JP6730072B2 - Salt, acid generator, resist composition, and method for producing resist pattern - Google Patents

Description

The present invention relates to a salt, an acid generator, a resist composition and a method for producing a resist pattern.

Patent Document 1 describes a resist composition containing a salt represented by the following formula as an acid generator.

JP2012-97074A

In the resist composition containing the above salt, the CD uniformity (CDU) of the obtained resist pattern may not always be satisfied.

The present invention includes the following inventions.
[1] A salt having a cation having a group represented by the formula (aa).
[In the formula (aa),
X ^a and X ^b each independently represent an oxygen atom or a sulfur atom.
X ¹ represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms and having at least one fluorine atom.
* Represents a bond. ]
[2] The salt according to [1], wherein the cation having a group represented by formula (aa) is a cation having a group represented by formula (aa1).
[In formula (aa1),
X ^a , X ^b , X ¹ and * have the same meanings as described above.
Ring W represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms, and the methylene group contained in the alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a carbonyl group or a sulfonyl group. Well, the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxy group or a hydrocarbon group having 1 to 12 carbon atoms, and the methylene group contained in the hydrocarbon group is an oxygen atom or It may be substituted with a carbonyl group. ]
[3] The salt according to [2], wherein the cation having a group represented by formula (aa1) is a cation having a group represented by formula (Ia).
[In the formula (Ia),
Rings W and * have the same meanings as above.
R ^f1 and R ^f2 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms.
n represents an integer of 1 to 10. When n is 2 or more, a plurality of R ^f1 and R ^f2 may be the same or different. ]
[4] The ring W is a ring represented by the formula (Iaa-1), a ring represented by the formula (Iaa-2), or a ring represented by the formula (Iaa-3) [2] or [3]. ] The salt described.
[In Formula (Iaa-1), Formula (Iaa-2), and Formula (Iaa-3),
The methylene group contained in the ring may be substituted with an oxygen atom, a sulfur atom, a carbonyl group or a sulfonyl group, and the hydrogen atom contained in the ring may be substituted with a hydroxy group or a hydrocarbon group having 1 to 12 carbon atoms. Alternatively, the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. ]
[5] The salt according to any one of [1] to [4], wherein the salt having a group represented by formula (aa) in the cation is a salt having a cation represented by formula (aa33).
[In the formula (aa33), X ^a , X ^b , X ¹ and W have the same meanings as described above.
X represents a sulfur atom or an iodine atom.
m represents an integer of 0 or 1.
When X is a sulfur atom, m is 1, and when X is an iodine atom, m is 0.
R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or R ³ and R ⁴ together with the sulfur atom to which they are bound are It may form a heterocycle.
L represents a single bond or a divalent hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—. ]
[6] The salt according to any one of [1] to [5], wherein the salt having a group represented by formula (aa) in the cation is a salt having a cation represented by formula (aa3).
[In the formula (aa3), X ^a , X ^b , X ¹ and W have the same meanings as described above.
X represents a sulfur atom or an iodine atom.
m represents an integer of 0 or 1.
When X is a sulfur atom, m is 1, and when X is an iodine atom, m is 0.
R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or R ³ and R ⁴ together with the sulfur atom to which they are bound are It may form a heterocycle. ]
[7] The salt according to any one of [1] to [6], wherein the anion is an organic anion.
[8] The salt according to any one of [1] to [7], wherein the anion is an anion represented by formula (IA).
[In formula (IA), Q ¹ and Q ² each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —CO—. The hydrogen atom contained in the hydrogen group may be substituted with a fluorine atom or a hydroxy group.
Y represents a saturated hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, _-CH 2 contained in the saturated hydrocarbon group - is -O -, - S -, - SO ₂ -Or-CO- may be substituted. ]
[9] The salt according to any one of [1] to [7], which has a group represented by the formula (aa) independently of each other in a cation and an anion.
[In the formula (aa),
X ^a , X ^b , X ¹ and * have the same meanings as described above. ]
[10] The salt according to [8] or [9], wherein the anion is an anion represented by formula (aa2).
[In the formula (aa2),
Q ¹ , Q ² , L ^b1 , X ^a , X ^b , X ¹ and W have the same meanings as described above. ]
^{[11] L b1} _{is, * - CO-O- (CH} 2) t - or _* -CH 2 is -O-CO-, t represents an integer of 0 to 6, and *, -C ^{(Q 1} ) The salt of [8] or [10], which represents a bond with (Q ² )-.
[12] An acid generator containing the salt according to any one of [1] to [11] as an active ingredient.
[13] A resist composition containing the acid generator according to [12] and a resin containing a structural unit having an acid labile group.
[14] The resist composition according to [13], further including an acid generator represented by formula (B1).
[In the formula (B1),
Q ¹ , Q ² L ^b1 and Y have the same meanings as described above.
Z ⁺ represents an organic cation. However, Z ⁺ does not include a group represented by the formula (aa). ]
[15] The resist composition according to [13] or [14], which further contains a resin containing a structural unit having a fluorine atom.
[16] The resist composition according to any one of [13] to [15], further containing a salt that generates an acid having a weaker acidity than the acid generated from the acid generator.
[17] (1) A step of applying the resist composition according to any one of [13] to [16] onto a substrate,
(2) a step of drying the composition after coating to form a composition layer,
(3) exposing the composition layer
A method for producing a resist pattern, which comprises (4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.

Provided is a salt capable of producing a resist pattern having good CD uniformity (CDU).

In the present specification, unless otherwise specified, in the description of the structural formula of the compound, “aliphatic hydrocarbon group” means a linear or branched hydrocarbon group, and “alicyclic hydrocarbon group” means an aliphatic hydrocarbon group. It means a group in which a number of hydrogen atoms corresponding to the valence is removed from the ring of a cyclic hydrocarbon. The "aromatic hydrocarbon group" also includes a group in which a hydrocarbon group is bonded to an aromatic ring. When stereoisomers are present, all stereoisomers are included.
In the present specification, "(meth) acrylic monomer" means at least one monomer having a _"CH 2 = _CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " structure of To do. Similarly, "(meth)acrylate" and "(meth)acrylic acid" mean "at least one of acrylate and methacrylate" and "at least one of acrylic acid and methacrylic acid", respectively. Further, in the groups described in the present specification, any of those having both a linear structure and a branched structure may be used.
In the present specification, the “solid content of the resist composition” means the total of components excluding the solvent (E) described below from the total amount of the resist composition.

<Salt (aa)>
The salt of the present invention (hereinafter sometimes referred to as “salt (aa)” is a salt having a group represented by the formula (aa) as a cation.
[In the formula (aa),
X ^a and X ^b each independently represent an oxygen atom or a sulfur atom.
X ¹ represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms and having at least one fluorine atom.
* Represents a bond. ]

X ^a and X ^b are preferably the same atom, and more preferably both oxygen atoms.
Examples of the saturated hydrocarbon group include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and two or more kinds of these groups are included. It may be a combination of.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1. , 6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group A linear alkanediyl group such as a dodecane-1,12-diyl group;
An alkyl group (especially, an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, etc.) to a linear alkanediyl group. Having a side chain of, for example, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group Group, a branched alkanediyl group such as a 2-methylbutane-1,4-diyl group;
Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,2-diyl group, 1-methylcyclohexane-1,2-diyl group, cyclohexane-1,4-diyl group, cyclo A monocyclic divalent alicyclic saturated hydrocarbon group which is a cycloalkanediyl group such as an octane-1,2-diyl group and a cyclooctane-1,5-diyl group;
Norbornane-2,3-diyl group, norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group and the like A divalent alicyclic saturated hydrocarbon group etc. are mentioned.
Further, the divalent alicyclic hydrocarbon group may be a group obtained by removing any one hydrogen atom from the monovalent alicyclic hydrocarbon group shown in the present specification.
At least one hydrogen atom contained in these saturated hydrocarbon groups is replaced with a fluorine atom.

The cation in the salt (aa) preferably has a group represented by the formula (aa1).
[In formula (aa1),
X ^a , X ^b , X ¹ and * have the same meanings as described above.
The ring W represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms, and the methylene group contained in the alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a carbonyl group or a sulfonyl group. Well, the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxy group or a hydrocarbon group having 1 to 12 carbon atoms, and the methylene group contained in the hydrocarbon group is an oxygen atom or It may be substituted with a carbonyl group. ]

Examples of the alicyclic hydrocarbon group having 3 to 36 carbon atoms in the ring W include rings represented by formulas (Iaa-1) to (Iaa-11), and alicyclic carbon atoms having 3 to 18 carbon atoms. A hydrogen group is preferable, and a ring represented by formula (Iaa-1), a ring represented by formula (Iaa-2), or a ring represented by formula (Iaa-3) is more preferable.
Any carbon atom in the ring represented by formula (Iaa1-1) to formula (Iaa1-11) may be bonded to X ^a and X ^b, and any carbon atom may be represented by * in formula (aa1). It may be a bond represented by.
Among them, the ring W is preferably a ring represented by the formula (Iaa-1), a ring represented by the formula (Iaa-2) or a ring represented by the formula (Iaa-3), and Those having a bond at a position are more preferable.

The hydrocarbon group having 1 to 12 carbon atoms which may be substituted with the alicyclic hydrocarbon group of formula (Iaa-1) to formula (Iaa-11) is preferably a saturated hydrocarbon, for example, methyl. Group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and other straight or branched saturated hydrocarbons, phenyl group, naphthyl group And aromatic hydrocarbon groups such as and cyclic saturated hydrocarbons such as the groups shown below.

The group in which the methylene group contained in the hydrocarbon group in formulas (Iaa-1) to (Iaa-11) is substituted with an oxygen atom or a carbonyl group is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, pentyl. Examples thereof include an oxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a carboxyl group, a methoxycarbonyl group and an ethoxycarbonyl group.
In particular, ring W preferably has a hydroxy group, an alkoxy group, or an alkoxycarbonyl group as a substituent.

The cation having a group represented by formula (aa1) is preferably a cation having a group represented by formula (Ia).
[In the formula (Ia),
Rings W and * have the same meanings as above.
R ^f1 and R ^f2 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms.
n represents an integer of 1 to 10. When n is 2 or more, a plurality of R ^f1 and R ^f2 may be the same or different. ]

Examples of the fluorinated alkyl group for R ^f1 and R ^f2 include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, and a 2,2,2-trifluoroethyl group. , 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, 1,1,2,2,3 , 3,4,4,5,5-decafluoropentyl group, 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl group, perfluoropentyl group, 2-(perfluoro Butyl)ethyl group, 1,1,2,2,3,3,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5 A 6,6-dodecafluorohexyl group, a perfluoropentylmethyl group and a perfluorohexyl group can be mentioned. Of these, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group and the like are preferable.
Both R ^f1 and R ^f2 are preferably fluorine atoms.

n is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, even more preferably an integer of 1 to 4, and even more preferably an integer of 1 to 3. .. Among them, it is preferable to contain the following —O—C—O—.

The cation having a group represented by formula (Ia) is preferably an organic onium cation, and examples thereof include an organic sulfonium cation, an organic iodonium cation, an organic ammonium cation, a benzothiazolium cation, and an organic phosphonium cation. Are organic sulfonium cations or organic iodonium cations, more preferably arylsulfonium cations.

The salt (aa) having a cation represented by the formula (aa1) is preferably a salt having a cation represented by the formula (aa33), and a salt having a cation represented by the formula (aa3). More preferably.
[In the formula (aa33), X ^a , X ^b , X ¹ and W have the same meanings as described above.
X represents a sulfur atom or an iodine atom.
m represents an integer of 0 or 1.
When X is a sulfur atom, m is 1, and when X is an iodine atom, m is 0.
R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or R ³ and R ⁴ together with the sulfur atom to which they are bound are It may form a heterocycle.
L represents a single bond or a divalent hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—. ]

[In the formula (aa3),
X ^a , X ^b , X ¹ , W, X, R ³ , R ⁴ and m have the same meanings as described above. ]

Examples of the divalent hydrocarbon group represented by L include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and a combination thereof. ..
Examples of the divalent aliphatic hydrocarbon group include alkanediyl groups having 1 to 12 carbon atoms such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group and hexanediyl group.
Examples of the divalent alicyclic hydrocarbon group include a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group and an adamantanediyl group.
Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group.
L _{is, ** - O-CH 2 -CO} -O-C 6 H 4 -, ** - CO-O-CH 2 -CO-O-C 6 H 4 -, ** - O-CO-C 6 _{H 4 -, ** - O-} CO-O-C 6 H 4 - or _{** - CO-O-C 6} H 4 - is _{preferably, ** - O-CH 2 -CO} -O-C ₆ H ₄ − or **-CO—O—C ₆ H ₄ — is more preferable. ** represents a bond with the ring W.

Examples of the hydrocarbon group for R ³ and R ⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined.
Examples of the aliphatic hydrocarbon 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, heptyl group. Group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and other alkyl groups, and preferably has 1 to 6 carbon atoms.
Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group and an adamantyl group.
Examples of the 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. And aryl groups such as biphenyl group, phenanthryl group, 2,6-diethylphenyl group, and 2-methyl-6-ethylphenyl.
Examples of the group obtained by combining the aliphatic hydrocarbon group and the alicyclic hydrocarbon group include an alkylcycloalkyl group and a cycloalkylalkyl group.

Examples of the substituent which the hydrocarbon group may have include a halogen atom, a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an acyl group having 2 to 4 carbon atoms and an acyloxy group having 2 to 4 carbon atoms. Can be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group and a butyryloxy group.
X is preferably a sulfur atom.

Examples of the heterocycle formed by combining R ³ and R ⁴ and the sulfur atom to which they are bound include the following rings.

Examples of such cations include the following.

The salt (aa) is preferably a salt having an organic anion. Examples of the organic anion include sulfonate anion, sulfonylimide anion, and sulfonylmethide anion. Among these, the sulfonate anion is preferable, and the anion represented by the formula (IA) is more preferable.
[In the formula (IA),
Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —CO—, and the saturated group The hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group.
Y represents a saturated hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, _-CH 2 contained in the saturated hydrocarbon group - is -O -, - S -, - SO ₂ -Or-CO- may be substituted. ]

The perfluoroalkyl group of Q ¹ and Q ² includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group and a perfluoroalkyl group. Hexyl group and the like can be mentioned.
Q ¹ and Q ² each independently is preferably a fluorine atom or a trifluoromethyl group, Q ¹ and Q ² is more preferably both fluorine atoms.

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 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 , Straight chain such as tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17-diyl group An 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- A branched alkanediyl group such as a 1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, a 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 and the like. 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 and adamantane-2,6-diyl group Groups and the like.

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

In the formulas (b1-1) to (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 carbon atoms before replacement is the saturated hydrocarbon group. The carbon number of
Examples of the divalent saturated hydrocarbon group include those similar to the divalent saturated hydrocarbon group of L ^b1 .

L ^b2 is preferably a single bond.
L ^b3 is preferably an alkanediyl 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 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 saturated hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
Especially, the group represented by Formula (b1-1) or Formula (b1-3) is preferable.

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

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

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

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

Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, a cyclohexylcarbonyloxy group and an adamantylcarbonyloxy group.
Examples of the acyloxy group having a substituent include an oxoadamantylcarbonyloxy group, a hydroxyadamantylcarbonyloxy group, an oxocyclohexylcarbonyloxy group and a hydroxycyclohexylcarbonyloxy group.

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

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

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

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

Among 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 followings.

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

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

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

Examples of the saturated hydrocarbon group for Y include an alkyl group, an alicyclic hydrocarbon group (including a condensed ring, a spiro ring, and the like) or a group in which these are combined.
Examples of the alkyl group of Y 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, heptyl group, 2 Examples thereof include alkyl groups such as an ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group, and preferably an alkyl group having 1 to 6 carbon atoms.
Examples of the alicyclic hydrocarbon group of Y include groups represented by formula (Y1) to formula (Y11) and formula (Y42) to formula (Y44).
Examples of the group in which the alkyl group and the alicyclic hydrocarbon group of Y are combined include a group in which one or more of each of the above-described alkyl group and alicyclic hydrocarbon group are combined in an arbitrary number, a bonding position, and the like.
In the saturated hydrocarbon group for Y, one or more —CH ₂ — contained in the saturated hydrocarbon group may be replaced with one or more —O—, —S—, —SO ₂ — or —CO—. Examples of such groups include groups represented by formula (Y12) to formula (Y41).

In Y, the hetero ring forming one of the two rings forming the spiro ring may include, for example, a ketal structure, or may include a structure in which an oxygen atom is bonded to different carbon atoms. Good. That is, in Y, two hydrogen atoms contained in the alicyclic hydrocarbon group are respectively replaced by oxygen atoms, and the two oxygen atoms together with the alkanediyl group having 1 to 8 carbon atoms form a ketal ring. You may. Moreover, the structure which the oxygen atom couple|bonded with each different carbon atom may be included. However, as will be described later, in the case of forming a spiro ring of formula (Y28) to formula (Y35) or the like, the alkanediyl group between two oxygen atoms preferably has one or more fluorine atoms. Further, among the alkanediyl groups contained in the ketal structure, it is preferable that the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom.

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

In particular, the saturated hydrocarbon group of Y is preferably one containing a group represented by the formula (aa).
[In the formula (aa), X ^a , X ^b , X ¹ and * represent the same meaning as described above. ]
For example, as represented by the structure in which the carbon atom in the chain hydrocarbon group is shared with the carbon atom in the heterocycle represented by formula (aa) and the above formulas (Y27) to (Y32), Includes structures that make up the ring. The two rings forming the spiro ring can be a multi-membered ring within the above-mentioned carbon number range. In the multi-membered ring here, the number of hetero atoms is also counted as the number of carbon atoms.

Examples of Y include the groups represented by the formula (aa4), in addition to the groups described above.
[In the formula (aa4), X ^a , X ^b , and X ¹ have the same meanings as described above.
* Represents a bond with L ^b1 .
Ring W represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a substituent, and the methylene group contained in the alicyclic hydrocarbon group is an oxygen atom, a sulfur atom or a carbonyl group. Alternatively, it may be substituted with a sulfonyl group. ]
Examples of the group represented by the formula (aa4) include the same groups as those represented by the formula (aa1) in the cation of the salt (aa).
The substituent in ring W is the same as the substituent of the alicyclic hydrocarbon group of ring W in the group represented by formula (aa1), the same as the following alkyl group and the substituent of the alicyclic hydrocarbon group. The following are listed. Of these, a hydroxy group, an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group are preferable.

As the substituent of the alkyl group of Y, for example, a halogen atom, a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, a glycidyloxy group or -(CH ^{_{2) ja -O-CO-R}} b1 group ^{(wherein, R b1} represents an alkyl group having 1 to 16 carbon atoms, an aromatic alicyclic hydrocarbon group or a C6-18 3 to 16 carbon atoms carbide Represents a hydrogen group, and ja represents an integer of 0 to 4) and the like.
Examples of the substituent of the alicyclic hydrocarbon group of 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 an aliphatic group having 3 to 16 carbon atoms. Cyclic hydrocarbon group, alkoxy group having 1 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 18 carbon atoms, aralkyl group having 7 to 21 carbon atoms, acyl group having 2 to 4 carbon atoms, glycidyloxy group or- _{(CH 2) ja -O-CO} -R b1 group ^{(wherein, R b1} represents an alkyl group having 1 to 16 carbon atoms, alicyclic hydrocarbon group or aromatic having 6 to 18 carbon atoms 3 to 16 carbon atoms Represents a group hydrocarbon group, and ja represents an integer of 0 to 4) and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the hydroxy group-containing alkyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group and a dodecyloxy group.
Examples of the 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. And aryl groups such as biphenyl group, phenanthryl group, 2,6-diethylphenyl group, and 2-methyl-6-ethylphenyl.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group and a naphthylethyl group.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.

Examples of Y include the following.

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and more preferably an adamantyl group which may have a substituent. The methylene group constituting the hydrogen group or adamantyl group may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Y is particularly preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group or a group represented by the following.

The anion represented by the formula (IA) is an anion represented by the formula (IA-1) to the formula (IA-46) [hereinafter, anion represented by the formula number is "anion (IA)". -1)" and so on. ] Are preferable, Formula (IA-1)-Formula (IA-4), Formula (IA-9), Formula (IA-10), Formula (IA-24)-Formula The anion represented by any one of (IA-33) and formula (IA-36) to formula (IA-40) is more preferable. Further, R ^{i2 to} R ⁱ⁴ are, for example, an alkyl group having 1 to 4 carbon atoms, and preferably a methyl group. L ⁴ is, for example, a single bond or an alkanediyl group having 1 to 4 carbon atoms. Q ¹ and Q ² are as defined above.

Among them, preferable anions include anions represented by formulas (Ia-1) to (Ia-22).

The anion having a group represented by the formula (aa) is more preferably an anion having a group represented by the formula (aa1), further preferably an anion having a group represented by the formula (Ia), The anion represented by (aa2) is even more preferable.

[In the formula (aa2),
Q ¹ , Q ² , L ^b1 , X ^a , X ^b , X ¹ and W have the same meanings as described above. ]

L ^b1 preferably represents a divalent saturated hydrocarbon group (the methylene group contained in the saturated monovalent hydrogen group may be replaced with —O— or —CO—), and more preferably the formula (b1). -4) or a group represented by the formula (b1-2), L ^b4 is an alkanediyl group having 1 to 10 carbon atoms, L ^b5 is a single bond, and more preferably * _{-CO-O- (CH 2) t} (t in. * is an integer from 0 to ^{6, C} (Q 1) (representing the binding position to the ^{Q 2).)} or _* -CH 2 -O-CO Represents-(* represents a bonding position to C(Q ¹ )(Q ² )).

Examples of the anion represented by the formula (aa2) include the followings.

As for the salt, the above-mentioned cation and anion can be arbitrarily combined.
Examples of the salt (aa) include the following salts.

<Method for producing salt (aa)>
The salt (I) composed of a cation represented by the formula (aa3) and an anion represented by the formula (aa2) is represented by, for example, the salt represented by the formula (Ia) and the formula (Ib). The compound can be produced by reacting the compound with an acid catalyst in a solvent.

[In the formula, Q ¹ , Q ² , L ^b1 , W, R ³ , R ⁴ , X ^a , X ^b, and X ¹ have the same meanings as described above. ]

Examples of the acid catalyst in this reaction include p-toluenesulfonic acid.
Examples of the solvent in this reaction include chloroform, acetonitrile, dimethylformamide and the like.
Examples of the compound represented by the formula (Ib) include 2,2,3,3-tetrafluoro-1,4-butanediol and the like, which can be easily obtained from the market.

The salt represented by the formula (Ia) can be produced by reacting the salt represented by the formula (Ic) with the salt represented by the formula (Id) in a solvent. ..

Examples of the solvent in this reaction include chloroform, acetonitrile, water and the like.
Examples of the salt represented by the formula (Ic) include the salts shown below and the like, which can be easily obtained from the market.

The salt represented by the formula (Ic) can be synthesized by the method described in JP2007-224008A, and examples thereof include the salts shown below.

<Acid generator>
The salt (aa) can act as an acid generator in the resist composition.
The acid generator of the present invention may contain the salt (aa) alone, or may include the salt (aa) and an acid generator known in the resist field (hereinafter referred to as the acid generator (B)). In some cases.) and. In the acid generator, the salt (aa) may contain two or more kinds, and the acid generator (B) may contain two or more kinds.
When the acid generator contains the acid generator (B), the ratio of the contents of the salt (aa) and the acid generator (B) in the acid generator (mass ratio; salt (a): acid generator ( B)) is usually 1:99 to 100:0, preferably 1:99 to 99:1, more preferably 2:98 to 98:2, and further preferably 5:95 to 95:. It is 5.

<Acid generator (B)>
The acid generator is classified into a nonionic type and an ionic type, and any of them may be used in the acid generator (B) of the resist composition of the present invention. Examples of the nonionic acid generator include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate) and sulfones. (For example, disulfone, ketosulfone, sulfonyldiazomethane) and the like are included. The ionic acid generator is typically an onium salt containing an onium cation (eg, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt). Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion and a sulfonylmethide anion.

Examples of the acid generator (B) include JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, and JP-A-63-163452. JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent 3914407, and European Patent 126,712. Compounds that generate an acid by the radiation 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 ¹ , Q ² , L ^b1 and Y have the same meanings as described above.
Z ⁺ represents an organic cation. However, Z ⁺ does not include a group represented by the formula (aa). ]
Y in the formula (B1) is a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (included in the saturated hydrocarbon group. —CH ₂ — may be replaced with —O—, —S—, —SO ₂ — or —CO—).

Specifically, the salts represented by any of the formulas (B1-1) to (B1-32) can be mentioned. Among them, those containing an arylsulfonium cation are preferable, and formula (B1-1), formula (B1-2), formula (B1-3), formula (B1-6), formula (B1-7), formula (B1-11). ), formula (B1-12), formula (B1-13), formula (B1-14), formula (B1-20), formula (B1-21), formula (B1-22), formula (B1-23). , A salt represented by formula (B1-24), formula (B1-25), formula (B1-26), formula (B1-29), formula (B1-31) or formula (B1-32). Is more preferable.

<Resist composition>
The resist composition of the present invention contains an acid generator and a resin having an acid labile group (hereinafter sometimes referred to as “resin (A)”). Here, the “acid-labile group” has a leaving group, the leaving group is released by contact with an acid, and the constituent unit has a hydrophilic group (for example, a hydroxy group or a carboxy group). Means a group to be converted to.
The acid generator described above can be used as the acid generator.
The resist composition preferably further contains a quencher (hereinafter sometimes referred to as “quencher (C)”) and/or a solvent (hereinafter sometimes referred to as “solvent (E)”).

<Acid generator>
In the resist composition, the content of the acid generator is preferably 1 to 40% by mass, more preferably 2-35% by mass, and 3 to 35% by mass with respect to the resin (A). It is more preferable that there is.
In particular, when only the salt (aa) is used as the acid generator, the content of the salt (aa) is preferably 1 to 40% by mass, and 2 to 35% by mass with respect to the resin (A). More preferably.
When the salt (aa) and the acid generator (B) are used as the acid generator, the content ratio of the salt (aa) and the acid generator (B) is preferably 1.5 mass with respect to the resin (A). % Or more, more preferably 3% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less.

<Resin (A)>
The resin (A) has a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). The resin (A) preferably further contains a structural unit other than the structural unit (a1). Structural units other than the structural unit (a1) include structural units 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 the group (1) and/or the group (2).
[In the formula (1), R ^{a1 to} R ^a3 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group in which these are combined, or ^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 bond. ]
[In formula (2), R ^{a1 ′} and R ^{a2 ′} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a2 ′} represents a hydrocarbon group having 1 to 20 carbon atoms. Or 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 to which they are bonded and X, and the hydrocarbon group and the divalent heterocyclic group. -CH ₂ contained in ring - may be replaced by -O- or -S-.
X represents an oxygen atom or a sulfur atom.
* Represents a bond. ]

^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 either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group and the following groups (* represents a bond). 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 in which an alkyl group and an alicyclic hydrocarbon group are combined include, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group and a norbornylethyl group. Can be mentioned.
na is preferably 0.

The following groups are mentioned as -C(R ^a1 )(R ^a2 )(R ^a3 ) when R ^a1 and R ^a2 are bonded to each other to form a divalent alicyclic hydrocarbon group. The divalent alicyclic hydrocarbon group preferably has 3 to 12 carbon atoms. * Represents a bond with -O-.

Examples of the group represented by the formula (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^{a1 to} R ^a3 are alkyl groups, preferably a tert-butoxycarbonyl group), 2- An alkyladamantan-2-yloxycarbonyl group (in the formula (1), 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) and the like.

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 above.
As the aromatic hydrocarbon group, phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl Group, phenanthryl group, 2,6-diethylphenyl group, aryl group such as 2-methyl-6-ethylphenyl, and the like.
^{Examples of the} divalent heterocyclic group formed by R ^{a2 ′} and R ^{a3 ′} bonded to each other and the carbon atom to which they are bonded and X include the following groups. * Represents a bond.
At least one of R ^{a1 ′} and R ^{a2 ′} is preferably a hydrogen atom.

Specific examples of the group represented by the formula (2) include the following groups. * Represents a bond.

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

Among the (meth)acrylic monomers having an acid labile group, those having an alicyclic hydrocarbon group having 5 to 20 carbon atoms are preferable. When 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.

The structural unit derived from the (meth)acrylic monomer having a group represented by the formula (1) is preferably a structural unit represented by the formula (a1-0) or a formula (a1-1). The structural unit or the structural unit represented by the formula (a1-2) can be mentioned. These may be used alone or in combination of two or more. In the present specification, the structural unit represented by the formula (a1-0), the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) are respectively represented by the structural unit (a1 -0), the structural unit (a1-1) and the structural unit (a1-2), a monomer that induces the structural unit (a1-0), a monomer that induces the structural unit (a1-1), and the structural unit (a1- The monomer that induces 2) may be referred to as a monomer (a1-0), a monomer (a1-1), and a monomer (a1-2), respectively.
[In formula (a1-0),
L ^a01 represents an oxygen atom or *—O—(CH ₂ ) _k01 —CO—O—, k01 represents an integer of 1 to 7, and * represents a bond with a carbonyl group.
R ^a01 represents a hydrogen atom or a methyl group.
R ^a02 , R ^a03 and R ^a04 each independently ^represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining these. ]

[In Formula (a1-1) and Formula (a1-2),
L ^a1 and L ^a2 each independently represent —O— or *—O—(CH ₂ ) _k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond with —CO—. Representing a hand.
R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.
R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining these.
m1 represents the integer of 0-14.
n1 represents the integer of 0-10.
n1' represents the integer of 0-3. ]

L ^a01 is preferably an oxygen atom or *—O—(CH ₂ ) _k01 —CO—O— (provided that k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably. Is an oxygen atom.
Examples of the alkyl group of R ^a02 , R ^a03, and R ^a04 , the alicyclic hydrocarbon group, and a group in which these are combined include the same groups as those described for R ^{a1 to} R ^a3 of the formula (1).
The alkyl group of R ^a02 , R ^a03 and R ^a04 preferably has 6 or less carbon atoms.
The number of carbon atoms of the alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 is preferably 8 or less, more preferably 6 or less.
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. Examples of such a group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a methyladamantyl group, a cyclohexylmethyl group, a methylcyclohexylmethyl group, an adamantylmethyl group, and a norbornylmethyl group. To be
R ^a02 and R ^a03 are independently of each other, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an ethyl group.
R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.

L ^a1 and L ^a2 are independently of each other, preferably —O— or *—O—(CH ₂ ) _k1′ —CO—O— (where k1′ is an integer of 1 to 4, preferably Is 1.), more preferably -O-.
R ^a4 and R ^a5 independently of each other are preferably methyl groups.
Examples of the alkyl group of R ^a6 and R ^a7 , the alicyclic hydrocarbon group, and a group in which these are combined include the same groups as the groups described for R ^{a1 to} R ^a3 of the formula (1).
The carbon number of the alkyl group of R ^a6 and R ^a7 is preferably 6 or less.
The alicyclic hydrocarbon group of R ^a6 and R ^a7 preferably has 8 or less carbon atoms, and more preferably 6 or less carbon atoms.
m1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1 is preferably an integer of 0 to 3, and more preferably 0 or 1.
n1′ is preferably 0 or 1.

As the structural unit (a1-0), for example, a structural unit represented by any of the formulas (a1-0-1) to (a1-0-12) is preferable, and the structural units (a1-0-1) to The structural unit represented by any of the formulas (a1-0-10) is more preferred.

In the above structural unit, a structural unit in which a methyl group corresponding to R ^a01 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a1-0).

Examples of the monomer (a1-1) include the monomers described in JP2010-204646A. Among them, the monomer represented by any of the formulas (a1-1-1) to (a1-1-8) is preferable, and any of the formulas (a1-1-1) to (a1-1-4) is preferable. The monomer represented by is more preferable.

Examples of the monomer (a1-2) include 1-methylcyclopentan-1-yl(meth)acrylate, 1-ethylcyclopentan-1-yl(meth)acrylate, 1-methylcyclohexane-1-yl(meth). Acrylate, 1-ethylcyclohexane-1-yl(meth)acrylate, 1-ethylcycloheptan-1-yl(meth)acrylate, 1-ethylcyclooctane-1-yl(meth)acrylate, 1-isopropylcyclopentane-1 Examples include -yl(meth)acrylate, 1-isopropylcyclohexane-1-yl(meth)acrylate and the like. The monomer represented by any of the formulas (a1-2-1) to (a1-2-12) is preferable, and the formula (a1-2-3), the formula (a1-2-4), and the formula (a1- 2-9) and the monomer represented by Formula (a1-2-10) are more preferable, and the monomers represented by Formula (a1-2-3) and Formula (a1-2-9) are still more preferable.

When the resin (A) contains the structural unit (a1-0), the structural unit (a1-1) and/or the structural unit (a1-2), the total content of these is based on the total structural units of the resin (A). Independently of each other, the content is usually 10 to 95 mol %, preferably 15 to 90 mol %, and more preferably 20 to 85 mol %.

Further, the structural unit (a1) having the group (1) also includes a structural unit represented by the formula (a1-3). The structural unit represented by the formula (a1-3) may be referred to as a structural unit (a1-3). Further, the monomer that induces the structural unit (a1-3) may be referred to as a monomer (a1-3).
[In the formula (a1-3),
R ^a9 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may have a hydroxy group, a carboxy group, a cyano group, a hydrogen atom or —COOR ^a13 .
R ^a13 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these, and the aliphatic hydrocarbon group and The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxy group, and —CH ₂ — contained in the aliphatic hydrocarbon group and the alicyclic hydrocarbon group is —O—. Alternatively, it may be replaced with -CO-.
R ^a10 , R ^a11 and R ^a12 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group formed by combining these; R ^a10 and R ^a11 are bonded to each other to form, together with the carbon atom to which they are bonded, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. ]

Here, examples of —COOR ^a13 include groups in which a carbonyl group is bonded to an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the aliphatic hydrocarbon group which may have a hydroxy group for R ^a9 include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a 2-hydroxyethyl group.
^Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms of R ^a13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and n. Examples include -hexyl group, n-heptyl group, 2-ethylhexyl group, and n-octyl group.
^Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ^a13 include a cyclopentyl group, a cyclopropyl group, an adamantyl group, an adamantyl methyl group, a 1-adamantyl-1-methylethyl group, and 2-oxo-oxolane-3-. Examples thereof include an yl group and a 2-oxo-oxolan-4-yl group.
^Examples of the alkyl group of R ^{a10 to} R ^a12 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, an n-hexyl group, Examples thereof include n-heptyl group, 2-ethylhexyl group and n-octyl group.
The alicyclic hydrocarbon group of R ^{a10 to} R ^a12 may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. And cycloalkyl groups such as cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1-(adamantan-1-yl)alkane-1-yl group, and norbornyl. Group, a methylnorbornyl group, an isobornyl group and the like.
As -C(R ^a10 )(R ^a11 )(R ^a12 ), when R ^a10 and R ^a11 are bonded to each other to form a divalent alicyclic hydrocarbon group together with the carbon atom to which they are bonded, The following groups are preferable.

Specific examples of the monomer (a1-3) include 5-tert-butyl 5-norbornene-2-carboxylic acid, 1-cyclohexyl-1-methylethyl 5-norbornene-2-carboxylic acid, and 5-norbornene-2-carboxylic acid. Acid 1-methylcyclohexyl, 5-norbornene-2-carboxylic acid 2-methyl-2-adamantyl, 5-norbornene-2-carboxylic acid 2-ethyl-2-adamantyl, 5-norbornene-2-carboxylic acid 1-(4 -Methylcyclohexyl)-1-methylethyl, 5-norbornene-2-carboxylic acid 1-(4-hydroxycyclohexyl)-1-methylethyl, 5-norbornene-2-carboxylic acid 1-methyl-1-(4-oxo Examples thereof include cyclohexyl)ethyl and 1-(1-adamantyl)-1-methylethyl 5-norbornene-2-carboxylic acid.

Since the resin (A) containing the structural unit (a1-3) contains a structurally bulky structural unit, the resin composition of the present invention containing such a resin (A) is higher than that of the resist composition of the present invention. A resist pattern can be obtained with a resolution. Further, since a rigid norbornane ring is introduced into the main chain, the obtained resist pattern tends to have excellent dry etching resistance.

When the resin (A) contains the structural unit (a1-3), its content is preferably 10 to 95 mol% with respect to the total of all structural units of the resin (A), and preferably 15 to 90 mol %. %, and more preferably 20 to 85 mol %.

As the structural unit (a1) having a group represented by the group (2), a structural unit represented by the formula (a1-4) (hereinafter, may be referred to as “structural unit (a1-4)”). Can 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 acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
la represents an integer of 0 to 4. When la is 2 or more, a plurality of R ^a33 may be the same or different from each other.
R ^a34 and ^{R a35} are independently of each other, 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 each And C—O to which they are bonded to form a divalent heterocyclic group having 3 to 20 carbon atoms, and —CH ₂ — contained in the hydrocarbon group and the divalent heterocyclic group is —O. It may be replaced by -or -S-. ]

^Examples of the alkyl group of 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, further preferably a methyl group.
Examples of the halogen atom of R ^a32 and R ^a33 include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group which may have a halogen atom include a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, a 1,1,1-trifluoroethyl group, 1,1,2,2-tetrafluoro Ethyl group, ethyl group, perfluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2,3,3,4,4-octafluoro Butyl group, butyl group, perfluoropentyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, n-pentyl group, n-hexyl group, n-perfluorohexyl group, etc. Can be mentioned.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
Examples of the hydrocarbon group R ^a34 and ^{R a35,} include the same groups as ^{R a1 'and R a2'} of formula (2).
R ^a36 is an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these. Can be 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 and an ethoxy group, and even more preferably a methoxy group.
la is preferably 0 or 1, and more preferably 0.
R ^a34 is preferably a hydrogen atom.
R ^a35 is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a methyl group or an ethyl group.
The hydrocarbon group for R ^a36 is preferably an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof. Examples of the group formed include an alkyl group having 1 to 18 carbon atoms, an alicyclic aliphatic hydrocarbon group having 3 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms.
The alkyl group and the alicyclic hydrocarbon group for R ^a36 are preferably unsubstituted.
When the aromatic hydrocarbon group for R ^a36 has a substituent, the substituent is preferably an aryloxy group having 6 to 10 carbon atoms.

Examples of the monomer that leads to the structural unit (a1-4) include the monomers described in JP2010-204646A. Among them, the monomers represented by formula (a1-4-1) to formula (a1-4-8) are preferable, and formula (a1-4-1) to formula (a1-4-5) and formula (a1-). The monomers represented by 4-8) are more preferable.

When the resin (A) has the structural unit (a1-4), its content is preferably 10 to 95 mol% relative to the total of all structural units of the resin (A), and preferably 15 to 90. It is more preferably mol%, and further preferably 20 to 85 mol%.

As the structural unit derived from the (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)” There is also).
[In the formula (a1-5),
^Ra8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
Z ^a1 represents a single bond or _{* - (CH 2) h3 -CO} -L 54 - represents, h3 represents an integer of 1 to 4, * represents a bond to ^{L 51.}
L ^<51> , L ^<52> , L ^<53> and L ^<54 > represent -O- or -S-, mutually independently.
s1 represents an integer of 1 to 3.
s1' represents the integer of 0-3. ]

Examples of the halogen atom include a fluorine atom and a chlorine atom, preferably a fluorine atom. 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 trifluoromethyl. 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.
It is preferable that one of L ⁵² and L ⁵³ is —O—, and the other is —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—.

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

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

Examples of the structural unit (a) having an acid labile group in the resin (A) include a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2) and a structural unit (a1-5). At least one selected from the group consisting of), more preferably at least two or more, and a combination of structural unit (a1-1) and structural unit (a1-2), structural unit (a1-1) and structural unit ( a1-5), structural unit (a1-1) and structural unit (a1-0), structural unit (a1-2) and structural unit (a1-0), structural unit (a1-5) And a combination of structural units (a1-0), structural units (a1-0), combinations of structural units (a1-1) and structural units (a1-2), structural units (a1-0), structural units (a1- 1) and the structural unit (a1-5) are more preferable, and the combination of the structural unit (a1-1) and the structural unit (a1-2), the structural unit (a1-1) and the structural unit (a1-5) Combinations are even more preferred.
The structural unit (a1) preferably includes the structural unit (a1-1).

<Structural unit (s)>
The structural unit (s) is derived from a monomer having no acid labile group (hereinafter sometimes referred to as “monomer (s)”). As the monomer that leads to the structural unit (s), a monomer that does not have an 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 structural unit 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 When 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 ray such as KrF excimer laser (248 nm), electron beam or EUV (ultra-ultraviolet light) is used as an exposure light source, it is used as a structural unit (a2). It is preferable to use the structural unit (a2) having a phenolic hydroxy group. When using an ArF excimer laser (193 nm) or the like, the structural unit (a2) is preferably a structural unit (a2) having an alcoholic hydroxy group, and more preferably the structural unit (a2-1). As the structural unit (a2), one type may be included alone, or two or more types may be included.

Examples of the structural unit (a2) having a phenolic hydroxy group include a structural unit represented by the formula (a2-0) (hereinafter sometimes referred to as “structural unit (a2-0)”).
[In the formula (a2-0),
R ^a30 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom.
R ^a31 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 acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents the integer of 0-4. When ma is an integer greater than or equal to 2, some R ^<a31 > may mutually be same or different. ]

^Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom of R ^a30 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, n-pentyl group, n-hexyl group Group, n-perfluorohexyl group and the like.
R ^a30 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.
^Examples of the alkoxy group for R ^a31 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. Among them, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is further preferable.
Examples of the acyl group include an acetyl group, a propionyl group and a butyryl group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group and the like.
ma is preferably 0, 1 or 2, more preferably 0 or 1, and even more preferably 0.

Examples of the monomer that induces the structural unit (a2-0) include the monomers described in JP 2010-204634 A.
Among them, the structural unit (a2-0) is represented by the formula (a2-0-1), the formula (a2-0-2), the formula (a2-0-3) and the formula (a2-0-4). The structural unit represented by formula (a2-0-1) or formula (a2-0-2) is more preferable.

The resin (A) containing the structural unit (a2-0) undergoes a polymerization reaction using a monomer in which the phenolic hydroxy group of the monomer that induces the structural unit (a2-0) is protected by a protective group, and then deprotected. It can be produced by processing. However, when performing the deprotection treatment, it is necessary to prevent the acid labile group contained in the structural unit (a1) from being significantly impaired. An acetyl group etc. are mentioned as such a protective group.

When the resin (A) has a structural unit (a2-0) having a phenolic hydroxy group, its content is 5 to 95 mol% based on the total of all structural units of the resin (A). Is preferable, 10-80 mol% is more preferable, and 15-80 mol% is further preferable.

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 is, -O- or _{* -O- (CH 2) k2 -CO} -O- the stands,
k2 represents an integer of 1 to 7. * Represents a bond with -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— (where f1 is an integer of 1 to 4), and more preferably -O-.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

Examples of the monomer that derives the structural unit (a2-1) include the monomers described in JP2010-204646A. The monomer represented by any of the formulas (a2-1-1) to (a2-1-6) is preferable, and the monomer represented by any of the formulas (a2-1-1) to (a2-1-4) is represented. Is more preferable, and the monomer represented by formula (a2-1-1) or formula (a2-1-3) is further preferable.

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

<Structural unit (a3)>
The lactone ring contained in the structural unit (a3) may be a single ring such as a β-propiolactone ring, a γ-butyrolactone ring, or a δ-valerolactone ring, or a condensed ring of a monocyclic lactone ring and another ring. But it's okay. Preferred is a γ-butyrolactone ring, an adamantane lactone ring, or a bridged ring containing a γ-butyrolactone ring structure.

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 may be contained alone or in combination of two or more.
[In the formula (a3-1),
L ^a4 represents a group represented by —O— or *—O—(CH ₂ ) _k3— CO—O— (k3 represents an integer of 1 to 7). * Represents a bond with the carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
p1 represents the integer of 0-5. When p1 is 2 or more, a plurality of R ^a21 may be the same or different.
In formula (a3-2),
L ^a5 represents -O- or _{* -O- (CH 2) k3 -CO} -O- (k3 represents. An integer of 1-7) is represented by the group. * Represents a bond with the carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
^Ra22 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
q1 represents an integer of 0 to 3. When q1 is 2 or more, a plurality of R ^a22 may be the same as or different from each other.
In formula (a3-3),
L ^a6 represents a group represented by —O— or *—O—(CH ₂ ) _k3— CO—O— (k3 represents an integer of 1 to 7). * Represents a bond with the carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
R ^a23 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
r1 represents an integer of 0 to 3. When r1 is 2 or more, a plurality of R ^a23 may be the same as or different from each other.
In formula (a3-4),
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 ^a25 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
^La7 is a single bond, ^{* -La8-} O-, ^{* -La8-} CO-O-, ^{* -La8-} CO-O- ^La9- CO-O- or ^{* -La8-} O-CO. Represents -L ^a9 -O-.
* Represents a bond with the carbonyl group.
L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.
w1 represents an integer of 0 to 8. When w1 is 2 or more, a plurality of R ^a25 may be the same as or different from each other. ]

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by R ^a21 , R ^a22 , R ^a23, and R ^a25 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-group. A butyl group and the like can be mentioned.
Examples of the halogen atom of 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. , Preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.
Examples of the alkyl group having a halogen atom of R ^a24 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, and a perfluoropentyl group. Hexyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group and the like can be mentioned.

^Examples of the alkanediyl group of L ^a8 and L ^a9 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, Examples thereof include 4-diyl group and 2-methylbutane-1,4-diyl group.

In formulas (a3-1) to (a3-3), L ^{a4 to} L ^a6 are independently of each other, preferably —O— or *—O—(CH ₂ ) in which k3 is an integer of 1 to 4. _k3 -CO-O-group represented by, more preferably -O- _{and, * - O-CH 2 -CO} -O-, more preferably an oxygen atom.
R ^{a18 to} R ^a21 are preferably methyl groups.
R ^a22 and R ^a23 are independently of each other, preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are independently of each other, preferably an integer of 0 to 2, and more preferably 0 or 1.

In formula (a3-4), R ^a24 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group. Is.
L ^a7 is preferably a single bond or ^* -L ^a8 -CO-O-, more preferably an a single ^bond, * -CH ₂ -CO-O- or ^* -C ₂ H ₄ -CO-O- and ..
R ^a25 is preferably a carboxy group, a cyano group or a methyl group.
w1 is preferably an integer of 0 to 2, and more preferably 0 or 1.
The formula (a3-4) is preferably the formula (a3-4)′.
(In the formula, R ^a24 and L ^a7 have the same meanings as described above.)

Examples of the monomer that leads to the structural unit (a3) include the monomer described in JP-A-2010-204646, the monomer described in JP-A-2000-122294, and the monomer described in JP-A-2012-41274. Can be mentioned. As the structural unit (a3), formula (a3-1-1) to formula (a3-1-4), formula (a3-2-1) to formula (a3-2-4), formula (a3-3-). 1) to the formula (a3-3-4) and the formula (a3-4-1) to the formula (a3-4-12), a structural unit represented by any one of the formula (a3-1-1), It is represented by any one of formula (a3-1-2), formula (a3-2-3) to formula (a3-2-4) and formula (a3-4-1) to formula (a3-4-12). The structural unit represented by formula (a3-4-1) to formula (a3-4-12) is more preferable, and the structural unit represented by any of formula (a3-4-1) to formula (a3-4-12) is further preferable. The structural unit represented by any of 4-6) is even more preferable.

In the following structural unit, a compound in which the methyl group corresponding to R ^a24 is replaced with a hydrogen atom can also be mentioned as a specific example of the structural unit (a3-4).

When the resin (A) contains the structural unit (a3), the total content thereof is usually 5 to 70 mol%, preferably 10 to 65 mol% with respect to the total of all structural units of the resin (A). And more preferably 10 to 60 mol %.
Moreover, the content rates of the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3), and the structural unit (a3-4) are the total of all structural units of the resin (A). On the other hand, it is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and further preferably 10 to 50 mol %.

<Other structural units (t)>
The resin (A) may include other structural units (hereinafter sometimes referred to as “structural units (t)”) as structural units other than the structural unit (a1) and the structural unit (s). As the structural unit (t), in addition to the structural unit (a2) and the structural unit (a3), a structural unit having a halogen atom (hereinafter, sometimes referred to as “structural unit (a4)”) and a non-eliminating hydrocarbon group. The structural unit (s) which it has (it may be hereafter called "structural unit (a5)") etc. are mentioned. The resin (A) may have a structural unit other than the above structural units, and examples of such a structural unit include structural units well known in the art.

Examples of the structural unit (a4) include structural units represented by the formula (a4-0).
[In the formula (a4-0),
R ⁵ 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 C 1-8 perfluoroalkanediyl group or a C 3-12 perfluorocycloalkanediyl group.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

Examples of the aliphatic saturated hydrocarbon group for L ⁵ include alkanediyl groups having 1 to 4 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group. Such as a straight-chain alkanediyl group, a straight-chain alkanediyl 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.

Examples of the perfluoroalkanediyl group for L ³ include difluoromethylene group, perfluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane-1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane-2,2. -Diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5-diyl group, perfluoropentane-2,2 -Diyl group, perfluoropentane-3,3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -Diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8-diyl group, perfluorooctane-2,2 -Diyl group, perfluorooctane-3,3-diyl group, perfluorooctane-4,4-diyl group and the like.
Examples of the perfluorocycloalkanediyl group of L ³ 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, and more preferably a single bond or a methylene group.
L ³ is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, and more preferably a perfluoroalkanediyl group having 1 to 3 carbon atoms.

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

Examples of the structural unit (a4) include structural units represented by the formula (a4-1).
[In the formula (a4-1),
R ^a41 represents a hydrogen atom or a methyl group.
R ^a42 represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ — contained in the hydrocarbon group may be replaced with —O— or —CO—. Good.
A ^a41 represents an ^optionally substituted alkanediyl group having 1 to 6 carbon atoms or a group represented by the formula (a-g1). ]
[In the formula (a-g1),
s represents 0 or 1.
A ^a42 and A ^a44 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
A ^a43 represents a single bond or an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
X ^a41 and X ^a42 each independently represent -O-, -CO-, ^-CO -O-, or -O-CO-.
However, the total number of carbon atoms of A ^a42 , A ^a43 , A ^a44 , X ^a41, and X ^a42 is 7 or less.
Of the two bonds represented by *, the * on the right side is a bond with -O-CO- ^Ra42 . ]

^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 a carbon-carbon unsaturated bond, but chain and cyclic aliphatic saturated hydrocarbon groups and combinations thereof are preferable. The aliphatic saturated hydrocarbon group includes a linear or branched alkyl group, a monocyclic or polycyclic alicyclic hydrocarbon group, and a fat formed by combining an alkyl group and an alicyclic hydrocarbon group. Group hydrocarbon groups and the like can be mentioned.

Examples of the chain type aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group. Group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group. Examples of the cyclic aliphatic hydrocarbon group include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other cycloalkyl groups; decahydronaphthyl group, adamantyl group, norbornyl group and the following groups (* are bonded And a polycyclic alicyclic hydrocarbon group such as.

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 of R ^a42 include a halogen atom or a group represented by the formula (a-g3). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom.
[In the formula (a-g3),
X ^a43 represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group.
A ^a45 represents an aliphatic hydrocarbon group having at least one halogen atom and having 1 to 17 carbon atoms.
* Represents a bond. ]

^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, and an aliphatic hydrocarbon group which has an alkyl group having a halogen atom and/or a group represented by the formula (a-g3). Is more preferable.
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 perfluoroalkyl group having 1 to 6 and particularly preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group and a perfluorooctyl group. Examples of the perfluorocycloalkyl group include a perfluorocyclohexyl group.
When R ^a42 is an aliphatic hydrocarbon group having a group represented by formula (a-g3), the aliphatic hydrocarbon including the number of carbon atoms contained in the group represented by formula (a-g3) The total number of carbon atoms in the group is preferably 15 or less, more preferably 12 or less. When the group represented by formula (a-g3) has a substituent, the number thereof is preferably one.

The aliphatic hydrocarbon group having a group represented by formula (a-g3) is more preferably a group represented by 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 carbon number 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 bond with the carbonyl group. ]

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

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

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

The aliphatic hydrocarbon group of A ^a42 , A ^a43, and 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) and an alicyclic hydrocarbon group, and an alkyl group and an alicyclic hydrocarbon group are combined. And an aliphatic hydrocarbon group formed by the above. Specifically, a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a 1-methylpropane-1,3-diyl group, Examples thereof include 2-methylpropane-1,3-diyl group and 2-methylpropane-1,2-diyl group.
^Examples of the substituent of the aliphatic hydrocarbon group of A ^a42 , A ^a43, and A ^a44 include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms.
s is preferably 0.

^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 bond, and ** is a bond with -O-CO-R ^a42 .

As the structural unit represented by formula (a4-1), the structural units represented by formula (a4-2) and formula (a4-3) are 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 hydrocarbon group having a fluorine atom and having 1 to 10 carbon atoms. ]

The alkanediyl group of A ^f1 includes a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group. , A linear 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 Examples thereof include branched alkanediyl groups such as -diyl group, 1-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a group formed by a chain structure, a ring structure and a combination thereof. The aliphatic hydrocarbon group is preferably an alkyl group or an alicyclic hydrocarbon group.
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 And an ethylhexyl group.
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 a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1-(adamantan-1-yl)alkane-1-yl group, a norbornyl group, Examples thereof include a methylnorbornyl group and an isobornyl group.

Examples of the hydrocarbon group having a fluorine atom of 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 difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 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-(perfluorobutyl)ethyl group, 1 , 1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro Examples thereof include fluorinated alkyl groups such as hexyl group, perfluoropentylmethyl group and perfluorohexyl group.
Examples of the alicyclic hydrocarbon group having a fluorine atom include a fluorinated cycloalkyl group such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

A ^f1 in formula (a4-2) is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.
R ^f2 is preferably a fluorinated alkyl group having 1 to 6 carbon atoms.

[In the formula (a4-3),
R ^f11 represents a hydrogen atom or a methyl group.
A ^f11 represents an alkanediyl group having 1 to 6 carbon atoms.
A ^f13 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms, which may have a fluorine atom.
X ^f12 represents a carbonyloxy group or an oxycarbonyl group.
A ^f14 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may have a fluorine atom.
However, at least one of A ^f13 and A ^f14 represents an aliphatic hydrocarbon group having a fluorine atom. ]

^Examples of the alkanediyl group of A ^f11 include the same groups as the alkanediyl group of A ^f1 .

The aliphatic hydrocarbon group for A ^f13 includes a chain and cyclic aliphatic hydrocarbon group, and a divalent aliphatic hydrocarbon group formed by combining these. This aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f13 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom, and more preferably a perfluoroalkanediyl group.
Examples of the divalent chain aliphatic hydrocarbon group which may have a fluorine atom include an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group and a pentanediyl group; a difluoromethylene group, a perfluoroethylene group. And perfluoroalkanediyl groups such as groups, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.
The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be a group containing either a monocyclic group or a polycyclic group. Examples of the monocyclic aliphatic hydrocarbon group include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group include an adamantanediyl group, a norbornanediyl group and a perfluoroadamantanediyl group.

The aliphatic hydrocarbon group for A ^f14 includes a chain and cyclic aliphatic hydrocarbon group, and an aliphatic hydrocarbon group formed by combining these. This aliphatic hydrocarbon may have a carbon-carbon unsaturated bond, but is preferably a saturated aliphatic hydrocarbon group.
The aliphatic hydrocarbon group which may have a fluorine atom of A ^f14 is preferably an aliphatic saturated hydrocarbon group which may have a fluorine atom.
Examples of the chain aliphatic hydrocarbon group which may have a fluorine 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, Examples thereof include a heptyl group, a perfluoroheptyl group, an octyl group, and a perfluorooctyl group.
The cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the group containing a monocyclic aliphatic hydrocarbon group include a cyclopropylmethyl group, a cyclopropyl group, a cyclobutylmethyl group, a cyclopentyl group, a cyclohexyl group and a perfluorocyclohexyl group. Examples of the group containing a polycyclic aliphatic hydrocarbon group include an adamantyl group, an adamantylmethyl group, a norbornyl group, a norbornylmethyl group, a perfluoroadamantyl group, a perfluoroadamantylmethyl group and the like.

In the formula ^{(a4-3), A f11} is preferably an ethylene group.
The aliphatic hydrocarbon group for A ^f13 is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and more preferably an aliphatic hydrocarbon group having 2 to 3 carbon atoms.
The aliphatic hydrocarbon group of A ^f14 is preferably an aliphatic hydrocarbon group having 3 to 12 carbon atoms, and more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms. Among them, A ^f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably a cyclopropylmethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group.

Examples of the structural unit represented by the formula (a4-2) include structural units represented by the formula (a4-1-1) to the formula (a4-1-22).

Examples of the structural unit represented by the formula (a4-3) include structural units represented by the formulas (a4-1'-1) to (a4-1'-22).

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

^Examples of the hydrocarbon group having a fluorine atom of R ^f22 include the same as the hydrocarbon group of R ^f2 in the formula (a4-2).
R ^f22 is preferably a ^C 1-10 alkyl group having a fluorine atom or a C 1-10 alicyclic hydrocarbon group having a fluorine atom, and a C 1-10 alkyl having a fluorine atom. A group is more preferable, and an alkyl group having a fluorine atom and having 1 to 6 carbon atoms is further preferable.

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

Examples of the structural unit represented by the formula (a4-4) include the following structural units.

When the resin (A) has the structural unit (a4), its content is preferably 1 to 20 mol%, and preferably 2 to 15 mol% with respect to the total of all structural units of the resin (A). Is more preferable, and 3 to 10 mol% is further preferable.

<Structural unit (a5)>
Examples of the non-eliminating hydrocarbon group contained in the structural unit (a5) include linear, branched or cyclic hydrocarbon groups. Among them, the structural unit (a5) is preferably an alicyclic hydrocarbon group.
Examples of the structural unit (a5) include structural units represented by the formula (a5-1).
[In the formula (a5-1),
R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and a hydrogen atom contained in the alicyclic hydrocarbon group is substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydroxy group. May be.
However, the hydrogen atom bonded to the carbon atom at the bonding position with 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, and the methylene group contained in the saturated hydrocarbon group may be replaced with 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.
The aliphatic hydrocarbon group having 1 to 8 carbon atoms includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, Examples thereof include alkyl groups such as octyl group and 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, and more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group for L ⁵⁵ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably a divalent aliphatic saturated hydrocarbon group. To be
Examples of the divalent saturated aliphatic hydrocarbon group include alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group.
The divalent alicyclic saturated hydrocarbon group may be either 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 groups represented by formula (L1-1) to formula (L1-4). In the following formula, * represents a bond with an oxygen atom.
[In the formula (L1-1),
X ^x1 represents a carbonyloxy group or an oxycarbonyl group.
L ^x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
L ^x2 represents a single bond or a C 1 to C 15 divalent saturated aliphatic hydrocarbon group.
However, the total carbon number of L ^x1 and L ^x2 is 16 or less.
In formula (L1-2),
L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.
L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.
However, the total carbon number of L ^x3 L ^x4 is 17 or less.
In formula (L1-3),
L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.
L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.
However, the total carbon number of L ^x5 , L ^x6, and L ^x7 is 15 or less.
In formula (L1-4),
L ^x8 and L ^x9 represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms.
W ^x1 represents a divalent alicyclic saturated hydrocarbon group having 3 to 15 carbon atoms.
However, the total carbon number of L ^x8 , L ^x9, and W ^x1 is 15 or less. ]

L ^x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond.
L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a methylene group or an ethylene group.
L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.
L ^x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.
L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, and more preferably a single bond or a methylene group.
W ^x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, and more preferably a cyclohexanediyl group or an adamantanediyl group.

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

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

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

Examples of the group represented by the formula (L1-4) include the following divalent groups.
L ⁵⁵ is preferably a single bond or a group represented by the formula (L1-1).

Examples of the structural unit (a5-1) include the followings.
In formulas (a5-1-1) to (a5-1-18), a structural unit in which a methyl group corresponding to R ⁵¹ is replaced with a hydrogen atom may be mentioned as a specific example of the structural unit (a5-1). it can.

When the resin (A) has the structural unit (a5), its content is preferably 1 to 30 mol%, and preferably 2 to 20 mol% with respect to the total of all structural units of the resin (A). Is more preferable, and 3 to 15 mol% is further preferable.

The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s), that is, a copolymer of the monomer (a1) and the monomer (s).
The structural unit (a1) is preferably at least one selected from the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), and more preferably the structural unit (a1). at least two kinds selected from a1-1) and structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group).
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.

The resin (A) contains the structural unit (particularly the structural unit (a1-1)) derived from the monomer having an adamantyl group in an amount of 15 mol% or more based on the content of the structural unit (a1). preferable. When the content of the structural unit having an adamantyl group is increased, the dry etching resistance of the resist pattern is improved.

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 induces these structural units. can do. The content of each structural unit of the resin (A) can be adjusted by the amount of the monomer used for polymerization.
The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more), 50,000 or less (more preferably 30,000 or less, further preferably). 15,000 or less).
In the present specification, the weight average molecular weight is a value determined by gel permeation chromatography. The gel permeation chromatography can be measured under the analysis conditions described in Examples.

<Resin other than resin (A)>
The resist composition of the present invention may contain a resin other than the resin (A). Examples of the resin other than the resin (A) include a resin composed of the structural unit (s) only. Among them, a resin containing the structural unit (a4) (however, it does not contain the structural unit (a1), and may be hereinafter referred to as “resin (X)”) is preferable.
In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, and more preferably 45 mol% or more, based on the total of all structural units of the resin (X). And more preferably 50 mol% or more.

Examples of the structural unit that the resin (X) may further have include structural units (a2), structural units (a3) and structural units derived from other known monomers.
The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more) and 80,000 or less (more preferably 60,000 or less). The means for measuring the weight average molecular weight of the resin (X) is the same as that for the resin (A).
When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, and further to 100 parts by mass of the resin (A). It is preferably 2 to 40 parts by mass, and particularly preferably 3 to 30 parts by mass.

The total content of the resin (A) and the resins other than the resin (A) is preferably 80% by mass or more and 99% by mass or less, and more preferably 90 to 99% by mass, based on the solid content of the resist composition. 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.

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

As the amine, 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, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, Ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, tri Isopropanolamine, 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 hindered amine compounds having a piperidine skeleton described in JP-A-11-52575, 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)ethane, di(2-pyridyl)ketone, 4,4′-dipyridyl sulfide, 4,4′-dipyridyl disulfide, 2,2′-dipyridylamine , 2,2′-dipicolylamine, bipyridine, and the like, preferably diisopropylaniline, and particularly preferably 2,6-diisopropylaniline.

Examples of ammonium salts include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide and 3-(trifluoromethyl)phenyltrimethyl. Examples thereof include ammonium hydroxide, tetra-n-butylammonium salicylate and choline.

Examples of the salt (a) and the salt that generates an acid having a weaker acidity than the acid generated from the acid generator (B) include salts represented by the following formulas, weak acid intramolecular salts represented by the formula (D), In addition, salts described in JP2012-229206A, JP2012-6908A, JP2012-72109A, JP2011-39502A and JP2011-191745A are also included. A weak acid inner salt represented by the formula (D) (hereinafter sometimes referred to as “weak acid inner salt (D)”) is preferable.
The acidity of a salt that generates an acid having a weaker acidity than the acid generated from the salt (a) and the acid generator (B) is represented by an acid dissociation constant (pKa). The salt that generates an acid having a weaker acidity than the acid generated from the salt (a) 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, The salt is preferably -1<pKa<7, more preferably 0<pKa<5.

[In the formula (D),
R ^D1 and R ^D2 are, independently of each other, a monovalent 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, and an acyloxy group having 2 to 7 carbon atoms. Represents an alkoxycarbonyl group having 2 to 7 carbon atoms, a nitro group or a halogen atom.
m′ and n′ each independently represent an integer of 0 to 4, when m′ is 2 or more, a plurality of R ^D1 may be the same or different, and when n′ is 2 or more, A plurality of R ^D2 may be the same or different. ]

In the weak acid inner salt (D), the hydrocarbon groups of R ^D1 and R ^D2 include a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group and The group etc. which are formed by combining these are mentioned.
Examples of the monovalent aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group and nonyl group.
The monovalent alicyclic hydrocarbon group may be either monocyclic or polycyclic, and may be saturated or unsaturated. Examples thereof include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclononyl group, cyclododecyl group, norbornyl group, adamantyl group and the like.
Examples of the monovalent aromatic hydrocarbon group include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4- Propylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, anthryl group, p-adamantylphenyl group, tolyl group, xylyl group And aryl groups such as cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group, and 2-methyl-6-ethylphenyl.
Examples of the group formed by combining these include an alkyl-cycloalkyl group, a cycloalkyl-alkyl group and an aralkyl group (for example, phenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl- 1-propyl group, 1-phenyl-2-propyl group, 2-phenyl-2-propyl group, 3-phenyl-1-propyl group, 4-phenyl-1-butyl group, 5-phenyl-1-pentyl group, 6-phenyl-1-hexyl group etc.) and the like.

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, a benzoyl group, a cyclohexanecarbonyl group and the like.
Examples of the acyloxy group include groups in which an oxy group (—O—) is bonded to the above acyl group.
Examples of the alkoxycarbonyl group include groups 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 formula (D), R ^D1 and R ^D2 are, independently of each other, 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, and 2 to 2 carbon atoms. It 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 preferably, independently of each other, an integer of 0 to 2, and more preferably 0. When m′ is 2 or more, the plurality of R ^D1 may be the same or different, and when n′ is 2 or more, the plurality of R ^D2 may be the same or different.

The weak acid inner salt (D) includes the following compounds.

The weak acid inner salt (D) can be produced by the method described in "Tetrahedron Vol. 45, No. 19, p6281-6296". As the weak acid inner salt (D), a commercially available compound can be used.

The content of the quencher (C) in the solid content of the resist composition 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. It is% by mass.

<Solvent (E)>
The content of the solvent (E) in the resist composition 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% by mass or less. Is. The content of the solvent (E) can be measured by a known analytical means such as liquid chromatography or gas chromatography.

Examples of the solvent (E) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate. And the like; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; Solvent (E) may contain 1 type independently and may contain 2 or more types.

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

<Preparation of resist composition>
The resist composition includes a resin (A) and a salt (a), and, if necessary, a resin other than the resin (A), an acid generator (B), a solvent (E), a quencher (C), and others. It can be prepared by mixing the component (F). The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can be selected from 10 to 40° C., and an appropriate temperature can be selected depending on the kind of the resin or the like and the solubility of the resin or the like in the solvent (E). As the mixing time, an appropriate 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 the components, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

<Method for manufacturing resist pattern>
The method for producing a resist pattern of the present invention,
(1) a step of applying the resist composition of the present invention onto a substrate,
(2) a step of drying the composition after coating to form a composition layer,
(3) 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 coating of the resist composition on the substrate can be carried out by a commonly used apparatus such as a spin coater. Examples of the substrate include inorganic substrates such as silicon wafers. The substrate may be washed before applying the resist composition, or an antireflection film or the like may be formed on the substrate.

The composition is dried to remove the solvent and form a composition layer. Drying is performed by evaporating the solvent using a heating device such as a hot plate (so-called prebaking) or using a decompression device. The heating temperature is preferably 50 to 200° C., and the heating time is preferably 10 to 180 seconds. The pressure during drying under reduced pressure is preferably about 1 to 1.0×10 ⁵ Pa.

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

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

The composition layer after heating is usually developed using a developing device using a developing solution. 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 manufactured by selecting the type of developer as follows.

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

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

It is preferable to wash the resist pattern after development with a rinse liquid. The rinse 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 preferably an alcohol solvent or an ester solvent can be used.
After the cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

<Use>
The resist composition of the present invention is 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, especially ArF. It is suitable as a resist composition for excimer laser exposure and is useful for fine processing of semiconductors.

A more specific description will be given with reference to examples. In the examples, “%” and “part” representing the content or the 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.
Device: 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 the molecular peak using mass spectrometry (LC is model 1100 manufactured by Agilent, and MASS is LC/MSD manufactured by Agilent). In the following examples, the value of this molecular peak is indicated by "MASS".

Example 1: Synthesis of salt represented by formula (I-1)
19.24 parts of the compound represented by the formula (I-1-a), 57.71 parts of methanol and 6.98 parts of sodium hydroxide were charged, and the mixture was stirred at 23° C. for 30 minutes. Then, a mixed solution of 23.15 parts of the compound represented by the formula (I-1-b) and 46.30 parts of methanol was added dropwise, and the mixture was stirred at 23° C. for 18 hours. The obtained reaction product was concentrated, 150 parts of ethyl acetate and 40 parts of ion-exchanged water were added, and the mixture was stirred at 23° C. for 30 minutes. Then, it left still and liquid-separated. To the recovered organic layer, 40 parts of ion-exchanged water was charged, stirred at 23° C. for 30 minutes, and separated to collect the organic layer. This operation of washing with water was performed three times. The obtained organic layer was concentrated to obtain 35.79 parts of a compound represented by the formula (I-1-c).

10.24 parts of silver oxide and 20.47 parts of acetonitrile were charged, and the mixture was stirred at 23° C. for 30 minutes. Then, 8.49 parts of methanesulfonic acid and 16.98 parts of acetonitrile were added dropwise, and the mixture was stirred at 23° C. for 1 hour. The obtained mixture was charged with 18.22 parts of the compound represented by the formula (I-1-c) and 44.30 parts of acetonitrile, stirred at 23° C. for 30 minutes, and represented by the formula (I-1-d). A mixed solution of 12.54 parts of the compound and 12.54 parts of methanol was added dropwise, and the mixture was stirred at 23° C. for 72 hours. The obtained reaction product was concentrated to obtain 13.07 parts of the salt represented by the formula (I-1-e).

The salt represented by the formula (I-1-f) was synthesized by the method described in JP2007-224008A.
Charge 6.01 parts of the salt represented by the formula (I-1-f) and 61.16 parts of chloroform and stir at 23° C. for 30 minutes to obtain 5.49 of the salt represented by the formula (I-1-e). And 44 parts of ion-exchanged water were charged, and the mixture was stirred at 23° C. for 12 hours. The obtained reaction product was filtered, and the collected filtrate was allowed to stand and separated. To the collected organic layer, 15 parts of ion-exchanged water was charged, and the mixture was stirred at 23° C. for 30 minutes and separated to collect the organic layer. This washing operation was repeated 10 times. The collected organic layer was concentrated, 20 parts of tert-butyl methyl ether was added to the obtained residue, and the mixture was stirred at 23° C. for 30 minutes, the supernatant was removed, and the mixture was concentrated. 5 parts of ethyl acetate and 20 parts of tert-butyl methyl ether were added to the obtained organic layer, and the mixture was stirred, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 4.24 parts of the salt represented by the formula (I-1-g).

4.64 parts of the salt represented by the formula (I-1-g) and 40 parts of 1,2-dichloroethane were charged and stirred at 23° C. for 30 minutes. Thereafter, 5.53 parts of the compound represented by the formula (I-1-h) and 0.30 part of p-toluenesulfonic acid were added, and the mixture was refluxed and stirred at 100° C. for 3 hours. The obtained reaction product was cooled to 23° C., 120 parts of chloroform and 35.4 parts of an 8.7% sodium hydrogen carbonate aqueous solution were added, and the mixture was stirred at 23° C. for 30 minutes. Then, it left still and liquid-separated. To the recovered organic layer, 120 parts of ion-exchanged water was charged, stirred at 23° C. for 30 minutes, and separated to collect the organic layer. This washing operation with water was performed 5 times. The organic layer obtained was charged with 1.00 part of activated carbon, stirred at 23° C. for 30 minutes and filtered. By concentrating the filtrate, 4.42 parts of the salt represented by the formula (I-1) was obtained.
MS (ESI(+) Spectrum): M ⁺ 365.1.
MS (ESI(-) Spectrum): M ^- 467.1.

Example 2: Synthesis of salt represented by formula (I-2)
5.02 parts of the salt represented by the formula (I-2-f) and 10.03 parts of acetonitrile were charged, the mixture was stirred at 23° C. for 30 minutes, and the salt represented by the formula (I-2-e) was 15.00. And 75 parts of deionized water were charged, and the mixture was stirred at 23° C. for 12 hours. The obtained reaction product was filtered, and the collected filtrate was concentrated. To the obtained residue, 40 parts of tert-butyl methyl ether was added, and the mixture was stirred at 23°C for 30 minutes, the supernatant was removed, and the mixture was concentrated. To the obtained organic layer, 3 parts of acetonitrile and 20 parts of tert-butyl methyl ether were added and stirred, and the supernatant liquid was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 8.55 parts of the salt represented by the formula (I-2-g).

6.99 parts of the salt represented by the formula (I-2-g) and 40 parts of 1,2-dichloroethane were charged and stirred at 23°C for 30 minutes. Thereafter, 5.53 parts of the compound represented by the formula (I-2-h) and 0.30 part of p-toluenesulfonic acid were added, and the mixture was refluxed and stirred at 100° C. for 3 hours. The obtained reaction product was cooled to 23° C., 120 parts of chloroform and 35.4 parts of an 8.7% sodium hydrogen carbonate aqueous solution were added, and the mixture was stirred at 23° C. for 30 minutes. Then, it left still and liquid-separated. To the recovered organic layer, 120 parts of ion-exchanged water was charged, stirred at 23° C. for 30 minutes, and separated to collect the organic layer. This washing operation with water was performed 5 times. The organic layer obtained was charged with 1.00 part of activated carbon, stirred at 23° C. for 30 minutes and filtered. By concentrating the filtrate, 5.89 parts of the salt represented by the formula (I-2) was obtained.
MS (ESI(+) Spectrum): M ⁺ 365.1.
MS (ESI(-) Spectrum): M ^- 189.0.

Example 3: Synthesis of salt represented by formula (I-3)
Charge 8.58 parts of the salt represented by the formula (I-2-f) and 20 parts of acetonitrile, stir for 30 minutes at 23° C., and 15.00 parts of the salt represented by the formula (I-3-e) and 75 parts of ion-exchanged water was charged and stirred at 23° C. for 12 hours. After filtering the obtained reaction product, the collected filtrate was concentrated. To the obtained residue, 40 parts of tert-butyl methyl ether was added, and the mixture was stirred at 23°C for 30 minutes, the supernatant was removed, and the mixture was concentrated. To the obtained organic layer, 3 parts of acetonitrile and 20 parts of tert-butyl methyl ether were added and stirred, and the supernatant liquid was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 11.02 parts of the salt represented by the formula (I-3-g).

9.55 parts of the salt represented by the formula (I-3-g) and 40 parts of 1,2-dichloroethane were charged, and the mixture was stirred at 23°C for 30 minutes. Then, 5.53 parts of the compound represented by the formula (I-3-h) and 0.30 part of p-toluenesulfonic acid were added, and the mixture was stirred under reflux at 100°C for 2 hours. The obtained reaction product was cooled to 23° C., 120 parts of chloroform and 35.4 parts of an 8.7% sodium hydrogen carbonate aqueous solution were added, and the mixture was stirred at 23° C. for 30 minutes. Then, it left still and liquid-separated. To the recovered organic layer, 120 parts of ion-exchanged water was charged, stirred at 23° C. for 30 minutes, and separated to collect the organic layer. This washing operation with water was performed 5 times. The organic layer obtained was charged with 1.00 part of activated carbon, stirred at 23° C. for 30 minutes and filtered. By concentrating the filtrate, 6.08 parts of the salt represented by the formula (I-2) was obtained.
MS (ESI(+) Spectrum): M ⁺ 365.1.
MS (ESI(-) Spectrum): M ^- 339.1.

Example 4: Synthesis of salt represented by formula (I-4-a)
2.70 parts of the salt represented by the formula (I-1-e) and 40 parts of 1,2-dichloroethane were charged and stirred at 23° C. for 30 minutes. Then, 2.77 parts of the compound represented by the formula (I-1-h) and 0.15 part of p-toluenesulfonic acid were added, and the mixture was stirred under reflux at 100° C. for 3 hours. The obtained reaction product was cooled to 23° C., 50 parts of chloroform and 17.7 parts of an 8.7% sodium hydrogen carbonate aqueous solution were added, and the mixture was stirred at 23° C. for 30 minutes. Then, it left still and liquid-separated. To the recovered organic layer, 50 parts of ion-exchanged water was charged, stirred at 23° C. for 30 minutes, and separated to collect the organic layer. This washing operation with water was performed 5 times. By concentrating the obtained organic layer, 2.75 parts of the salt represented by the formula (I-4-a) was obtained.

Example 5: Synthesis of salt represented by formula (I-4)
Charge 2.00 parts of the salt represented by the formula (I-1-f) and 20.39 parts of chloroform, stir at 23° C. for 30 minutes, and then the salt represented by the formula (I-4-a) 2.66. And 17 parts of deionized water were charged, and the mixture was stirred at 23° C. for 12 hours. The obtained reaction product was filtered, and the collected filtrate was allowed to stand and separated. The recovered organic layer was charged with 15 parts of ion-exchanged water, stirred at 23° C. for 30 minutes, and separated to collect the organic layer. This washing operation with water was performed 5 times. The recovered organic layer was concentrated, 20 parts of tert-butyl methyl ether was added to the obtained residue, and the mixture was stirred at 23° C. for 30 minutes, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 2.98 parts of the salt represented by the formula (I-4).
MS (ESI(+) Spectrum): M ⁺ 365.1.
MS (ESI(-) Spectrum): M ^- 323.0

Example 6: Synthesis of salt represented by formula (I-5)
2.21 parts of lithium aluminum hydride was added to 10 parts of tetrahydrofuran at 5° C., and the mixture was stirred at 5° C. for 30 minutes. Then, a mixed solution of 8.22 parts of the compound represented by the formula (I-5-a) and 30 parts of tetrahydrofuran was added dropwise thereto over 1 hour, and the mixture was further stirred at 23° C. for 18 hours. The obtained reaction product was charged with 30 parts of 1N hydrochloric acid and concentrated. To the recovered concentrate, 82 parts of acetonitrile was added, stirred, filtered, and the obtained filtrate was concentrated to obtain 6.28 parts of a compound represented by the formula (I-5-b).
13.25 parts of the compound represented by the formula (I-5-c) and 40 parts of acetonitrile were added, and the mixture was stirred at 23°C for 30 minutes. 11.63 parts of the compound represented by the formula (I-5-d) was added to the obtained mixed solution, and the mixture was further stirred at 40°C for 1 hr. A mixed solution of 6.28 parts of the compound represented by the formula (I-5-b) and 13.20 parts of acetonitrile was added to the obtained reaction mass, and the mixture was further stirred at 23° C. for 16 hours. To the obtained reaction product, 30 parts of acetonitrile was added and stirred, filtered, and the obtained filtrate was concentrated to obtain 9.06 parts of the compound represented by the formula (I-5-e).
0.91 part of the compound represented by formula (I-5-e), 1.57 part of the compound represented by formula (I-4-a), 2 parts of acetonitrile, 10 parts of chloroform and 5% aqueous oxalic acid solution 3 0.14 parts was added, and the mixture was stirred at 23° C. for 2 hours. The obtained reaction solution was separated. To the recovered organic layer, 2 parts of a 5% oxalic acid aqueous solution was added, and the mixture was stirred at 23° C. for 30 minutes, separated, and the organic layer was taken out. To the collected organic layer, 2 parts of a 5% sodium hydrogen carbonate aqueous solution was added, and the mixture was stirred at 23° C. for 30 minutes, separated, and the organic layer was taken out. 5 parts of ion-exchanged water was added to the collected organic layer, and the mixture was stirred at 23° C. for 30 minutes, separated, and the organic layer was taken out. This water washing operation was repeated 3 times. The collected organic layer was concentrated, 5 parts of tert-butyl methyl ether was added to the obtained residue, and the mixture was stirred at 23° C. for 30 minutes, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to obtain 1.22 parts of the compound represented by the formula (I-5).
MASS (ESI(+) Spectrum): M ⁺ 365.1
MASS (ESI (-) Spectrum): M ^- 337.1

Example 7: Synthesis of salt represented by formula (I-6)
1.06 parts of the compound represented by formula (I-5), 0.37 part of the compound represented by formula (I-6-a) and 10 parts of 1,2-dichloroethane are added, and the mixture is added at 23° C. for 30 minutes. It was stirred. 0.01 parts of p-toluenesulfonic acid was added to the obtained mixed solution, and the mixture was stirred under reflux at 100° C. for 3 hours. The obtained reaction product was cooled to 23° C., 15 parts of chloroform and 5 parts of a 5% sodium hydrogen carbonate aqueous solution were added, and the mixture was stirred at 23° C. for 30 minutes. Then, it left still and liquid-separated. The recovered organic layer was charged with 10 parts of ion-exchanged water, stirred at 23° C. for 30 minutes, and separated to collect the organic layer. This washing operation with water was performed 5 times. The collected organic layer was concentrated, 5 parts of tert-butyl methyl ether was added to the obtained residue, and the mixture was stirred at 23° C. for 30 minutes, and the supernatant was removed. The obtained residue was dissolved in acetonitrile and concentrated to give 0.92 part of the compound represented by the formula (I-6).
MASS (ESI(+) Spectrum): M ⁺ 365.1
MASS (ESI (-) Spectrum): M ^- 481.1

Synthesis Example 1: Synthesis of salt represented by formula (B1-5)
50.49 parts of the salt represented by the formula (B1-5-a) and 252.44 parts of chloroform were charged into a reactor and stirred at 23° C. for 30 minutes to obtain a compound represented by the formula (B1-5-b). 16.27 parts was added dropwise, and the mixture was stirred at 23° C. for 1 hour to obtain a solution containing a salt represented by the formula (B1-5-c). To the obtained solution containing the salt represented by the formula (B1-5-c), 48.80 parts of the salt represented by the formula (B1-5-d) and 84.15 parts of ion-exchanged water were added, The mixture was stirred at 23°C for 12 hours. Since the obtained reaction liquid was separated into two layers, the chloroform layer was separated and taken out, and further 84.15 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. To the obtained chloroform layer, 3.88 parts of activated carbon was added, stirred and filtered. The collected filtrate was concentrated, and 125.87 parts of acetonitrile was added to the obtained residue and stirred to be concentrated. To the obtained residue, 20.62 parts of acetonitrile and 309.30 parts of tert-butyl methyl ether were added, and the mixture was stirred at 23° C. for 30 minutes, the supernatant was removed, and the mixture was concentrated. To the obtained residue, 200 parts of n-heptane was added, stirred at 23° C. for 30 minutes, and filtered to obtain 61.54 parts of the salt represented by the formula (B1-5).

MASS (ESI (+) Spectrum): M ⁺ 375.2
MASS (ESI (-) Spectrum): M ^- 339.1

Synthesis Example 2: Synthesis of salt represented by formula (B1-21)
30.00 parts of a compound represented by the formula (B1-21-b) obtained by the method described in JP 2008-209917 A, a salt represented by the formula (B1-21 -a) 35.50. Parts, 100 parts of chloroform and 50 parts of deionized water were charged and stirred at 23° C. for 15 hours.
Since the obtained reaction liquid was separated into two layers, the chloroform layer was separated and taken out, and further 30 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer was concentrated, 100 parts of tert-butyl methyl ether was added to the obtained residue, the mixture was stirred at 23° C. for 30 minutes, and filtered to give the salt of the formula (B1-21-c) 48. 57 parts were obtained.

20.00 parts of the salt represented by the formula (B1-21-c), 2.84 parts of the compound represented by the formula (B1-21-d) and 250 parts of monochlorobenzene were charged, and the mixture was stirred at 23° C. for 30 minutes. ..
0.21 part of copper(II) dibenzoate was added to the obtained mixed liquid, and the mixture was further stirred at 100° C. for 1 hour. The obtained reaction solution was concentrated, 200 parts of chloroform and 50 parts of ion-exchanged water were added to the obtained residue, and the mixture was stirred at 23° C. for 30 minutes. Then, liquid separation was performed and the organic layer was taken out. 50 parts of ion-exchanged water was added to the collected organic layer, the mixture was stirred at 23° C. for 30 minutes, and liquid-separated to take out the organic layer. This water washing operation was repeated 5 times. The obtained organic layer was concentrated, and the obtained residue was dissolved in 53.51 parts of acetonitrile and concentrated. Thereafter, 113.05 parts of tert-butyl methyl ether was added, stirred, and filtered to obtain 10.47 parts of the salt represented by the formula (B1-21).

MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 339.1

Synthesis Example 3: Synthesis of salt represented by formula (B1-22)
11.26 parts of the salt represented by the formula (B1-22-a), 10.00 parts of the compound represented by the formula (B1-22-b), 50 parts of chloroform and 25 parts of deionized water were charged, and the temperature was 23°C. It was stirred for 15 hours. Since the obtained reaction liquid was separated into two layers, the chloroform layer was separated and taken out, and further 15 parts of ion-exchanged water was added to the chloroform layer and washed with water. This operation was repeated 5 times. The chloroform layer was concentrated, 50 parts of tert-butyl methyl ether was added to the obtained residue, the mixture was stirred at 23° C. for 30 minutes, and filtered to obtain a salt represented by the formula (B1-22-c). Obtained 75 parts.

11.71 parts of the salt represented by the formula (B1-22-c), 1.70 parts of the compound represented by the formula (B1-22-d) and 46.84 parts of monochlorobenzene were charged, and the mixture was heated at 23° C. for 30 minutes. It was stirred. After adding 0.12 part of copper(II) dibenzoate to the obtained mixed liquid, the mixture was further stirred at 100° C. for 30 minutes. The obtained reaction solution was concentrated, 50 parts of chloroform and 12.50 parts of ion-exchanged water were added to the obtained residue, the mixture was stirred at 23° C. for 30 minutes, and then separated, and the organic layer was taken out. 12.50 parts of ion-exchanged water was added to the collected organic layer, the mixture was stirred at 23° C. for 30 minutes, and liquid-separated to take out the organic layer. This water washing operation was repeated 8 times. The obtained organic layer was concentrated. Then, 50 parts of tert-butyl methyl ether was added to the obtained residue, and the mixture was stirred and filtered to obtain 6.84 parts of a salt represented by the formula (B1-22).

MASS (ESI (+) Spectrum): M ⁺ 237.1
MASS (ESI (-) Spectrum): M ^- 323.0

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

Synthesis Example 4: Synthesis of Resin A1 As the monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (a2-1-3) and a monomer (a3-4-2) are used. The molar ratio [monomer (a1-1-3):monomer (a1-2-9):monomer (a2-1-3):monomer (a3-4-2)] was 45:14:2.5:38. The mixture was mixed so as to be 5, and propylene glycol monomethyl ether acetate in an amount of 1.5 times the total amount of the monomers was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in an amount of 1 mol% and 3 mol% based on the total amount of the monomers, respectively, and these were heated at 73° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol/water to precipitate a resin, and the resin was filtered. The resin thus obtained is again dissolved in propylene glycol monomethyl ether acetate, the solution obtained is poured into a mixed solvent of methanol/water to precipitate the resin, and the resin is filtered again to perform reprecipitation operation twice. Resin A1 having a molecular weight of 7.6×10 ³ was obtained with a yield of 68%. This resin A1 has the following structural units.

Synthesis Example 5: Synthesis of Resin X1 As the monomer, the monomer (a4-1-7) was used, and methyl isobutyl ketone in an amount of 1.5 times the total amount of the monomer was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in an amount of 0.7 mol% and 2.1 mol% with respect to the total amount of monomers, respectively, and these were added at 75°C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of a mixed solvent of methanol/water to precipitate a resin, and the resin was filtered. The obtained resin is again dissolved in dioxane, the solution obtained is poured into a methanol/water mixed solvent to precipitate the resin, and the resin is filtered again to perform reprecipitation operation twice, and a weight average molecular weight of 1.7. Resin X1 of ×10 ⁴ was obtained with a yield of 77%. This resin X1 has the following structural units.

Synthesis Example 6: Synthesis of Resin X2 The monomer (a4-0-12) was used as a monomer, and methyl isobutyl ketone in an amount of 1.5 times the total amount of the monomer was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as initiators in an amount of 0.7 mol% and 2.1 mol% with respect to the total amount of monomers, respectively, 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 a resin, and the resin was filtered to obtain a resin X2 having a weight average molecular weight of 1.5×10 ⁴ with a yield of 77%. This resin X2 has the following structural units.

Synthesis Example 7: Synthesis of Resin X3 As the monomer, a monomer (a5-1-1) and a monomer (a4-0-12) were used, and the molar ratio thereof was [monomer (a5-1-1): monomer (a4-0-). 12)] was mixed at 50:50, and 1.2 mass times of the total amount of monomers was added to prepare methyl isobutyl ketone. Azobis(2,4-dimethylvaleronitrile) as an initiator was added to this solution in an amount of 3 mol% based on the total amount of the monomers, and the mixture was heated at 70° C. for about 5 hours. The obtained reaction mixture was poured into a large amount of a methanol/water mixed solvent to precipitate a resin, and the resin was filtered to obtain a resin X having a weight average molecular weight of 1.0×10 ^{4 in} a yield of 91%. This resin X3 has the following structural units.

<Preparation of resist composition>
As shown in Table 1, the following components were mixed, and the resulting mixture was filtered through a fluororesin filter having a pore size of 0.2 μm to prepare a resist composition.

<Resin>
A1, X1 to X3: Resin A1, Resin X1 to Resin X3
<Acid generator>
I-1: Salt represented by formula (I-1) I-2: Salt represented by formula (I-2) I-3: Salt represented by formula (I-3) I-4: Formula Salt represented by (I-4) I-5: Salt represented by formula (I-5) I-6: Salt represented by formula (I-7) B1-5: Formula (B1-5) B1-21: a salt represented by formula (B1-21) B1-22: a salt represented by formula (B1-22) B1-X: according to the examples of JP2012-97074A Synthesis
<Compound (D)>
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

<Production of resist pattern and its evaluation>
A silicon wafer is coated with a composition for organic antireflection film (ARC-29; manufactured by Nissan Chemical Co., Ltd.) and baked at 205° C. for 60 seconds to give an organic reflection film having a film thickness of 78 nm on the wafer. The prevention film was formed. Next, the above resist composition was applied (spin-coated) on the organic antireflection film so that the film thickness after drying was 85 nm. After the coating, the silicon wafer was prebaked on the direct hot plate at the temperature described in the "PB" column of Table 1 for 60 seconds to form a composition layer. A contact hole pattern (hole pitch 90 nm) was formed on a silicon wafer on which the composition layer was formed, using an ArF excimer stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA=1.35, 3/4 Annular XY polarized light). /Hole diameter 55 nm) was used, and the exposure amount was changed stepwise using the mask for exposure. Ultrapure water was used as the immersion medium.
After exposure, post-exposure bake was performed for 60 seconds on the hot plate at the temperature described in the "PEB" column of Table 1. Then, the composition layer on the silicon wafer was developed by butyl acetate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a developing solution at 23° C. for 20 seconds by a dynamic dispensing method to form a negative resist pattern. Manufactured.

In the resist pattern obtained after development, the exposure amount at which the hole diameter formed using the mask becomes 50 nm was defined as the effective sensitivity.

<CD uniformity (CDU) evaluation>
In terms of effective sensitivity, the hole diameter of a pattern formed by a mask having a hole diameter of 55 nm was measured 24 times for each hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was calculated by using the population obtained by measuring the average hole diameter of the pattern formed by the mask with the hole diameter of 70 nm in the same wafer at 400 points,
When the standard deviation is less than 1.65 nm, it is evaluated as showing a very good CDU, and "◎" is given.
When the standard deviation is 1.65 nm or more and 1.80 nm or less, it is evaluated as showing a good CDU, and “◯” is given.
When the standard deviation was larger than 1.80 nm, the CDU was evaluated to be insufficient, and was designated as "x". The results are shown in Table 2.

From the above results, it can be seen that the resist composition of the present invention has good CD uniformity (CDU).

The salt, acid generator and resist composition of the present invention have good CD uniformity (CDU) and are useful for fine processing of semiconductors.

Claims (15)

A salt having a cation represented by formula (aa33), which has a group represented by formula (aa) in the cation .
[In Formula (aa) and Formula (aa33) ,
X ^a and X ^b each independently represent an oxygen atom or a sulfur atom.
X ¹ represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms and having at least one fluorine atom .
The ring W represents an alicyclic hydrocarbon group having 3 to 36 carbon atoms, and the methylene group contained in the alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a carbonyl group or a sulfonyl group. Well, the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a hydroxy group or a hydrocarbon group having 1 to 12 carbon atoms, and the methylene group contained in the hydrocarbon group is an oxygen atom or It may be substituted with a carbonyl group.
X represents a sulfur atom or an iodine atom.
m represents an integer of 0 or 1.
When X is a sulfur atom, m is 1, and when X is an iodine atom, m is 0.
R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or R ³ and R ⁴ together with the sulfur atom to which they are bonded are It may form a heterocycle.
L represents a divalent hydrocarbon group of a single bond or a 1 to 24 carbon atoms, -CH ₂ contained in the hydrocarbon group - may be replaced by -O- or -CO-.
* Represents a bond. ] Luke thione represented by the formula (aa33) are salt according to claim 1, wherein a cation having a group represented by the formula (Ia).
[In the formula (Ia),
Rings W and * have the same meanings as above.
R ^f1 and R ^f2 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms.
n represents an integer of 1 to 10. When n is 2 or more, a plurality of R ^f1 and R ^f2 may be the same or different. ] The salt according to claim 1 or 2 , wherein the ring W is a ring represented by the formula (Iaa-1), a ring represented by the formula (Iaa-2) or a ring represented by the formula (Iaa-3).
[In Formula (Iaa-1), Formula (Iaa-2), and Formula (Iaa-3),
The methylene group contained in the ring may be substituted with an oxygen atom, a sulfur atom, a carbonyl group or a sulfonyl group, and the hydrogen atom contained in the ring may be substituted with a hydroxy group or a hydrocarbon group having 1 to 12 carbon atoms. Alternatively, the methylene group contained in the hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. ] Salts having represented Luke thione by the formula (aa33) are salt according to any one of claims 1 to 3 is a salt having a cation represented by the formula (aa3).
[In the formula (aa3), X ^a , X ^b , X ¹ and W have the same meanings as described above.
X represents a sulfur atom or an iodine atom.
m represents an integer of 0 or 1.
When X is a sulfur atom, m is 1, and when X is an iodine atom, m is 0.
R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, or R ³ and R ⁴ together with the sulfur atom to which they are bound are It may form a heterocycle. ] Anion salt according to any one of claims 1-4 is an organic anion. Anion salt according to any one of claims 1-5 is an anion of the formula (I-A).
[In formula (IA), Q ¹ and Q ² each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms.
L ^b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group may be replaced with —O— or —CO—. The hydrogen atom contained in the hydrogen group may be substituted with a fluorine atom or a hydroxy group.
Y represents a saturated hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, _-CH 2 contained in the saturated hydrocarbon group - is -O -, - S -, - SO ₂ -Or-CO- may be substituted. ] A group represented by the formula (aa), independently of one another, salts of any of claims 1-6 having the cations and anions.
[In the formula (aa),
X ^a , X ^b , X ¹ and * have the same meanings as described above. ] The salt according to claim 6 or 7 , wherein the anion is an anion represented by formula (aa2).
[In the formula (aa2),
Q ¹ , Q ² , L ^b1 , X ^a , X ^b , X ¹ and W have the same meanings as described above. ] L ^b1 _{is, * - CO-O- (CH} 2) t - or _* -CH 2 is -O-CO-, t represents an integer of 0 to 6, and *, -C ^(Q 1) ^{(Q 2} ) A salt according to claim 6 or 8, which represents a bond with (-). Acid generator containing, as an active ingredient a salt according to any one of claims 1-9. A resist composition comprising the acid generator according to claim 10 and a resin containing a structural unit having an acid labile group. The resist composition according to claim 11 , further comprising an acid generator represented by formula (B1).
[In the formula (B1),
Q ¹ , Q ² , L ^b1 and Y have the same meanings as described above.
Z ⁺ represents an organic cation. However, Z ⁺ does not include a group represented by the formula (aa). ] The resist composition according to claim 11 , further comprising a resin containing a structural unit having a fluorine atom. The resist composition according to any one of claims 11 to 13 , further comprising a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. (1) A step of applying the resist composition according to any one of claims 11 to 14 onto a substrate,
(2) a step of drying the composition after coating to form a composition layer,
(3) exposing the composition layer
A method for producing a resist pattern, which comprises (4) a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating.