KR102370244B1 - Salt, acid generator, resist composition and method for producing resist pattern - Google Patents

Abstract

[식 (I) 중,
R¹ 및 R²는, 각각 독립적으로, 치환기를 가져도 되는 탄소수 6∼18의 방향족 탄화수소기를 나타낸다.
R³은, 산 불안정기를 나타낸다.
X¹은, 탄소수 1∼12의 2가의 지방족 포화 탄화수소기를 나타내고, 당해 2가의 지방족 포화 탄화수소기를 구성하는 메틸렌기는, 산소 원자 또는 카르보닐기로 치환되어 있어도 된다.
A^-는, 유기 아니온을 나타낸다.]A salt represented by formula (I).

[In formula (I),
R ¹ and R ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.
R ³ represents an acid labile group.
X ¹ represents a divalent saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and the methylene group constituting the divalent saturated aliphatic hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.
A ^- represents an organic anion.]

Description

Salt, acid generator, resist composition, and method for producing a resist pattern {SALT, ACID GENERATOR, RESIST COMPOSITION AND METHOD FOR PRODUCING RESIST PATTERN}

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

Japanese Unexamined Patent Application Publication No. 2010-44347 describes a resist composition containing a salt represented by the following formula as an acid generator.

Japanese Patent Laid-Open No. 2013-47209 discloses a resist composition each containing a salt represented by the following formula as an acid generator.

The present invention includes the following inventions.

[1] A salt represented by formula (I).

[In formula (I),

R ¹ and R ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.

R ³ represents a group having an acid labile group.

X ¹ represents a divalent saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and the methylene group constituting the divalent saturated aliphatic hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. A ^- represents an organic anion.]

[2] X ¹ in the formula (I) is -X ¹² -OX ²² -* (X ¹² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the methylene group constituting the divalent aliphatic hydrocarbon group is an oxygen atom or may be substituted with a carbonyl group. X ²² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. However, the total number of carbon atoms in X ¹² and X ²² is 11. * represents a bond with R ³ .) The salt according to [1], wherein the group represented by

[3] The salt according to [1] or [2], wherein R ¹ and R ² in the formula (I) are each independently a phenyl group which may have a substituent.

[4] The salt according to any one of [1] to [3], wherein R ³ in the formula (I) is a group that forms a hydroxy group or a carboxy group by releasing a leaving group when contacted with an acid.

[5] The salt according to any one of [1] to [4], wherein R ³ of the formula (I) is a group represented by the formula (1).

[In formula (1), R ^a1 to R ^a3 each independently represent an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^a1 and R ^a2 is bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.

ma and na each independently represent 0 or 1, and at least one of ma and na is 1.

* indicates a bonding hand.]

[6] The salt according to [5], wherein ma of the formula (1) is 0 and na is 1.

[7] An acid generator containing the salt according to any one of [1] to [6].

[8] A resist composition comprising an acid generator and a resin comprising a structural unit having an acid labile group, and comprising the salt according to any one of [1] to [6] as the acid generator.

[9] The resist composition according to [8], further comprising a salt that generates an acid having a lower acidity than the acid generated from the acid generator.

[10] (1) a step of applying the resist composition according to [8] or [9] on a substrate;

(2) drying the composition after application to form a composition layer;

(3) exposing the composition layer;

(4) heating the composition layer after exposure, and

(5) a step of developing the composition layer after heating;

A method of manufacturing a resist pattern comprising a.

In this specification, a "(meth)acrylic-type monomer" means at least 1 sort(s) of the monomer which has a structure of "CH2=CH _- CO-" or "CH2 _{= C} (CH3)-CO-". Similarly, "(meth)acrylate" and "(meth)acrylic acid" mean "at least 1 type of acrylate and methacrylate" and "at least 1 type of acrylic acid and methacrylic acid", respectively.

In the present specification, "the solid content of the resist composition" means the total amount of components excluding the solvent (E), which will be described later, from the total amount of the resist composition.

The resist composition of the present invention contains a resin (A) having an acid labile group and a salt represented by the formula (I) (hereinafter referred to as “salt (I)” in some cases). In the resist composition, salt (I) is contained as an acid generator.

The acid generator of this invention contains salt (I), and may contain acid generators (B) other than salt (I). The resist composition of the present invention may, if necessary, be higher than the acid generated from the resin (X) other than the resin (A), the solvent (E), the solvent (C), the salt (I) and the acid generator (B). It contains a salt which generates an acid with low acidity, and other component (F). Hereinafter, these are demonstrated.

<Salt Represented by Formula (I)>

The salt of the present invention is a salt (salt (I)) represented by formula (I).

[In formula (I),

R ¹ and R ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent.

R ³ represents an acid labile group.

X ¹ represents a divalent saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and the methylene group constituting the divalent saturated aliphatic hydrocarbon group may be substituted with an oxygen atom or a carbonyl group.

A ^- represents an organic anion.]

In the formula (I), when -CH ₂ - contained in the aliphatic saturated hydrocarbon group is substituted with -O- or -C(=O)-, the number of carbon atoms before substitution is the number of carbon atoms in the aliphatic saturated hydrocarbon group.

<Cathion constituting formula (I)>

Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ¹ and R ² include aryl groups such as a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group and a fluorenyl group, a phenyl group, a naphthyl group, and An anthryl group is preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is still more preferable.

Examples of the substituent which the aromatic hydrocarbon group having 6 to 18 carbon atoms for R ¹ and R ² may have include a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and The group which combined these is mentioned.

Examples of the alkyl group having 1 to 12 carbon atoms 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 nonyl group, a decyl group, an undecyl group, and a dodecyl group.

Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, and an unde. A siloxy group, a dodecyloxy group, etc. are mentioned.

Examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include groups shown below. * is a bond with a ring.

Among these substituents, it is preferably a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, more preferably a hydroxyl group or an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 12 carbon atoms, A C1-C6 alkyl group is still more preferable.

The aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent represented by R ¹ and R ² is preferably a phenyl group.

<Acid unstable phase>

R ³ represents an acid labile group. The "acid labile group" means a group that has a leaving group and forms a hydrophilic group (eg, a hydroxy group, a carboxy group, or an amino group) when the leaving group is released when contacted with an acid.

In the acid labile group represented by R ³ , the atom bonded to X ¹ is usually an oxygen atom or a carbon atom constituting the carbonyl group.

Examples of the acid-labile group include a group represented by the formula (1) (hereinafter referred to as “acid-labile group (1)” in some cases), a group represented by the formula (2) (hereinafter sometimes referred to as “ acid labile group (2)"), and the like.

[In formula (1), R ^a1 to R ^a3 each independently represent an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ^a1 and R ^a2 combine with each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.

ma and na each independently represent 0 or 1, and at least one of ma and na is 1.

* indicates a bonding hand.]

[In formula (2), R ^{a1 '} and R ^{a2 '} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R ^{a3 '} represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^{a2 '} and R ^a3' combine with each other to form a heterocycle having 3 to 20 carbon atoms together with the carbon atom and X to which they are bonded, and the non-aromatic hydrocarbon ring and the methylene group contained in the heterocycle may be substituted with an oxygen atom or a sulfur atom do.

X represents an oxygen atom or a sulfur atom.

na' represents 0 or 1.

* indicates a bonding hand.]

Examples of the alkyl group represented by R ^a1 to R ^a3 include a methyl group, an ethyl group, a propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group.

The alicyclic hydrocarbon group represented by R ^a1 to R ^a3 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond). The carbon number of the alicyclic hydrocarbon group of R ^a1 to R ^a3 is preferably 3 to 16.

As a substituent of the C1-C8 alkyl group which may have a substituent, a C3-C20 alicyclic hydrocarbon group is mentioned. As a substituent of the C3-C20 alicyclic hydrocarbon group which may have a substituent, a C1-C8 alkyl group is mentioned. More specifically, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, norbornylethyl group etc. are mentioned.

Preferably, ma is 0 and na is 1.

-C(R ^a1 )(R ^a2 )(R ^a3 ) when R ^a1 and R ^a2 combine with each other to form a non-aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring and a polycyclic non-aromatic hydrocarbon ring , and specifically, the following ring is mentioned. The non-aromatic hydrocarbon ring preferably has 3 to 12 carbon atoms. * represents a bond with -O-.

As the group represented by formula (1), in formula (1), R ^a1 to R ^a3 are an alkyl group (preferably a tert-butoxycarbonyl group), and in formula (1), R ^a1 and R ^a2 are bonded to each other to form an adamantane ring together with the carbon atom to which they are bonded, a group in which R ^a3 is an alkyl group, a group in which R ^a1 and R ^a2 in the formula (1) are an alkyl group, and a group in which R ^a3 is an adamantyl group; can

Examples of the hydrocarbon group for R ^{a1 ′} to R ^{a3 ′} include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group formed by combining these groups.

Examples of the alkyl group and the alicyclic hydrocarbon group are the same as those described above.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a biphenyl group, and a phenane group. Aryl groups, such as a toryl group, a 2, 6- diethylphenyl group, and 2-methyl-6-ethylphenyl group, etc. are mentioned.

Examples of the heterocycle formed by bonding R ^{a2 ′} and R ^{a3 ′} together with the carbon atom and X to which they are bonded include the following rings. * represents a bond.

It is preferable that at least one of R ^{a1 '} and R ^{a2 '} is a hydrogen atom.

Specific examples of the acid labile group (1) include the following groups. * indicates a bond.

Specific examples of the acid labile group (2) include the following groups. * indicates a bond.

The acid-labile group represented by R ³ is preferably a group having an acid-labile group (1), and R ^a1 and R ^a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded. more preferably, R ^a1 and R ^a2 are bonded to each other to form a polycyclic non-aromatic hydrocarbon ring together with the carbon atom to which they are bonded, and R ^a1 and R ^a2 are bonded to each other to form a It is more preferable to form an adamantane ring together with a carbon atom.

Examples of the divalent aliphatic saturated hydrocarbon group represented by X ¹ include an alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and a combination of two or more of these 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 alkanediyl groups such as diaries;

Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group;

Monocyclic 2 that is a cycloalkanediyl group such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a cyclooctane-1,5-diyl group a valent alicyclic saturated hydrocarbon group;

polycyclic divalent groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group An alicyclic saturated hydrocarbon group etc. are mentioned.

The methylene group constituting the aliphatic saturated hydrocarbon group of X ¹ may be substituted with an oxygen atom or a carbonyl group, for example, an ether bond, an ester bond (-CO-O- or -O-CO-) and -O-CO- It may be an aliphatic saturated hydrocarbon group substituted with O or the like.

Group represented by X ¹ WHEREIN: A methylene group couple|bonds with R ³ normally.

Specifically, X ¹ is -X ¹² -OX ²² -* (X ¹² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the methylene group constituting the divalent aliphatic hydrocarbon group is substituted with an oxygen atom or a carbonyl group, X ²² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, with the proviso that the total number of carbon atoms of X ¹² and X ²² is 11. * represents a bond with R ³ ). desirable.

The divalent aliphatic hydrocarbon group represented by X ¹² and X ²² is preferably an alkanediyl group, and more preferably an alkanediyl group having 1 to 6 carbon atoms.

Specific examples of the organic cation constituting the salt (I) include organic cations represented by the following formulas (I-c-1) to (I-c-24).

The cation (I) is preferably a cation represented by a formula (Ic-1) to a formula (Ic-20), and more preferably a cation represented by a formula (Ic-1) to a formula (Ic-14). and a cation represented by a formula (Ic-1), a formula (Ic-2), or a formula (Ic-7) is more preferable.

<Organic anions constituting salt (I)>

Examples of the organic anion (A ^- ) constituting the salt (I) include a sulfonic acid anion, a sulfonylimide anion, a sulfonylmethide anion and a carboxylic acid anion. Among these, a sulfonic acid anion is preferable, and the sulfonic acid anion represented by Formula (IA) is more preferable.

[In formula (I-A),

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, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group is fluorine It may be substituted with an atom or a hydroxyl group.

Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -SO ₂ - or -CO - may be substituted.]

In Formula (IA), when -CH ₂ - contained in a saturated hydrocarbon group or an alicyclic hydrocarbon group is substituted with -O-, -C(=O)- or -SO ₂ -, the number of carbon atoms before substitution is each Let it be the carbon number of the said saturated hydrocarbon group and the said alicyclic hydrocarbon group.

Examples of the perfluoroalkyl group for Q ¹ and Q ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, A perfluoro tert-butyl group, a perfluoropentyl group, a perfluorohexyl group, etc. are mentioned.

It is preferable that Q< ¹ > and Q< ² > are mutually independently a fluorine atom or a trifluoromethyl group, and it is more preferable that both are a fluorine atom.

Examples of the divalent saturated hydrocarbon group for L ^b1 include a straight-chain or branched alkanediyl group and a monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group, and may be a group formed by combining two or more of these groups. .

Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1, 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group Diyl, 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 straight-chain alkanediyl groups such as diaries;

Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- branched alkanediyl groups such as 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4-diyl group;

Monocyclic 2 that is a cycloalkanediyl group such as a cyclobutane-1,3-diyl group, a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, and a cyclooctane-1,5-diyl group a valent alicyclic saturated hydrocarbon group;

polycyclic divalent groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, and adamantane-2,6-diyl group An alicyclic saturated hydrocarbon group etc. are mentioned.

As a group in which -CH ₂ - contained in the divalent saturated hydrocarbon group of L ^b1 is substituted with -O- or -CO-, for example, a group represented by any of formulas (b1-1) to (b1-3) can be lifted On the other hand, in formulas (b1-1) to (b1-3) and the following specific examples, * represents a bond with -Y.

[In formula (b1-1),

L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.

L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group, and -CH ₂ - contained in the saturated hydrocarbon group is , -O- or -CO- may be substituted.

However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.

In formula (b1-2),

L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.

L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group, and -CH ₂ - contained in the saturated hydrocarbon group is , -O- or -CO- may be substituted.

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 hydroxyl group.

L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group, and -CH ₂ - contained in the saturated hydrocarbon group is , -O- or -CO- may be substituted.

However, the total carbon number of L ^b6 and L ^b7 is 23 or less.]

In the formulas (b1-1) to (b1-3), when -CH ₂ - contained in the saturated hydrocarbon group is substituted with -O- or -CO-, the number of carbon atoms before substitution is the number of carbon atoms in the saturated hydrocarbon group. do it with

Examples of the divalent saturated hydrocarbon group and the group in which -CH ₂ - or hydrogen atom contained in the saturated hydrocarbon group may be substituted as described above include the same groups as the divalent saturated hydrocarbon group of L ^b1 .

L ^b2 is preferably a single bond.

L ^b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, more 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, a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom, more preferably an alkanediyl group having 1 to 4 carbon atoms .

L ^b5 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond.

L ^b6 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.

L ^b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group, and contained in the divalent saturated hydrocarbon group - CH ₂ - may be substituted with -O- or -CO-.

The group in which -CH ₂ - contained in the divalent saturated hydrocarbon group of L ^b1 is substituted with -O- or -CO- is preferably a group represented by formula (b1-1) or (b1-2), In b1-1), L ^b2 is a single bond, L ^b3 is an alkanediyl group having 1 to 4 carbon atoms, and in formula (b1-2), L ^b4 is an alkanediyl group having 1 to 4 carbon atoms, and L The group in which ^b5 is a single bond is more preferable.

Examples of the formula (b1-1) include groups represented by any of the formulas (b1-4) to (b1-8).

[In 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 hydroxyl 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 a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl 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 a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl 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 a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group.

However, the total carbon number of L ^b13 to 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 divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group.

However, the total number of carbon atoms in L ^b16 to L ^b18 is 19 or less.]

L ^b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

L ^b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L ^b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L ^b11 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L ^b12 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L ^b13 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.

L ^b14 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.

L ^b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 8 carbon atoms.

L ^b16 is preferably a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.

L ^b17 is preferably a divalent saturated hydrocarbon group having 1 to 6 carbon atoms.

L ^b18 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, more preferably a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

As formula (b1-3), group represented by any of formulas (b1-9) - formula (b1-11) is mentioned.

[In formula (b1-9),

L ^b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.

L ^b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. -CH ₂ - contained in the alkylcarbonyloxy group may be substituted with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxyl 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 a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.

L ^b22 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. -CH ₂ - contained in the alkylcarbonyloxy group may be substituted with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxyl group.

L ^b23 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. -CH ₂ - contained in the alkylcarbonyloxy group may be substituted with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxyl group.

However, the total number of carbon atoms of L ^b21 to L ^b23 is 21 or less.

In formula (b1-11),

L ^b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom.

L ^b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. -CH ₂ - contained in the alkylcarbonyloxy group may be substituted with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxyl group.

L ^b26 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the divalent saturated hydrocarbon group may be substituted with a fluorine atom, a hydroxy group or an alkylcarbonyloxy group. -CH ₂ - contained in the alkylcarbonyloxy group may be substituted with -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be substituted with a hydroxyl group.

However, the total number of carbon atoms in L ^b24 to L ^b26 is 21 or less.]

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

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

The following groups are mentioned as group represented by Formula (b1-4).

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

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

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

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

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

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

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

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

Examples of the monovalent alicyclic hydrocarbon group represented by Y in formula (I-A) include groups represented by formulas (Y1) to (Y11) and (Y36) to (Y38).

When -CH ₂ - contained in the monovalent alicyclic hydrocarbon group represented by Y is substituted with -O-, -SO ₂ - or -CO-, the number may be one, or two or more may be sufficient. Examples of such groups include groups represented by formulas (Y12) to (Y35).

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

When Y constitutes a spiro ring of formulas (Y28) to (Y33), it is preferable that the alkanediyl group between two oxygens has one or more fluorine atoms. Moreover, it is preferable that the fluorine atom is not substituted by the methylene group adjacent to an oxygen atom among the alkanediyl groups contained in a ketal structure.

Examples of the substituent for the methyl group represented by Y in the formula (IA) include a halogen atom, a hydroxyl 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, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. ja is, represents the integer of any one of 0-4) etc. are mentioned.

Examples of the substituent of the monovalent alicyclic hydrocarbon group represented by Y in the formula (IA) include a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxyl group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, and 1 carbon atom. -12 alkoxy group, C6-C18 aromatic hydrocarbon group, C7-C21 aralkyl group, C2-4 acyl group, glycidyloxy group, or -(CH2) _ja -O _- CO- ^Rb1 group (Wherein, R ^b1 represents an alkyl group having 1 to 16 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. ja is an integer from 0 to 4 shown) and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an adamantyl group.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, and a p-adamantylphenyl group; and aryl groups such as tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, phenanthryl group, 2,6-diethylphenyl group and 2-methyl-6-ethylphenyl 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, heptyl group, 2 -Ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. are mentioned.

As an alkyl group which may be substituted with the hydroxyl group, hydroxyalkyl groups, such as a hydroxymethyl group and a hydroxyethyl group, are mentioned.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.

As an acyl group, an acetyl group, a propionyl group, a butyryl group, etc. are mentioned.

The following groups are mentioned as a C1-C18 alicyclic hydrocarbon group which may have a substituent represented by Y in Formula (I-A).

Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, more preferably an adamantyl group which may have a substituent, and -CH constituting the alicyclic hydrocarbon group or adamantyl group ₂ - may be substituted with -O-, -SO ₂ -, or -CO-. Y is more preferably an adamantyl group, a hydroxyadamantyl group, an oxoadamantyl group, or a group shown below.

As the sulfonic acid anion represented by the formula (IA), the anion represented by the formulas (B1-A-1) to (B1-A-54) [hereinafter, according to the formula number, “anion (B1-A- 1)", etc.] preferably, formulas (B1-A-1) to (B1-A-4), (B1-A-9), (B1-A-10), Formula (B1-A-24) to Formula (B1-A-33), Formula (B1-A-36) to Formula (B1-A-40), Formula (B1-A-47) to Formula (B1-A) -54), the anion represented by any one is more preferable.

[Formula (B1-A-1) to formula (B1-A-54),

R ⁱ² to R ⁱ⁷ represent an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.

R ⁱ⁸ represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group; an ethyl group, a cyclohexyl group, or an adamantyl group.

L ^A41 is a single bond or an alkanediyl group having 1 to 4 carbon atoms.

Q ¹ and Q ² have the same meaning as above.]

Examples of the sulfonic acid anion represented by formula (I-A) include anions represented by formulas (B1a-1) to (B1a-30).

Among them, the sulfonic acid anion is an anion represented by any of the formulas (B1a-1) to (B1a-3) and (B1a-7) to (B1a-19) and (B1a-22). desirable.

As a specific example of the salt represented by Formula (I), the salt which combined said cation and anion arbitrarily is mentioned. Specific examples of the salt represented by the formula (I) are shown in Tables 1 to 14.

In each table|surface, each code|symbol shows the code|symbol which attached the structure which shows the above-mentioned anion and a cation. For example, salt (I-1) is a salt which consists of an anion represented by Formula (BIa-1) and a cation represented by Formula (I-c-1), and is a salt shown below.

When salt (I) is used as an acid generator (I0) described later, salt (I-1), salt (I-2), salt (I-3), salt (I-16), salt (I-) 17), salt (I-18), salt (I-19), salt (I-22), salt (I-23), salt (I-24), salt (I-25), salt (I-38) ), salt (I-39), salt (I-40), salt (I-41), salt (I-44), salt (I-45), salt (I-46), salt (I-47) , salt (I-60), salt (I-61), salt (I-62), salt (I-63), salt (I-66), salt (I-133), salt (I-134), Preference is given to using salts (I-135), salts (I-148), salts (I-149), salts (I-150), salts (I-151) and salts (I-154).

<Method for producing salt represented by formula (I)>

In formula (I), when X ¹ and R ³ are the following groups, salt (I) [salt (I) represented by the following formula (I1) (salt (I1))] is represented by formula (I1-a) It can be produced by reacting a compound represented by , and a salt represented by formula (I1-b) in a solvent in the presence of a base catalyst.

X ¹ represents -X ¹² -OX ²² -*(X ¹² and a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the methylene group constituting the divalent aliphatic saturated hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. X ²² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, with the proviso that the total number of carbon atoms of X ¹² and X ²² is 11. * represents a bond with R ³ ).

R ³ is a case of ma=0 and na=1 in the group represented by formula (1) (*-CO-O-CR ^a1 R ^a2 R ^a3 (* represents a bond)).

[In the formula, all the symbols each have the same meaning as above.]

Acetonitrile etc. are mentioned as a solvent.

As a base catalyst, triethylamine etc. are mentioned.

The reaction is usually carried out at a temperature of 15 to 90°C for 0.5 to 24 hours.

Examples of the compound represented by the formula (I1-a) include the compounds shown below and can be easily obtained from the market.

The salt represented by the formula (I1-b) can be produced by reacting the salt represented by the formula (I1-c) with the compound represented by the formula (I1-d) in the presence of a catalyst in a solvent.

[In the formula, all the symbols each have the same meaning as above.]

Copper(II) benzoate etc. are mentioned as a catalyst, monochlorobenzene etc. are mentioned as a solvent.

The reaction is usually carried out at a temperature of 20 to 120°C for 0.5 to 24 hours.

As a salt represented by Formula (I1-c), the salt represented below is mentioned, It can obtain easily from a market.

Examples of the compound represented by the formula (I1-d) include the compounds shown below, and can be easily obtained from the market.

In formula (I), R ³ is a group represented by formula (1) (*-CO-O-CR ^a1 R ^a2 R ^a3 (* represents a bond)), and further, ma=0, na In the case of =1, salt (I) [salt (I) (salt (I2)) represented by the following formula (I2)] is prepared by dissolving the salt represented by formula (I2-b) and carbonyldiimidazole in a solvent. After the reaction, it can be produced by further reacting the compound represented by the formula (I2-a).

[In the formula, all the symbols each have the same meaning as above.]

As a solvent, acetonitrile, chloroform, etc. are mentioned.

The reaction is usually carried out at a temperature of 15 to 80°C for 0.5 to 24 hours.

Examples of the compound represented by the formula (I2-a) include the compounds shown below and can be easily obtained from the market.

Examples of the compound represented by the formula (I2-b) include the compounds represented below and can be easily obtained from the market.

In formula (I), R ³ is a group represented by formula (1) (*-O-CR ^a1 R ^a2 R ^a3 (* represents a bond)), and further, ma=1, na=0 Salt (I) in the case of [salt (I) (salt (I3)) represented by the following formula (I3)] is a compound represented by formula (I2-a) and a salt represented by formula (I1-b) can be prepared by reacting in a solvent in the presence of a base catalyst.

[In the formula, all the symbols each have the same meaning as above.]

Acetonitrile etc. are mentioned as a solvent.

Potassium hydroxide etc. are mentioned as a base catalyst.

The reaction is usually carried out at a temperature of 5 to 80°C for 0.5 to 24 hours.

In formula (I), R ³ is a group represented by formula (1) (*-O-CO-O-CR ^a1 R ^a2 R ^a3 (* represents a bond)), and further, ma=1, Salt (I) [salt (I) represented by the following formula (I4) (salt (I4))] in the case of na = 1 is a compound represented by formula (I4-a) and formula (I1-b) The salt represented by can be prepared by reacting in a solvent in the presence of a base catalyst.

[In the formula, all the symbols each have the same meaning as above.]

Acetonitrile etc. are mentioned as a solvent.

Examples of the base catalyst include triethylamine and dimethylaminopyridine.

The reaction is usually carried out at a temperature of 5 to 80°C for 0.5 to 24 hours.

Examples of the compound represented by the formula (I4-a) include the compounds shown below, and can be easily obtained from the market.

In formula (I), R ³ is a group represented by formula (2) (*-CO-O-CR ^a1' R ^{a2 '} -XR ^a3' (* represents a bond)), and further, na' Salt (I) [salt (I) (salt (I5)) represented by the following formula (I5)] in the case of =1 is a compound represented by formula (I5-a) and a formula (I2-b) The represented salt can be produced by reacting in a solvent in the presence of a base catalyst.

[In the formula, all the symbols each have the same meaning as above.]

Acetonitrile etc. are mentioned as a solvent.

Examples of the base catalyst include triethylamine and dimethylaminopyridine.

The reaction is usually carried out at a temperature of 5 to 80°C for 0.5 to 24 hours.

As for the compound represented by Formula (I5-a), the compound represented below is mentioned, It can obtain easily from a market.

In formula (I), R ³ is a group represented by formula (2) (*-O-CR ^a1' R ^{a2 '} -XR ^a3' (* represents a bond.)), and further, na'=0 Salt (I) in the case of [salt (I) (salt (I6)) represented by the following formula (I6)] is a compound represented by formula (I6-a) and a compound represented by formula (I1-b) The salt can be prepared by reacting in a solvent in the presence of a base catalyst.

[In the formula, all the symbols have the same meaning as described above, respectively. R ^{a2 ''} is a group obtained by removing a hydrogen atom from R ^{a2 '} .]

Acetonitrile etc. are mentioned as a solvent.

Examples of the base catalyst include p-toluenesulfonic acid.

The reaction is usually carried out at a temperature of 5 to 80°C for 0.5 to 24 hours.

Examples of the compound represented by the formula (I6-a) include the compounds shown below, and can be easily obtained from the market.

<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)"). The resist composition contains salt (I) as an acid generator. Here, the "acid labile group" means a group having a leaving group, and the leaving group is released by contact with an acid, and the structural unit is converted into a structural unit having a hydrophilic group (eg, a hydroxy group or a carboxy group).

The resist composition of the present invention preferably contains a salt or the like that generates an acid having a weaker acidity than the acid generated from the acid generator (hereinafter sometimes referred to as "the agent (C)"). , it is preferable to contain a solvent (hereinafter, sometimes referred to as "solvent (E)").

<Acid generator>

The acid generator of the present invention contains salt (I). The acid generator of this invention contains 1 type(s) or 2 or more types in salt (I), and it is preferable to contain 2 types. Hereinafter, especially the salt (I) as an acid generator may be called "acid generator (I0)".

The acid generator of the present invention may contain other acid generators known in the resist field other than the acid generator (I0) (hereinafter sometimes referred to as “acid generator (B)”).

When the acid generator (I0) and the acid generator (B) are contained as the acid generator, the content of the acid generator (I0) and the acid generator (B) is, in mass ratio, the acid generator (I0): The acid generator (B) is usually 1:99 to 99:1, preferably 2:98 to 98:2, more preferably 5:95 to 95:5, still more preferably 25:75 to It is 75:25.

In the resist composition, the content of the acid generator (I0) is preferably 1.5 to 40 parts by weight, more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the resin (A).

<Acid generator (B)>

As the acid generator (B), a known acid generator can be used, and an ionic acid generator or a nonionic acid generator may be used. Examples of nonionic acid generators include organic halides, sulfonate esters (eg, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphtho). quinone 4-sulfonate), sulfones (eg, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include an ionic acid generator composed of a combination of a known cation and a known anion, and an onium salt containing an onium cation (eg, a diazonium salt, a phosphonium salt, sulfonium salts and iodonium salts) are representative. Examples of the anion of the onium salt include a sulfonic acid anion, a sulfonylimide anion, and a sulfonylmethide anion.

As the acid generator (B), JP-A-63-26653, JP-A-55-164824, JP-A 62-69263, JP-A 63-146038 Japanese Patent Application Laid-Open No. 63-163452, Japanese Patent Application Laid-Open No. 62-153853, Japanese Patent Application Laid-Open No. 63-146029, U.S. Patent No. 3,779,778, U.S. Patent No. 3,849,137, German Patent No. Compounds that generate acids by radiation described in Japanese Patent Application Laid-Open No. 3914407, European Patent No. 126,712, etc. An acid generator or the like can be used. Moreover, you may use the compound manufactured by a well-known method.

Examples of the acid generator (B) include organic sulfonic acid salts, preferably a fluorine-containing acid generator, and more preferably an acid generator represented by formula (B1) (hereinafter referred to as “acid generator”). (B1)") is mentioned.

[In formula (B1),

Q ¹¹ and Q ¹² 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, -CH ₂ - contained in the divalent saturated hydrocarbon group may be substituted with -O- or -CO-, and contained in the divalent saturated hydrocarbon group The hydrogen atom may be substituted with a fluorine atom or a hydroxyl group.

Y ^B1 represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -SO ₂ - or - It may be substituted with CO-.

Z ⁺ represents an organic cation.]

Examples of the perfluoroalkyl group for Q ¹¹ and Q ¹² include the same groups as those mentioned for the perfluoroalkyl group represented by Q ¹ and Q ² .

Q ¹¹ and Q ¹² are each independently preferably a fluorine atom or a trifluoromethyl group, and more preferably a fluorine atom. It is more preferable that both Q ¹¹ and Q ¹² are fluorine atoms.

Examples of the divalent saturated hydrocarbon group represented by L ^B1 include the same divalent saturated hydrocarbon group represented by L ^b1 .

As a group in which -CH ₂ - contained in the divalent saturated hydrocarbon group represented by L ^B1 is substituted with -O- or -CO-, -CH ₂ - contained in the divalent saturated hydrocarbon group represented by L ^b1 is -O- or the same group substituted with -CO-. Specific examples thereof include groups represented by formulas (b1-1) to (b1-3) described above. On the other hand, when ^LB1 is a group represented by formulas (b1-1) to (b1-3), * in the group represented by formulas (b1-1) to (b1-3) is a bond with Y ^B1 Show your hand.

L ^B1 is preferably any of groups represented by formulas (b1-1) to (b1-3), *2-CO-O-(CH ₂ ) _t1- , *2-(CH ₂ ) _t2 -O-CO- (t1 represents any integer from 0 to 6. t2 represents any integer from 1 to 6. *2 represents a bond with -C(Q ¹¹ )(Q ¹² )-. ) is more preferable.

The monovalent alicyclic hydrocarbon group represented by Y ^B1 may be monocyclic, polycyclic, or spiro-cyclic. Specifically, a monovalent alicyclic hydrocarbon group represented by Y ^B1 (such as a group represented by the above formulas (Y1) to (Y38)) is exemplified. Among the groups represented by Y ^B1 , a preferable group is the same as the preferable range of the group represented by Y .

Examples of the anion of the salt represented by the formula (B1) include formulas (B1-A-1) to (B1-A-55). An anion represented by the formulas (B1-A-1) to (B1-A-55) [hereinafter sometimes referred to as “anion (B1-A-1)” etc. depending on the formula number] is preferable; , Formula (B1-A-1) to Formula (B1-A-4), Formula (B1-A-9), Formula (B1-A-10), Formula (B1-A-24) to Formula (B1- A-33), an anion represented by any of the formulas (B1-A-36) to (B1-A-40), (B1-A-47) to (B1-A-55) is more preferable. Do.

Here, R ⁱ² to R ⁱ⁷ are, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group.

R ⁱ⁸ is, for example, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or a group formed by combining these, more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

L ⁴⁴ is a single bond or an alkanediyl group having 1 to 4 carbon atoms.

Q ¹¹ and Q ¹² are the same as above.

Examples of the anion in the salt represented by the formula (B1) include an anion represented by the formulas (B1a-1) to (B1a-34).

Among them, formulas (B1a-1) to (B1a-3) and (B1a-7) to (B1a-16), (B1a-18), (B1a-19), and (B1a-22) ) to an anion represented by any of the formulas (B1a-34) is preferred.

As cation Z ⁺ in the acid generator (B1), it is preferable that it is an organic onium cation. Examples of the organic onium cation include organic sulfonium cation, organic iodonium cation, organic ammonium cation, benzothiazolium cation, and organic phosphonium cation, preferably organic sulfonium cation or It is an organic iodonium cation, More preferably, it is an arylsulfonium cation.

Among them, a cation represented by any of formulas (b2-1) to (b2-4) (hereinafter, may be referred to as "cation (b2-1)" etc. depending on formula numbers) is preferable.

[Formula (b2-1) to formula (b2-4),

R ^b4 to R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is, It may be substituted with a hydroxyl group, a C1-C12 alkoxy group, a C3-C12 alicyclic hydrocarbon group, or a C6-C18 aromatic hydrocarbon group, and the hydrogen atom contained in the said alicyclic hydrocarbon group is a halogen atom, a C1-C12 It may be substituted with an aliphatic hydrocarbon group of 18, an alkylcarbonyl group of 2 to 4 carbon atoms, or a glycidyloxy group, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms. .

R ^b4 and R ^b5 may become one to form a ring containing a sulfur atom to which they are bonded, and -CH ₂ - contained in the ring is -O-, -S(=O)- or -C( =O)- may be substituted.

R ^b7 and R ^b8 each independently represent a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

m2 and n2 each independently represent any integer of 0-5.

When m2 is 2 or more, a plurality of R ^b7 may be the same or different from each other, and when n2 is 2 or more, a plurality of R ^b8 may be the same or different from each other.

R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms.

R ^b9 and R ^b10 may become one to form a ring containing a sulfur atom to which they are bonded, and -CH ₂ - contained in the ring is -O-, -S(=O)- or -C( =O)- may be substituted.

R ^b11 represents a hydrogen atom, a C1-C36 aliphatic hydrocarbon group, a C3-C36 alicyclic hydrocarbon group, or a C6-C18 aromatic hydrocarbon group.

R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is an aromatic hydrocarbon group having 6 to 18 carbon atoms. The group may be substituted, and the hydrogen atom contained in the said aromatic hydrocarbon group may be substituted by the C1-C12 alkoxy group or the C1-C12 alkylcarbonyloxy group.

R ^b11 and R ^b12 may form a ring containing -CH-C(=O)- to which they are bonded, and -CH ₂ - contained in the ring is -O-, -S( It may be substituted with =O)- or -C(=O)-.

R ^b13 to R ^b18 each independently represent a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

L ^b31 represents -S- or -O-.

o2, p2, s2, and t2 each independently represent any integer of 0-5.

q2 and r2 each independently represent any integer of 0-4.

u2 represents 0 or 1.

When o2 is 2 or more, a plurality of R ^b13 may be the same or different from each other, when p2 is 2 or more, a plurality of R ^b14 may be the same or different from each other, and when q2 is 2 or more, a plurality of R b14 R ^b15 may be the same or different from each other, when r2 is 2 or more, a plurality of R ^b16 may be the same or different from each other, and when s2 is 2 or more, a plurality of R ^b17 may be the same or different from each other may be formed, and when t2 is 2 or more, a plurality of R ^b18 may be the same or different from each other.]

The aliphatic hydrocarbon group represents a chain hydrocarbon group and an alicyclic hydrocarbon group.

Examples of the chain hydrocarbon group include an alkyl group of a methyl group, an ethyl group, a pyroyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and a 2-ethylhexyl group. .

In particular, the chain hydrocarbon group of R ^b9 to R ^b12 preferably has 1 to 12 carbon atoms.

The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Cycloalkyl groups, such as a cyclodecyl group, are mentioned. Examples of the polycyclic hydrocarbon group include a decahydronaphthyl group, an amantyl group, a norbornyl group, and the following groups.

In particular, the alicyclic hydrocarbon group of R ^b9 to R ^b12 preferably has 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms.

Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-methyladamantan-2-yl group, a 2-ethyladamantan-2-yl group, and a 2-isopropyla group. A dantan-2-yl group, a methyl norbornyl group, an isobornyl group, etc. are mentioned. In the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an aliphatic hydrocarbon group, the total carbon number of the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably 20 or less.

Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a p-cyclohexylphenyl group, a p-adamantylphenyl group, a biphenyl group, and a naphthyl group. and aryl groups such as phenantholyl group, 2,6-diethylphenyl group, and 2-methyl-6-ethylphenyl group.

Moreover, when a chain hydrocarbon group or an alicyclic hydrocarbon group is contained in the aromatic hydrocarbon group, a C1-C18 chain hydrocarbon group and a C3-C18 alicyclic hydrocarbon group are preferable.

Examples of the aromatic hydrocarbon group in which a hydrogen atom is substituted with an alkoxy group include a p-methoxyphenyl group.

Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.

Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, a sec-butylcarbonyloxy group, and a tert-butylcarbonyl group. A bornyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, 2-ethylhexylcarbonyloxy group, etc. are mentioned.

The ring formed by combining R ^b4 and R ^b5 with the sulfur atom to which they are bonded may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. As for this ring, a C3-C18 ring is mentioned, Preferably it is a C4-C18 ring. Moreover, as for the ring containing a sulfur atom, a 3-membered ring - a 12-membered ring is mentioned, Preferably they are a 3-membered ring - a 7-membered ring, For example, the following ring is mentioned.

The ring formed together by R ^b9 and R ^b10 may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of the ring include a 3- to 12-membered ring, and preferably a 3- to 7-membered ring. For example, a thiolan-1-ium ring (tetrahydrothiophenium ring), a thiane-1-ium ring, a 1, 4- oxathian-4-ium ring, etc. are mentioned.

The ring formed by R ^b11 and R ^b12 together may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. Examples of the ring include a 3- to 12-membered ring, and preferably a 3- to 7-membered ring. An oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, an oxoadamantane ring, etc. are mentioned.

Among cation (b2-1) - cation (b2-4), Preferably, it is cation (b2-1).

As a cation (b2-1), the following cations are mentioned.

As a cation (b2-2), the following cations are mentioned.

As a cation (b2-3), the following cations are mentioned.

As a cation (b2-4), the following cations are mentioned.

Among them, formulas (b2-c-1), (b2-c-10), (b2-c-12), (b2-c-14), (b2-c-27), (b2-c-30 ) and cations represented by (b2-c-31) are preferred.

Examples of the acid generator (B) include organic sulfonic acids and organic sulfonium salts. For example, Japanese Patent Laid-Open No. 2013-68914, Japanese Patent Application Laid-Open No. 2013-3155, and Japanese Patent Laid-Open No. 2013- The acid generator described in Publication No. 11905, etc. are mentioned. Specific examples thereof include those represented by any of formulas (B1-1) to (B1-48). Among these, those containing an arylsulfonium cation are preferable, and formulas (B1-1) to (B1-3), (B1-5) to (B1-7), and (B1-11) to formulas (B1-14), formula (B1-17), formula (B1-20) - formula (B1-26), formula (B1-29), formula (B1-31) - formula (B1-48) in any of The salt shown is more preferable.

<Structural unit of resin (A)>

Resin (A) has a structural unit (hereinafter, sometimes referred to as "structural unit (a1)") having an acid-labile group. It is preferable that resin (A) contains structural units other than structural unit (a1). Structural units other than the structural unit (a1) include a structural unit having no acid-labile group (hereinafter sometimes referred to as “structural unit (s)”) and other structural units (hereinafter referred to as “structural unit (t)”). there are cases).

<Structural unit having an acid labile group (a1)>

The structural unit (a1) is derived from a monomer having an acid labile group (hereinafter sometimes referred to as “monomer (a1)”). Here, the "acid-labile group" means a group having a leaving group and forming a hydrophilic group (eg, a hydroxy group or a carboxy group) by releasing the leaving group by contact with an acid.

<Acid unstable phase>

Examples of the acid-labile group contained in the structural unit (a1) in the resin (A) include a group represented by the formula (1), a group represented by the formula (2), and the like.

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

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

<Specific example of structural unit (a1)>

A structural unit derived from a (meth)acrylic monomer having a group represented by formula (1), preferably a structural unit represented by formula (a1-0) (hereinafter referred to as structural unit (a1-0) ), a structural unit represented by formula (a1-1) (hereinafter sometimes referred to as structural unit (a1-1)) or a structural unit represented by formula (a1-2) (hereinafter, structural unit (a1-) 2) may be mentioned. These may be used independently and may use 2 or more types together.

[In formula (a1-0),

L ^a01 represents an oxygen atom or ^* -O-(CH ₂ ) _k01 -CO-O-, k01 represents any integer from 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 them.]

L ^a01 is preferably an oxygen atom or ^* -O-(CH ₂ ) _k01 -CO-O-, and more preferably an oxygen atom. k01 is preferably any integer from 1 to 4, more preferably 1.

Examples of the alkyl group, alicyclic hydrocarbon group, and combinations thereof for R ^a02 , R ^a03 and R ^a04 include the same groups as those mentioned for R ^a1 to R ^a3 in Formula (1).

The alkyl group of R ^a02 , R ^a03 and R ^a04 preferably has 6 or less carbon atoms.

The alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 preferably has 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms.

As for the group which combined an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total carbon number which combined these alkyl group and an alicyclic hydrocarbon group is 18 or less. Examples of such groups include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.

R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, 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, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group.

[In formulas (a1-1) and (a1-2),

L ^a1 and L ^a2 each independently represent -O- or ^* -O-(CH ₂ ) _k1 -CO-O-, k1 represents any integer from 1 to 7, and * is a bond with -CO- Show your 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 them.

m1 represents any integer from 0 to 14.

n1 represents any integer from 0 to 10.

n1' represents any integer from 0 to 3.]

L ^a1 and L ^a2 are preferably -O- or ^* -O-(CH ₂ ) _k1' -CO-O-, and more preferably -O-. k1' is any integer from 1-4, Preferably it is 1.

R ^a4 and R ^a5 are preferably a methyl group.

Examples of the alkyl group for R ^a6 and R ^a7 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- A heptyl group, 2-ethylhexyl group, n-octyl group, etc. are mentioned.

The alicyclic hydrocarbon group of R ^a6 and R ^a7 may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. and cycloalkyl groups such as a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclooctyl group and a 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)alkyl group, a norbornyl group; A methyl norbornyl group, an isobornyl group, etc. are mentioned.

Examples of the group formed by combining the alkyl group of R ^a6 and R ^a7 and the alicyclic hydrocarbon group include an aralkyl group, and a benzyl group and a phenethyl group.

The number of carbon atoms in the alkyl group of R ^a6 and R ^a7 is preferably 6 or less.

The carbon number of the alicyclic hydrocarbon group of R ^a6 and R ^a7 is preferably 3 to 8, more preferably 3 to 6.

m1 is preferably any integer from 0 to 3, more preferably 0 or 1.

n1 is preferably any integer from 0 to 3, 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 formulas (a1-0-1) to (a1-0-12) is preferable, and formula (a1-0-1) The structural unit represented by any one of - formula (a1-0-10) is more preferable.

Specific examples of the structural unit (a1-0) also include structural units in which the methyl group corresponding to R ^a01 is substituted with a hydrogen atom in the formulas (a1-0-1) to (a1-0-12). .

As a structural unit (a1-1), the structural unit derived from the monomer of Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Preferably, it is a structural unit represented by any one of formula (a1-1-1) - formula (a1-1-8).

The structural unit (a1-2) is preferably a monomer represented by any of the formulas (a1-2-1) to (a1-2-12), more preferably the formula (a1-2-3). ), a monomer represented by the formula (a1-2-4), the formula (a1-2-9), or the formula (a1-2-10).

When the resin (A) contains the structural unit (a1-0) and/or the structural unit (a1-1) and/or the structural unit (a1-2), the total content thereof is the total structure of the resin (A). It is usually 10-95 mol% with respect to the total of units, Preferably it is 15-90 mol%, More preferably, it is 20-85 mol%.

As the structural unit (a1) having an acid-labile group, a structural unit represented by the formula (a1-5) (hereinafter sometimes referred to as “structural unit (a1-5)”) can also be used.

[In formula (a1-5),

R ^a8 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom, or a halogen atom.

Z ^a1 represents a single bond or *-(CH ₂ ) _h3 -CO-L ⁵⁴ -, h3 represents any integer from 1 to 4, and * represents a bond with L ⁵¹ .

L ⁵¹ , L ⁵² , L ⁵³ and L ⁵⁴ each independently represent -O- or -S-.

s1 represents any integer from 1 to 3.

s1' represents any integer from 0 to 3.]

In formula (a1-5), it is preferable that R ^a8 is a hydrogen atom, a methyl group, or a trifluoromethyl group.

L ⁵¹ is preferably -O-.

As for L ⁵² and L ⁵³ , it is preferable that one is -O- and the other is -S-.

As s1, 1 is preferable.

As s1', any integer from 0 to 2 is preferable.

As Z ^a1 , a single bond or *-CH ₂ -CO-O- is preferable.

As a monomer which induces a structural unit (a1-5), the monomer of Unexamined-Japanese-Patent No. 2010-61117 is mentioned, for example. Among them, the structural unit represented by any of the formulas (a1-5-1) to (a1-5-4) is preferable, and is preferably represented by the formula (a1-5-1) or (a1-5-2). A structural unit that loses is more preferable.

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

Moreover, as a structural unit (a1), the following structural units are also mentioned.

When resin (A) contains the said structural unit, 10-95 mol% is preferable with respect to the total structural unit of resin (A), as for the content rate, 15-90 mol% is more preferable, 20-85 mol% is more preferable.

As the structural unit (a1) having an acid-labile group in the resin (A), the group consisting of a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2), and a structural unit (a1-5) At least one or more selected from the group consisting of preferably at least two or more, a combination of a structural unit (a1-1) and a structural unit (a1-2), a structural unit (a1-1) and a structural unit (a1) a combination of -5), a combination of a structural unit (a1-1) and a structural unit (a1-0), a combination of a structural unit (a1-2) and a structural unit (a1-0), a structural unit (a1-5) and Combination of structural unit (a1-0), structural unit (a1-0), combination of structural unit (a1-1) and structural unit (a1-2), structural unit (a1-0), structural unit (a1-1) ) and the structural unit (a1-5) are more preferable, 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 particularly preferred.

<Structural unit without acid labile group (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 (s) from which the structural unit (s) is derived, a monomer having no acid labile group known in the field of resists can be used.

As the structural unit (s), a structural unit having a hydroxyl group or a lactone ring and not having an acid labile group is preferable. A structural unit having a hydroxyl group and not having an acid labile group (hereinafter sometimes referred to as "structural unit (a2)") and/or a structural unit having a lactone ring and not having an acid labile group (hereinafter referred to as "structural unit (a3)") )") is used in the resist composition of the present invention, the resolution of the resist pattern and adhesion to the substrate can be improved.

<Structural unit (a2)>

A phenolic hydroxyl group may be sufficient as the hydroxyl group which structural unit (a2) has, and an alcoholic hydroxyl group may be sufficient as it.

When producing a resist pattern from the resist composition of the present invention, when high energy rays such as KrF excimer laser (248 nm), electron beam, or EUV (ultra-ultraviolet light) are used as the exposure light source, as the structural unit (a2), phenolic It is preferable to include the structural unit (a2) which has a hydroxyl group. In the case of using an ArF excimer laser (193 nm) or the like, the structural unit (a2) preferably includes a structural unit (a2) having an alcoholic hydroxy group, and a structure represented by formula (a2-1) to be described later. It is more preferable to include a unit. As a structural unit (a2), 1 type may be included individually, and 2 or more types may be included.

As a structural unit (a2) which has a phenolic hydroxyl group, the structural unit derived from the monomer described in Unexamined-Japanese-Patent No. 2010-204634 is mentioned, for example.

When resin (A) has a structural unit (a2-0) which has a phenolic hydroxyl group, 5-95 mol% is preferable with respect to the total structural unit of resin (A), and the content rate is 10-80 mol. % is more preferable, and 15 to 80 mol% is still more preferable.

Examples of the structural unit (a2) having an alcoholic hydroxyl group include a structural unit represented by the formula (a2-1) (hereinafter sometimes referred to as “structural unit (a2-1)”).

[In formula (a2-1),

L ^a3 represents -O- or *-O-(CH ₂ ) _k2 -CO-O-,

k2 represents any integer from 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 any integer from 0 to 10.]

In formula (a2-1), L ^a3 is preferably -O-, -O-(CH ₂ ) _f1 -CO-O- (the above f1 is any integer from 1 to 4), more preferably It is usually -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 any integer from 0 to 3, and more preferably 0 or 1.

Structural unit (a2-1) is, for example, the thing of Unexamined-Japanese-Patent No. 2010-204646 is mentioned, It is represented by any one of Formula (a2-1-1) - Formula (a2-1-6), Structural units are preferable, and structural units represented by any of formulas (a2-1-1) to (a2-1-4) are more preferable, and formula (a2-1-1) or (a2-1) The structural unit represented by -3) is more preferable.

As a monomer which guide|induced the structural unit (a2) which has an alcoholic hydroxyl group, the monomer of Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example.

When the resin (A) contains the structural unit (a2) having an alcoholic hydroxyl group, the content thereof is usually 1 to 45 mol%, preferably 1 to 40 mol%, based on all the structural units of the resin (A). More preferably, it is 1-35 mol%, More preferably, it is 2-20 mol%.

<Structural unit (a3)>

The lactone ring of the structural unit (a3) may be a monocyclic ring such as a β-propiolactone ring, a γ-butyrolactone ring or a δ-valerolactone ring, or may be a condensed ring of a monocyclic lactone ring and another ring. , preferably a bridged ring containing a γ-butyrolactone ring, an adamantane lactone ring or a γ-butyrolactone ring structure.

The structural unit (a3) is preferably a structural unit represented by any one of formulas (a3-1) to (a3-4). Resin (A) may contain these 1 type individually, and may contain 2 or more types.

[In formula (a3-1),

L ^a4 represents a group represented by -O- or *-O-(CH ₂ ) _k3 -CO-O- (k3 represents any integer from 1 to 7). * represents a bond with a 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 any integer from 0 to 5; When p1 is 2 or more, a plurality of R ^a21 may be the same as or different from each other.

In formula (a3-2),

L ^a5 represents a group represented by -O- or *-O-(CH ₂ ) _k3 -CO-O- (k3 represents any integer from 1 to 7). * represents a bond with a carbonyl group.

R ^a19 represents a hydrogen atom or a methyl group.

R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

q1 represents any integer from 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 any integer from 1 to 7). * represents a bond with a 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 any integer from 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.

L ^a7 is *-O-, *-OL ^a8 -O-, *-OL ^a8 -CO-O-, *-OL ^a8 -CO-OL ^a9 -CO-O- or *-OL ^a8 -O-CO -L ^a9 -O-.

* represents a bond with a carbonyl group.

R ^a25 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

w represents the integer of any one of 0-8.

L ^a8 and L ^a9 each independently represent an alkanediyl group having 1 to 6 carbon atoms.]

Examples of the aliphatic hydrocarbon group for R ^a21 , R ^a22 , R ^a23 and R ^a25 include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. there is.

Examples of the halogen atom for R ^a24 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group for R ^a24 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group, Preferably it is a C1-C4 alkyl group, More preferably, it is a methyl group or an ethyl group.

Examples of the alkyl group having a halogen atom for R ^a24 include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluoro and a rhotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a tribromomethyl group, and a triiodomethyl group.

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

In formulas (a3-1) to (a3-3), L ^a4 to L ^a6 are each independently *-O-(CH ₂ ), preferably -O- or k3 is any integer from 1 to 4 _k3 is a group represented by -CO-O-, more preferably -O- and *-O-CH ₂ -CO-O-, still more preferably -O-.

R ^a18 to R ^a21 are preferably a methyl group.

R ^a22 and R ^a23 each independently represent a carboxy group, a cyano group or a methyl group.

p1, q1, r1, and w each independently represent any integer from 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 still more preferably a hydrogen atom or a methyl group.

L ^a7 is preferably *-O- or *-OL ^a8 -CO-O-, more preferably *-O-, *-O-, *-O-CH ₂ -CO-O- or * -OC ₂ H ₄ -CO-O-.

The formula (a3-4) is particularly preferably a formula (a3-4)'.

(In the formula, R ^a24 and L ^a7 have the same meanings as above.)

As a monomer for inducing the structural unit (a3), 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 heard 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- Structural units represented by any of 1) to formulas (a3-3-4) and (a3-4-1) to (a3-4-12) are preferable, and formulas (a3-1-1), formulas (a3-1-1), (a3-1-2), a structural unit represented by any of the formulas (a3-2-3) to (a3-2-4) and (a3-4-1) to (a3-4-12) is more preferably, a structural unit represented by any of formulas (a3-4-1) to (a3-4-12) is still more preferable, and formulas (a3-4-1) to (a3-4-6) ) is more preferably a structural unit represented by any one of.

A structural unit (a3) may contain individually by 1 type, and may contain 2 or more types. Examples of the structural unit (a3) include the following structural units.

In the structural unit represented by the formulas (a3-4-1) to (a3-4-12), the compound in which the methyl group corresponding to R ^a24 is substituted with a hydrogen atom is also a specific example of the structural unit (a3-4). can be heard as

When the resin (A) contains the structural unit (a3), the total content is usually 5-70 mol%, preferably 10-65 mol%, with respect to all the structural units of the resin (A), more Preferably it is 10-60 mol%.

Each content rate of the structural unit represented by Formula (a3-1), Formula (a3-2), Formula (a3-3), and Formula (a3-4) is 5 normally with respect to all the structural units of resin (A). It is -60 mol%, Preferably it is 5-50 mol%, More preferably, it is 10-50 mol%.

<Other structural units (t)>

The resin (A) may further contain another structural unit (t). As the structural unit (t), a structural unit other than the structural unit (a2) and the structural unit (a3) having a halogen atom (hereinafter, sometimes referred to as “structural unit (a4)”) and a non-departing hydrocarbon group Structural units (hereinafter, sometimes referred to as "structural unit (a5)") etc. are mentioned.

<Structural unit (a4)>

The halogen atom in the structural unit (a4) is preferably a fluorine atom. As a structural unit (a4), the structural unit represented by Formula (a4-0) is mentioned.

[in 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 perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluorocycloalkanediyl group having 5 to 12 carbon atoms.

R ⁶ represents a hydrogen atom or a fluorine atom.]

Examples of the saturated aliphatic hydrocarbon group for L ⁵ include an alkanediyl group having 1 to 4 carbon atoms, for example, a methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, etc. of a straight-chain alkanediyl group, a straight-chain alkanediyl group that has a side chain of an alkyl group (especially, a methyl group, an ethyl group, etc.), an ethane-1,1-diyl group, a propane-1,2-diyl group, a butane- and branched alkanediyl groups such as 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 a difluoromethylene group, a perfluoroethylene group, a perfluoroethylfluoromethylene group, a perfluoropropane-1,3-diyl group, and a perfluoropropane-1 group. ,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-di Diyl, 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, perfluoro A rooctane-3,3-diyl group, a perfluorooctane-4,4-diyl group, etc. are mentioned.

Examples of the perfluorocycloalkanediyl group for 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 following.

In the structural unit described above, a structural unit in which a methyl group corresponding to R ⁵ is substituted with a hydrogen atom is also mentioned as a specific example of the structural unit (a4-0).

As a structural unit (a4), the structural unit represented by Formula (a4-1) is mentioned.

[In 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 substituted with -O- or -CO-.

A ^a41 represents a C1-C6 alkanediyl group which may have a substituent, or the group represented by a formula (a-g1). However, at least one of A ^a41 and R ^a42 has a halogen atom (preferably a fluorine atom) as a substituent.

[In formula (a-g1),

s represents 0 or 1.

A ^a42 and A ^a44 each independently represent a C1-C5 divalent aliphatic hydrocarbon group which may have a substituent.

A ^a43 represents a C1-C5 divalent aliphatic hydrocarbon group or a single bond 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 6 or less.

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

However, at least one of A ^a41 and R ^a42 is a group having a halogen atom as a substituent.]

s is preferably 0.

Examples of the hydrocarbon group for R ^a42 include chain and cyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining them. Examples of the chain aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, a pentadecyl group, a hexyldecyl group, and a heptadecyl group. Alkyl groups, such as a real group and an octadecyl group, are mentioned. Examples of the cyclic aliphatic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Polycyclic alicyclic hydrocarbon groups, such as a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* represents a bond), are mentioned.

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.

The hydrocarbon group for R ^a42 is preferably a chain or cyclic aliphatic hydrocarbon group or a group formed by combining them. Although these groups may have a carbon-carbon unsaturated bond, linear and cyclic aliphatic saturated hydrocarbon groups and groups formed by combining these groups are more preferable.

Examples of the substituent for R ^a42 include a halogen atom and a group represented by the formula (a-g3). As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom is mentioned.

[In 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 1 to 17 carbon atoms and having at least one halogen atom.

* represents a bond with the hydrocarbon group of R ^a42 .]

Examples of the aliphatic hydrocarbon group for A ^a45 include the same groups as the aliphatic hydrocarbon groups exemplified for R ^a42 .

R ^a42 is preferably an aliphatic hydrocarbon group which may have a halogen atom, more preferably an alkyl group having a halogen atom and/or an aliphatic hydrocarbon group having a group represented by formula (a-g3).

When R ^a42 is an aliphatic hydrocarbon group having a halogen atom, it is preferably an aliphatic hydrocarbon group having a fluorine atom, more preferably a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably having 1 to 6 carbon atoms. It is a perfluoroalkyl group, Especially preferably, it is a C1-C3 perfluoroalkyl group. Examples of the perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluoro An octyl group etc. are mentioned. As a perfluorocycloalkyl group, a perfluorocyclohexyl group etc. are mentioned.

When R ^a42 is an aliphatic hydrocarbon group having a group represented by the formula (a-g3), the total number of carbon atoms in the aliphatic hydrocarbon group including the number of carbon atoms contained in the group represented by the formula (a-g3) is preferably 15 or less, , 12 or less are more preferable. When it has the group represented by a formula (a-g3) as a substituent, the number is preferably one.

The aliphatic hydrocarbon group having a group represented by the formula (a-g3) is more preferably a group represented by the formula (a-g2).

[In 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 a C1-C17 aliphatic hydrocarbon group which may have a halogen atom.

However, the total number of carbon atoms of A ^a46 , A ^a47 and X ^a44 is 18 or less, and at least one of A ^a46 and A ^a47 has at least one halogen atom.

* indicates a bond with a carbonyl group.]

1-6 are preferable and, as for carbon number of the aliphatic hydrocarbon group of A ^a46 , 1-3 are more preferable.

4-15 are preferable, as for carbon number of the aliphatic hydrocarbon group of A ^a47 , 5-12 are more preferable, and a cyclohexyl group or an adamantyl group is still more preferable.

The following groups are mentioned as group represented by a formula (a-g2).

Examples of the alkanediyl group for A ^a41 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. straight-chain alkanediyl groups such as; Propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, 2-methylbutane-1,4 - A branched alkanediyl group, such as a diyl group, is mentioned.

As a substituent in the alkanediyl group of A ^a41 , a hydroxyl group, a C1-C6 alkoxy group, etc. are mentioned.

A ^a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 4 carbon atoms, and still more preferably an ethylene group.

Examples of the aliphatic hydrocarbon group of A ^a42 , A ^a43 and A ^a44 in the group represented by the formula (a-g1) (hereinafter referred to as “group (a-g1)” in some cases) include a methylene group, an ethylene group, Propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group , a 2-methylpropane-1,2-diyl group, and the like. As these substituents, a hydroxyl group, a C1-C6 alkoxy group, etc. are mentioned.

Examples of the group (a-g1) in which X ^a42 is an oxygen atom include the following groups. In the following examples, * and ** each represent a bond, and ** denote a bond with -O-CO-R ^a42 .

Examples of the group (a-g1) in which X ^a42 is a carbonyl group include the following groups.

Examples of the group (a-g1) in which X ^a42 is a carbonyloxy group include the following groups.

Examples of the group (a-g1) in which X ^a42 is an oxycarbonyl group include the following groups.

As a structural unit represented by a formula (a4-1), the structural unit represented by a formula (a4-2) and a formula (a4-3) is preferable.

[In formula (a4-2),

R ^f1 represents a hydrogen atom or a methyl group.

A ^f1 represents a C1-C6 alkanediyl group.

R ^f2 represents a C1-C10 hydrocarbon group having a fluorine atom.]

Examples of the alkanediyl group for A ^f1 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. , straight-chain alkanediyl groups such as hexane-1,6-diyl groups; 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4-diyl group, 2- and branched alkanediyl groups such as methylbutane-1,4-diyl groups.

The hydrocarbon group of R ^f2 includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group includes a chain type, a cyclic group, and a group formed by combining these groups. As an aliphatic hydrocarbon group, an alkyl group and an alicyclic hydrocarbon group are preferable.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group and 2-ethyl group. A hexyl group is mentioned.

The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a dimethylcyclohexyl group. Cycloalkyl groups, such as a sil group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group, are 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)alkan-1-yl group, a norbornyl group; A methyl norbornyl group and an isobornyl group are mentioned.

Examples of the hydrocarbon group having a fluorine atom for R ^f2 include an alkyl group having a fluorine atom, an alicyclic hydrocarbon group having a fluorine atom, and the like.

Specifically, examples of the alkyl group having a fluorine atom include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, 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- (trifluoro methyl)-1,2,2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluoro Robutyl 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, perfluoro Pentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3 and fluorinated alkyl groups such as ,4,4,5,5,6,6-dodecafluorohexyl 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.

In the formula (a4-2), A ^f1 is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

As R ^f2 , a C1-C6 fluorinated alkyl group is preferable.

[In formula (a4-3),

R ^f11 represents a hydrogen atom or a methyl group.

A ^f11 represents a C1-C6 alkanediyl group.

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

The aliphatic hydrocarbon group of A ^f13 includes either a chain or a cyclic group, and a divalent aliphatic hydrocarbon group formed by combining them. Although this aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, Preferably it is a saturated aliphatic hydrocarbon group.

The aliphatic hydrocarbon group which may have a fluorine atom as 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 alkanediyl groups such as methylene group, ethylene group, propanediyl group, butanediyl group and pentanediyl group; and perfluoroalkanediyl groups such as difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluorobutanediyl group and perfluoropentanediyl group.

The divalent cyclic aliphatic hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. 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.

Examples of the aliphatic hydrocarbon group for A ^f14 include either chain or cyclic, and an aliphatic hydrocarbon group formed by combining them. Although this aliphatic hydrocarbon group may have a carbon-carbon unsaturated bond, Preferably it is a saturated aliphatic hydrocarbon group.

The aliphatic hydrocarbon group which may have a fluorine atom as 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 a trifluoromethyl group, a difluoromethyl group, a methyl group, a perfluoroethyl group, 1,1,1-trifluoroethyl group, and 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, purple A luorohexyl group, a heptyl group, a perfluoroheptyl group, an octyl group, a perfluorooctyl group, etc. are mentioned.

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, and a perfluoroadamantylmethyl group.

In formula (a4-3), as A ^f11 , an ethylene group is preferable.

The aliphatic hydrocarbon group of A ^f13 preferably has 1 to 6 carbon atoms, more preferably 2 to 3 carbon atoms.

The aliphatic hydrocarbon group of A ^f14 preferably has 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms. Among them, A ^f14 is preferably a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, 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 the structural units shown below and the structural units in which the methyl group corresponding to R ^f1 in the following structural units is substituted with a hydrogen atom.

Examples of the structural unit represented by the formula (a4-3) include the structural units shown below and the structural units in which the methyl group corresponding to R ^f11 in the structural units is substituted with a hydrogen atom.

Examples of the structural unit (a4) include the following structural units and structural units in which a methyl group bonded to the main chain is substituted with a hydrogen atom.

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

<Structural unit (a5)>

Examples of the non-departing hydrocarbon group in the structural unit (a5) include a straight-chain, branched or cyclic hydrocarbon group, and preferably an alicyclic hydrocarbon group. As a structural unit (a5), the structural unit represented by Formula (a5-1) is mentioned, for example.

[In 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 the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alicyclic hydrocarbon group having 1 to 8 carbon atoms. 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 substituted 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.

Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and alkyl groups such as 2-ethylhexyl group.

Examples of the alicyclic hydrocarbon group having a substituent include a 3-methyladamantyl group and the like.

R ⁵² is preferably an unsubstituted alicyclic hydrocarbon group having 3 to 18 carbon atoms, more preferably an adamantyl group, a norbornyl group or a cyclohexyl group.

Examples of the divalent saturated hydrocarbon group for L ⁵⁵ include a divalent aliphatic saturated hydrocarbon group and a divalent alicyclic saturated hydrocarbon group, and preferably a divalent aliphatic saturated hydrocarbon group.

Examples of the divalent aliphatic saturated 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 a cyclopentanediyl group and a 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 substituted with an oxygen atom or a carbonyl group include groups represented by formulas (L1-1) to (L1-4). In the following formula, * represents a bond with an oxygen atom.

[In 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 divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.

However, the total carbon number of L ^x1 and L ^x2 is 16 or less.

In formula (L1-2),

L ^x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms.

L ^x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms.

However, the total carbon number of L ^x3 and L ^x4 is 17 or less.

In formula (L1-3),

L ^x5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms.

L ^x6 and L ^x7 each independently represent a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 14 carbon atoms.

However, the total number of carbon atoms of L ^x5 , L ^x6 and L ^x7 is 15 or less.

In formula (L1-4),

L ^x8 and L ^x9 each independently 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 number of carbon atoms of L ^x8 , L ^x9 and W ^x1 is 15 or less.]

L ^x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.

L ^x2 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond.

L ^x3 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.

L ^x4 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.

L ^x5 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.

L ^x6 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group.

L ^x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms.

L ^x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group.

L ^x9 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a single bond or a methylene group.

W ^x1 is preferably a divalent alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms, more preferably a cyclohexanediyl group or an adamantanediyl group.

As group represented by Formula (L1-1), the divalent group shown below is mentioned, for example.

As group represented by Formula (L1-2), the divalent group shown below is mentioned, for example.

As group represented by Formula (L1-3), the divalent group shown below is mentioned, for example.

As group represented by Formula (L1-4), the divalent group shown below is mentioned, for example.

L ⁵⁵ is preferably a single bond, a methylene group, an ethylene group, or a group represented by the formula (L1-1), and more preferably a single bond or a group represented by the formula (L1-1).

Examples of the structural unit (a5-1) include the structural units shown below and structural units in which the methyl group corresponding to R ⁵¹ in the structural units is substituted with a hydrogen atom.

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

Resin (A) may have structural units other than the structural unit mentioned above, As such structural unit, a structural unit well-known in the said technical field is mentioned.

<Resin (A)>

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 group consisting of the structural unit (a1-1) and the structural unit (a1-2) (preferably the structural unit having a cyclohexyl group or a cyclopentyl group), more preferably Preferably, it is at least 2 types selected from structural unit (a1-1) or structural unit (a1-1) and structural unit (a1-2) (preferably the said structural unit which has a cyclohexyl group and a cyclopentyl group).

The structural unit (s) is preferably at least one of a structural unit (a2) and a structural unit (a3). The structural unit (a2) is preferably a structural unit represented by formula (a2-1). The structural unit (a3) is preferably a structural unit represented by formulas (a3-1-1) to (a3-1-4), and formulas (a3-2-1) to (a3-2-4) and at least one selected from structural units represented by formulas (a3-4-1) to (a3-4-2).

Each structural unit constituting the resin (A) may be used alone or in combination of two or more, using a monomer that induces these structural units, by a known polymerization method (for example, radical polymerization method) can be manufactured. The content rate of each structural unit which resin (A) has can be adjusted by the usage-amount of the monomer used for superposition|polymerization.

The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more, still more preferably 3,000 or more), and 50,000 or less (more preferably 30,000 or less, still more preferably 15,000 or less). . In this specification, a weight average molecular weight is the value calculated|required according to the conditions described in the Example by gel permeation chromatography.

<Resin (X) other than Resin (A)>

The resist composition of the present invention may contain a resin (X) that does not contain the structural unit (a1) having an acid-labile group other than the resin (A). As such resin (X), resin containing a structural unit (t) is mentioned, for example.

As resin (X), resin containing the structural unit (a4) illustrated as structural unit (t) is preferable. In the resin (X), the content of the structural unit (a4) is preferably 40 mol% or more, more preferably 45 mol% or more, and furthermore 50 mol% or more, based on all the structural units of the resin (X). desirable.

Examples of the structural unit which the resin (X) may further include include a structural unit (a2) having no acid-labile group, a structural unit (a3), and a structural unit derived from other known monomers.

The weight average molecular weight of the resin (X) is preferably 8,000 or more (more preferably 10,000 or more) and 80,000 or less (more preferably 60,000 or less). The measuring means of such a weight average molecular weight of resin (X) is the same as that in the case of resin (A).

When the resist composition contains the resin (X), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, further preferably 1 to 60 parts by mass with respect to 100 parts by mass of the resin (A). is 1-40 mass parts, More preferably, it is 1-20 mass parts, Especially preferably, it is 1.5-10 mass parts.

The total content of the resin (A) and the resin (X) is preferably 80% by mass or more and 99% by mass or less with respect to the solid content of the resist composition. The solid content of the resist composition and the resin content thereof can be measured by known analytical means such as liquid chromatography or gas chromatography.

<Solvent (E)>

The content of the solvent (E) in the resist composition is usually 90% by mass or more, preferably 92% by mass or more, more preferably 94% by mass or more, 99.9% by mass or less, preferably 99% by mass or more. is below. The content rate of a solvent (E) can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

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

<??wife (C)>

A salt which generates an acid with lower acidity than the acid which generate|occur|produces from a basic nitrogen-containing organic compound or an acid generator is mentioned as for (C). It is preferable that the content of the material (C) is about 0.01 to 5 mass% based on the solid content of the resist composition.

<Basic nitrogen-containing organic compound>

An amine and an ammonium salt are mentioned as a basic nitrogen-containing organic compound. Examples of the amine include aliphatic amines and aromatic amines. As an aliphatic amine, a primary amine, a secondary amine, and a tertiary amine are mentioned.

Examples of the amine include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-dimethylaniline , diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethyl Amine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyldihexyl Amine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldi Octylamine, ethyldinonylamine, ethyl didecylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldi Phenylmethane, 2,2'-methylenebisaniline, 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, etc. are mentioned, Preferably diisopropylaniline is mentioned, More preferably, 2,6-diisopropylaniline is mentioned.

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

<A salt that generates an acid having a lower acidity than that generated from an acid generator>

A salt that generates an acid having a weaker acidity than the acid generated from the acid generator, when containing only salt (I) as the acid generator, generates an acid having a weaker acidity than the acid generated from the salt (I) means, and in the case of containing the salt (I) as the acid generator and the acid generator (B) which is an acid generator other than this, the acidity is higher than that of the acid generated from the salt (I) and the acid generator (B). A salt that generates a weak acid.

The acidity in the salt which generate|occur|produces the acid lower in acidity than the acid which generate|occur|produces from the acid generator is represented by the acid dissociation constant (pKa). The salt that generates an acid having a lower acidity than the acid generated from the acid generator is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3<pKa, preferably -1<pKa<7. , more preferably 0<pKa<5.

As a salt which generate|occur|produces the acid lower in acidity than the acid which generate|occur|produces from the acid generator, the salt represented by the following formula, and Unexamined-Japanese-Patent No. 2012-229206, Unexamined-Japanese-Patent No. 2012-6908, Unexamined-Japanese-Patent No. The salts of Unexamined-Japanese-Patent No. 2012-72109, Unexamined-Japanese-Patent No. 2011-39502, and Unexamined-Japanese-Patent No. 2011-191745 are mentioned.

<Other components (F)>

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

<Preparation of resist composition>

The resist composition of the present invention comprises a resin (A) and a salt (I) of the present invention, and, if necessary, a resin (X), an acid generator (B), a solvent (E), a dissolving agent (C), and It can prepare by mixing another component (F). The mixing order is arbitrary and is not specifically limited. The temperature at the time of mixing is 10-40 degreeC, and an appropriate temperature can be selected according to the kind of resin, etc., solubility with respect to the solvent (E), etc. of resin. As for the mixing time, an appropriate time can be selected from 0.5 to 24 hours according to the mixing temperature. On the other hand, there is no restriction|limiting in particular also in a mixing means, A stirring mixing etc. can be used.

After mixing each component, it is preferable to filter using a filter with a pore diameter of about 0.003-0.2 micrometer.

<Method for producing resist pattern>

The method for producing a resist pattern of the present invention comprises:

(1) a step of applying the resist composition of the present invention on a substrate;

(2) drying the composition after application to form a composition layer;

(3) exposing the composition layer;

(4) heating the composition layer after exposure, and

(5) The process of developing the composition layer after heating is included.

In order to apply|coat a resist composition on a board|substrate, it can carry out with a normally used apparatus, such as a spin coater. Inorganic substrates, such as a silicon wafer, are mentioned as a board|substrate. Before apply|coating a resist composition, a board|substrate may be wash|cleaned, and the antireflection film etc. may be formed on the board|substrate.

By drying the composition after application|coating, a solvent is removed and a composition layer is formed. Drying is performed, for example by evaporating a solvent using heating apparatuses, such as a hotplate (so-called prebaking), or performing using a pressure reduction apparatus. It is preferable that heating temperature is 50-200 degreeC, and, as for heating time, it is preferable that it is 10-180 second. Moreover, it is preferable that the pressure at the time of drying under reduced pressure is about 1-1.0x10 ⁵ Pa.

The obtained composition layer is exposed using an exposure machine normally. The exposure machine may be an immersion exposure machine. Examples of the exposure light source include: KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F ₂ excimer laser (wavelength: 157 nm); A variety of methods can be used, such as wavelength conversion of laser light from a semiconductor laser, etc. to emit harmonic laser light in the deep ultraviolet region or vacuum ultraviolet region, or irradiation with electron beams or ultra-ultraviolet light (EUV). In addition, in this specification, irradiating these radiations may be generically called "exposure". At the time of exposure, exposure is normally performed through the mask corresponded to the requested|required pattern. When an exposure light source is an electron beam, you may expose by drawing directly, without using a mask.

The composition layer after exposure is heat-treated (so-called post-exposure bake) in order to accelerate the deprotection reaction in the acid labile group. Heating temperature is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.

The composition layer after heating is usually developed using a developing device and a developing solution. As a developing method, the dip method, the paddle method, the spray method, the dynamic dispensing method, etc. are mentioned. It is preferable that image development temperature is 5-60 degreeC, for example, and it is preferable that image development time is 5-300 second, for example. A positive type resist pattern or a negative type resist pattern can be manufactured by selecting the kind of developing solution as follows.

When producing a positive resist pattern from the resist composition of the present invention, an alkaline developer is used as the developer. The alkaline developer may be various alkaline aqueous solutions used in this field. For example, the aqueous solution of tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (common name choline), etc. are mentioned. The alkali developer may contain surfactant.

It is preferable to wash the resist pattern after development with ultrapure water, and then to remove the water remaining on the substrate and the pattern.

When producing a negative resist pattern from the resist composition of the present invention, a developer containing an organic solvent (hereinafter, sometimes referred to as an "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; glycol ether solvents such as propylene glycol monomethyl ether; amide solvents such as N,N-dimethylacetamide; Aromatic hydrocarbon solvents, such as anisole, etc. are mentioned.

In organic developing solution, 90 mass % or more and 100 mass % or less are preferable, as for the content rate of an organic solvent, 95 mass % or more and 100 mass % or less are more preferable, It is still more preferable that it is substantially only an organic solvent.

Especially, as an organic developing solution, the developing solution containing butyl acetate and/or 2-heptanone is preferable. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50 mass % or more and 100 mass % or less, more preferably 90 mass % or more and 100 mass % or less, and substantially butyl acetate and/or 2-heptanone. It is more preferable that it is only Thanon.

The organic developer may contain a surfactant. In addition, a trace amount of water may be contained in the organic developer.

At the time of development, you may stop development by substituting with the solvent of a different kind from an organic-type developing solution.

It is preferable to wash the resist pattern after development with a rinse solution. 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 an alcohol solvent or an ester solvent is preferable.

After 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 suitable as a resist composition for KrF excimer laser exposure, a resist composition for ArF excimer laser exposure, a resist composition for electron beam (EB) exposure, or a resist composition for EUV exposure, and is more suitable as a resist composition for ArF excimer laser exposure. It is suitable and useful for microfabrication of semiconductors.

[Example]

By way of Examples, the present invention will be more specifically described. In the examples, "%" and "part" indicating the content or the amount used are based on mass unless otherwise specified.

A weight average molecular weight is the value calculated|required by gel permeation chromatography. In addition, the analysis conditions of the gel permeation chromatography are as follows.

Column: TSKgel Multipore HXL-M x 3+guardcolumn (manufactured by Tosoh Corporation)

Eluent: tetrahydrofuran

Flow rate: 1.0 mL/min

Detector: RI Detector

Column temperature: 40°C

Injection volume: 100 μL

Molecular weight standard: standard polystyrene (manufactured by Tosoh Corporation)

The structure of the compound was confirmed by measuring molecular ion peaks using mass spectrometry (LC: Model 1100 manufactured by Agilent, MASS was LC/MSD type manufactured by Agilent). In the following examples, the value of this molecular ion peak is expressed as "MASS".

[Example 1] Synthesis of salt represented by formula (I-2)

2.98 parts of the salt represented by the formula (I-2-a), 0.63 parts of the compound represented by the formula (I-2-b), and 24 parts of monochlorobenzene were put into a reactor, and the mixture was stirred at 23° C. for 30 minutes. Then, after adding 0.03 parts of copper benzoate represented by Formula (I-2-c) and heating up to about 100 degreeC, it stirred at the same temperature for 1 hour. After concentrating the obtained reaction product, 45 parts of chloroform and 15 parts of ion-exchanged water were added to the obtained concentrate, followed by stirring at 23°C for 30 minutes. Then, it left still and liquid-separated, and obtained the organic layer. 15 parts of ion-exchange water was added to the obtained organic layer, and it stirred at 23 degreeC for 30 minute(s). Then, it left still and liquid-separated, and obtained the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the obtained filtrate was concentrated. To the obtained concentrate, 20 parts of tert-butylmethyl ether was added and stirred. The obtained supernatant was removed, and the residue after removal of the supernatant was further concentrated. After dissolving the obtained concentrate in acetonitrile, 1.59 parts of salts represented by Formula (I-2-d) were obtained by concentrating.

0.63 parts of the salt represented by the formula (I-2-d), 0.26 parts of the compound represented by the formula (I-2-e), and 15 parts of acetonitrile were mixed, followed by stirring at 23° C. for 30 minutes. To the obtained mixture, 0.12 parts of triethylamine was added, and the mixture was stirred at 75°C for 3 hours. The obtained mixture was cooled to 23 degreeC, 30 parts of chloroform and 20 parts of ion-exchange water were added, and it stirred at 23 degreeC for 30 minutes. The obtained mixture was left still and liquid-separated, and the organic layer was obtained. This washing operation was further repeated 5 times. 0.5 parts of activated carbon was added to the recovered organic layer, stirred, and filtered. The obtained filtrate was concentrated, and 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butylmethyl ether was added and stirred. The obtained supernatant was removed, and the residue after removal of the supernatant was further concentrated. After dissolving the obtained concentrate in acetonitrile, 0.33 parts of salts represented by Formula (I-2) were obtained by concentrating.

MASS(ESI(+)Spectrum): M ⁺ 507.3

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

[Example 2] Synthesis of salt represented by formula (I-3)

2.91 parts of the salt represented by the formula (I-3-a), 0.63 parts of the compound represented by the formula (I-2-b) and 24 parts of monochlorobenzene were placed in a reactor, and stirred at 23° C. for 30 minutes. After adding 0.03 parts of copper benzoate represented by Formula (I-2-c) to the obtained mixture and heating up to about 100 degreeC, it stirred at the same temperature for 1 hour. The resulting reaction was concentrated. 45 parts of chloroform and 15 parts of ion-exchanged water were added to the obtained concentrate, and it stirred at 23 degreeC for 30 minutes. Then, it left still and liquid-separated, and obtained the organic layer. 15 parts of ion-exchange water was added to the obtained organic layer, and it stirred at 23 degreeC for 30 minute(s). Then, it left still and liquid-separated, and obtained the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the obtained filtrate was concentrated. To the obtained concentrate, 20 parts of tert-butylmethyl ether was added and stirred. The obtained supernatant was removed, and the residue after removal of the supernatant was further concentrated. After dissolving the obtained concentrate in acetonitrile, 1.72 parts of salts represented by Formula (I-3-d) were obtained by concentrating.

0.61 parts of the salt represented by the formula (I-3-d), 0.26 parts of the compound represented by the formula (I-2-e), and 15 parts of acetonitrile were mixed, followed by stirring at 23° C. for 30 minutes. To the obtained mixture, 0.12 parts of triethylamine was added, and the mixture was stirred at 75°C for 3 hours. The obtained mixture was cooled to 23 degreeC, 30 parts of chloroform and 20 parts of ion-exchange water were added, and it stirred at 23 degreeC for 30 minutes. The obtained mixture was left still and liquid-separated, and the organic layer was obtained. This washing operation was further repeated 5 times. 0.5 parts of activated carbon was added to the recovered organic layer, stirred, and filtered. The obtained filtrate was concentrated, and 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butylmethyl ether was added and stirred. The obtained supernatant was removed, and the residue after removal of the supernatant was further concentrated. After the obtained concentrate was dissolved in acetonitrile, 0.42 parts of a salt represented by the formula (I-3) was obtained by concentration.

MASS(ESI(+)Spectrum): M ⁺ 507.3

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

[Example 3] Synthesis of salt represented by formula (I-18)

2.98 parts of the salt represented by the formula (I-18-a), 0.63 parts of the compound represented by the formula (I-2-b), and 24 parts of monochlorobenzene were put into a reactor, and the mixture was stirred at 23° C. for 30 minutes. After adding 0.03 parts of copper benzoate represented by Formula (I-2-c) to the obtained mixture and heating up to about 100 degreeC, it stirred at the same temperature for 1 hour. The resulting reaction was concentrated. 45 parts of chloroform and 15 parts of ion-exchanged water were added to the obtained concentrate, and it stirred at 23 degreeC for 30 minutes. Then, it left still and liquid-separated, and obtained the organic layer. 15 parts of ion-exchange water was added to the obtained organic layer, and it stirred at 23 degreeC for 30 minute(s). Then, it left still and liquid-separated, and obtained the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the obtained filtrate was concentrated. To the obtained concentrate, 20 parts of tert-butylmethyl ether was added and stirred. The obtained supernatant was removed, and the residue after removal of the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 1.62 parts of a salt represented by the formula (I-18-d).

0.63 parts of the salt represented by the formula (I-18-d), 0.26 parts of the compound represented by the formula (I-2-e), and 15 parts of acetonitrile were mixed, and stirred at 23° C. for 30 minutes. To the obtained mixture, 0.12 parts of triethylamine was added, and the mixture was stirred at 75°C for 3 hours. The obtained mixture was cooled to 23 degreeC, 30 parts of chloroform and 20 parts of ion-exchange water were added, and it stirred at 23 degreeC for 30 minutes. The obtained mixture was left still and liquid-separated, and the organic layer was obtained. This washing operation was further repeated 5 times. 0.5 parts of activated carbon was added to the recovered organic layer, stirred, and filtered. The obtained filtrate was concentrated, and 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butylmethyl ether was added and stirred. The obtained supernatant was removed, and the residue after removal of the supernatant was further concentrated. After dissolving the obtained concentrate in acetonitrile, 0.39 parts of salts represented by Formula (I-18) were obtained by concentrating.

MASS(ESI(+)Spectrum): M ⁺ 507.3

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

[Example 4] Synthesis of salt represented by formula (I-19)

2.97 parts of the salt represented by the formula (I-19-a), 0.63 parts of the compound represented by the formula (I-2-b), and 24 parts of monochlorobenzene were placed in a reactor, and stirred at 23° C. for 30 minutes. After adding 0.03 parts of copper benzoate represented by Formula (I-2-c) to the obtained mixture and heating up to about 100 degreeC, it stirred at the same temperature for 1 hour. The resulting reaction was concentrated. 45 parts of chloroform and 15 parts of ion-exchanged water were added to the obtained concentrate, and it stirred at 23 degreeC for 30 minutes. Then, it left still and liquid-separated, and obtained the organic layer. 15 parts of ion-exchange water was added to the obtained organic layer, and it stirred at 23 degreeC for 30 minute(s). Then, it left still and liquid-separated, and obtained the organic layer. This washing operation was repeated 5 times. After filtering the recovered organic layer, the obtained filtrate was concentrated. To the obtained concentrate, 20 parts of tert-butylmethyl ether was added and stirred. The obtained supernatant was removed, and the residue after removal of the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 1.82 parts of a salt represented by the formula (I-19-d).

0.62 parts of the salt represented by the formula (I-19-d), 0.26 parts of the compound represented by the formula (I-2-e), and 15 parts of acetonitrile were mixed, and stirred at 23° C. for 30 minutes. To the obtained mixture, 0.12 parts of triethylamine was added, and the mixture was stirred at 75°C for 3 hours. The obtained mixture was cooled to 23 degreeC, 30 parts of chloroform and 20 parts of ion-exchange water were added, and it stirred at 23 degreeC for 30 minutes. The obtained mixture was left still and liquid-separated, and the organic layer was obtained. This washing operation was further repeated 5 times. 0.5 parts of activated carbon was added to the recovered organic layer, stirred, and filtered. The obtained filtrate was concentrated, and 10 parts of ethyl acetate was added and stirred, and the supernatant was removed. To the obtained residue, 10 parts of tert-butylmethyl ether was added and stirred. The obtained supernatant was removed, and the residue after removal of the supernatant was further concentrated. The obtained concentrate was dissolved in acetonitrile and then concentrated to obtain 0.44 parts of a salt represented by the formula (I-19).

MASS(ESI(+)Spectrum): M ⁺ 507.3

MASS(ESI(-)Spectrum): M ^- 337.1

<Synthesis of Resin (A) and Resin (X)>

The compounds (monomers) used for the synthesis of Resin (A1) and Resin (A2) which are Resin (A), and Resin (X1) and Resin (X2) which are Resin (X) are shown below. Hereinafter, these compounds are called "monomer (a1-1-3)" etc. according to the formula number.

[Synthesis Example 1] Synthesis of Resin (A1)

As a monomer, a monomer (a1-1-3), a monomer (a1-2-9), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio [monomer (a1-1) -3):monomer (a1-2-9):monomer (a2-1-1):monomer (a3-4-2)] is mixed so that 35:15:2.5:47.5 is obtained, and 1.5 mass of the total amount of monomers Pear propylene glycol monomethyl ether acetate was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators were added to this solution, respectively, based on the total amount of monomers, and these were added at 75°C for about 5 hours. heated. The obtained reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a methanol/water mixed solvent, repulped, and then purified twice by filtration to obtain a resin (A1) having a weight average molecular weight of 8.0×10 ³ in a yield of 69%. This resin (A1) has the following structural units.

[Synthesis Example 2] Synthesis of Resin (A2)

As a monomer, a monomer (a1-1-3), a monomer (a1-2-11), a monomer (a2-1-1) and a monomer (a3-4-2) are used, and the molar ratio [monomer (a1-1) -3):monomer (a1-2-11):monomer (a2-1-1):monomer (a3-4-2)] is mixed so that 35:15:2.5:47.5] is 1.5 mass of the total amount of monomers Pear propylene glycol monomethyl ether acetate was added to make a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators were added to this solution, respectively, based on the total amount of monomers, and these were added at 75°C for about 5 hours. heated. The obtained reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate a resin, and the resin was filtered. The obtained resin was added to a methanol/water mixed solvent, repulped and filtered twice, to obtain a resin (A2) having a weight average molecular weight of 7.9×10 ³ in a yield of 65%. This resin (A2) has the following structural units.

[Synthesis Example 3] Synthesis of Resin (X1)

As a monomer, the monomer (a4-1-7) was used, 1.5 mass times of methyl isobutyl ketone of the total amount of monomers was added, and it was set as the solution. To the solution, azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators were added 0.7 mol% and 2.1 mol%, respectively, based on the total amount of monomers, and these were added at 75° C. for about 5 hours. heated. 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 Resin X1 having a weight average molecular weight of 1.8×10 ⁴ in a yield of 77%. This resin X1 has the following structural units.

[Synthesis Example 4] Synthesis of Resin (X2)

As a monomer, a monomer (a5-1-1) and a monomer (a4-0-12) are used, and the molar ratio [monomer (a5-1-1):monomer (a4-0-12)] is 50:50. The mixture was mixed as much as possible, and 1.2 times by mass of methyl isobutyl ketone of the total amount of monomers was added to obtain a solution. To this solution, 3 mol% of azobis(2,4-dimethylvaleronitrile) as an initiator was added with respect to the total amount of monomers, and the mixture was heated at 70°C for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol/water mixed solvent to precipitate a resin, and the resin was filtered to obtain Resin X2 (copolymer) having a weight average molecular weight of 1.0×10 ⁴ in a yield of 91%. This resin X2 has the following structural units.

<Preparation of resist composition>

Each of the components and solvents shown in Table 15 were mixed, and the resulting mixture was filtered through a fluororesin filter having a pore diameter of 0.2 µm to prepare resist compositions.

<Resin>

A1, A2, X1, X2: Resin (A1), Resin (A2), Resin (X1), Resin (X2)

<Acid generator (B)>

B1-21: a salt represented by the formula (B1-21) (synthesized according to the examples of Japanese Patent Application Laid-Open No. 2012-224611)

B1-22: a salt represented by the formula (B1-22) (synthesized according to the examples of Japanese Patent Application Laid-Open No. 2012-224611)

<Salt using comparative composition>

IX-1: (Synthesis according to the examples of Japanese Patent Laid-Open No. 2010-44347)

IX-2: (Synthesis according to an example of Japanese Patent Laid-Open No. 2013-47209)

IX-3: (Synthesis according to an example of Japanese Patent Application Laid-Open No. 2013-47209)

<??wife (C)>

D1: (manufactured by Tokyo Chemical Industry Co., Ltd.)

<solvent>

265 parts of propylene glycol monomethyl ether acetate

Propylene glycol monomethyl ether 20 parts

2-heptanone 20 parts

γ-butyrolactone 3.5 parts

[Examples 5 to 13, Comparative Examples 1 to 3] Preparation of resist patterns and evaluation thereof

A composition for an organic antireflection film (ARC-29; manufactured by Nissan Chemical Co., Ltd.) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an organic antireflection film having a thickness of 78 nm on the wafer. Next, on the organic antireflection film, the resist composition was applied (spin coat) to a film thickness of 85 nm after drying. After application, the silicon wafer was prebaked on a direct hot plate at the temperature of PB described in the "PB/PEB" column of Table 15 for 60 seconds to form a composition layer. A contact hole pattern (hole pitch 90 nm/hole diameter 55 nm) was formed on a silicon wafer on which the composition layer was formed with an ArF excimer stepper for immersion exposure (XT: 1900 Gi; manufactured by ASML, NA = 1.35, 3/4 annular XY polarization). The exposure was performed by changing the exposure amount stepwise using a mask for the following. In addition, ultrapure water was used as an immersion medium.

After exposure, on a hot plate, post-exposure baking was performed for 60 seconds at the temperature of PEB described in the "PB/PEB" column of Table 15. Next, the composition layer on the silicon wafer was developed by the dynamic dispensing method at 23° C. for 20 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer, thereby producing a negative resist pattern.

The resist pattern obtained after development WHEREIN: The exposure amount at which the hole diameter formed using the said mask became 45 nm was made into effective sensitivity.

<CD Uniformity (CDU) Evaluation>

In the effective sensitivity, the hole diameter of a pattern formed by a mask having a hole diameter of 55 nm was measured 24 times for one hole, and the average value was taken as the average hole diameter of one hole. The standard deviation was calculated|required using what was measured 400 points|pieces of the average hole diameter of the pattern formed by the mask with a hole diameter of 55 nm in the same wafer as a parent group.

A case where the standard deviation was 1.80 nm or less was evaluated as A as the CDU was good.

A case where the standard deviation was larger than 1.80 nm was evaluated as B because the CDU was not good.

The results are shown in Table 16. Numerical values in parentheses indicate standard deviation (nm).

<Evaluation of Mask Error Factor (MEF)>

In the effective sensitivity, the resist pattern was formed using a mask having mask hole diameters (hole diameters of the light-transmitting portion of the mask) of 57 nm, 56 nm, 55 nm, 54 nm, and 53 nm (all of which have a hole pitch of 90 nm). formed. The slope of the regression line when the mask hole diameter is plotted on the horizontal axis and the hole diameter of the resist pattern formed (transferred) on the substrate by exposure is plotted on the vertical axis was calculated as the MEF value.

A MEF value of 4.8 or less was evaluated as A as MEF was favorable.

MEF value exceeding 4.8 was evaluated as B as MEF was not favorable.

The results are shown in Table 16. Numerical values in parentheses indicate MEF values.

The salt of the present invention and the resist composition containing the salt can obtain a resist pattern having good CD uniformity (CDU), so they are suitable for microfabrication of semiconductors and are very useful industrially.

Claims (10)

A salt represented by formula (I).

[In formula (I),
R ¹ and R ² each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and the substituents are a hydroxyl group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a carbon number It is an alicyclic hydrocarbon group of 3-12.
R ³ represents group represented by Formula (1).

[In formula (1), R ^a1 to R ^a3 are each independently an alkyl group having 1 to 8 carbon atoms which may have an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an alkyl group having 1 to 8 carbon atoms which may have an alkyl group having 3 to 8 carbon atoms Represents an alicyclic hydrocarbon group of 20, or R ^a1 and R ^a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.
ma represents 0, and na represents 1.
* indicates a bonding hand.]
X ¹ is -X ¹² -OX ²² -* (X ¹² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the methylene group constituting the divalent aliphatic hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. X ²² represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, with the proviso that the total number of carbon atoms of X ¹² and X ²² is 11 or less. * represents a bond with R ³ ).
A ^- represents the sulfonic acid 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, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-, and a hydrogen atom contained in the saturated hydrocarbon group is fluorine It may be substituted with an atom or a hydroxyl group.
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -SO ₂ - or -CO - may be substituted.
The substituent which the methyl group represented by Y may have is a halogen atom, a hydroxyl 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.
The substituent which the alicyclic hydrocarbon group represented by Y may have is a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxyl group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, an alkoxy group having 1 to 12 carbon atoms. , an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or a -(CH ₂ ) _ja -O-CO-R ^b1 group.
R ^b1 represents an alkyl group having 1 to 16 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
Said ja represents an integer of any one of 0-4.] The method of claim 1,
In X ¹ of the formula (I), X ¹² is an alkanediyl group having 1 to 6 carbon atoms, the methylene group constituting the alkanediyl group may be substituted with an oxygen atom or a carbonyl group, and X ²² is methylene Gin salt. 3. The method of claim 1 or 2,
R ¹ and R ² in the formula (I) are each independently a phenyl group which may have a substituent, and the substituent is a hydroxy group, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 3 carbon atoms. A salt which is an alicyclic hydrocarbon group of ~12. 3. The method of claim 1 or 2,
In R ³ of Formula (I), R ^a1 and R ^a2 are bonded to each other to form a non-aromatic hydrocarbon ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded, and R ^a3 is an alkyl group having 1 to 8 carbon atoms. salt. 3. The method of claim 1 or 2,
A salt in which L ^b1 in the formula (IA) is a group represented by any of formulas (b1-1) to (b1-3).

[In formula (b1-1),
L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group, and -CH ₂ - contained in the saturated hydrocarbon group is , -O- or -CO- may be substituted.
However, the total number of carbon atoms of L ^b2 and L ^b3 is 22 or less.
In formula (b1-2),
L ^b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom.
L ^b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group, and -CH ₂ - contained in the saturated hydrocarbon group is , -O- or -CO- may be substituted.
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 hydroxyl group.
L ^b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxyl group, and -CH ₂ - contained in the saturated hydrocarbon group is , -O- or -CO- may be substituted.
However, the total carbon number of L ^b6 and L ^b7 is 23 or less.
* indicates a bond with Y.] 3. The method of claim 1 or 2,
Y in the formula (IA) is an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and -CH ₂ - contained in the alicyclic hydrocarbon group is -O-, -SO ₂ - or -CO- The substituents which may be substituted with and which the alicyclic hydrocarbon group represented by Y may have include a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxy group, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, and a carbon number An alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, an acyl group having 2 to 4 carbon atoms, a glycidyloxy group, or -(CH ₂ ) _ja -O-CO-R ^b1 A group (wherein, R ^b1 represents an alkyl group having 1 to 16 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 16 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. ja is an integer from 0 to 4 is represented.) is a salt. An acid generator comprising the salt according to claim 1 or 2. A resist composition comprising the acid generator containing the salt according to claim 1 or 2 and a resin comprising a structural unit having an acid labile group. 9. The method of claim 8,
A resist composition further comprising a salt that generates an acid having a lower acidity than an acid generated from the acid generator, wherein the acid dissociation constant of the acid generated from the salt is -3 < pKa. (1) a step of applying the resist composition according to claim 8 on a substrate;
(2) drying the composition after application to form a composition layer;
(3) exposing the composition layer;
(4) heating the composition layer after exposure, and
(5) a step of developing the composition layer after heating;
A method of manufacturing a resist pattern comprising a.