represented by the formula (a2-1).
The structural unit (a3) is preferably selected from the structural unit represented by the formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-4). At least one kind.

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

<Resist composition>
The resist composition of the present invention contains at least a resin and an acid generator. The resist composition of the present invention may contain a resin having the structural unit (I) or an acid generator containing the compound (I). The resist composition of the present invention is preferably a resist composition containing a resin having the structural unit (I).
The resist composition of the present invention preferably further contains a quencher (hereinafter sometimes referred to as “quencher (C)”) and / or a solvent (hereinafter sometimes referred to as “solvent (E)”).

<resin>
The resist composition of the present invention only needs to contain at least one resin having a structural unit having an acid labile group. Examples of the resin having a structural unit having an acid labile group include a resin (A), a resin having the above structural unit (a1) and not having a structural unit derived from the compound (I) (hereinafter “resin (AA)”). In some cases). The resin (AA) is at least one structural unit selected from the group consisting of the structural unit (a1), the structural unit (a2), the structural unit (a3), the structural unit (a4), and the structural unit (a5). The resin which consists of is mentioned.
Especially, as above-mentioned, the resist composition containing resin (A) is preferable.

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). Examples of such a resin include a resin (AA), a resin composed only of the structural unit (t), and the like. Specific examples of the resin other than the resin (A) include a resin having the structural unit (a4) but not the structural unit (a1) (hereinafter sometimes referred to as “resin (X)”). The resin (X) may have a structural unit derived from the structural unit (a2), the structural unit (a3), and other known monomers.
In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more with respect to the total of all the structural units of the resin (X). And more preferably 50 mol% or more. Other structural units can be appropriately adjusted in the same manner as the range included in the resin (A) or according to these ranges.
Moreover, the range of each structural unit contained in resin other than resin (A) can also be suitably adjusted similarly to the range contained in resin (A) or according to these ranges.
The content of the resin (X) is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, further preferably 100 parts by mass of the resin having a structural unit having an acid labile group. Is 2 to 40 parts by mass, more preferably 2 to 30 parts by mass, and particularly preferably 2 to 10 parts by mass.
Moreover, in resin other than resin (A), each structural unit should just be contained with the content rate similar to each content rate mentioned above.
The weight average molecular weight of the resin (X) is preferably 5,000 or more (more preferably 6,000 or more) and 80,000 or less (more preferably 60,000 or less).

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

<Acid generator>
The acid generator in the resist composition of the present invention comprises an acid generator containing only the compound (I) described above, an acid generator containing only the acid generator (B), compound (I) and an acid generator (B). Any of the acid generators contained may be sufficient.
When the resin does not have the structural unit (I), the acid generator contains the compound (I).
In the resist composition, when the compound (I) is contained as an acid generator, the content of the compound (I) is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin having an acid labile group. 2 to 15 parts by mass is more preferable.

<Acid generator (B)>
The acid generator (B) may be either a nonionic acid generator or an ionic acid generator. Nonionic acid generators include organic halogen compounds, sulfonate ester compounds (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), and sulfone compounds. (For example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) and the like. Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  As the acid generator (B), JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, Kaisho 62-153853, JP 63-146029, U.S. Pat. No. 3,779,778, U.S. Pat. No. 3,849,137, German Patent 3914407, European Patent 126,712 The compound which generate | occur | produces an acid by the radiation as described in etc. can be used. Moreover, you may use the compound manufactured by the well-known method.

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

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

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

Examples of the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group of L ^b1 is replaced by —O— or —CO— include any of formulas (b1-1) to (b1-3) The group represented by these is mentioned. * Represents a binding site to -Y.
[In the formula (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In formula (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b4 and L ^b5 is 22 or less.
In formula (b1-3),
L ^b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, and the saturated The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
However, the total number of carbon atoms of L ^b6 and L ^b7 is 23 or less. ]

In Formula (b1-1) to Formula (b1-3), when the methylene group contained in the saturated hydrocarbon group is replaced with an oxygen atom or a carbonyl group, the number of carbons before the replacement is represented by the carbon number of the saturated hydrocarbon group. It is a number.
Examples of the divalent saturated hydrocarbon group include the same divalent saturated hydrocarbon group of L ^b1.

L ^b2 is preferably a single bond.
L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The methylene group contained in the divalent saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

As the group in which —CH ₂ — contained in the divalent saturated hydrocarbon group for L ^b1 is replaced by —O— or —CO—, a group represented by the formula (b1-1) or the formula (b1-3) Is preferred.

Examples of formula (b1-1) include groups represented by formula (b1-4) to formula (b1-8).
[In the formula (b1-4),
L ^b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
In formula (b1-5),
^Lb9 represents a C1-C20 bivalent saturated hydrocarbon group.
L ^b10 represents a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b9 and L ^b10 is 20 or less.
In formula (b1-6),
L ^b11 represents a C1-C21 divalent saturated hydrocarbon group.
L ^b12 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^b11 and L ^b12 is 21 or less.
In formula (b1-7),
L ^b13 represents a divalent saturated hydrocarbon group having 1 to 19 carbon atoms.
L ^b14 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms.
L ^b15 represents a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^{b13 to} L ^b15 is 19 or less.
In formula (b1-8),
L ^b16 represents a C1-C18 divalent saturated hydrocarbon group.
L ^b17 represents a C1- ^C18 divalent saturated hydrocarbon group.
L ^b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group. .
However, the total carbon number of L ^{b16 to} L ^b18 is 19 or less. ]

L ^b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.
L ^b9 is preferably a C 1-8 divalent saturated hydrocarbon group.
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 ^C 1-6 divalent saturated hydrocarbon group.
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 formula (b1-3) include groups represented by formula (b1-9) to formula (b1-11), respectively.
[In the formula (b1-9),
L ^b19 represents a single bond or a ^C1-C23 divalent saturated hydrocarbon group, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an acyloxy group. Also good. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^b19 and L ^b20 is 23 or less.
In formula (b1-10),
L ^b21 represents a single bond or a ^C1-C21 divalent saturated hydrocarbon group, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to ²¹ carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
However, the total carbon number of L ^{b21 to} L ^b23 is 21 or less.
In formula (b1-11),
L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms.
L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group is substituted with a fluorine atom, a hydroxy group, or an acyloxy group. May be. The methylene group contained in the acyloxy group may be replaced with an oxygen atom or a carbonyl group, and the hydrogen atom contained in the acyloxy group may be substituted with a hydroxy group.
^However, the total number of carbon atoms of L b24 ^{~L b26} is 21 or less. ]

  In formulas (b1-9) to (b1-11), when a hydrogen atom contained in a divalent saturated hydrocarbon group is substituted with an acyloxy group, the number of carbon atoms in the acyloxy group, CO in the ester bond, and The number of carbon atoms of the divalent saturated hydrocarbon group including the number of O is used.

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

Of the groups represented by formula (b1-1), examples of the group represented by formula (b1-4) include the following.

Of the groups represented by the formula (b1-1), examples of the group represented by the formula (b1-5) include the following.

Of the groups represented by formula (b1-1), examples of the group represented by formula (b1-6) include the following.

Of the groups represented by the formula (b1-1), examples of the group represented by the formula (b1-7) include the following.

Of the groups represented by the formula (b1-1), 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.

Of the groups represented by formula (b1-3), examples of the group represented by formula (b1-9) include the following.

Of the groups represented by the formula (b1-3), examples of the group represented by the formula (b1-10) include the following.

Of the groups represented by formula (b1-3), examples of the group represented by formula (b1-11) include the following.

Examples of the alicyclic hydrocarbon group represented by Y include groups represented by formulas (Y1) to (Y11).
The groups in which —CH ₂ — contained in the alicyclic hydrocarbon group represented by Y is replaced by —O—, —SO ₂ — or —CO— are represented by formulas (Y12) to (Y38). Group.

  That is, Y represents a hydrogen atom contained in an alicyclic hydrocarbon group, each substituted with an oxygen atom, and the two oxygen atoms together with an alkanediyl group having 1 to 8 carbon atoms form a ketal ring. Alternatively, a structure in which an oxygen atom is bonded to each of different carbon atoms may be included. However, when a spiro ring such as formula (Y28) to formula (Y33) is formed, the alkanediyl group between two oxygens preferably has one or more fluorine atoms. Of the alkanediyl groups contained in the ketal structure, those in which the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom are preferred.

  Among them, the group represented by any one of the formulas (Y1) to (Y20), the formula (Y30), and the formula (Y31) is preferable, and the formula (Y11), the formula (Y15), and the formula (Y Y16), a group represented by formula (Y20), formula (Y30) or formula (Y31), and more preferably a group represented by formula (Y11), formula (Y15) or formula (Y30).

Examples of the substituent of the methyl group represented by Y include a halogen atom, a hydroxy group, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, and a glycidyloxy group. Or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or 6 to 18 carbon atoms). And ja represents an integer of 0 to 4, and the like.
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, a hydroxy group-containing alkyl group having 1 to 12 carbon atoms, and 3 to 16 carbon atoms An alicyclic 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 acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or — (CH ₂ ) _ja —O—CO—R ^b1 group (wherein R ^b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a group having 6 to 18 carbon atoms. Represents an aromatic hydrocarbon group (ja represents an integer of 0 to 4).

Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy group.
Examples of the monovalent aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group; tolyl group, xylyl group, cumenyl group, mesityl group. Group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl group, and the like.
Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and naphthylethyl group.
Examples of the acyl 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 Y include the following.

In the case where Y is a methyl group and L ^b1 is a divalent linear or branched saturated hydrocarbon group having 1 to 17 carbon atoms, the divalent saturated carbonization at the position where Y is bonded. The hydrogen group —CH ₂ — is preferably replaced by —O— or —CO—.

Y is preferably a monovalent 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. The methylene group constituting the group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group represented by the following.

  As the sulfonate anion in the salt represented by the formula (B1), an anion represented by the formula (B1-A-1) to the formula (B1-A-54) [hereinafter, anion (B1 -A-1) "or the like. ] Is preferable, Formula (B1-A-1)-Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24)-Formula It is represented by any one of (B1-A-33), formula (B1-A-36) to formula (B1-A-40), formula (B1-A-47) to formula (B1-A-54). An anion is more preferable.

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

Examples of the sulfonate anion in the salt represented by Formula (B1) include anions represented by Formula (B1a-1) to Formula (B1a-30), respectively.

  Especially, Formula (B1a-1)-Formula (B1a-3) and Formula (B1a-7)-Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), Formula (B1a-22) ) To (B1a-30) are preferred.

Examples of the organic cation of Z ⁺ include organic onium cations, specifically, organic sulfonium cations, organic iodonium cations, organic ammonium cations, benzothiazolium cations, organic phosphonium cations, etc., preferably organic sulfonium cations or organic cations An iodonium cation is mentioned, More preferably, an aryl sulfonium cation is mentioned.
Z ⁺ in formula (B1) is preferably a cation represented by any one of formulas (b2-1) to (b2-4) exemplified as the cation of compound (I) described above.

  The acid generator (B1) is a combination of the above-described sulfonate anion and the above-mentioned organic cation, and these can be arbitrarily combined. The acid generator (B1) is preferably an anion and a cation (b2) represented by any one of formulas (B1a-1) to (B1a-3) and (B1a-7) to (B1a-16). -1) or a combination with a cation (b2-3).

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

An acid generator (B) may contain 2 or more types.
When the resist composition has compound (I) and acid generator (B) as an acid generator, the content of compound (I) and acid generator (B) has a structural unit having an acid labile group. Preferably, it is 1 part by mass or more (more preferably 3 parts by mass or more), preferably 40 parts by mass or less (more preferably 30 parts) with respect to 100 parts by mass of the resin (that is, the total of the resin (A) and the resin (AA)). Or less).

<Solvent (E)>
The content of the solvent (E) is usually 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more, and usually 99.9% by mass or less, preferably 99% in the total mass of the resist composition. It is below mass%. The content rate of a solvent (E) can be measured by well-known analysis means, such as a liquid chromatography or a gas chromatography.
Solvent (E) includes glycol ether ester solvents such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ether solvents such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate Ester solvents; ketone solvents such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic ester solvents such as γ-butyrolactone; and the like. A solvent (E) may contain 1 type independently, and may contain 2 or more types.

<Quencher (C)>
Examples of the quencher (C) include a basic nitrogen-containing organic compound or a salt that generates an acid having a lower acidity than an acid generated from the acid generator (B) or the compound (I).
Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. Examples of amines include aliphatic amines and aromatic amines. Aliphatic amines include primary amines, secondary amines and tertiary amines.

  Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, hexylamine, Heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tri Heptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexylamine, Rudicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyl Didecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, piperazine, morpholine, piperidine and JP-A-11- Hindered amine compounds having a piperidine skeleton described in Japanese Patent No. 2575, imidazole, 4-methylimidazole, 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) Examples include ethane, di (2-pyridyl) ketone, 4,4′-dipyridyl sulfide, 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine, 2,2′-dipicolylamine, bipyridine, and the like. Includes diisopropylaniline, particularly preferably 2,6-diisopropylaniline.

  As ammonium salts, tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3- (trifluoromethyl) phenyltrimethyl Ammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like can be mentioned.

As a salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) or the compound (I), a salt represented by the following formula, a weak acid inner salt represented by the formula (D), Moreover, the salt of Unexamined-Japanese-Patent No. 2012-229206, Unexamined-Japanese-Patent No. 2012-6908, Unexamined-Japanese-Patent No. 2012-72109, Unexamined-Japanese-Patent No. 2011-39502, and Unexamined-Japanese-Patent No. 2011-191745 is mentioned. Preferably, it is a weak acid inner salt represented by the formula (D) (hereinafter sometimes referred to as “weak acid inner salt (D)”).
The acidity in a salt that generates an acid having a lower acidity than the acid generated from the acid generator (B) is indicated by an acid dissociation constant (pKa). The salt that generates an acid having a lower acidity than the acid generated from the compound (I) and the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually −3 <pKa, A salt of −1 <pKa <7 is preferable, and a salt of 0 <pKa <5 is more preferable.

[In the formula (D),
R ^D1 and R ^D2 are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, an acyloxy group having 2 to 7 carbon atoms, or a carbon number Represents 2 to 7 alkoxycarbonyl groups, nitro groups or halogen atoms.
m ′ and n ′ each independently represents an integer of 0 to 4, and when m ′ is 2 or more, the plurality of R ^D1 may be the same or different, and n ′ is 2 or more. In this case, the plurality of R ^D2 may be the same or different. ]

Examples of the hydrocarbon group of R ^D1 and R ^D2 include an alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; and a norbornyl group Monocyclic or polycyclic adamantyl group, saturated or unsaturated monovalent alicyclic hydrocarbon group; phenyl group, naphthyl group, methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, monovalent aromatic hydrocarbon groups such as p-adamantylphenyl group, tolyl group, xylyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group;
Examples include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group, an aralkyl group (for example, a group formed by combining these, such as a phenylmethyl group and a 1-phenylethyl group).
Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the acyl group include an acetyl group, a propanoyl group, and a benzoyl group.
Examples of the acyloxy group include a group in which an oxy group (—O—) is bonded to the acyl group.
Examples of the alkoxycarbonyl group include a group in which a carbonyl group (—CO—) is bonded to the above alkoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
In the formula (D), R ^D1 and R ^D2 are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 2 to 2 carbon atoms. 4 is preferably an acyl group having 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group or a halogen atom.
m ′ and n ′ are each independently an integer of 0 to 2, and more preferably 0.

  The content of the quencher (C) is preferably 0.01 to 5% by mass, more preferably 0.01 to 4% by mass, and particularly preferably 0.01 to 3% by mass in the solid content of the resist composition. %.

<Other ingredients>
The resist composition may contain components other than those described above (hereinafter may be referred to as “other components (F)”) as necessary. As the other component (F), known additives in the resist field, such as a sensitizer, a dissolution inhibitor, a surfactant, a stabilizer, a dye, and the like can be used.

<Preparation of resist composition>
Resist composition is a mixture of resin (A) or compound (I) and, if necessary, other resin, acid generator (B), solvent (E), quencher (C) and other components (F). Can be prepared. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature from 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (E), such as resin. An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for producing resist pattern>
The method for producing a resist pattern of the present invention comprises:
(1) A step of applying the resist composition of the present invention on a substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

  The resist composition can be applied onto the substrate by a commonly used apparatus such as a spin coater. Examples of the substrate include an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be washed, or an antireflection film or the like may be formed on the substrate.

By drying the composition after coating, the solvent is removed and a composition layer is formed. Drying is performed, for example, by evaporating the solvent using a heating device such as a hot plate (so-called pre-baking), or using a decompression device. The heating temperature is preferably 50 to 200 ° C., and the heating time is preferably 10 to 180 seconds. Moreover, it is preferable that the pressure at the time of drying under reduced pressure is about 1-1.0 * 10 < ⁵ > Pa.

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. As an exposure light source, a laser beam emitting in the ultraviolet region such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F ₂ excimer laser (wavelength 157 nm), a solid-state laser light source (YAG or semiconductor laser) Etc.) Using various lasers such as those that convert wavelength of laser light from the laser and emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams or extreme ultraviolet light (EUV), etc. Can do. In this specification, the irradiation of these radiations may be collectively referred to as “exposure”. At the time of exposure, exposure is usually performed through a mask corresponding to a required pattern. When the exposure light source is an electron beam, exposure may be performed by direct drawing without using a mask.

  The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection reaction in the acid labile group. The heating temperature is usually about 50 to 200 ° C, preferably about 70 to 150 ° C.

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., and the development time is preferably 5 to 300 seconds. A positive resist pattern or a negative resist pattern can be produced by selecting the type of developer as follows.

When producing a positive resist pattern from a resist composition, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. Examples thereof include an aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly known as choline). The alkali developer may contain a surfactant.
It is preferable to wash the resist pattern with ultrapure water after development, and then remove the water remaining on the substrate and the pattern.

In the case of producing a negative resist pattern from a resist composition, a developer containing an organic solvent as a developer (hereinafter sometimes referred to as “organic developer”) is used.
Organic solvents contained in the organic developer include ketone solvents such as 2-hexanone and 2-heptanone; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ester solvents such as butyl acetate; glycols such as propylene glycol monomethyl ether Examples include ether solvents; amide solvents such as N, N-dimethylacetamide; aromatic hydrocarbon solvents such as anisole.
In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and substantially only the organic solvent. More preferably.
As the organic developer, a developer containing butyl acetate and / or 2-heptanone is preferable. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and substantially. More preferably, it is only butyl acetate and / or 2-heptanone.
The organic developer may contain a surfactant. The organic developer may contain a trace amount of water.
At the time of development, the development may be stopped by substituting a solvent of a different type from the organic developer.

It is preferable to wash the developed resist pattern with a rinse solution. The rinsing liquid is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used, and an alcohol solvent or an ester solvent is preferable.
After the cleaning, it is preferable to remove the rinse solution remaining on the substrate and the pattern.

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

An example is given and it demonstrates more concretely. In the examples, “%” and “parts” representing the content or amount used are based on mass unless otherwise specified.
The weight average molecular weight is a value determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
Column: TSKgel Multipore H _XL -M x 3 + guardcolumn (manufactured by 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 molecular peaks using mass spectrometry (LC: Agilent model 1100, MASS: Agilent LC / MSD model). In the following examples, the value of this molecular peak is indicated by “MASS”.

Example 1: Synthesis of compound represented by formula (I-1)
5 parts of the salt represented by the formula (I-1-a), 25 parts of dimethylformamide, 1.58 parts of potassium carbonate and 0.47 parts of potassium iodide were mixed, and then stirred at 40 ° C. for 1 hour. To the obtained mixture, 1.22 parts of the compound represented by the formula (I-1-b) was added dropwise at 40 ° C. over 10 minutes, stirred at 40 ° C. for 2 hours, and further stirred at 100 ° C. for 14 hours. did. The obtained mixture was cooled to 23 ° C., 35 parts of chloroform and 35 parts of ion-exchanged water were added to the mixture, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. To the collected organic layer, 25 parts of 1% oxalic acid water was added, stirred at 23 ° C. for 30 minutes, allowed to stand, and separated. 25 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23 ° C. for 30 minutes, allowed to stand, and separated to wash the organic layer with water. This washing operation was repeated 5 times. The collected organic layer was concentrated, and 40 parts of ethyl acetate was added to the concentrated mass, followed by stirring, followed by filtration to obtain 1.44 parts of the salt represented by the formula (I-1-c).

0.22 part of a compound represented by the formula (I-1-d) and 10 parts of chloroform are mixed and stirred at 23 ° C. for 30 minutes, and a mixed solution of 0.00012 part of camphorsulfonic acid and 0.6 part of chloroform is added. The mixture was further stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 1.37 parts of the compound represented by the formula (I-1-c) in 1.37 parts of chloroform was added dropwise to the obtained mixture over 30 minutes, and the mixture was further stirred at 23 ° C. for 18 hours. . To the obtained mixture, 0.003 part of triethylamine was added and stirred. Thereafter, 5 parts of a 2% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. To the recovered organic layer, 5 parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was further performed 5 times. The obtained organic layer was concentrated. To the obtained concentrate, 10 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 0.88 parts of a compound represented by the formula (I-1).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (-) Spectrum): M ^- 331.0

Example 2: Synthesis of compound represented by formula (I-5)
0.68 part of a compound represented by the formula (I-5-d) and 10 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 0.00012 part of camphorsulfonic acid and 0.60 part of chloroform was mixed and further stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 1.37 parts of the compound represented by the formula (I-1-c) in 1.37 parts of chloroform was added dropwise to the obtained mixture over 30 minutes, and the mixture was further stirred at 23 ° C. for 18 hours. . To the obtained mixture, 0.003 part of triethylamine was added and stirred. Thereafter, 5 parts of a 2% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. To the recovered organic layer, 5 parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was further performed 5 times. The obtained organic layer was concentrated. To the obtained concentrate, 10 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 1.19 parts of a compound represented by the formula (I-5).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 509.1

Example 3: Synthesis of compound represented by formula (I-127)
0.46 part of the compound represented by the formula (I-127-d) and 10 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 0.00012 part of camphorsulfonic acid and 0.60 part of chloroform was mixed and further stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 1.37 parts of the compound represented by the formula (I-1-c) in 1.37 parts of chloroform was added dropwise to the obtained mixture over 30 minutes, and the mixture was further stirred at 23 ° C. for 18 hours. . To the obtained mixture, 0.003 part of triethylamine was added and stirred. Thereafter, 5 parts of a 2% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. To the recovered organic layer, 5 parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was further performed 5 times. The obtained organic layer was concentrated. To the obtained concentrate, 10 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 0.99 parts of a compound represented by the formula (I-127).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 423.1

Example 4: Synthesis of compound represented by formula (I-128)
0.53 part of the compound represented by the formula (I-128-d) and 10 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixture, a mixed solution of 0.00012 part of camphorsulfonic acid and 0.60 part of chloroform was mixed and further stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 1.37 parts of the compound represented by the formula (I-1-c) in 1.37 parts of chloroform was added dropwise to the obtained mixture over 30 minutes, and the mixture was further stirred at 23 ° C. for 18 hours. . To the obtained mixture, 0.003 part of triethylamine was added and stirred. Thereafter, 5 parts of a 2% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. To the recovered organic layer, 5 parts of ion-exchanged water was added to the recovered organic layer, stirred at 23 ° C. for 30 minutes, and separated to recover the organic layer. This washing operation was further performed 5 times. The obtained organic layer was concentrated. To the obtained concentrate, 10 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 0.99 parts of a compound represented by the formula (I-128).
MASS (ESI (+) Spectrum): M ⁺ 263.1
MASS (ESI (−) Spectrum): M ^- 451.1

Synthesis of Resin (A) The compound (monomer) used for the synthesis of resin (A) is shown below. Hereinafter, these compounds are referred to as “monomer (a1-1-2)” or the like according to the formula number.

Example 5 [Synthesis of Resin A1]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and compound (I-1) ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3) ): Compound (I-1)] is mixed at a ratio of 30: 14: 6: 20: 25: 5, and 1.5% of the total mass of all monomers is added to this monomer mixture. The mass times propylene glycol monomethyl ether acetate was mixed. Into the obtained mixture, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were respectively added to 1.00 mol% and 3.00 mol% with respect to the total number of moles of all monomers. It added so that it might become. This was polymerized by heating at 73 ° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin A1 having a weight average molecular weight of 6.9 × 10 ^{3 in} a yield of 70%. This resin A1 has the following structural units.

Example 6 [Synthesis of Resin A2]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (I-1) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (I-1)] is 45:14: Resin A2 having a weight average molecular weight of 6.8 × 10 ³ was obtained in a yield of 60% by the same method as in Example 5 except that the mixture was mixed to 2.5: 33.5: 5. This resin A2 has the following structural units.

Example 7 [Synthesis of Resin A3]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and compound (I-5) ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3) ): Compound (I-5)] was mixed at a ratio of 30: 14: 6: 20: 25: 5 and was the same as in Example 5 except that heating was performed at 75 ° C. for about 5 hours. By the method, a resin A3 having a weight average molecular weight of 6.7 × 10 ³ was obtained in a yield of 68%. This resin A3 has the following structural units.

Example 8 [Synthesis of Resin A4]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (I-5) were used, The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (I-5)] is 45:14: Resin A4 having a weight average molecular weight of 6.8 × 10 ^{3 was} obtained in the same manner as in Example 5 except that the mixture was mixed at 2.5: 33.5: 5 and heating was performed at 75 ° C. for about 5 hours. Was obtained in a yield of 58%. This resin A4 has the following structural units.

Example 9 [Synthesis of Resin A5]
Monomer (a1-1-2), Monomer (a1-2-3), Monomer (a2-1-1), Monomer (a3-1-1), Monomer (a3-2-3) and Compound (I-127 ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3) ): Compound (I-127)] was mixed at a ratio of 30: 14: 6: 20: 25: 5, and the same as Example 5 except that heating for about 5 hours was performed at 75 ° C. By the method, resin A5 having a weight average molecular weight of 6.7 × 10 ³ was obtained in a yield of 72%. This resin A5 has the following structural units.

Example 10 [Synthesis of Resin A6]
Monomer (a1-1-2), Monomer (a1-2-3), Monomer (a2-1-1), Monomer (a3-1-1), Monomer (a3-2-3) and Compound (I-128) ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3) ): Compound (I-128)] was mixed at a ratio of 30: 14: 6: 20: 25: 5, and the same as Example 5 except that heating for about 5 hours was performed at 75 ° C. By the method, a resin A6 having a weight average molecular weight of 6.9 × 10 ³ was obtained in a yield of 70%. This resin A6 has the following structural units.

Example 11 [Synthesis of Resin A7]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (I-127) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (I-127)] is 45:14: Resin A7 having a weight average molecular weight of 7.0 × 10 ^{3 was} obtained in the same manner as in Example 5 except that the mixture was mixed at 2.5: 33.5: 5 and heating was performed at 75 ° C. for about 5 hours. Was obtained in a yield of 62%. This resin A7 has the following structural units.

Example 12 [Synthesis of Resin A8]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (I-128) were used, The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (I-128)] is 45:14: Resin A8 having a weight average molecular weight of 7.2 × 10 ^{3 was} obtained in the same manner as in Example 5 except that the mixture was mixed at 2.5: 33.5: 5 and heating was performed at 75 ° C. for about 5 hours. Was obtained in a yield of 60%. This resin A8 has the following structural units.

Synthesis Example 1 [Synthesis of Resin AX1]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and compound (IX-1) ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3) ): Compound (IX-1)] was mixed in a ratio of 30: 14: 6: 20: 25: 5 in the same manner as in Example 5 except that the weight average molecular weight was 6.7 × 10 ^3. Of AX1 was obtained with a yield of 65%. This resin AX1 has the following structural units.

Synthesis Example 2 [Synthesis of Resin AX2]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1), monomer (a3-2-3) and compound (IX-2) ) In the molar ratio [monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3) ): Compound (IX-2)] was mixed in a ratio of 30: 14: 6: 20: 25: 5 in the same manner as in Example 5 except that the weight average molecular weight was 6.7 × 10 ^3. Of AX2 was obtained in a yield of 67%. This resin AX2 has the following structural units.

Synthesis Example 3 [Synthesis of Resin AX3]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (IX-1) were used, and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (IX-1)] is 45:14: Resin AX3 having a weight average molecular weight of 6.9 × 10 ³ was obtained in a yield of 55% by the same method as in Example 5 except that the mixing was performed to 2.5: 33.5: 5. This resin AX3 has the following structural units.

Synthesis Example 4 [Synthesis of Resin AX4]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-4-2) and compound (IX-2) were used and their moles The ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-4-2): compound (IX-2)] is 45:14: A resin AX4 having a weight average molecular weight of 6.9 × 10 ³ was obtained in a yield of 59% by the same method as in Example 5 except that the mixing was performed to 2.5: 33.5: 5. This resin AX4 has the following structural units.

Synthesis Example 5 [Synthesis of Resin AA1]
Monomer (a1-1-2), monomer (a1-2-3), monomer (a2-1-1), monomer (a3-1-1) and monomer (a3-2-3) are mixed in a molar ratio [ Monomer (a1-1-2): monomer (a1-2-3): monomer (a2-1-1): monomer (a3-1-1): monomer (a3-2-3)] is 30:14 : Resin AA1 having a weight average molecular weight of 7.8 × 10 ³ was obtained in a yield of 76% by the same method as in Example 5 except that the mixing was performed at a ratio of 6:20:30. This resin AA1 has the following structural units.

Synthesis Example 6 [Synthesis of Resin AA2]
As the monomer, monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3) and monomer (a3-4-2) were used, and the molar ratio [monomer (a1-1 -3): Monomer (a1-2-9): Monomer (a2-1-3): Monomer (a3-4-2)] were mixed so as to be 45: 14: 2.5: 38.5 In the same manner as in Example 5, resin AA2 having a weight average molecular weight of 7.8 × 10 ³ was obtained in a yield of 65%. This resin AA2 has the following structural units.

Synthesis Example 7 [Synthesis of Resin X1]
Monomer (a4-1-7) was used as a monomer, and methyl isobutyl ketone 1.2 times the total monomer amount was added to prepare a solution. To this solution, 0.7 mol% and 2.1 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), respectively, as initiators were added with respect to the total monomer amount, and these were added at 75 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The obtained resin was repulped in a methanol / water mixed solvent and filtered to obtain a resin X1 having a weight average molecular weight of 1.7 × 10 ^{4 in} a yield of 76%. This resin X1 has the following structural units.

(Preparation of resist composition)
Each of the components shown below was mixed in parts by mass shown in Table 2, dissolved in a solvent described later, and filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

In Table 2, each symbol represents the following components.
<Resin (A)>
A1 to A8, AX1 to AX4, AA1, AA2, X1: Resin A1 to Resin A8, Resin AX1 to Resin AX4, Resin AA1, Resin AA2, Resin X1
<Acid generator>
I-1: Compound represented by Formula (I-1) I-5: Compound represented by Formula (I-5) IX-1: Compound represented by Formula (IX-1): JP2007- IX-2: Compound represented by formula (IX-2): synthesized according to example of JP 2014-197168 B1-21: represented by formula (B1-21) Compound (synthesized according to the examples of JP2012-224611)
B1-22: Compound represented by the formula (B1-22) (synthesized according to Examples in JP 2012-224611 A)
<Quencher (C)>
D1: Compound represented by the formula (D1) (manufactured by Tokyo Chemical Industry Co., Ltd.)
<Solvent>
Propylene glycol monomethyl ether acetate 265 parts Propylene glycol monomethyl ether 20 parts 2-heptanone 20 parts γ-butyrolactone 3.5 parts

<Manufacture of resist pattern and its evaluation>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to obtain a thickness of 78 nm. An organic antireflection film was formed. Next, the above resist composition was spin-coated on the organic antireflection film so that the film thickness after drying (pre-baking) was 85 nm.
The obtained silicon wafer was pre-baked (PB) for 60 seconds on a direct hot plate at the temperature described in the “PB” column of Table 2. Using the ArF excimer stepper for immersion exposure [XT: 1900Gi; manufactured by ASML, NA = 1.35, 3/4 Annular XY polarized light] on the wafer on which the resist composition film is formed in this manner, the exposure amount is stepwise. The line and space pattern was subjected to immersion exposure. Note that ultrapure water was used as the immersion medium.
After the exposure, post exposure bake (PEB) is performed on the hot plate at the temperature described in the “PEB” column of Table 2 for 60 seconds, and further with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Paddle development was performed to obtain a resist pattern.

  In each of the obtained resist pattern films, an exposure amount at which the 50 nm line and space pattern becomes an exposure amount of 1: 1 was defined as an effective sensitivity.

<Line edge roughness evaluation (LER)>
The wall surface of the resist pattern obtained by the method for producing a resist pattern was observed with a scanning electron microscope, and the unevenness fluctuation width (nm) of the side wall of the resist pattern was determined. Table 3 shows the result of the deflection width.

<Manufacture of negative resist pattern / Immersion exposure evaluation of resist composition>
An organic antireflective coating composition [ARC-29; manufactured by Nissan Chemical Industries, Ltd.] was applied onto a 12-inch silicon wafer, and baked under the conditions of 205 ° C. and 60 seconds, whereby an organic layer having a thickness of 78 nm was obtained. An antireflection film was formed. Next, the resist composition was spin-coated on the organic antireflection film so that the film thickness of the composition layer after drying (pre-baking) was 100 nm. After coating, this silicon wafer was pre-baked on a direct hot plate for 60 seconds at the temperature described in the “PB” column of Table 2 to form a composition layer on the silicon wafer.
An ArF excimer laser stepper for immersion exposure [XT: 1900 Gi; manufactured by ASML, NA = 1.35, Annual σ _out = 0.85 σ _in = 0.65 XY− pol. Illumination], using a mask for forming a trench pattern (pitch 120 nm / trench width 40 nm), the exposure amount was changed stepwise to perform exposure. Note that ultrapure water was used as the immersion medium.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 2. Next, the composition layer on the silicon wafer is developed by using a butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developing solution by a dynamic dispensing method at 23 ° C. for 20 seconds, thereby forming a negative resist pattern. Manufactured.

  In the obtained resist pattern, the exposure amount at which the width of the trench pattern was 40 nm was defined as effective sensitivity.

<Line edge roughness evaluation (LER)>
The wall surface of the resist pattern obtained by the negative resist pattern manufacturing method was observed with a scanning electron microscope, and the unevenness fluctuation width (nm) of the side wall of the resist pattern was determined. Table 4 shows the results of the deflection width.

  From the above results, it can be seen that the line edge roughness is good according to the resist composition of the present invention.

  The compounds and polymers of the present invention are useful as materials for resist compositions having good line edge roughness. The resist composition is suitable for semiconductor microfabrication.

Claims (14)

A compound represented by formula (I).
[In the formula (I),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * 1-CO—O—, * 1-O—CO—, —O—CO—O— or —O—, and * 1 represents C (R ¹ ) (R ² ) or C ( Q ¹ ) represents a binding site with (Q ² ).
A ¹ represents an optionally substituted divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, — CO— or —SO ₂ — may be substituted.
X ² represents * 2-CO—O—, —O—CO—O— or —O—, and * 2 represents a binding site with A ¹ .
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
X ³ represents a group represented by any one of formula (X ³ -1) to formula (X ³ -8).
(In the formula (X ³ -1) to the formula (X ³ -8),
* Represents a binding site with C (R ³ ) (R ⁴ ). )
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ⁺ represents an organic cation. ] The compound according to claim 1, wherein X ¹ is * 1-CO-O-. A ¹ is, according to claim 1 or 2 A compound according a good adamantane-diyl group which may have an alkanediyl group or a substituent having 2 to 6 carbon atoms which may have a substituent. The compound according to claim 1, wherein X ² is —O—. X ³ is A compound according to any one of claims 1 to 4, a group represented by the formula radical or formula represented by ^{(X 3 -1) (X 3} -7).   The acid generator containing the compound in any one of Claims 1-5.   The polymer which has a structural unit derived from the compound in any one of Claims 1-5.   Furthermore, the polymer of Claim 7 which has a structural unit which has an acid labile group.   A resist composition comprising the compound according to claim 1 and a resin.   A resist composition comprising the polymer according to claim 7 or 8 and an acid generator. The resist composition according to claim 10, wherein the acid generator contains a compound represented by formula (I).
[In the formula (I),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * 1-CO—O—, * 1-O—CO—, —O—CO—O— or —O—, and * 1 represents C (R ¹ ) (R ² ) or C ( Q ¹ ) represents a binding site with (Q ² ).
A ¹ represents an optionally substituted divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —S—, — CO— or —SO ₂ — may be substituted.
X ² represents * 2-CO—O—, —O—CO—O— or —O—, and * 2 represents a binding site with A ¹ .
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
X ³ represents a group represented by any one of formula (X ³ -1) to formula (X ³ -8).
(In the formula (X ³ -1) to the formula (X ³ -8),
* Represents a binding site with C (R ³ ) (R ⁴ ). )
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ⁺ represents an organic cation. ] (1) The process of apply | coating the resist composition in any one of Claims 9-11 on a board | substrate,
(2) The process of drying the composition after application | coating and forming a composition layer,
(3) a step of exposing the composition layer;
(4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating,
A method for producing a resist pattern including: The compound represented by the formula (I ′) obtained by reacting the compound represented by the formula (Ia) and the compound represented by the formula (Ib) in a solvent in the presence of an acid catalyst. The manufacturing method of the compound made.
[Where:
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * —CO—O—, * —O—CO—, —O—CO—O— or —O—, and * represents C (R ¹ ) (R ² ) or C (Q ¹ ). It represents a binding site with (Q ² ).
A ¹ represents a divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ —. The hydrogen atom contained in the hydrocarbon group may be a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 13 carbon atoms, an acyloxy group having 2 to 13 carbon atoms, a cyano group, or a carboxyl group. It may be substituted with one or more groups selected from the group consisting of groups.
X ² represents * —CO—O—, —O—CO—O— or —O—, and * represents a binding site to A ¹ .
R ³ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ^{4 ′} represents a group obtained by removing one hydrogen atom from a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ^{4 ″} represents a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
X ³ represents a group represented by any one of formula (X ³ -1) to formula (X ³ -8).
(In the formula (X ³ -1) to the formula (X ³ -8),
* Represents a binding site with C (R ³ ) (R ⁴ ). )
R ⁵ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ⁺ represents an organic cation. ] A compound represented by formula (Ia).
[In the formula (Ia),
Q ¹ and Q ² each independently represents a fluorine atom or a C 1-6 perfluoroalkyl group.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, or a C 1-6 perfluoroalkyl group.
z represents an integer of 0 to 6, and when z is 2 or more, the plurality of R ¹ and R ² may be the same as or different from each other.
X ¹ represents * —CO—O—, * —O—CO—, —O—CO—O— or —O—, and * represents C (R ¹ ) (R ² ) or C (Q ¹ ). It represents a binding site with (Q ² ).
A ¹ represents a divalent hydrocarbon group having 2 to 36 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is replaced with —O—, —S—, —CO— or —SO ₂ —. The hydrogen atom contained in the hydrocarbon group may be a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 13 carbon atoms, an acyloxy group having 2 to 13 carbon atoms, a cyano group, or a carboxyl group. It may be substituted with a group or a combination thereof.
X ² represents * —CO—O—, —O—CO—O— or —O—, and * represents a binding site to A ¹ .
R ³ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
R ^{4 ′} represents a group obtained by removing one hydrogen atom from a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms.
Z ⁺ represents an organic cation. ]