JP6331404B2 - Resist composition and method for producing resist pattern - Google Patents

Description

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

Patent Document 1 describes a resist composition containing an acid generator, a resin composed of a structural unit represented by the following formula, and polybutyl methacrylate.

JP 2012-181522 A

  In some cases, the resist pattern produced from the resist composition is not always satisfactory in shape and resolution.

［式（ａ１−０）中、
Ｌ^a01は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k01−ＣＯ−Ｏ−を表し、ｋ０１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合わせた基を表す。］

［式（ａ１−１）中、
Ｌ^a1は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_h1−ＣＯ−Ｏ−を表し、ｈ１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a4は、水素原子又はメチル基を表す。
Ｒ^a6は、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合わせた基を表す。
ｍ１は、０〜１４の整数を表す。］

［式（ａ１−２）中、
Ｌ^a2は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_h2−ＣＯ−Ｏ−を表し、ｈ２は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a5は、水素原子又はメチル基を表す。
Ｒ^a7は、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合わせた基を表す。
ｎ１は、０〜１０の整数を表す。
ｎ１’は、０〜３の整数を表す。］

［式（ａ１−４）、
Ｒ¹⁰は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ¹¹は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｌａは０〜４の整数を表す。ｌａが２以上のとき、複数のＲ¹¹は同一又は相異なる。
Ｒ¹²及びＲ¹³は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表す。
Ｙ^a3は、置換基を有していてもよい炭素数１〜１８の炭化水素基を表し、該炭化水素基に含まれるメチレン基は、酸素原子、硫黄原子、カルボニル基、スルホニル基又は−Ｎ（Ｒ^ｃ）−に置き換わっていてもよい。
Ｒ^ｃは、水素原子又は炭素数１〜６のアルキル基を表す。］

［式（ａ２−０）中、
Ｒ^a30は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｍａは０〜４の整数を表す。ｍａが２以上のとき、複数のＲ^a31は同一又は相異なる。］

［式（ａ５−１）中、
Ｒ^a50は、水素原子又はメチル基を表す。
Ｒ^a51は、炭素数１〜１８の飽和炭化水素基を表す。］
〔２〕樹脂（Ａ１）が、式（ａ１−１）で表される構造単位及び式（ａ１−２）で表される構造単位からなる群から選ばれる少なくとも一種の構造単位を含む樹脂であり、
樹脂（Ａ２）が、式（ａ１−４）で表される構造単位及び式（ａ２−０）で表される構造単位を含む樹脂（ただし、式（ａ１−１）で表される構造単位及び式（ａ１−２）で表される構造単位を含まない。）であり、
樹脂（Ａ３）が、式（ａ５−１）で表される構造単位を含む樹脂（ただし、式（ａ１−１）で表される構造単位及び式（ａ１−２）で表される構造単位を含まず、かつ、式（ａ１−４）で表される構造単位及び式（ａ２−０）で表される構造単位の少なくとも一方を含まない。）である〔１〕記載のレジスト組成物。
〔３〕酸発生剤が、式（Ｂ１）で表される化合物及び式（Ｂ２）で表される塩からなる群から選ばれる少なくとも一種を含む酸発生剤である〔１〕又は〔２〕記載のレジスト組成物。

［式（Ｂ１）中、Ｒ^ｂ１及びＲ^ｂ２は、互いに独立に、炭素数１〜１０の炭化水素基を表す。］

［式（Ｂ２）中、Ｒ^ｂ３は、炭素数１〜２４の炭化水素基を表し、該炭化水素基に含まれる水素原子は、ヒドロキシ基又はカルボキシ基に置換されていてもよく、該炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ａ^＋は有機カチオンを表す。］
〔４〕（１）〔１〕〜〔３〕のいずれかに記載のレジスト組成物を基板上に塗布する工程、
（２）塗布後の組成物を乾燥して組成物層を形成する工程、
（３）組成物層に露光する工程、
（４）露光後の組成物層を加熱する工程、及び
（５）加熱後の組成物層を現像する工程
を含むレジストパターンの製造方法。 The present invention includes the following inventions.
[1] A resist composition containing resin (A1), resin (A2), resin (A3) and an acid generator.
Resin (A1): at least selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2) Resin containing one type of structural unit Resin (A2): Structural unit represented by formula (a1-4) and resin containing a structural unit represented by formula (a2-0) (however, in formula (a1-0) (The structural unit represented, the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) are not included.)
Resin (A3): Resin containing a structural unit represented by formula (a5-1) (however, a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a formula (The structural unit represented by (a1-2) is not included, and at least one of the structural unit represented by formula (a1-4) and the structural unit represented by formula (a2-0) is not included.)

[In the formula (a1-0),
L ^a01 represents an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, k01 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a01 independently 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 obtained by combining these. ]

[In the formula (a1-1),
L ^a1 represents an oxygen atom or ^* —O— (CH ₂ ) _h1 —CO—O—, h1 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a4 represents a hydrogen atom or a methyl group.
R ^a6 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these.
m1 represents the integer of 0-14. ]

[In the formula (a1-2),
L ^a2 represents an oxygen atom or ^* —O— (CH ₂ ) _h2 —CO—O—, h2 represents an integer of 1 to 7, and * represents a bond with a carbonyl group.
R ^a5 represents a hydrogen atom or a methyl group.
R ^a7 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these.
n1 represents the integer of 0-10.
n1 ′ represents an integer of 0 to 3. ]

[Formula (a1-4),
R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
R ¹¹ is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ¹¹ are the same or different.
R ¹² and R ¹³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
Y ^a3 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the hydrocarbon group is an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or —N (R ^c )-may be substituted.
R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

[In the formula (a2-0),
R ^a30 represents a C 1-6 alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents an integer of 0 to 4. When ma is 2 or more, the plurality of R ^a31 are the same or different. ]

[In the formula (a5-1),
R ^a50 represents a hydrogen atom or a methyl group.
R ^a51 represents a saturated hydrocarbon group having 1 to 18 carbon atoms. ]
[2] The resin (A1) is a resin containing at least one structural unit selected from the group consisting of the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2). ,
Resin (A2) includes a structural unit represented by the formula (a1-4) and a structural unit represented by the formula (a2-0) (provided that the structural unit represented by the formula (a1-1) and The structural unit represented by formula (a1-2) is not included.)
Resin (A3) is a resin containing a structural unit represented by formula (a5-1) (however, a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2)) And the resist composition does not contain at least one of the structural unit represented by the formula (a1-4) and the structural unit represented by the formula (a2-0).
[3] The acid generator is an acid generator containing at least one selected from the group consisting of a compound represented by the formula (B1) and a salt represented by the formula (B2) [1] or [2] Resist composition.

[In Formula (B1), R ^b1 and R ^b2 each independently represent a hydrocarbon group having 1 to 10 carbon atoms. ]

[In the formula (B2), R ^b3 represents a hydrocarbon group having 1 to 24 carbon atoms, and the hydrogen atom contained in the hydrocarbon group may be substituted with a hydroxy group or a carboxy group. The methylene group contained in the group may be replaced with an oxygen atom or a carbonyl group.
A ⁺ represents an organic cation. ]
[4] (1) A step of applying the resist composition according to any one of [1] to [3] on a substrate,
(2) A step of drying the composition after application to form a composition layer,
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern, comprising: a step of heating the composition layer after exposure; and (5) a step of developing the composition layer after heating.

  According to the resist composition of the present invention, an excellent shape and high-resolution resist pattern can be produced.

In the present specification, unless otherwise specified, in the description of the structural formula of a compound, “aliphatic hydrocarbon group” means a linear or branched hydrocarbon group, and “alicyclic hydrocarbon group” means A group obtained by removing a number of hydrogen atoms corresponding to the valence from the ring of an alicyclic hydrocarbon. The “aromatic hydrocarbon group” also includes a group in which a hydrocarbon group is bonded to an aromatic ring. When stereoisomers exist, all stereoisomers are included.
Further, in the present specification, "(meth) acrylic monomer", "CH ₂ = CH-CO-" or _{"CH 2 = C (CH 3)} -CO- " at least one monomer having the structure Means. Similarly, “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.

<Resist composition>
The resist composition of the present invention contains a resin (A1), a resin (A2), a resin (A3), and an acid generator (B).
Resin (A1): at least selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2) Resin containing one type of structural unit Resin (A2): Structural unit represented by formula (a1-4) and resin containing a structural unit represented by formula (a2-0) (however, in formula (a1-0) (The structural unit represented, the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) are not included.)
Resin (A3): Resin containing a structural unit represented by formula (a5-1) (however, a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a formula (The structural unit represented by (a1-2) is not included, and at least one of the structural unit represented by formula (a1-4) and the structural unit represented by formula (a2-0) is not included.)
Furthermore, the resist composition of the present invention preferably contains a basic compound (C) and / or a solvent (D).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

[Resin (A1)]
The resin (A1) is a structural unit represented by the formula (a1-0) (hereinafter sometimes referred to as “structural unit (a1-0)”), a structural unit represented by the formula (a1-1) (hereinafter referred to as “structural unit (a1-0)”). Selected from the group consisting of “structural unit (a1-1)” and structural unit represented by formula (a1-2) (hereinafter sometimes referred to as “structural unit (a1-2)”). A resin containing at least one structural unit.

［式（ａ１−０）中、
Ｌ^a01は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k01−ＣＯ−Ｏ−を表し、ｋ０１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a01は、それぞれ独立に、水素原子又はメチル基を表す。
Ｒ^a02、Ｒ^a03及びＲ^a04は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合わせた基を表す。］ The structural unit (a1-0) is represented by the following formula (a1-0).

[In the formula (a1-0),
L ^a01 represents an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, k01 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a01 independently 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 obtained by combining these. ]

L ^a02 is preferably an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, and more preferably an oxygen atom. k01 is preferably an integer of 1 to 4, more preferably 1.
Examples of the alkyl group of R ^a02 , R ^a03, and R ^a04 , the alicyclic hydrocarbon group, and the group obtained by combining these include the same groups as those described for R ^{a1 to} R ^a3 in formula (1).
The alkyl group for R ^a02 , R ^a03 and R ^a04 preferably has 6 or less carbon atoms.
The alicyclic hydrocarbon group ^{represented by} R ^a02 , R ^a03 and R ^a04 preferably has 8 or less carbon atoms, more preferably 6 or less.
The group combining the alkyl group and the alicyclic hydrocarbon group preferably has a total carbon number of 18 or less, combining the alkyl group and the alicyclic hydrocarbon group. Examples of such a group 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, and more preferably a methyl group, an ethyl group, a cyclohexyl group, or an adamantyl group.

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

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

  The content of the structural unit (a1-0) is usually 3 to 80 mol%, preferably 5 to 70 mol%, more preferably 10 to 60 mol% with respect to all the structural units of the resin (A1). %.

［式（ａ１−１）中、
Ｌ^a1は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_h1−ＣＯ−Ｏ−を表し、ｈ１は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a4は、水素原子又はメチル基を表す。
Ｒ^a6は、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合わせた基を表す。
ｍ１は、０〜１４の整数を表す。］ The structural unit (a1-1) is represented by the following formula (a1-1).

[In the formula (a1-1),
L ^a1 represents an oxygen atom or ^* —O— (CH ₂ ) _h1 —CO—O—, h1 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a4 represents a hydrogen atom or a methyl group.
R ^a6 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these.
m1 represents the integer of 0-14. ]

アルキル基と脂環式炭化水素基とを組合わせた基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基等が挙げられる。アルキル基と脂環式炭化水素基とを組合わせた基は、好ましくは炭素数２０以下である。 ^Examples of the alkyl group for R ^a6 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and preferably has 1 to 6 carbon atoms.
The alicyclic hydrocarbon group for R ^a6 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* represents a bond). The alicyclic hydrocarbon group for R ^a6 preferably has 3 to 16 carbon atoms.

Examples of the group obtained by combining an alkyl group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group. A group in which an alkyl group and an alicyclic hydrocarbon group are combined preferably has 20 or less carbon atoms.

h1 is preferably an integer of 1 to 4, more preferably 1.
L ^a1 is preferably an oxygen atom.
R ^a4 is preferably a methyl group.
R ^a6 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
m1 is preferably an integer of 0 to 3, more preferably 0 or 1.

As a monomer which introduce | transduces structural unit (a1-1), the monomer described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example. Among these, a monomer represented by any one of formula (a1-1-1) to formula (a1-1-8) is preferable, and any one of formula (a1-1-1) to formula (a1-1-4) is preferable. The monomer represented by is more preferable.

  The content of the structural unit (a1-1) is usually from 5 to 80 mol%, preferably from 15 to 70 mol%, more preferably from 25 to 60 mol%, based on all structural units of the resin (A1). %.

［式（ａ１−２）中、
Ｌ^a2は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_h2−ＣＯ−Ｏ−を表し、ｈ２は１〜７の整数を表し、＊はカルボニル基との結合手を表す。
Ｒ^a5は、水素原子又はメチル基を表す。
Ｒ^a7は、炭素数１〜８のアルキル基、炭素数３〜１８の脂環式炭化水素基又はこれらを組合わせた基を表す。
ｎ１は、０〜１０の整数を表す。
ｎ１’は、０〜３の整数を表す。］ The structural unit (a1-2) is represented by the following formula (a1-2).

[In the formula (a1-2),
L ^a2 represents an oxygen atom or ^* —O— (CH ₂ ) _h2 —CO—O—, h2 represents an integer of 1 to 7, and * represents a bond with a carbonyl group.
R ^a5 represents a hydrogen atom or a methyl group.
R ^a7 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these.
n1 represents the integer of 0-10.
n1 ′ represents an integer of 0 to 3. ]

h2 is preferably an integer of 1 to 4, more preferably 1.
L ^a2 is preferably an oxygen atom.
R ^a5 is preferably a methyl group.
R ^a7 includes the same groups as R ^a6 , preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. It is an alkyl group.
n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
n1 ′ is preferably 0 or 1.

Examples of the monomer that leads to the structural unit (a1-2) include 1-ethylcyclopentan-1-yl (meth) acrylate, 1-ethylcyclohexane-1-yl (meth) acrylate, and 1-ethylcycloheptane-1- Il (meth) acrylate, 1-methylcyclopentan-1-yl (meth) acrylate, 1-isopropylcyclopentan-1-yl (meth) acrylate, and the like can be given. Monomers represented by the formula (a1-2-1) to the formula (a1-2-12) are preferred, and the formula (a1-2-3) to the formula (a1-2-4) or the formula (a1-2-9) The monomer represented by formula (a1-2-10) is more preferable, and the monomer represented by formula (a1-2-3) or formula (a1-2-9) is more preferable.

  The content rate of a structural unit (a1-2) is 3-80 mol% normally with respect to all the structural units of resin (A1), Preferably it is 5-70 mol%, More preferably, it is 10-60 mol%. %.

  The total content of the structural unit (a1-0), the structural unit (a1-1) and the structural unit (a1-2) is usually from 3 to 95 mol% with respect to all the structural units of the resin (A1). Preferably it is 10-95 mol%, More preferably, it is 15-90 mol%, More preferably, it is 20-85 mol%.

The resin (A1) preferably contains at least one selected from the group consisting of the structural unit (a1-1) and the structural unit (a1-2).
The resin (A1) is also preferably a resin containing two or more selected from the group consisting of the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2). A resin that is a combination of 1) and the structural unit (a1-2) is more preferable.

  The resin (A1) may contain a structural unit other than the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2). Such a structural unit includes a structural unit having an alcoholic hydroxy group (hereinafter sometimes referred to as “structural unit (a2)”) and a structural unit having a lactone ring (hereinafter referred to as “structural unit (a3)”). In some cases). In the resist composition of the present invention containing the resin (A1) having these structural units, the film and / or composition layer applied to the substrate tends to be excellent in adhesion to the substrate. Can be manufactured.

［式（ａ２−１）中、
Ｌ^a3は、酸素原子又は^＊−Ｏ−（ＣＨ₂）_k2−ＣＯ−Ｏ−（ｋ２は１〜７の整数を表し、＊はカルボニル基との結合手を表す。）を表す。
Ｒ^a14は、水素原子又はメチル基を表す。
Ｒ^a15及びＲ^a16は、互いに独立に、水素原子、メチル基又はヒドロキシ基を表す。
ｏ１は、０〜１０の整数を表す。］ Examples of the structural unit (a2) include a structural unit represented by the formula (a2-1) (hereinafter may be referred to as “structural unit (a2-1)”).

[In the formula (a2-1),
L ^a3 represents an oxygen atom or ^* —O— (CH ₂ ) _k2 —CO—O— (k2 represents an integer of 1 to 7, and * represents a bond to a carbonyl group).
R ^a14 represents a hydrogen atom or a methyl group.
R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxy group.
o1 represents an integer of 0 to 10. ]

L ^a3 is preferably an oxygen atom or a group represented by —O— (CH ₂ ) _k2 —CO—O—, wherein k2 is an integer of 1 to 4, more preferably an oxygen atom or —O. —CH ₂ —CO—O—, and more preferably an oxygen atom.
R ^a14 is preferably a methyl group.
R ^a15 is preferably a hydrogen atom.
R ^a16 is preferably a hydrogen atom or a hydroxy group.
o1 is preferably an integer of 0 to 3, more preferably 0 or 1.

Examples of the structural unit (a2-1) include structural units derived from the monomers described below and JP-A 2010-204646.

  Among these, the structural unit represented by any one of formula (a2-1-1), formula (a2-1-2), formula (a2-1-3) and formula (a2-1-4) is preferable. The structural unit represented by formula (a2-1-1) or (a2-1-3) is more preferable.

  When the resin (A1) has the structural unit (a2-1), the content is preferably 1 to 45 mol%, more preferably 2 to 35 mol%, based on all the structural units of the resin (A1). 2.5-30 mol% is more preferable.

  The lactone ring contained in the structural unit (a3) may be, for example, a monocycle such as a β-propiolactone ring, γ-butyrolactone ring, or δ-valerolactone ring, and condensation of a monocyclic lactone ring with another ring. It may be a ring. Among these lactone rings, a bridged ring containing a γ-butyrolactone ring or a γ-butyrolactone ring structure is preferable.

  The structural unit (a3) is preferably a structural unit represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or the formula (a3-4). These 1 type may be used independently and may use 2 or more types together.

［式（ａ３−１）中、
Ｌ^a4は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−（ｋ４は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a18は、水素原子又はメチル基を表す。
ｐ１は０〜５の整数を表す。
Ｒ^a21は炭素数１〜４の脂肪族炭化水素基を表し、ｐ１が２以上の場合、複数のＲ^a21は同じであってもよい。
式（ａ３−２）中、
Ｌ^a5は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−（ｋ４は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a19は、水素原子又はメチル基を表す。
ｑ１は、０〜３の整数を表す。
Ｒ^a22は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表し、ｑ１が２以上の場合、複数のＲ^a22は同じであってもよい。
式（ａ３−３）中、
Ｌ^a6は、酸素原子又は＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−（ｋ４は１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a20は、水素原子又はメチル基を表す。
ｒ１は、０〜３の整数を表す。
Ｒ^a23は、カルボキシ基、シアノ基又は炭素数１〜４の脂肪族炭化水素基を表し、ｒ１が２以上の場合、複数のＲ^a23は同じであってもよい。
式（ａ３−４）中、
Ｌ^a７は、酸素原子、＊−Ｏ−（ＣＨ₂）_k4−Ｏ−、＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−、＊−Ｏ−（ＣＨ₂）_k4−ＣＯ−Ｏ−（ＣＨ₂）_k５−ＣＯ−Ｏ−又は＊−Ｏ−（ＣＨ₂）_k4−Ｏ−ＣＯ−（ＣＨ₂）_k５−Ｏ−（ｋ４及びｋ５は、それぞれ独立に、１〜７の整数を表す。）で表される基を表す。＊はカルボニル基との結合手を表す。
Ｒ^a2４は、水素原子又はメチル基を表す。］

[In the formula (a3-1),
L ^a4 represents an oxygen atom or a group represented by * —O— (CH ₂ ) _k4 —CO—O— (k4 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a18 represents a hydrogen atom or a methyl group.
p1 represents an integer of 0 to 5.
R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and when p1 is 2 or more, the plurality of R ^a21 may be the same.
In formula (a3-2),
L ^a5 represents an oxygen atom or a group represented by * —O— (CH ₂ ) _k4 —CO—O— (k4 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a19 represents a hydrogen atom or a methyl group.
q1 represents an integer of 0 to 3.
R ^a22 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and when q1 is 2 or more, a plurality of R ^a22 may be the same.
In formula (a3-3),
L ^a6 represents an oxygen atom or a group represented by * —O— (CH ₂ ) _k4 —CO—O— (k4 represents an integer of 1 to 7). * Represents a bond with a carbonyl group.
R ^a20 represents a hydrogen atom or a methyl group.
r1 represents an integer of 0 to 3.
R ^a23 represents a carboxy group, a cyano group, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and when r1 is 2 or more, a plurality of R ^a23 may be the same.
In formula (a3-4),
L ^a7 is an oxygen atom, * —O— (CH ₂ ) _k4 —O—, * —O— (CH ₂ ) _k4 —CO—O—, * —O— (CH ₂ ) _k4 —CO—O— ( CH _{2) k5} -CO-O- or _{* -O- (CH 2) k4 -O} -CO- (CH 2) k5 -O- (k4 and k5 independently represents an integer of 1-7. ) Represents a group represented by * Represents a bond with a carbonyl group.
R ^a24 represents a hydrogen atom or a methyl group. ]

Examples of L ^{a4 to} L ^a7 include the same groups as those in L ^a3 of the formula (a2-1).
L ^{a4 to} L ^a7 are each independently an oxygen atom or a group represented by * —O— (CH ₂ ) _k4 —CO—O—, wherein k4 is an integer of 1 to 4, preferably an oxygen atom and * —O—CH ₂ —CO—O— is more preferable, and an oxygen atom is more preferable.
R ^{a18 to} R ^a21 and R ^a24 are preferably methyl groups.
R ^a22 and R ^a23 are each independently preferably a carboxy group, a cyano group or a methyl group.
p1, q1 and r1 are preferably integers of 0 to 2, more preferably 0 or 1. When p1 is 2, two R ^a21 are the same or different. When q1 is 2, two R ^a22 are the same or different. When r1 is 2, two R ^a23 are the same or different.

Examples of the monomer that leads to the structural unit (a3-1) include, for example, the formula (a3-1-1), the formula (a3-1-2), the formula (a3-1-3), and the formula (a3-1-4). And monomers described in JP 2010-204646 A, and the like.

Examples of the monomer that leads to the structural unit (a3-2) include, for example, the formula (a3-2-1), the formula (a3-2-2), the formula (a3-2-3), and the formula (a3-2-4). And monomers described in JP 2010-204646 A, and the like.

Examples of the monomer that leads to the structural unit (a3-3) include, for example, the formula (a3-3-1), the formula (a3-3-2), the formula (a3-3-3), and the formula (a3-3-4). And monomers described in JP 2010-204646 A, and the like.

Examples of the monomer that leads to the structural unit (a3-4) include, for example, the formula (a3-4-1), the formula (a3-4-2), the formula (a3-4-3), and the formula (a3-4-4). , Monomers represented by any one of formula (a3-4-5) and formula (a3-4-6), and monomers described in JP2012-41274A.

In the above compound, a compound in which a methyl group corresponding to R ^a24 is replaced with a hydrogen atom can also be exemplified as a monomer for deriving the structural unit (a3-4).

  Among structural units (a3), formula (a3-1-1), formula (a3-1-2), formula (a3-2-3), formula (a3-2-4), formula (a3-4-) 1) or a structural unit derived from a monomer represented by the formula (a3-4-2) is more preferable, and the formula (a3-1-1), the formula (a3-2-3) or the formula (a3-4-2) The structural unit derived from a monomer represented by

When the resin (A1) includes the structural unit (a3), the total content is usually 5 to 70 mol%, preferably 10 to 65 mol%, based on all the structural units of the resin (A1). More preferably, it is 10-60 mol%.
Moreover, content of a structural unit (a3-1), a structural unit (a3-2), a structural unit (a3-3), and a structural unit (a3-4) is respectively with respect to all the structural units of resin (A1). 5-70 mol% is preferable, 5-65 mol% is more preferable, and 5-60 mol% is further more preferable.

  Furthermore, the resin (A1) may have a structural unit represented by the following formula (a1-4), formula (a2-0), or formula (a5-1).

  The weight average molecular weight of the resin (A1) is preferably 2,500 or more and 100,000 or less, more preferably 2,700 or more and 50,000 or less, and further preferably 3,000 or more and 30,000 or less. .

  Each structural unit constituting the resin (A1) can be produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. The content rate of each structural unit can be adjusted with the usage-amount of the monomer used when manufacturing resin (A1).

[Resin (A2)]
The resin (A2) has a structural unit represented by the formula (a1-4) (hereinafter sometimes referred to as “structural unit (a1-4)”) and a structural unit represented by the formula (a2-0) (hereinafter referred to as “structural unit (a1-4)”). A resin including “structural unit (a2-0)”). However, the resin (A2) does not include the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2).

［式（ａ１−４）、
Ｒ¹⁰は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ¹¹は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｌａは０〜４の整数を表す。ｌａが２以上のとき、複数のＲ¹¹は同一又は相異なる。
Ｒ¹²及びＲ¹³は、それぞれ独立に、水素原子又は炭素数１〜１２の炭化水素基を表す。
Ｙ^a3は、置換基を有していてもよい炭素数１〜１８の炭化水素基を表し、該炭化水素基に含まれるメチレン基は、酸素原子、硫黄原子、カルボニル基、スルホニル基又は−Ｎ（Ｒ^ｃ）−に置き換わっていてもよい。
Ｒ^ｃは、水素原子又は炭素数１〜６のアルキル基を表す。］ The structural unit (a1-4) is represented by the following formula (a1-4).

[Formula (a1-4),
R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
R ¹¹ is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ¹¹ are the same or different.
R ¹² and R ¹³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
Y ^a3 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the hydrocarbon group is an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or —N (R ^c )-may be substituted.
R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

R ¹⁰ is preferably an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, more preferably a methyl group or a hydrogen atom, and still more preferably a hydrogen atom.
The alkoxy group of R ¹¹ is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and further preferably a methoxy group.
The hydrocarbon group of R ¹² and R ¹³ is preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably 1 to 12 carbon atoms. It is an aliphatic hydrocarbon group.
The hydrocarbon group for Y ^a3 is preferably an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a combination thereof, and more preferably one having 1 carbon atom. An aliphatic hydrocarbon group having 18 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. The aliphatic hydrocarbon group is preferably an unsubstituted aliphatic hydrocarbon group. As the substituent of the aromatic hydrocarbon group, an alkyl group having 1 to 6 carbon atoms and an aryloxy group having 6 to 10 carbon atoms are preferable.
The methylene group contained in the hydrocarbon group of Y ^a3 may be replaced with an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or —N (R ^c ) —, but a methylene group at the bonding position with the oxygen atom Does not replace these groups.
la is preferably 0.

  Examples of the monomer that leads to the structural unit (a1-4) include monomers described in JP 2010-204646 A. Among these, a monomer represented by any one of formula (a1-4-1) to formula (a1-4-14) is preferable, and any one of formula (a1-4-1) to formula (a1-4-8) is preferable. The monomer represented by is more preferable.

  10-95 mol% is preferable with respect to all the structural units of resin (A2), and, as for the content rate of a structural unit (a1-4), 15-90 mol% is more preferable, and 20-85 mol% is more preferable.

［式（ａ２−０）中、
Ｒ^a30は、ハロゲン原子を有してもよい炭素数１〜６のアルキル基、水素原子又はハロゲン原子を表す。
Ｒ^a31は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数２〜４のアシル基、炭素数２〜４のアシルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を表す。
ｍａは、０〜４の整数を表す。ｍａが２以上のとき、複数のＲ^a31は同一又は相異なる。］ The structural unit (a2-0) is represented by the following formula (a2-0).

[In the formula (a2-0),
R ^a30 represents a C 1-6 alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents an integer of 0 to 4. When ma is 2 or more, the plurality of R ^a31 are the same or different. ]

R ^a30 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
The alkoxy group for R ^a31 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and further preferably a methoxy group.
As the alkyl group for R ^a31 , an alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is further preferable.
ma is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.

Examples of the structural unit (a2-0) include structural units derived from monomers described in JP 2010-204634 A, and preferably the formula (a2-0-1) to the formula (a2- 0-4).

  5-90 mol% is preferable with respect to all the structural units of resin (A2), and, as for the content rate of a structural unit (a2-0), 10-85 mol% is more preferable, and 15-80 mol% is more preferable.

The resin (A2) may have a structural unit other than the structural unit (a1-4) and the structural unit (a2-0). As such a structural unit, for example, a structural unit derived from a carboxy group-containing monomer such as acrylic acid or methacrylic acid, the above structural unit (a2), the above structural unit (a3), a structural unit derived from styrene, Examples include a structural unit derived from alkoxystyrene and a structural unit derived from acyloxystyrene.
The resin (A2) may have a structural unit represented by the formula (a5-1) described later.

The structural unit derived from the alkoxystyrene is, for example, a structural unit in which a hydroxy group of the structural unit (a2-0) is substituted with an alkoxy group. Examples of the monomer that leads to the structural unit include methoxystyrene, ethoxystyrene, isopropoxystyrene, tert-butoxystyrene, and the like.
The structural unit derived from the acyloxystyrene is, for example, a structural unit in which a hydroxy group of the structural unit (a2-0) is substituted with an acyloxy group. Examples of the monomer for deriving the structural unit include benzoyloxystyrene, acetyloxystyrene, and pivaloyloxystyrene.

  When resin (A2) contains structural units other than structural unit (a1-4) and structural unit (a2-0), the content rate is 1-50 mol% with respect to all the structural units of resin (A2). Is preferable, and 3 to 30 mol% is more preferable.

  The weight average molecular weight of the resin (A2) is preferably 2,500 or more and 100,000 or less, more preferably 2,700 or more and 50,000 or less, and further preferably 3,000 or more and 40,000 or less. .

  Each structural unit constituting the resin (A2) can be produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. The content rate of each structural unit can be adjusted with the usage-amount of the monomer used when manufacturing resin (A2).

[Resin (A3)]
The resin (A3) is a resin having a structural unit represented by the formula (a5-1) (hereinafter sometimes referred to as “structural unit (a5-1)”). However, the resin (A3) does not include the structural unit (a1-0), the structural unit (a1-1), and the structural unit (a1-2), and the structural unit (a1-4) and the structural unit (a2- 0) is not included. The resin (A3) is preferably any of the structural unit (a1-0), the structural unit (a1-1), the structural unit (a1-2), the structural unit (a1-4), and the structural unit (a2-0). This resin does not contain

［式（ａ５−１）中、
Ｒ^a50は、水素原子又はメチル基を表す。
Ｒ^a51は、炭素数１〜１８の飽和炭化水素基を表す。］ The structural unit (a5-1) is represented by the following formula (a5-1).

[In the formula (a5-1),
R ^a50 represents a hydrogen atom or a methyl group.
R ^a51 represents a saturated hydrocarbon group having 1 to 18 carbon atoms. ]

アルキル基と脂環式飽和炭化水素基とを組合わせた基としては、例えば、メチルシクロヘキシル基、ジメチルシクロへキシル基、メチルノルボルニル基等が挙げられる。 ^Examples of the saturated hydrocarbon group for R ^a51 include an alkyl group, an alicyclic saturated hydrocarbon group, and a group obtained by combining these.
^Examples of the alkyl group for ^Ra51 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic saturated hydrocarbon group for R ^a51 may be monocyclic or polycyclic. Examples of the monocyclic alicyclic saturated 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 saturated hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group (* represents a bond). The alicyclic saturated hydrocarbon group for R ^a51 preferably has 3 to 16 carbon atoms.

Examples of the group in which an alkyl group and an alicyclic saturated hydrocarbon group are combined include a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylnorbornyl group.

Examples of the structural unit (a5-1) include the following structural units.

In the above structural unit, a structural unit in which a methyl group corresponding to R ^a50 is replaced with a hydrogen atom can also be given as a specific example of the structural unit (a5-1).

  The content of the structural unit (a5-1) is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, and 90 mol% with respect to all the structural units of the resin (A3). The above is particularly preferable. The resin (A3) may have a structural unit other than the structural unit (a5-1), but it is particularly preferable that the resin (A3) consists essentially of the structural unit (a5-1).

［式（ａ４）中、
Ｒ^３は、水素原子又はメチル基を表す。
Ｒ^４は、フッ素原子を有する炭素数１〜２０の飽和炭化水素基を表す。］ Examples of the structural unit other than the structural unit (a5-1) that the resin (A3) may have include the structural unit (a2), the structural unit (a3), and the following formula (a4). Structural units (hereinafter sometimes referred to as “structural units (a4)”) and the like.

[In the formula (a4),
R ³ represents a hydrogen atom or a methyl group.
R ⁴ represents a saturated hydrocarbon group having 1 to 20 carbon atoms having a fluorine atom. ]

Examples of the saturated hydrocarbon group having a fluorine atom for R ⁴ include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, Perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) -1,2 , 2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoro (Ropropyl) 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, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, 1,1,2, 2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group, perfluoropentyl Examples thereof include fluorinated alkyl groups such as a methyl group and a perfluorohexyl group; and alicyclic saturated hydrocarbon groups having a fluorine atom such as a perfluorocyclohexyl group and a perfluoroadamantyl group.

［式（ａ４−１）中、
Ｒ^５は、水素原子又はメチル基を表す。
Ｌ^４は、炭素数１〜４の脂肪族飽和炭化水素基を表す。
Ｌ^３は、炭素数１〜８のペルフルオロアルカンジイル基を表す。
Ｒ^６は、水素原子又はフッ素原子を表す。］ The structural unit (a4) is preferably a structural unit represented by the formula (a4-1).

[In the formula (a4-1),
R ⁵ represents a hydrogen atom or a methyl group.
L ⁴ represents an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms.
L ³ represents a C 1-8 perfluoroalkanediyl group.
R ⁶ represents a hydrogen atom or a fluorine atom. ]

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

L ⁴ is preferably a methylene group.
L ³ is preferably a C 1-3 perfluoroalkanediyl group.

Examples of the structural unit (a4) include the following.

In the above structural unit, a structural unit in which a methyl group corresponding to R ³ is replaced by a hydrogen atom can also be given as a specific example of the structural unit (a4).

  When the resin (A3) contains the structural unit (a4), the content is preferably from 5 to 90 mol%, more preferably from 10 to 70 mol%, based on all the structural units of the resin (A3). 50 mol% is more preferable.

  The weight average molecular weight of the resin (A3) is preferably 5,000 or more and 100,000 or less, more preferably 6,000 or more and 50,000 or less, and further preferably 8,000 or more and 40,000 or less. .

  Each structural unit constituting the resin (A3) can be produced by a known polymerization method (for example, radical polymerization method) using a monomer that derives these structural units. The content rate of each structural unit can be adjusted with the usage-amount of the monomer used when manufacturing resin (A3).

[Acid generator (B)]
The acid generator (B) is classified into a nonionic type and an ionic type, and any of them may be used.
Nonionic acid generators include organic halides, sulfonate esters (for example, 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4). -Sulfonate) and sulfones (for example, disulfone, ketosulfone, sulfonyldiazomethane) and the like. Examples of the ionic acid generator include onium salts containing onium cations (for example, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts) and the like. Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethide anion.

  Examples of the acid generator (B) include JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, JP-A-62-153853, JP-A-63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. 126,712 The compound which generate | occur | produces an acid by the radiation as described in etc. can be used.

As the acid generated from the acid generator, sulfonic acid is preferable, and sulfonic acid containing no fluorine atom is more preferable.
When the acid generator (B) includes an acid generator that generates a sulfonic acid not containing a fluorine atom, the content of the acid generator is preferably 50 masses with respect to the total amount of the acid generator (B). % Or more, more preferably 60% by mass or more, and still more preferably 90% by mass or more.

［式（Ｂ１）中、Ｒ^ｂ１及びＲ^ｂ２は、互いに独立に、炭素数１〜１０の炭化水素基を表す。］ As the nonionic acid generator that generates a sulfonic acid not containing a fluorine atom, a compound represented by the formula (B1) is preferable.

[In Formula (B1), R ^b1 and R ^b2 each independently represent a hydrocarbon group having 1 to 10 carbon atoms. ]

Examples of the hydrocarbon group for R ^b1 and R ^b2 include an alkyl group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include an adamantyl group and a norbornyl group.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2- And aryl groups such as methyl-6-ethylphenyl.

Specific examples of the compound represented by the formula (B1) include the following compounds.

［式（Ｂ２）中、
Ｒ^ｂ３は、炭素数１〜２４の炭化水素基を表し、該炭化水素基に含まれる水素原子は、ヒドロキシ基又はカルボキシ基に置換されていてもよく、該炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
Ａ^＋は有機カチオンを表す。］ As the ionic acid generator that generates a sulfonic acid not containing a fluorine atom, a salt represented by the formula (B2) is preferable.

[In the formula (B2),
R ^b3 represents a hydrocarbon group having 1 to 24 carbon atoms, the hydrogen atom contained in the hydrocarbon group may be substituted with a hydroxy group or a carboxy group, and the methylene group contained in the hydrocarbon group is , Oxygen atom or carbonyl group may be substituted.
A ⁺ represents an organic cation. ]

The hydrocarbon group of R ^b3 is, for example, an aliphatic hydrocarbon group having 1 to 24 carbon atoms, an alicyclic hydrocarbon group having 3 to 24 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, and a combination thereof. And a group having 24 or less carbon atoms.
Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, hexadecyl group, pentadecyl group, hexyl. Examples thereof include alkyl groups such as decyl group, heptadecyl group, octadecyl group and icosyl group.
Examples of the alicyclic hydrocarbon group include a monocyclic alicyclic hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group; 2.1] Polycyclic alicyclic hydrocarbon groups such as heptyl group, adamantyl group and the following groups.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, biphenyl group. And aryl groups such as phenanthryl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, 2,4,6-trimethylphenyl group, 2,4,6-triisopropylphenyl group, and the like. .
Examples of the group obtained by combining an aliphatic hydrocarbon group and an alicyclic hydrocarbon group include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, and an isobornyl group.
Examples of the group obtained by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the group in which the hydrogen atom contained in the hydrocarbon group is substituted with a hydroxy group or a carboxy group include the following groups.

Examples of the group in which the methylene group contained in the hydrocarbon group is replaced with an oxygen atom or a carbonyl group include the following groups.

R ^b3 is preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms or an alicyclic hydrocarbon group having 3 to 24 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is a hydroxy group or a carboxy group. The methylene group contained in the aromatic hydrocarbon group and the alicyclic hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.

［式（Ｂ３）中、
Ｒ^ｂ３０は、ヒドロキシ基、カルボキシ基又は炭素数１〜８の炭化水素基を表し、該炭化水素基に含まれるメチレン基は、酸素原子又はカルボニル基に置き換わっていてもよい。
ｍｘは、０〜５の整数を表す。ｍｘが２以上のとき、複数のＲ^ｂ３０は同一又は相異なり、さらに複数のＲ^ｂ３０が炭素数１〜８の炭化水素基を表す場合、その合計炭素数は１８以下である。］ R ^b3 is more preferably a group represented by the formula (B3).

[In the formula (B3),
R ^b30 represents a hydroxy group, a carboxy group or a hydrocarbon group having 1 to 8 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group.
mx represents an integer of 0 to 5. When mx is 2 or more, the plurality of R ^b30 are the same or different, and when the plurality of R ^b30 represent a hydrocarbon group having 1 to 8 carbon atoms, the total carbon number is 18 or less. ]

Examples of the hydrocarbon group having 1 to 8 carbon atoms of R ^b30 include an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 8 carbon atoms, and an aromatic carbon group having 6 to 8 carbon atoms. A hydrogen group and a group having 8 or less carbon atoms, and a combination thereof, preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms. Specific examples include the above.
R ^b30 is preferably a hydroxy group, a carboxy group, or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. More preferably, it is a C1-C8 aliphatic hydrocarbon group.

  As the group represented by the formula (B3), a phenyl group, a 2,4,6-trimethylphenyl group or a 2,4,6-triisopropylphenyl group is particularly preferable.

Examples of the sulfonate anion represented by the formula (B2) include anions represented by any one of the formulas (B2-a-1) to (B2-a-19), and preferably the formula (B2-a) −8) to formula (B2-a-16), and more preferably, an anion represented by formula (B2-a-8) to formula (B2-a-11) or formula (B2-a). -15) and an anion represented by formula (B2-a-16).

A ⁺ is preferably a cation represented by any one of formulas (b2-1) to (b2-4).

In formula (b2-1) to formula (b2-4),
^Do R ^b4 , R ^b5 and R ^b6 each independently represent an alkyl group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 36 carbon atoms? , R ^b4 and R ^b5 together form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) containing a sulfur atom. The hydrogen atom contained in the alkyl group is substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 18 carbon atoms, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an alkoxy group having 1 to 12 carbon atoms.
R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 represent the integer of 0-5 independently of each other. When m2 is 2 or more, the plurality of R ^b7 are the same or different, and when n2 is 2 or more, the plurality of R ^b8 are the same or different.
R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or R ^b9 and R ^b10 are They are bonded to each other together with the sulfur atom to be bonded to form a 3- to 12-membered ring (preferably a 3- to 7-membered ring). The methylene group contained in the ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms.
R ^b12 represents an alkyl 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. The hydrogen atom contained in the alkyl group may be substituted with an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is an alkoxy group having 1 to 12 carbon atoms. Alternatively, it may be substituted with an alkylcarbonyloxy group having 1 to 12 carbon atoms.
R ^b11 and R ^b12 may form a 3- to 12-membered ring (preferably a 3- to 7-membered ring) together with —CH—CO— to which they are bonded, The contained methylene group may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
R ^{b13 to} R ^b18 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents an oxygen atom or a sulfur atom.
o2, p2, s2, and t2 each independently represent an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, multiple R ^b13 are the same or different, when p2 is 2 or more, multiple R ^b14 are the same or different, and when s2 is 2 or more, multiple R ^b15 are the same or different , T2 is 2 or more, the plurality of R ^b18 are the same or different.

特に、Ｒ^b9〜Ｒ^b11の脂環式炭化水素基は、好ましくは炭素数４〜１２である。 Examples of the alkyl group 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 2-ethylhexyl group. Can be mentioned. In particular, the alkyl group of R ^{b9 to} R ^b12 preferably has 1 to 12 carbon atoms.
Examples of the alkyl group in which a hydrogen atom is substituted with an alicyclic hydrocarbon group include a 1- (adamantan-1-yl) alkane-1-yl group.
The alicyclic hydrocarbon group may be monocyclic or polycyclic, and the hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an alkyl group. In this case, the carbon number of the alicyclic hydrocarbon group is 20 or less including the carbon number of the alkyl group. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups.

In particular, the alicyclic hydrocarbon group of R ^{b9 to} R ^b11 preferably has 4 to 12 carbon atoms.

  Examples of the alicyclic hydrocarbon group in which a hydrogen atom is substituted with an alkyl group include a methylcyclohexyl group, a dimethylcyclohexyl group, a 2-alkyladamantan-2-yl group, a methylnorbornyl group, and an isobornyl group. Can be mentioned.

Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4-cyclohexylphenyl group, 4-adamantyl group. Substituted or unsubstituted phenyl groups such as phenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group; biphenylyl group, naphthyl group, phenanthryl group and the like.
As an aromatic hydrocarbon group by which the hydrogen atom was substituted by the alkoxy group, 4-methoxyphenyl group etc. are mentioned, for example.
Examples of the alkyl group in which a hydrogen atom is substituted with an aromatic hydrocarbon group, that is, an aralkyl group, include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.
In addition, when an alkyl group or an alicyclic hydrocarbon group is contained in an aromatic hydrocarbon group, a C1-C12 alkyl group and a C3-C18 alicyclic hydrocarbon group are preferable.

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

The ring containing a sulfur atom which may be formed by combining R ^b4 and R ^b5 is any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated rings. If it contains one or more sulfur atoms, it may further contain one or more sulfur atoms and / or one or more oxygen atoms. As the ring, a ring having 3 to 18 carbon atoms is preferable, and a ring having 4 to 18 carbon atoms is more preferable.

The hydrocarbon groups for R ^b4 , R ^b5 and R ^b6 are preferably independently of each other an alkyl group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a carbon group having 6 to 18 carbon atoms. It is an aromatic hydrocarbon group, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with a halogen atom, an acyl group having 2 to 4 carbon atoms, or a glycidyloxy group, and the aromatic hydrocarbon group includes a halogen atom, a hydroxy group, or It may be substituted with an alkoxy group having 1 to 12 carbon atoms.

Examples of the ring formed together with the sulfur atom to which R ^b9 and R ^b10 are bonded include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, and 1,4-oxathian-4-ium. A ring etc. are mentioned.
Examples of the ring formed with —CH—CO— in which R ^b11 and R ^b12 are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

  As a cation represented by Formula (b2-1)-Formula (b2-4), what was described in Unexamined-Japanese-Patent No. 2010-204646 is mentioned, for example.

Preferred examples of the salt represented by the formula (B2) include the following salts.

  The acid generator (B) is preferably an acid generator containing a compound represented by the formula (B1) and a salt represented by the formula (B2). When the acid generator (B) is such an acid generator, the content ratio of the compound represented by the formula (B1) and the salt represented by the formula (B2) is preferably 50% by mass. : 50 to 95: 5, more preferably 60:40 to 90:10.

[Basic compound (C)]
The content of the basic compound (C) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and particularly preferably 0.01 to 5% by mass in the solid content of the resist composition. 1% by mass.

The basic compound (C) is preferably a salt having a lower acidity than an acid generated from a basic nitrogen-containing organic compound or an acid generator (B).
Examples of the basic nitrogen-containing organic compound include amines and ammonium salts. The basic compound (C) is used as a quencher in the resist composition of the present invention. A quencher is a compound having an action of capturing an acid generated from an acid generator upon exposure. Amines include aliphatic and aromatic amines; primary amines, secondary amines and tertiary amines. The basic compound (C) is preferably at least one selected from the group consisting of a compound represented by any one of the formulas (C1) to (C8) and an ammonium salt, more preferably the formula (C1). Or at least one selected from the group consisting of ammonium salts, more preferably ammonium salts.

［式（Ｃ１）中、Ｒ^c1、Ｒ^c2及びＲ^c3は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数５〜１０の脂環式炭化水素基又は炭素数６〜２０の芳香族炭化水素基を表し、該アルキル基及び該脂環式炭化水素基に含まれる水素原子は、ヒドロキシ基、アミノ基又は炭素数１〜６のアルコキシ基で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜６のアルコキシ基で置換されていてもよい。］

[In formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 5 to 10 carbon atoms, or 6 to 6 carbon atoms. 20 represents an aromatic hydrocarbon group, the hydrogen atom contained in the alkyl group and the alicyclic hydrocarbon group may be substituted with a hydroxy group, an amino group or an alkoxy group having 1 to 6 carbon atoms, The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 6 carbon atoms. ]

［式（Ｃ１−１）中、Ｒ^c2及びＲ^c3は、上記と同じ意味を表す。
Ｒ^c4は、炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基、炭素数５〜１０の脂環式炭化水素又は炭素数６〜１０の芳香族炭化水素基を表す。
ｍ３は０〜３の整数を表し、ｍ３が２以上のとき、複数のＲ^c4は同一又は相異なる。］ The compound represented by the formula (C1) is preferably a compound represented by the formula (C1-1).

[In Formula (C1-1), R ^c2 and R ^c3 represent the same meaning as described above.
R ^c4 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alicyclic hydrocarbon having 5 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
m3 represents an integer of 0 to 3, and when m3 is 2 or more, the plurality of R ^c4 are the same or different. ]

［式（Ｃ２）、式（Ｃ３）及び式（Ｃ４）中、Ｒ^c5、Ｒ^c6、Ｒ^c7及びＲ^c8は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c9は、炭素数１〜６のアルキル基、炭素数３〜６の脂環式炭化水素基又は炭素数２〜７のアシル基を表す。
ｎ３は０〜８の整数を表し、ｎ３が２以上のとき、複数のＲ^c9は同一又は相異なる。］

[In Formula (C2), Formula (C3) and Formula (C4), R ^c5 , R ^c6 , R ^c7 and R ^c8 each independently represent the same meaning as R ^c1 .
R ^c9 represents an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an acyl group having 2 to 7 carbon atoms.
n3 represents an integer of 0 to 8, and when n3 is 2 or more, the plurality of R ^c9 are the same or different. ]

［式（Ｃ５）及び式（Ｃ６）中、Ｒ^c10、Ｒ^c11、Ｒ^c12、Ｒ^c13及びＲ^c16は、それぞれ独立に、Ｒ^c1と同じ意味を表す。
Ｒ^c14、Ｒ^c15及びＲ^c17は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｏ３及びｐ３は、それぞれ独立に、０〜３の整数を表し、ｏ３が２以上のとき、複数のＲ^c1４は同一又は相異なり、ｐ３が２以上のとき、複数のＲ^c15は同一又は相異なる。
Ｌ^c1は、炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

[In Formula (C5) and Formula (C6), R ^c10 , R ^c11 , R ^c12 , R ^c13 and R ^c16 each independently represent the same meaning as R ^c1 .
R ^c14 , R ^c15 and R ^c17 each independently represent the same meaning as R ^c4 .
o3 and p3 each independently represent an integer of 0 to 3, when o3 is 2 or more, the plurality of R ^c14 are the same or different, and when p3 is 2 or more, the plurality of R ^c15 are the same or different. .
L ^c1 represents an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

［式（Ｃ７）及び式（Ｃ８）中、Ｒ^c18、Ｒ^c19及びＲ^c20は、それぞれ独立に、Ｒ^c4と同じ意味を表す。
ｑ３、ｒ３及びｓ３は、それぞれ独立に０〜３の整数を表し、ｑ３が２以上のとき、複数のＲ^c18は同一又は相異なり、ｒ３が２以上のとき、複数のＲ^c1９は同一又は相異なり、ｓ３が２以上のとき、複数のＲ^c20は同一又は相異なる。
Ｌ^c2は、単結合又は炭素数１〜６のアルカンジイル基、−ＣＯ−、−Ｃ（＝ＮＨ）−、−Ｓ−又はこれらを組合せた２価の基を表す。］

Wherein (C7) and formula ^{(C8), R c18, R} c19 and R ^c20 in each occurrence independently represent the same meaning as R ^c4.
q3, r3 and s3 each independently represents an integer of 0 to 3, and when q3 is 2 or more, a plurality of R ^c18 are the same or different, and when r3 is 2 or more, a plurality of R ^c19 are the same or different. In contrast, when s3 is 2 or more, the plurality of R ^c20 are the same or different.
L ^c2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms, —CO—, —C (═NH) —, —S—, or a divalent group obtained by combining these. ]

In formula (C1) to formula (C8) and formula (C1-1), the alkyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, alkoxy group, alkanediyl group are the same as those described above. Is mentioned.
Examples of the acyl group include acetyl group, 2-methylacetyl group, 2,2-dimethylacetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, and 2,2-dimethylpropionyl group.

  Examples of the compound represented by the formula (C1) include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N, N- Dimethylaniline, diphenylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, triethylamine, trimethylamine, tripropylamine, tributylamine, tri Pentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine, methyl Hexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldinonylamine, methyldidecylamine, ethyldibutylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldinonyl Amine, ethyldidecylamine, dicyclohexylmethylamine, tris [2- (2-methoxyethoxy) ethyl] amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diamino-1,2- Examples include diphenylethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3,3′-diethyldiphenylmethane, and preferably diisopropyl. Piruanirin. Particularly preferred include 2,6-diisopropylaniline.

Examples of the compound represented by the formula (C2) include piperazine.
Examples of the compound represented by the formula (C3) include morpholine.
Examples of the compound represented by the formula (C4) include piperidine and hindered amine compounds having a piperidine skeleton described in JP-A No. 11-52575.
Examples of the compound represented by the formula (C5) include 2,2′-methylenebisaniline.
Examples of the compound represented by the formula (C6) include imidazole and 4-methylimidazole.
Examples of the compound represented by the formula (C7) include pyridine and 4-methylpyridine.
Examples of the compound represented by the formula (C8) include 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′-dipiconylamine, bipyridine and the like.

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

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

Examples of the salt having a lower acidity than the acid generated from the acid generator (B) include a salt represented by the following formula.

［式（Ｅ）中、
Ｒ^Ｄ１及びＲ^Ｄ２は、それぞれ独立に、炭素数１〜１２の１価の炭化水素基、炭素数１〜６のアルコキシ基、炭素数２〜７のアシル基、炭素数２〜７のアシルオキシ基、炭素数２〜７のアルコキシカルボニル基、ニトロ基又はハロゲン原子を表す。
ｍ’及びｎ’は、それぞれ独立に、０〜４の整数を表し、ｍ’が２以上の場合、複数のＲ^Ｄ１は同一又は相異なり、ｎ’が２以上の場合、複数のＲ^Ｄ２は同一又は相異なる。］ The salt having a weaker acidity than the acid generated from the acid generator (B) is a weak acid intramolecular salt represented by the following formula (E) (hereinafter sometimes referred to as “weak acid intramolecular salt (E)”). And salts described in JP 2012-229206 A, JP 2012-6908 A, JP 2012-72109 A, JP 2011-39502 A, and JP 2011-191745 A.

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

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

Examples of the alkoxy group include a methoxy group and an ethoxy group.
Examples of the acyl group include an acetyl group, a propanoyl group, a benzoyl group, and a cyclohexanecarbonyl group.
Examples of the acyloxy group include a group in which an oxy group (—O—) is bonded to the acyl group.
Examples of the alkoxycarbonyl group include a group in which a carbonyl group (—CO—) is bonded to the above alkoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In Formula (E), R ^D1 and R ^D2 are each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 2 to 4 carbon atoms. And an acyloxy group having 2 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms, a nitro group, or a halogen atom is preferable.
m ′ and n ′ are each independently preferably an integer of 0 to 2, and more preferably 0. When m ′ is 2 or more, the plurality of R ^D1 are the same or different, and when n ′ is 2 or more, the plurality of R ^D2 are the same or different.

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

  The weak acid inner salt (E) can be produced by the method described in “Tetrahedron Vol. 45, No. 19, p6281-6296”. Moreover, what is marketed can be used for the weak acid inner salt (E).

[Solvent (D)]
The solvent (D) can be appropriately selected from the viewpoint of the coating properties of the resist composition, etc., depending on the type and amount of the resin and acid generator used. The content of the solvent (D) is, for example, 75% by mass or more in the resist composition, preferably 80% by mass or more, more preferably 85% by mass or more, for example 99.9% by mass or less, preferably 99% by mass or less. It is. The content rate of a solvent (D) can be measured with well-known analysis means, such as a liquid chromatography or a gas chromatography, for example.

  Examples of the solvent (D) include glycol ether esters such as ethyl cellosolve acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; glycol ethers such as propylene glycol monomethyl ether; ethyl lactate, butyl acetate, amyl acetate and pyruvic acid Examples thereof include esters such as ethyl; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; and cyclic esters such as γ-butyrolactone. The solvent (D) may contain only 1 type and may contain 2 or more types.

[Other components (hereinafter may be referred to as “other components (F)”)]
The resist composition of the present invention may contain other components (F) as needed in addition to the components described above. There are no particular limitations on the other component (F), and examples include additives known in the art, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, and dyes.

[Method for producing resist composition]
The resist composition of the present invention is prepared by mixing the resin and the acid generator (B), and the solvent (D), basic compound (C), and other components (F) used as necessary. be able to. The mixing order is arbitrary and is not particularly limited. The temperature at the time of mixing can select an appropriate temperature range from the range of 10-40 degreeC according to the kind etc. of resin etc., the solubility with respect to solvents (D), such as resin. An appropriate mixing time can be selected from 0.5 to 24 hours depending on the mixing temperature. The mixing means is not particularly limited, and stirring and mixing can be used.
After mixing each component, it is preferable to filter using a filter having a pore size of about 0.003 to 0.2 μm.

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

  Application of the resist composition onto the substrate can be performed by a commonly used apparatus such as a spin coater. By adjusting the conditions of the coating apparatus, the film thickness of the composition after coating can be adjusted. Examples of the substrate include a silicon wafer. Before applying the resist composition, the substrate may be washed or an antireflection film may be formed using a commercially available organic antireflection film composition.

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

The obtained composition layer is usually exposed using an exposure machine. The exposure machine may be an immersion exposure machine. Exposure light sources include those that emit laser light in the ultraviolet region such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm), solid-state laser light source (YAG or semiconductor laser) Etc.) using various types of laser light such as those that convert the wavelength of laser light from the laser to emit harmonic laser light in the far-ultraviolet region or vacuum ultraviolet region, those that irradiate electron beams, extreme ultraviolet light (EUV), etc. it can. In this specification, irradiating these radiations may be collectively referred to as “exposure”. The exposure is usually performed through a mask corresponding to a desired resist pattern. When the exposure light source is an electron beam, a desired pattern may be directly drawn without using a photomask.

  The composition layer after exposure is subjected to heat treatment (so-called post-exposure baking) in order to promote the deprotection reaction of the acid labile group of the resin (A). As heating temperature, it is about 50-200 degreeC normally, Preferably it is about 70-150 degreeC.

  The heated composition layer is usually developed using a developer using a developing device. Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dispensing method. The development temperature is preferably 5 to 60 ° C., for example, and the development time is preferably 5 to 300 seconds, for example.

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

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

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

<Application>
Since the resist composition of the present invention is excellent in the shape of the resist pattern to be obtained, the resist composition for KrF excimer laser exposure, the resist composition for electron beam (EB) irradiation, or the resist composition for EUV exposure is particularly preferred. It is suitable and useful for fine processing of semiconductors.

The present invention will be described more specifically with reference to examples. In the examples,% and parts representing the content and the amount used are based on mass unless otherwise specified.
The weight average molecular weight of the resin is a value determined by gel permeation chromatography under the following conditions.
Apparatus: HLC-8120GPC type (manufactured by Tosoh Corporation)
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)

(Resin synthesis)
The monomers used for resin synthesis are shown below. Hereinafter, these monomers are referred to as “monomer (a1-1-3)” or the like according to the formula number.

Synthesis Example 1 [Synthesis of Resin A1-1]
As the monomer, using monomer (a1-1-3), monomer (a1-2-9), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1), The molar ratio [monomer (a1-1-3): monomer (a1-2-9): monomer (a2-1-3): monomer (a3-2-3): monomer (a3-1-1)] 45: 14: 2.5: 22: 16.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to make a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.95 mol% and 2.85 mol%, respectively, based on the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin obtained was dissolved again in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and the weight-average molecular weight was 7. 9 × 10 ³ resin A1-1 was obtained with a yield of 73%. This resin A1-1 has the following structural units.

Synthesis Example 2 [Synthesis of Resin A1-2]
As the monomer, monomer (a1-2-9), monomer (a2-1-1) and monomer (a3-2-3) were used, and the molar ratio [monomer (a1-2-9): monomer (a2-1) -1): monomer (a3-2-3))] was mixed at 50:20:30, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount was added to obtain a solution. To this solution, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added in an amount of 0.85 mol% and 2.55 mol%, respectively, with respect to the total monomer amount, and these were added at 73 ° C. Heated for about 5 hours. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin obtained was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin. 1 × 10 ⁴ resin A1-2 was obtained with a yield of 70%. This resin A1-1 has the following structural units.

Synthesis Example 3 [Synthesis of Resin A1-3]
As the monomer, using monomer (a1-1-3), monomer (a1-0-6), monomer (a2-1-3), monomer (a3-2-3) and monomer (a3-1-1), The molar ratio [monomer (a1-1-3): monomer (a1-0-6): monomer (a2-1-3): monomer (a3-2-3): monomer (a3-1-1)] 45: 14: 2.5: 22: 16.5, and 1.5 mass times propylene glycol monomethyl ether acetate of the total monomer amount 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 the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin obtained was dissolved again in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin, and the weight-average molecular weight was 7. 7 × 10 ³ resin A1-3 was obtained with a yield of 73%. This resin A1-3 has the following structural units.

Synthesis Example 4 [Synthesis of Resin A2-1]
100 parts of polyvinylphenol (“VP-15000” manufactured by Nippon Soda Co., Ltd.) and 400 parts of acetone were added, and then 46.0 parts of potassium carbonate, 28.3 parts of 2-iodopropane and 4.6 parts of water were added. The mixture was stirred and refluxed for 30 hours. Thereafter, 200 parts of methyl isobutyl ketone was added to the reaction solution, and then 258 parts of 2% oxalic acid water was added and stirred for separation. Further, 258 parts of 2% oxalic acid water was added to the organic layer, and the mixture was stirred and separated two times. The operation of separating and washing by adding 300 parts of methyl isobutyl ketone and 166 parts of ion-exchanged water to the organic layer after the separation was performed 4 times. The organic layer after washing was concentrated, and 300 parts of methyl isobutyl ketone was further added and concentrated again to obtain 448 parts of a methyl isobutyl ketone solution of resin A2-1-1 (solid content 22%).
176 parts of a methyl isobutyl ketone solution of resin A2-1-1, 330 parts of methyl isobutyl ketone and 0.004 part of p-toluenesulfonic acid dihydrate were charged and concentrated until the total amount of the mixed solution was 273 parts. 8.01 parts of ethyl vinyl ether was added dropwise to the concentrated resin solution, and the mixture was stirred for 2.5 hours for reaction. Thereafter, 58.2 parts of ion-exchanged water and 0.005 part of triethylamine were added to the reaction solution, and the mixture was stirred and separated. Subsequently, 58.2 parts of ion-exchanged water was added to the organic layer and liquid separation was performed 4 times. The organic layer after washing was concentrated, 260 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 143 parts of a propylene glycol monomethyl ether acetate solution of resin A2-1 (solid content 30%). Resin A2-1 had a weight average molecular weight of 1.70 × 10 ⁴ , an introduction rate of isopropyl group with respect to all structural units was 14.2 mol%, and an introduction rate of ethoxyethyl group was 29.7 mol%. Resin A2-1 has the following structural units.

Synthesis Example 5 [Synthesis of Resin A2-2]
40 parts of polyvinylphenol (“VP-15000” manufactured by Nippon Soda Co., Ltd.), 240 parts of methyl isobutyl ketone and 0.006 part of p-toluenesulfonic acid dihydrate are added, and the total amount of this mixed solution becomes 200 parts. Until concentrated. To the concentrated resin solution, 10.55 parts of isobutyl vinyl ether was added dropwise and stirred for 2.5 hours. Thereafter, the mixture was diluted with 80 parts of methyl isobutyl ketone, 120 parts of ion-exchanged water and 0.005 part of triethylamine were added to the solution, stirred and separated. Subsequently, the operation of adding 120 parts of ion-exchanged water to the organic layer and separating the liquid was performed 4 times. The organic layer after washing was concentrated, added with 392 parts of propylene glycol monomethyl ether acetate, and concentrated again to obtain 157 parts of propylene glycol monomethyl ether acetate solution of resin A2-2 (solid content 31%). The weight average molecular weight of Resin A2-2 was 2.00 × 10 ⁴ , and the introduction ratio of isobutoxyethyl groups with respect to all the structural units was 27.2 mol%. Resin A2-2 has the following structural units.

Synthesis Example 6 [Synthesis of Resin A2-3]
100 parts of polyvinylphenol (“VP-15000” manufactured by Nippon Soda Co., Ltd.) and 400 parts of acetone were added, then 13.6 parts of triethylamine was added and stirred, and 12.6 parts of benzoyl chloride was added dropwise. After stirring the mixed solution for 2 hours, 200 parts of methyl isobutyl ketone was added, and then 242 parts of 0.5% aqueous oxalic acid was added and stirred for liquid separation. Further, 242 parts of 0.5% oxalic acid water was added to the organic layer and stirred, followed by liquid separation twice. The operation of separating and washing by adding 300 parts of methyl isobutyl ketone and 166 parts of ion-exchanged water to the organic layer after the separation was performed 4 times. The organic layer after washing was concentrated, 300 parts of methyl isobutyl ketone was further added, and the mixture was concentrated again to obtain 356 parts of a methyl isobutyl ketone solution of resin A2-3-1 (solid content 27%).
145 parts of a methyl isobutyl ketone solution of resin A2-3-1, 375 parts of methyl isobutyl ketone and 0.004 part of p-toluenesulfonic acid dihydrate were charged and concentrated until the total amount of this mixed solution was 280 parts. To the resin solution after concentration, 9.66 parts of ethyl vinyl ether was added dropwise and stirred for 2.5 hours. Thereafter, 60.4 parts of ion-exchanged water and 0.005 part of triethylamine were added and stirred for separation. Subsequently, 60.4 parts of ion-exchanged water was added to the organic layer and liquid separation was performed 4 times. The organic layer after the washing was concentrated, 300 parts of propylene glycol monomethyl ether acetate was added, and the mixture was concentrated again to obtain 162 parts of a propylene glycol monomethyl ether acetate solution of resin A2-3 (solid content 29%). Resin A2-3 had a weight average molecular weight of 1.80 × 10 ⁴ , a benzoyl group protection rate of 10.2%, and an ethoxyethyl group introduction rate of 35.3% with respect to all structural units. Resin A2-3 has the following structural units.

Synthesis Example 7 [Synthesis of Resin A3-1]
Monomer (a5-1-1) was used as a monomer, and 1.5 mass times propylene glycol monomethyl ether acetate as the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin obtained was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin. 1 × 10 ⁴ resin A3-1 was obtained with a yield of 78%. This resin A3-1 has the following structural units.

Synthesis Example 8 [Synthesis of Resin A3-2]
Monomer (a5-1-4) was used as a monomer, and 1.5 mass times propylene glycol monomethyl ether acetate as the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 73 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin obtained was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin. 2 × 10 ⁴ resin A3-2 was obtained with a yield of 93%. This resin A3-2 has the following structural units.

Synthesis Example 9 [Synthesis of Resin A3-3]
As the monomer, monomer (a5-1-1) and monomer (a5-1-4) were used, and the molar ratio [monomer (a5-1-1): monomer (a5-1-4))] was 70: The mixture was mixed to 30 and propylene glycol monomethyl ether acetate of 1.5 mass times the total monomer amount was added to prepare a solution. To this solution, 1 mol% and 3 mol% of azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) as initiators were added to the total monomer amount, respectively, and these were heated at 75 ° C. for about 5 hours. did. The obtained reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, and this resin was filtered. The resin obtained was again dissolved in propylene glycol monomethyl ether acetate, and the resulting solution was poured into a methanol solvent to precipitate the resin, followed by two reprecipitation operations of filtering the resin. 2 × 10 ⁴ resin A3-3 was obtained with a yield of 88%. This resin A3-3 has the following structural units.

Examples 1 to 10, Reference Examples 1 to 3 and Comparative Example 1
(Preparation of resist composition)
The resist composition was prepared by filtering the mixture obtained by mixing and melt | dissolving each component shown in Table 1, and the following solvent with the filter made from a fluororesin with the hole diameter of 0.2 micrometer.

<Resin>
A1-1: Resin A1-1
A1-2: Resin A1-2
A1-3: Resin A1-3
A2-1: Resin A2-1
A2-2: Resin A2-2
A2-3: Resin A2-3
A3-1: Resin A3-1
A3-2: Resin A3-2
A3-3: Resin A3-3

Ｂ２：トリフェニルスルホニウム ２，４，６-トリイソプロピルベンゼンスルホナート（東洋合成工業（株）製）

<Acid generator (B)>
B1: Bis (tert-butanesulfonyl) diazomethane; trade name “WPAG-170” (manufactured by Wako Pure Chemical Industries, Ltd.)

B2: Triphenylsulfonium 2,4,6-triisopropylbenzenesulfonate (manufactured by Toyo Gosei Co., Ltd.)

<Basic compound: Quencher>
C1: Tetramethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
C2: salt represented by the following formula (synthesized according to Examples in JP 2012-197261 A)

<Solvent>
Propylene glycol monomethyl ether acetate 130 parts Propylene glycol monomethyl ether 16 parts γ-butyrolactone 6 parts

(Manufacture of resist pattern)
A silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 ° C. for 60 seconds, and then spin-resisted on the silicon wafer so that the film thickness after pre-baking the resist composition was 0.285 μm. Coated.
Thereafter, the composition layer was formed by prebaking on a direct hot plate for 60 seconds at the temperature shown in the column “PB” in Table 1. The composition layer formed on the wafer was exposed to a line-and-space pattern using a KrF excimer laser stepper (NSR-2205EX12B NA0.55 σ0.8 conv. Exposure) while changing the exposure stepwise.
After the exposure, post-exposure baking was performed for 60 seconds on the hot plate at the temperature described in the “PEB” column of Table 1. Next, a negative resist pattern is produced by developing the composition layer on the silicon wafer by dipping at 23 ° C. for 30 seconds using butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a developer. did.
The exposure amount at which the line width and space width of the 250 nm line and space pattern were 1: 1 was defined as the effective sensitivity.

(Resolution evaluation)
In terms of effective sensitivity, the resist pattern was observed with a scanning electron microscope, and the resolved minimum line width was defined as the resolution. The results are shown in Table 2.
(Evaluation of resist pattern shape)
The cross-sectional shape of the obtained resist pattern was observed with a scanning electron microscope. In the effective sensitivity, when the bottom shape of the 180 nm line and space pattern is not skirted and the pattern collapse is not recognized, ○, and when the skirt and / or the pattern collapse is recognized as x, Table 2 shows Indicated. When the 180 nm line and space pattern was not resolved, the resolved minimum line width pattern was observed.

  The resist composition of the present invention can produce a high-resolution resist pattern with an excellent pattern shape.

Claims (4)

Resist composition for developing with organic solvent containing resin (A1), resin (A2), resin (A3) and acid generator.
Resin (A1): at least selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1), and a structural unit represented by formula (a1-2) Resin containing one type of structural unit Resin (A2): Structural unit represented by formula (a1-4) and resin containing a structural unit represented by formula (a2-0) (however, in formula (a1-0) (The structural unit represented, the structural unit represented by the formula (a1-1) and the structural unit represented by the formula (a1-2) are not included.)
Resin (A3): Resin consisting only of the structural unit represented by formula (a5-1)

[In the formula (a1-0),
L ^a01 represents an oxygen atom or ^* —O— (CH ₂ ) _k01 —CO—O—, k01 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a01 independently 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 obtained by combining these. ]

[In the formula (a1-1),
L ^a1 represents an oxygen atom or ^* —O— (CH ₂ ) _h1 —CO—O—, h1 represents an integer of 1 to 7, and * represents a bond to a carbonyl group.
R ^a4 represents a hydrogen atom or a methyl group.
R ^a6 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these.
m1 represents the integer of 0-14. ]

[In the formula (a1-2),
L ^a2 represents an oxygen atom or ^* —O— (CH ₂ ) _h2 —CO—O—, h2 represents an integer of 1 to 7, and * represents a bond with a carbonyl group.
R ^a5 represents a hydrogen atom or a methyl group.
R ^a7 represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group obtained by combining these.
n1 represents the integer of 0-10.
n1 ′ represents an integer of 0 to 3. ]

[Formula (a1-4),
R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom.
R ¹¹ is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
la represents an integer of 0 to 4. When la is 2 or more, the plurality of R ¹¹ are the same or different.
R ¹² and R ¹³ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
Y ^a3 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and the methylene group contained in the hydrocarbon group is an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or —N (R ^c )-may be substituted.
R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

[In the formula (a2-0),
R ^a30 represents a C 1-6 alkyl group which may have a halogen atom, a hydrogen atom or a halogen atom.
R ^a31 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an acyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or Represents a methacryloyloxy group.
ma represents an integer of 0 to 4. When ma is 2 or more, the plurality of R ^a31 are the same or different. ]

[In the formula (a5-1),
R ^a50 represents a hydrogen atom or a methyl group.
R ^a51 represents a saturated hydrocarbon group having 1 to 18 carbon atoms. ] Resin (A1) is a resin containing at least one structural unit selected from the group consisting of a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2),
Resin (A2) includes a structural unit represented by formula (a1-4) and a structural unit represented by formula (a2-0) (however, a structural unit represented by formula (a1-0), The structural unit represented by formula (a1-1) and the structural unit represented by formula (a1-2) are not included.)
The resist composition for organic solvent development according to claim 1, wherein the resin (A3) is a resin composed only of a structural unit represented by the formula (a5-1). The organic solvent developing agent according to claim 1 or 2, wherein the acid generator is an acid generator containing at least one selected from the group consisting of a compound represented by the formula (B1) and a salt represented by the formula (B2). Resist composition.

[In Formula (B1), R ^b1 and R ^b2 each independently represent a hydrocarbon group having 1 to 10 carbon atoms. ]

[In the formula (B2), R ^b3 represents a hydrocarbon group having 1 to 24 carbon atoms, and the hydrogen atom contained in the hydrocarbon group may be substituted with a hydroxy group or a carboxy group. The methylene group contained in the group may be replaced with an oxygen atom or a carbonyl group.
A ⁺ represents an organic cation. ] (1) The process of apply | coating the resist composition for organic solvent development in any one of Claims 1-3 on a board | substrate,
(2) A step of drying the composition after application to form a composition layer,
(3) a step of exposing the composition layer;
(4) A method for producing a resist pattern, comprising a step of heating the composition layer after exposure, and (5) a step of developing the composition layer after heating with an organic solvent.