JP5572520B2 - Actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method using the same - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a lithography process performed in a manufacturing process such as a VLSI, a high-capacity microchip, an imprint mold structure, and other photofabrication processes. And a resist film and a pattern forming method using the same. More specifically, the present invention relates to a positive resist composition for electron beam, X-ray or EUV light preferably applied to the above process, and a resist film and a pattern forming method using the same.

  In recent years, microfabrication by lithography has been demanded to form ultrafine patterns on the order of several tens of nanometers as integrated circuits are highly integrated. Along with this requirement, there is a tendency to shorten the exposure wavelength from g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is being developed.

  In addition, microfabrication using a resist composition is not only directly used for the production of integrated circuits, but also recently applied to the production of so-called imprint mold structures (for example, Patent Documents 1 and 2; And non-patent document 1).

  In particular, electron beam lithography is positioned as a next-generation or next-generation pattern forming technique, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is an extremely important issue for shortening the wafer processing time. However, in positive resists for electron beams, when trying to increase sensitivity, not only the resolution is lowered, but also the line edge. Roughness deteriorates, and development of a resist that satisfies these characteristics at the same time is strongly desired. Here, the line edge roughness means that when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered. Particularly in the ultrafine region of 0.25 μm or less, the line edge roughness is an extremely important improvement issue. High sensitivity, high resolution, good pattern shape, and good line edge roughness are in a trade-off relationship, and it is very important how to satisfy them simultaneously.

  Similarly, in lithography using X-rays or EUV light, it is important to satisfy high sensitivity, high resolution, good pattern shape, and good line edge roughness at the same time. is necessary.

  As one method for solving these problems, use of a resin having a photoacid generator in a polymer main chain or a side chain has been studied (see, for example, Patent Documents 3 to 8 and Non-Patent Document 2). However, since the technique disclosed in Patent Document 3 is a mixed system of a resin having a photoacid generator and a dissolution inhibiting compound whose solubility in an alkaline developer is increased by acid decomposition, these materials are mixed unevenly. It was difficult to obtain a good pattern shape and line edge roughness due to the property.

  On the other hand, Patent Documents 4 to 7 disclose resins having, in the same molecule, a photoacid-generating group and a group whose solubility in an alkali developer increases by acid decomposition, but ArF and ArF immersion exposure are assumed. In order to maintain transparency with respect to 193 nm light, an aromatic ring group was not introduced into the resin other than the cation portion of the photoacid generating group. In lithography using an electron beam or EUV light, for example, an aromatic ring site such as polyhydroxystyrene generates secondary electrons by exposure to the electron beam or EUV light, and the photoacid generator is decomposed by the secondary electrons. It is generally thought that acid is generated. Therefore, it is difficult to say that the sensitivity to electron beam, X-ray or EUV light is sufficient.

Patent Document 8 and Non-Patent Document 2 describe ternary copolymers of hydroxystyrene, an adamantyl group-containing acrylate, and a photoacid generator-containing acrylate.
Patent Document 9 contains a resin containing a repeating unit that is sensitive to high energy rays or heat and generates sulfonic acid at a fluorine-containing terminal of a side chain in order to improve high resolution, density dependency, and exposure margin. A resist is disclosed.
Patent Document 10 discloses that as a repeating unit having a photoacid generator in the side chain, a resin containing a repeating unit having a sulfonium cation structure and sulfonic acid, bis (alkylsulfonyl) amide or the like by irradiation with actinic rays or radiation. A resist composition containing a compound that generates tris (alkylsulfonyl) methine is disclosed.

  However, in lithography using a resin having a photoacid generating group and an acid decomposable group in the side chain (particularly lithography using electron beam, X-ray or EUV light), sensitivity, resolution, and exposure latitude are further increased. The reality is that improvement is required.

JP 2004-158287 A JP 2008-162101 A JP-A-9-325497 JP-A-10-221852 JP 2007-197718 A International Publication No. 06/121096 JP 2009-93137 A US Patent Application Publication No. 2007/117043 JP 2008-133448 A JP 2006-259509 A

Nanoimprint Basics and Technology Development / Application Development-Nanoimprint Substrate Technology and Latest Technology Deployment-Editing: Yoshihiko Hirai Frontier Publishing (issued in June 2006) Proc. of SPIE Vol. 6923, 692312, 2008

  In view of the above-mentioned background art, the present invention, particularly in lithography using an electron beam, X-rays or EUV light as an exposure light source, has high sensitivity, high resolution, and actinic ray sensitivity that satisfies the excellent exposure latitude at the same time. An object is to provide a radiation-sensitive resin composition, a resist film using the same, and a pattern forming method.

一般式（ＩＶ）中、Ｒ _４１ 、Ｒ _４２ 及びＲ _４３ は、各々独立に、水素原子、アルキル基、１価の脂肪族炭化水素環基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。またＲ _４２ はＡｒ _４ と結合して環を形成していてもよく、その場合のＲ _４２ はアルキレン基を表す。
Ｘ _１ は、単結合又は２価の連結基を表す。
Ａｒ _４ は、２価の芳香環基を表し、Ｒ _４２ と結合して環を形成する場合には３価の芳香環基を表す。
ｎは、１〜４の整数を表す。
＜４＞
前記化合物（Ｂ）が下記一般式（ＺＩ’−１−１）で表される、上記＜１＞〜＜３＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

Ｒ _１ 〜Ｒ _１５ は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アルキルカルボニルオキシ基、又はアリール基を表す。Ｒ _１ とＲ _１５ が互いに結合し環を形成してもよく、この場合、Ｒ _１ 及びＲ _１５ は単結合又は２価の連結基を形成する。
Ｒ _１６ 及びＲ _１７ は、それぞれ独立に、アルキル基を表す。Ｒ _１６ とＲ _１７ が互いに結合し環を形成してもよい。
＜５＞
上記一般式（ＺＩ’−１−１）において、Ｒ _１６ 及びＲ _１７ の各々が、少なくとも一つのフッ素原子を含む、上記＜４＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜６＞
上記一般式（ＺＩ’−１−１）において、Ｒ _１６ 及びＲ _１７ は、それぞれ独立して、フッ素原子若しくはフルオロアルキル基で置換されたアルキル基である、上記＜４＞又は＜５＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜７＞
Ｒ _１６ とＲ _１７ が互いに結合し環を形成している、上記＜４＞〜＜６＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜８＞
前記繰り返し単位（Ｂ）が、下記一般式（ＶＩ）で表される繰り返し単位である、上記＜１＞〜＜７＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（ＶＩ）中、Ｒ _６１ 、Ｒ _６２ 、Ｒ _６３ は、各々独立に、水素原子、アルキル基、１価の脂肪族炭化水素環基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。Ｒ _６２ はＡｒ _６ と結合して環を形成していてもよく、その場合のＲ _６２ はアルキレン基を表わす。
Ａｒ _６ は、２価の芳香環基を表し、Ｒ _６２ と結合して環を形成する場合には３価の芳香環基を表す。
Ｙは、水素原子又は酸の作用により脱離する基を表し、Ｙが複数存在する場合、複数のＹは同じであっても異なっていてもよい。但し、Ｙの少なくとも１つは、酸の作用により脱離する基を表す。
ｍは、１〜４の整数を表す。
＜９＞
上記＜１＞〜＜８＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成されたレジスト膜。
＜１０＞
上記＜９＞に記載のレジスト膜を、露光、現像する工程を有する、パターン形成方法。
本発明は上記＜１＞〜＜１０＞に記載した事項に関するものであるが参考のためにその他の事項（たとえば下記〔１〕〜〔１３〕に記載した事項など）についても記載した。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention shown below.
<1>
Repeating unit (A) having an ionic structure site that decomposes by irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin and repeating unit (B) that decomposes by the action of an acid to generate a phenolic hydroxyl group And a resin (P) having
A compound (B) different from the resin (P) that generates bis (alkylsulfonyl) amide upon irradiation with actinic rays or radiation;
An actinic ray-sensitive or radiation-sensitive resin composition containing
<2>
Repeating unit (A) having an ionic structure site that decomposes by irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin, repeating unit (B) that decomposes by the action of an acid to generate an alkali-soluble group ), And a resin (P) having a repeating unit having an aromatic ring group different from the repeating unit (A) and the repeating unit (B);
A compound (B) different from the resin (P) that generates bis (alkylsulfonyl) amide upon irradiation with actinic rays or radiation;
An actinic ray-sensitive or radiation-sensitive resin composition containing
<3>
The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, wherein the resin (P) further has a repeating unit (C) represented by the following general formula (IV).

In the general formula (IV), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to Ar ₄ to form a ring, in which case R ₄₂ represents an alkylene group.
X ₁ represents a single bond or a divalent linking group.
Ar ₄ represents a divalent aromatic ring group, and represents a trivalent aromatic ring group when bonded to R ₄₂ to form a ring.
n represents an integer of 1 to 4.
<4>
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <3>, wherein the compound (B) is represented by the following general formula (ZI′-1-1).

R _{1 to} R ₁₅ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyloxy group, or an aryl group. R ₁ and R ₁₅ may be bonded to each other to form a ring. In this case, R ₁ and R ₁₅ form a single bond or a divalent linking group.
R ₁₆ and R ₁₇ each independently represents an alkyl group. R ₁₆ and R ₁₇ may be bonded to each other to form a ring.
<5>
The actinic ray-sensitive or radiation-sensitive resin composition according to the above <4>, wherein in the general formula (ZI′-1-1), each of R ₁₆ and R ₁₇ contains at least one fluorine atom.
<6>
In the above general formula (ZI′-1-1), R ₁₆ and R ₁₇ are each independently an alkyl group substituted with a fluorine atom or a fluoroalkyl group, described in <4> or <5> above An actinic ray-sensitive or radiation-sensitive resin composition.
<7>
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above <4> to <6>, wherein R ₁₆ and R ₁₇ are bonded to each other to form a ring.
<8>
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <7>, wherein the repeating unit (B) is a repeating unit represented by the following general formula (VI): .

In general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents an alkylene group.
Ar ₆ represents a divalent aromatic ring group, and represents a trivalent aromatic ring group when bonded to R ₆₂ to form a ring.
Y represents a hydrogen atom or a group capable of leaving by the action of an acid. When a plurality of Y are present, the plurality of Y may be the same or different. However, at least one of Y represents a group capable of leaving by the action of an acid.
m represents an integer of 1 to 4.
<9>
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <8> above.
<10>
The pattern formation method which has the process of exposing and developing the resist film as described in said <9>.
The present invention relates to the items described in <1> to <10> above, but other items (for example, items described in [1] to [13] below) are also described for reference.

[1] Resin (P) having a repeating unit (A) having an ionic structure site that decomposes upon irradiation with actinic rays or radiation to generate acid anions in the side chains of the resin, and upon irradiation with actinic rays or radiation An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (B) different from the resin (P) that generates bis (alkylsulfonyl) amide.
[2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the compound (B) is represented by the following general formula (ZI′-1-1).

R _{1 to} R ₁₅ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyloxy group, or an aryl group. R ₁ and R ₁₅ may be bonded to each other to form a ring. In this case, R ₁ and R ₁₅ form a single bond or a divalent linking group.
R ₁₆ and R ₁₇ each independently represents an alkyl group. R ₁₆ and R ₁₇ may be bonded to each other to form a ring.

[3] The radiation-sensitive resin composition according to [2], wherein each of R ₁₆ and R _{17 in} the general formula (ZI′-1-1) includes at least one fluorine atom.

[4] In the general formula (ZI′-1-1), R ₁₆ and R ₁₇ are each independently an alkyl group substituted with a fluorine atom or a fluoroalkyl group, or a fluorine atom or a fluoroalkyl group. The radiation-sensitive resin composition according to the above [2] or [3], which is a substituted phenyl group.

[5] The radiation sensitive resin composition according to any one of [2] to [4], wherein R ₁₆ and R ₁₇ are bonded to each other to form a ring.

[6] The actinic ray-sensitive property according to any one of [1] to [5], wherein the resin (P) further includes a repeating unit (C) represented by the following general formula (IV). Or a radiation sensitive resin composition.

In the general formula (IV), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to Ar ₄ to form a ring, in which case R ₄₂ represents an alkylene group.
X ₁ represents a single bond or a divalent linking group.
Ar ₄ represents a divalent aromatic ring group, and represents a trivalent aromatic ring group when bonded to R ₄₂ to form a ring.
n represents an integer of 1 to 4.

[7] The sensation according to any one of [1] to [6], wherein the resin (P) further has a repeating unit (B) that is decomposed by the action of an acid to generate an alkali-soluble group. Actinic ray-sensitive or radiation-sensitive resin composition.

[8] The actinic ray-sensitive or radiation-sensitive resin composition according to [7], wherein the repeating unit (B) is a repeating unit represented by the following general formula (V) or (VI).

In the general formula (V), R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring, and R ₅₂ in this case represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring. However, _R55 and _R56 are not simultaneously hydrogen atoms.
In general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents an alkylene group.
Ar ₆ represents a divalent aromatic ring group, and represents a trivalent aromatic ring group when bonded to R ₆₂ to form a ring.
Y represents a hydrogen atom or a group capable of leaving by the action of an acid. When a plurality of Y are present, the plurality of Y may be the same or different. However, at least one of Y represents a group capable of leaving by the action of an acid.
m represents an integer of 1 to 4.

[9] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].

[10] A pattern forming method including a step of exposing and developing the resist film according to [9].

  The present invention preferably further has the following configuration.

[11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8] above, wherein R ₁₆ and R ₁₇ are groups represented by the following general formula.

In the above general formula,
R ₁₈ represents a perfluoroalkylene group or a phenylene group substituted with at least one of a fluorine atom and a fluoroalkyl group.
Ax represents a single bond or a divalent linking group.
R ₁₉ represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, or an aryl group.
* Represents a bond bonded to the sulfonyl group.

[12] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], which is exposed to an electron beam, an X-ray, or EUV light.

[13] The pattern forming method according to [10], wherein an electron beam, an X-ray, or EUV light is used as the exposure light source.

  According to the present invention, particularly in lithography using electron beam, X-ray or EUV light as an exposure light source, actinic ray-sensitive or radiation-sensitive resin that simultaneously satisfies high sensitivity, high resolution, and excellent exposure latitude. A composition, and a resist film and a pattern forming method using the composition can be provided.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, “active light” or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, soft X-rays, electron beams, etc. means. In the present invention, light means actinic rays or radiation.
In addition, the term “exposure” in the present specification is not limited to exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams, unless otherwise specified. Include drawing in exposure.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises a repeating unit (A) having an ionic structure site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin. And a resin (P) different from the resin (P) that generates bis (alkylsulfonyl) amide.

According to the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, high sensitivity, high resolution, and excellent exposure latitude can be satisfied at the same time.
In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, since the resin (P) has an ionic structure site that generates an acid anion in the side chain, the ion having a cationic group in the side chain In particular, the exposure latitude and the resolution are excellent as compared with the case where the structure has a reproducible structure portion. When using a resin having an ionic structure site that generates an acid anion in the side chain, the acid group generated in the exposed area is bonded to the resin, thereby suppressing the acid from diffusing too much. On the other hand, when a resin having an ionic structure site having a cationic group in the side chain is used, it is assumed that the acid generated in the exposed area is likely to diffuse.
In addition, bis (alkylsulfonyl) amide that generates compound (B) upon irradiation with actinic rays or radiation has high reactivity as an acid, whereby the reaction in the exposed area is performed with high efficiency and reliability. . As a result, it is presumed that the sensitivity and resolution are improved and the exposure latitude is excellent.

  The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is, for example, a positive composition, typically a positive resist composition. Hereinafter, the structure of this composition is demonstrated.

[1] Resin (P)
The resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has an ionic structure site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin. It has a repeating unit (A).

[Repeating unit (A)]
The repeating unit (A) is preferably a repeating unit that decomposes upon irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin.
More specifically, the repeating unit (A) is preferably a repeating unit represented by any one of the following general formulas (I) to (III).

First, general formula (I) will be described.
In the formula (I), R ₁₁ , R ₁₂ and R ₁₃ each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group.

  The alkyl group is a linear or branched alkyl group which may have a substituent, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or n-butyl which may have a substituent. Group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, particularly preferably 3 or less carbon atoms. Of the alkyl group.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₁₁ , R ₁₂ and R ₁₃ are preferable.

  Examples of the monovalent aliphatic hydrocarbon ring group include a monocyclic or polycyclic aliphatic hydrocarbon ring group which may have a substituent. Preferably, a monocyclic monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, may be mentioned.

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

Preferred substituents in each of the above groups are a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkyl group exemplified in R _{11 to} R ₁₃ , or a methoxy group. , Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acetoxy group , Acyloxy groups such as butyryloxy groups, and carboxy groups. In particular, a hydroxyl group and a halogen atom are preferable.

R ₁₁ , R ₁₂ and R ₁₃ in the formula (I) are more preferably a hydrogen atom, an alkyl group or a halogen atom, a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ) or a hydroxymethyl group. (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferred.

X ₁₁ is —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.

In —NR—, the alkyl group represented by R is a linear or branched alkyl group which may have a substituent, and is the same as the alkyl group in R ₁₁ , R ₁₂ and R ₁₃ above. An example is given. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

  In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means a non-aromatic heterocyclic group having at least one nitrogen atom, preferably 3 to 8 members, specifically, for example, Examples thereof include a divalent linking group having a structure.

X ₁₁ is more preferably —O—, —CO—, —NR— (R is a hydrogen atom or an alkyl group), or a combination thereof, —COO—, —CONR— (R is a hydrogen atom or Alkyl groups) are particularly preferred.

L ₁₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R Is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent aromatic ring group, or a combination thereof.

The alkylene group in L ₁₁ may be linear or branched, and examples thereof include 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.

As the alkenylene group in any position of the alkylene group described above L _11, includes a group having a double bond.

  The divalent aliphatic hydrocarbon ring group may be monocyclic type or polycyclic type. For example, cyclobutylene group, cyclopentylene group, cyclohexylene group, norbornanylene group, adamantylene group, di Preferable examples include C3-C17 divalent aliphatic hydrocarbon ring groups such as an amantannylene group. A divalent aliphatic hydrocarbon ring group having 5 to 12 carbon atoms is more preferable, and a divalent aliphatic hydrocarbon ring group having 6 to 10 carbon atoms is particularly preferable.

  Examples of the divalent aromatic ring group as the linking group include an arylene group optionally having a substituent having 6 to 14 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group, or a thiophene group, a furan group, and the like. , Pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like.

Specific examples of —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group include the same specific examples as those described above for X ₁₁ , and preferred examples are also the same.

L ₁₁ is an alkylene group, a divalent aliphatic hydrocarbon ring group, or a group in which an alkylene group or a divalent aliphatic hydrocarbon ring group is combined through —OCO—, —O—, or —CONH— ( For example, -alkylene group-O-alkylene group-, -alkylene group-OCO-alkylene group-, -valent aliphatic hydrocarbon ring group-O-alkylene group-, -alkylene group-CONH-alkylene group-, etc.) Is particularly preferred.

X ₁₂ and X ₁₃ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.

Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₁₂ and X ₁₃ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

X ₁₂ is more preferably a single bond, —S—, —O—, —CO—, —SO ₂ —, or a combination thereof, and is a single bond, —S—, —OCO—, —OSO _2. -Is particularly preferred.

X ₁₃ is more preferably —O—, —CO—, —SO ₂ — or a combination thereof, and particularly preferably —OSO ₂ —.

Ar ₁ represents a divalent aromatic ring group or a group obtained by combining a divalent aromatic ring group and an alkylene group. The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, or a naphthylene group, an arylene group having 6 to 18 carbon atoms, and a carbon number. Aralkylene groups in which 1 to 8 alkylenes are combined, or divalent containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, etc. An aromatic ring group can be mentioned as a preferred example.

Preferred substituents in each of the above groups are alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups and other aryl groups such as phenyl groups, and phenyl groups such as R _{11 to} R _13. Is mentioned.
Examples of the group in which the divalent aromatic ring group and the alkylene group are combined include the above-described divalent aromatic ring group and, for example, 1 carbon atom such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. Preferred examples include aralkylene groups in which ˜8 alkylene groups (which may be linear or branched) are combined.

Ar ₁ is preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, or an aralkylene group in which an arylene group having 6 to 18 carbon atoms and an alkylene having 1 to 4 carbon atoms are combined, and a phenylene group A phenylene group substituted with a naphthylene group, a biphenylene group or a phenyl group is particularly preferred.

L ₁₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All are substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, or a cyano group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

L ₁₂ is an alkylene group, a divalent aromatic ring group, or a combination thereof, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group and a divalent aromatic ring group in which at least a part or all of them are substituted with a fluorine atom are particularly preferable. L ₁₂ is most preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

The alkylene group for L ₁₂ may be linear or branched, and examples thereof include 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. The alkylene group is a preferred example. An alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is particularly preferable.

  The alkenylene group includes a group having a double bond at an arbitrary position of the alkylene group.

  The divalent aliphatic hydrocarbon ring group may be monocyclic type or polycyclic type, for example, cyclobutylene group, cyclopentylene group, cyclohexylene group, norbornanylene group, adamantylene group, di Preferable examples include C3-C17 divalent aliphatic hydrocarbon ring groups such as an amantannylene group.

Examples of the divalent aromatic ring group include the same groups as the specific examples given for the divalent aromatic ring group as the linking group in L ₁₁ described above.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₁₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

Below, while indicating preferred embodiments of L _12, not particularly limited thereto.

Z ₁ represents a site that becomes a sulfonic acid group when irradiated with actinic rays or radiation.
As the site represented by Z ₁ , an onium salt is preferable. As the onium salt, a sulfonium salt or an iodonium salt is preferable, and a structure represented by the following general formula (ZI) or (ZII) is preferable.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group. The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure (including a condensed ring), and the ring contains an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Also good. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group).
Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include (ZI-1), (ZI-2) and (ZI-3) described below as preferred groups of the group represented by the general formula (ZI). And the corresponding group in the group represented by

The (ZI-1) group is a group having an arylsulfonium as a cation, wherein at least one of R _{201 to} R ₂₀₃ in the general formula (ZI) is an aryl group.

All of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a monovalent aliphatic hydrocarbon ring group.

  For example, groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, aryldicycloalkylsulfonium can be exemplified.

  The aryl group in the arylsulfonium is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include structures such as pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

When arylsulfonium has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or monovalent aliphatic hydrocarbon ring group that arylsulfonium has as necessary is a linear or branched alkyl group having 1 to 15 carbon atoms and monovalent aliphatic carbonization having 3 to 15 carbon atoms. A hydrogen ring group is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and monovalent aliphatic hydrocarbon ring group represented by R _{201 to} R ₂₀₃ are an alkyl group (for example, having 1 to 15 carbon atoms) and a monovalent aliphatic hydrocarbon ring group (for example, having 3 to 15 carbon atoms). ), An aryl group (for example, having 6 to 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, monovalent aliphatic hydrocarbon ring groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms. And more preferably an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

  As one embodiment of the group represented by (ZI-1), a structure represented by the following general formula (ZI-1A) can be mentioned.

In general formula (ZI-1A),
R ^{1a to} R ^13a each independently represents a hydrogen atom or a substituent, and at least one of R ^{1a to} R ^13a is preferably a substituent containing an alcoholic hydroxyl group.

Za is a single bond or a divalent linking group.
The alcoholic hydroxyl group represents a hydroxyl group bonded to a carbon atom of a chain or cyclic alkyl group.

When R < ^1a > -R <^13a> is a substituent containing an alcoholic hydroxyl group, R < ^1a > -R <^13a> is represented by -W-Y. However, Y is a chain or cyclic alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

As the chain or cyclic alkyl group of Y, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, Nonyl group, decyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group etc. can be mentioned, preferably ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, It is a sec-butyl group, more preferably an ethyl group, a propyl group, or an isopropyl group. Y particularly preferably contains a —CH ₂ CH ₂ OH structure.

  W is preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, an alkoxycarbonyl group, and any hydrogen atom in the carbamoyl group replaced with a single bond. It is a divalent group, more preferably a divalent group in which any hydrogen atom in a single bond, acyloxy group, alkylsulfonyl group, acyl group or alkoxycarbonyl group is replaced with a single bond.

When R ^{1a to} R ^13a are a substituent containing an alcoholic hydroxyl group, the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4. .

The substituent containing an alcoholic hydroxyl group as R ^{1a to} R ^13a may have two or more alcoholic hydroxyl groups. The number of alcoholic hydroxyl groups of the substituent containing an alcoholic hydroxyl group as R ^{1a to} R ^13a is 1 to 6, preferably 1 to 3, and more preferably 1.

The number of alcoholic hydroxyl groups contained in the compound represented by the general formula (ZI-1A) is from 1 to 10 in total, preferably from 1 to 6, more preferably from R ^{1a to} R ^13a. Is 1 to 3.

When R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are preferably a hydrogen atom or a halogen atom, an alkyl group (including a monovalent aliphatic hydrocarbon ring group), an alkenyl group (cycloalkenyl). Group, bicycloalkenyl group), alkynyl group, aryl group, cyano group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxy Carbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group Imido group, a silyl group, a ureido group.

When R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are more preferably a hydrogen atom or a halogen atom, an alkyl group (including a monovalent aliphatic hydrocarbon ring group), a cyano group, and an alkoxy group. Group, acyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl and arylsulfonyl group, alkoxycarbonyl group and carbamoyl group.

Further, when R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are particularly preferably a hydrogen atom or an alkyl group (including a monovalent aliphatic hydrocarbon ring group), a halogen atom, and an alkoxy group. It is.

Further, two adjacent ones of R ^{1a to} R ^13a are combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These are further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, Pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring , Phenanthridine ring, acridine , Phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

In general formula (ZI-1A), at least one of R ^{1a to} R ^13a contains an alcoholic hydroxyl group, and preferably at least one of R ^{9 to} R ¹³ contains an alcoholic hydroxyl group.

Za represents a single bond or a divalent linking group, and examples of the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, A thioether group, an amino group, a disulfide group, an acyl group, an alkylsulfonyl group, —CH═CH—, —C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, and the like, and may have a substituent. . These substituents are the same as the substituents shown for R ^{1a to} R ^13a above. Za preferably has a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, —CH═CH—, —C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, or the like. A substituent, more preferably a single bond, an ether group or a thioether group, particularly preferably a single bond.

  Next, the (ZI-2) group will be described.

The (ZI-2) group is a group in which R _{201 to} R ₂₀₃ in the general formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a monovalent aliphatic hydrocarbon ring group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2- An oxoaliphatic hydrocarbon ring group and an alkoxycarbonylmethyl group, particularly preferably a linear or branched 2-oxoaliphatic hydrocarbon ring group.

The alkyl group and the aliphatic hydrocarbon ring group represented by R _{201 to} R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group). , Norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferable examples of the aliphatic hydrocarbon ring group include a 2-oxoaliphatic hydrocarbon ring group.

  The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.

  Preferred examples of the 2-oxoaliphatic hydrocarbon ring group include a group having> C═O at the 2-position of the above aliphatic hydrocarbon ring group.

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  Next, the (ZI-3) group will be described.

The (ZI-3) group is a group represented by the following general formula (ZI-3), which is a group having a phenacylsulfonium salt structure.

In General Formula (ZI-3), R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an alkoxy group, or a halogen atom.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group or a monovalent aliphatic hydrocarbon ring group.

R _x and R _y each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an allyl group or a vinyl group.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group.

Further, the monovalent aliphatic hydrocarbon ring group as R _{1c to} R _7c may be monocyclic or polycyclic, for example, monovalent aliphatic carbonization having 3 to 8 carbon atoms. Examples thereof include a hydrogen ring group (for example, cyclopentyl group, cyclohexyl group).

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a monovalent aliphatic hydrocarbon ring group, or a linear, branched or cyclic alkoxy group, and more preferably R _{1c to} R 5 The sum of the carbon number of _5c is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

Examples of the alkyl group and monovalent aliphatic hydrocarbon ring group as R _x and R _y include the same alkyl group and monovalent aliphatic hydrocarbon ring group as in R _{1c to} R _7c , and 2- An oxoalkyl group, a 2-oxoaliphatic hydrocarbon ring group, and an alkoxycarbonylmethyl group are more preferable.

Examples of the 2-oxoalkyl group and 2-oxoaliphatic hydrocarbon ring group include a group having> C═O at the 2-position of the alkyl group and aliphatic hydrocarbon ring group as R _{1c to} R _7c .

As for the alkoxy group in the alkoxycarbonylmethyl group, the same alkoxy groups as in R _{1c to} R _5c can be exemplified.

R _x and R _y are preferably an alkyl group having 4 or more carbon atoms or a monovalent aliphatic hydrocarbon ring group, more preferably 6 or more, still more preferably 8 or more alkyl groups or a monovalent An aliphatic hydrocarbon ring group.

  Next, general formula (ZII) will be described.

In the general formula (ZII), R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group, or a monovalent aliphatic hydrocarbon ring group.

Aryl groups R ₂₀₄ and R _205, an alkyl group, a monovalent Specific examples of the aliphatic hydrocarbon ring group, an aryl group mentioned in the previous (ZI-1) group, an alkyl group, a monovalent aliphatic hydrocarbon The thing similar to a hydrogen ring group can be mentioned.

Aryl groups R ₂₀₄ and R _205, an alkyl group, a monovalent aliphatic hydrocarbon ring group may have a substituent. Aryl groups R ₂₀₄ and R _205, an alkyl group, Examples of the monovalent aliphatic hydrocarbon ring group substituents which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a monovalent aliphatic An aromatic hydrocarbon ring group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

The polymerizable monomer unit corresponding to the repeating unit of the general formula (I) is exemplified below as a sulfonic acid unit generated by cation elimination upon irradiation with actinic rays or radiation.

Next, general formula (II) will be described.
In the general formula (II), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. Furthermore, R ₂₂ may be bonded to Ar ₂ to form a ring (particularly preferably a 5-membered or 6-membered ring), in which case R ₂₂ represents an alkylene group.

The alkyl group of R ₂₁ , R ₂₂ and R ₂₃ is a linear or branched alkyl group which may have a substituent, preferably a methyl group, an ethyl group which may have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl having 8 or less carbon atoms. Group, particularly preferably an alkyl group having 3 or less carbon atoms.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₂₁ , R ₂₂ and R ₂₃ are preferable.

  Examples of the monovalent aliphatic hydrocarbon ring group include a monocyclic or polycyclic cycloalkyl group which may have a substituent. Preferably, a monocyclic monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, may be mentioned.

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

Preferred substituents in each of the above groups are a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkyl group exemplified in R _{21 to} R ₂₃ , and a methoxy group. , Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acetoxy group , Acyloxy groups such as butyryloxy groups, and carboxy groups. In particular, a hydroxyl group and a halogen atom are preferable.

In addition, when R ₂₂ is an alkylene group and is bonded to Ar ₂ to form a ring, the alkylene group is preferably a carbon number such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Examples include 1 to 8 alkylene groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.

R ₂₁ and R ₂₃ in formula (II) are more preferably a hydrogen atom, an alkyl group or a halogen atom, and R ₂₂ is a hydrogen atom, an alkyl group, a halogen atom or an alkylene group in the case of forming a ring with Ar _2. Is more preferable.

Ar ₂ represents a divalent aromatic ring group (provided that the ring is bonded to R ₂₂ to form a ring). The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or a thiophene, furan, pyrrole, benzo Preferred examples include divalent aromatic ring groups containing a heterocycle such as thiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.
When Ar ₂ is bonded to R ₂₂ to form a ring, specific examples of the trivalent aromatic ring group as Ar ₂ include, for example, any one of the above specific examples of the divalent aromatic ring group And a trivalent aromatic ring group formed by removing the hydrogen atom.

X ₂₁ represents —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.
Specific examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₁ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

X ₂₁ is more preferably —O—, —S—, —CO—, —SO ₂ — or a combination thereof, and particularly preferably —O—, —OCO— or —OSO ₂ —.

X ₂₂ represents a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or And represents a combination of these.
Specific examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₁ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.
X ₂₂ is more preferably —O—, —S—, —CO—, —SO ₂ —, or a combination thereof, and particularly preferably —O—, —OCO—, or —OSO ₂ —.

L ₂₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

As the alkylene group, alkenylene group and divalent aliphatic hydrocarbon ring group in L _21, the alkylene group, alkenylene group and divalent aliphatic hydrocarbon ring group in L ₁₁ in the general formula (I) are as described above. Specific examples similar to the preferable specific examples described can be given.

Examples of the divalent aromatic ring group in L ₂₁ include an arylene group optionally having a substituent having 6 to 14 carbon atoms such as a phenylene group, a tolylene group, and a naphthylene group, or, for example, thiophene, furan, Examples thereof include a divalent aromatic ring group which may have a substituent containing a heterocycle such as pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₁ include the same specific examples as those described above for X ₁₁ , and preferred examples are also the same.

L ₂₁ includes, for example, a single bond, an alkylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these (for example, -alkylene group-2 divalent aromatic ring group- , -Valent aliphatic hydrocarbon ring group -alkylene group-, etc.), or a group in which two or more of these are combined through -OCO-, -COO-, -O- or -S- as a linking group (For example, -alkylene group-OCO-2 valent aromatic ring group-, -alkylene group-S-2 valent aromatic ring group-, -alkylene group-O-alkylene group-2 valent aromatic ring group-, etc.) Particularly preferred.

L ₂₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All may be substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, or a cyano group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

L ₂₂ is an alkylene group, a divalent aromatic ring group, or a combination thereof, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group and a divalent aromatic ring group in which at least a part or all of them are substituted with a fluorine atom are particularly preferable. L ₂₂ is most preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

Specific examples of the alkylene group, alkenylene group, group aliphatic hydrocarbon ring group, divalent aromatic ring group and a combination of two or more of these represented by L ₂₂ include those represented by L ₁₂ in the general formula (I). The same group as the specific example illustrated previously is mentioned.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

Z ₂ represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation. Specific examples of Z ₂ include the same groups as the specific examples previously exemplified as Z ₁ in formula (I).

  The polymerizable monomer unit corresponding to the repeating unit of the general formula (II) is exemplified below as a sulfonic acid unit generated by detachment of a cation by irradiation with actinic rays or radiation.

Next, general formula (III) is demonstrated.
In the general formula (III), R ₃₁ , R ₃₂ and R ₃₃ each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. Furthermore, when X ₃₁ described later is a single bond and L ₃₁ is a divalent aromatic ring group, R ₃₂ may form a ring with the aromatic ring group of L ₃₁ , in which case R ₃₂ is Represents an alkylene group.

Specific examples of the alkyl group, monovalent aliphatic hydrocarbon ring group, halogen atom, cyano group and alkoxycarbonyl group in R ₃₁ , R ₃₂ and R ₃₃ include R ₂₁ , R ₂₂ and R in the general formula (II). The same group as the specific example illustrated previously about ₂₃ is mentioned.

X ₃₁ and X ₃₂ each independently represent a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (wherein R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.

Specific examples of —NR— and a divalent nitrogen-containing non-aromatic heterocyclic group include specific examples of —NR— and a divalent nitrogen-containing non-aromatic heterocyclic group in X ₁₁ in the general formula (I). Are the same groups as those mentioned above, and preferred examples are also the same.

X ₃₁ is more preferably a single bond, —O—, —CO—, —NR— (wherein R is a hydrogen atom or an alkyl group), and a group obtained by combining these, and a single bond, —COO—, —CONR— (R is a hydrogen atom or an alkyl group) is particularly preferred.

X ₃₂ is more preferably —O—, —S—, —CO—, —SO ₂ —, a divalent nitrogen-containing non-aromatic heterocyclic group, or a group obtained by combining these, —O—, — OCO -, - OSO ₂ - is particularly preferred.

L ₃₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. However, when X ₃₁ is a single bond and L ₃₁ is bonded to R ₃₂ to form a ring, L ₃₁ represents a trivalent aromatic ring group. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

As the alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group and divalent aromatic ring group in L _31, the alkylene group, alkenylene group and divalent aliphatic carbon group in L ₂₁ in the general formula (II) are used. Specific examples similar to the preferred specific examples described above as the hydrogen ring group and the divalent aromatic ring group can be given.
When L ₃₁ is bonded to R ₃₂ to form a ring, specific examples of the trivalent aromatic ring group as L ₃₁ include, for example, a divalent aromatic ring group in L ₂₁ in the general formula (II). In the specific examples described above, a trivalent aromatic ring group formed by removing any one hydrogen atom can be exemplified.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₁ include the same specific examples as those in L ₂₁ described above, and preferred examples are also the same.

L ₃₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, the 2 or more groups combined may be different even in the same, also, -O as a linking group -, - S -, - CO -, - SO 2 -, - NR- (R May be a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

  An alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group formed by combining two or more of these, a part or all of the hydrogen atoms are fluorine atoms, fluorinated alkyl groups It is preferably substituted with a substituent selected from a nitro group or a cyano group.

L ₃₂ is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group and a divalent aromatic ring group in which at least a part or all of them are substituted with fluorine atoms are particularly preferable. L ₃₂ is most preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

Specific examples of the alkylene group, the alkenylene group, the divalent aliphatic hydrocarbon ring group, the divalent aromatic ring group, and a group obtained by combining two or more of these represented by L ₂₂ include those in the general formula (I). Examples of L ₁₂ include the same groups as the specific examples exemplified above.

Specific examples of the —NR— linking group and divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₂ include the same specific examples as those described above for X ₁₁ , and preferred examples are also the same.

In the case where X ₃ is a single bond and L ₃₁ is an aromatic ring group, when R ₃₂ forms a ring with the aromatic ring group of L ₃₁ , the alkylene group represented by R ₃₂ is preferably methylene. Group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group and the like, and an alkylene group having 1 to 8 carbon atoms. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 or 2 carbon atoms is particularly preferable.

Z ₃ represents an onium salt that becomes an imido acid group or a methido acid group upon irradiation with actinic rays or radiation.
The onium salt represented by Z ₃ is preferably a sulfonium salt or an iodonium salt, and a structure represented by the following general formula (ZIII) or (ZIV) is preferred.

In general formulas (ZIII) and (ZIV), Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ each independently represent —CO— or —SO ₂ —, and more preferably —SO ₂ —. It is.

Rz ₁ , Rz ₂ and Rz ₃ each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group. An embodiment in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluoroalkyl group (more preferably a perfluoroalkyl group) is more preferred, and an embodiment in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom is particularly preferred. .

  The alkyl group may be linear or branched, and preferably has 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. Take as an example. An alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

  The monovalent aliphatic hydrocarbon ring group is preferably a monovalent aliphatic hydrocarbon ring group having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and a monovalent aliphatic hydrocarbon ring group having 3 to 6 carbon atoms. An aliphatic hydrocarbon ring group is more preferable.

  As the aryl group, an aryl group having 6 to 18 carbon atoms is preferable, an aryl group having 6 to 10 carbon atoms is more preferable, and a phenyl group is particularly preferable.

  Preferred examples of the aralkyl group include an aralkyl group in which an alkylene group having 1 to 8 carbon atoms and the aryl group are bonded. An aralkyl group in which an alkylene group having 1 to 6 carbon atoms and the aryl group are bonded is more preferable, and an aralkyl group in which an alkylene group having 1 to 4 carbon atoms and the aryl group are bonded is particularly preferable.

A ⁺ represents a sulfonium cation or an iodonium cation, and preferred examples include the sulfonium cation in the general formula (ZI) and the iodonium cation structure in the general formula (ZII).

  The polymerizable monomer unit corresponding to the repeating unit of the general formula (III) is exemplified below as an imidic acid or methide acid unit generated by detachment of a cation by irradiation with actinic rays or radiation.

  The polymerizable compound corresponding to the repeating units of the general formulas (I) to (III) can be synthesized by using a general sulfonic acid esterification reaction or sulfonamidation reaction. For example, a method of selectively reacting one sulfonyl halide part of a bissulfonyl halide compound with an amine, alcohol, etc. to form a sulfonamide bond or a sulfonate ester bond, and then hydrolyzing the other sulfonyl halide part, Alternatively, it can be obtained by a method of opening a cyclic sulfonic anhydride with an amine or alcohol. Also, US Pat. Fluorine Chem. 105 (2000) 129-136; Fluorine Chem. 116 (2002) 45-48 can also be easily synthesized.

  The polymerizable compounds corresponding to the repeating units of the general formulas (I) to (III) are specially selected from lithium, sodium and potassium salts of organic acids synthesized above and hydroxides, bromides and chlorides of iodonium or sulfonium. It can be easily synthesized using the salt exchange method described in Table No. 11-501909 or JP-A No. 2003-246786.

Specific examples of the cation of the onium salt represented by Z _{1 to} Z ₃ in the general formulas (I) to (III) are shown below.

  In addition, specific examples of the polymerizable compound (M) corresponding to the repeating units of the general formulas (I) to (III) are shown in the following table as cation structures ((Z-1) to (Z-58) exemplified above) and anions. In the structure (previously exemplified (I-1) to (I-16), (II-1) to (II-21), (III-1) to (III-16), the hydrogen atom of the organic acid was removed. It is shown as a combination of anions).

  The content of the repeating unit (A) in the resin (P) is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 60 mol%, still more preferably with respect to all the repeating units. Is in the range of 3-40 mol%.

[Repeating unit (B)]
In addition to the repeating unit (A), the resin (P) is a repeating unit (B) that decomposes by the action of an acid to generate an alkali-soluble group (hereinafter referred to as “a repeating unit having an acid-decomposable group”). It is preferable to have.

Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.

Examples of the group capable of leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), -C (= O) -O- _{C (R 36) (R 37} ) (R 38), - C (R 01) (R 02) -C (= O) -O-C (R 36) (R 37) (R 38), - CH ( R ₃₆ ) (Ar) and the like.
In the formula, each of R _{36 to} R ₃₉ independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, a group obtained by combining an alkylene group and a monovalent aromatic ring group, or an alkenyl group. Represent. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ are each independently a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, a group combining an alkylene group and a monovalent aromatic ring group, or an alkenyl group. Represents.
Ar represents a monovalent aromatic ring group.
The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.

The monovalent aliphatic hydrocarbon ring group for R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably an aliphatic hydrocarbon ring group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, an aliphatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, A tetracyclododecyl group, an androstanyl group, etc. can be mentioned. In addition, a part of carbon atoms in the aliphatic hydrocarbon ring group may be substituted with a hetero atom such as an oxygen atom.
The monovalent aromatic ring group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ and Ar is preferably a monovalent aromatic ring group having 6 to 10 carbon atoms, for example, an aryl such as a phenyl group, a naphthyl group, and an anthryl group. And a divalent aromatic ring group containing a heterocyclic ring such as a group, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.

The group in which the alkylene group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ and the monovalent aromatic ring group are combined is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, or a naphthylmethyl group. Etc.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. As the monocyclic type, an aliphatic hydrocarbon ring structure having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. Can do. As the polycyclic type, an aliphatic hydrocarbon ring structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of carbon atoms in the aliphatic hydrocarbon ring structure may be substituted with a hetero atom such as an oxygen atom.

Each of the groups as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar may have a substituent. Examples of the substituent include an alkyl group and a monovalent aliphatic hydrocarbon ring group. , Aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc. The number of carbon atoms of the substituent is preferably 8 or less.

  As the repeating unit (B), a repeating unit represented by the following general formula (V) or (VI) is more preferable.

In the general formula (V), R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring (preferably a 5-membered or 6-membered ring), in which case R ₅₂ represents an alkylene group.

L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.

R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may combine with each other to form a ring.

However, _R55 and _R56 are not simultaneously hydrogen atoms.

In general formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may combine with Ar ₆ to form a ring (preferably a 5-membered or 6-membered ring), and R ₆₂ in this case represents an alkylene group.
Ar ₆ represents a divalent aromatic ring group, and represents a trivalent aromatic ring group when bonded to R ₆₂ to form a ring.
Y represents a hydrogen atom or a group capable of leaving by the action of an acid. When a plurality of Y are present, the plurality of Y may be the same or different. However, at least one of Y represents a group capable of leaving by the action of an acid.
m represents an integer of 1 to 4.

The general formula (V) will be described in more detail.
As the alkyl group of R _{51 to} R ₅₃ in the general formula (V), a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.
The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in the above R _{51 to} R ₅₃ .
Examples of the monovalent aliphatic hydrocarbon ring group include monovalent aliphatic hydrocarbon ring groups that may be monocyclic or polycyclic. Preferably, a monocyclic monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, may be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

  Preferred substituents in each of the above groups include, for example, alkyl groups, monovalent aliphatic hydrocarbon ring groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups. Group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

When R ₅₂ represents an alkylene group, the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.
R ₅₁ and R ₅₃ in Formula (V) are more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₃ ). _2- OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferable. R ₅₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with Q), and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group ( -CH ₂ -OH), a chloromethyl group _(-CH 2 -Cl), a fluorine atom (-F), a methylene group _{(L 5} forms a ring with), ethylene group _{(L 5} forms a ring with) is particularly preferred.

Examples of the divalent linking group represented by L _5, an alkylene group, a divalent aromatic ring _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Etc. Here, L ₁ represents an alkylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, a group in which an alkylene group and a divalent aromatic ring group are combined, and further a substituent such as a fluorine atom. May be substituted.

L ₅ is a single bond, —COO-L ₁ — (L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group or a propylene group) or a group represented by a divalent aromatic ring group. Is preferred.

The alkyl group for R _{54 to} R ₅₆ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Particularly preferred are those having 1 to 4 carbon atoms such as a group, an isobutyl group and a t-butyl group.

The monovalent aliphatic hydrocarbon ring group represented by R ₅₅ and R ₅₆ is preferably a group having 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group and a cyclohexyl group, A polycyclic group such as a norbornyl group, an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group may be used.

The ring formed by combining R ₅₅ and R ₅₆ with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. A polycyclic group such as an adamantyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R ₅₄ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

The monovalent aromatic ring groups represented by R ₅₅ and _{R 56,} preferably has 6 to 20 carbon atoms, for example, a phenyl group, a naphthyl group, and the like. When one of R ₅₅ and R ₅₆ is a hydrogen atom, the other is preferably a monovalent aromatic ring group.

  As a method for synthesizing a monomer corresponding to the repeating unit represented by the general formula (V), a general method for synthesizing a polymerizable group-containing ester can be applied and is not particularly limited.

  Specific examples of the repeating unit represented by the general formula (V) are shown below, but the present invention is not limited thereto.

  The general formula (VI) will be described in detail.

As the alkyl group of R _{61 to} R ₆₃ in the general formula (VI), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, and more preferable examples include alkyl groups having 8 or less carbon atoms.

As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{61 to} R ₆₃ are preferable.

  The monovalent aliphatic hydrocarbon ring group may be monocyclic or polycyclic, and preferably has 3 to 8 carbon atoms such as a cyclopropyl group, cyclopentyl group, or cyclohexyl group, which may have a substituent. And a monocyclic monovalent aliphatic hydrocarbon ring group.

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

If R ₆₂ represents an alkylene group, the alkylene group, preferably a methylene group which may have a substituent group, an ethylene group, a propylene group, butylene group, hexylene group, 1 to 8 carbon atoms such as octylene Can be mentioned.

Ar ₆ represents a divalent aromatic ring group. Specific examples of the divalent aromatic ring group and specific examples of the substituent that the aromatic ring group may have are the same as Ar ₂ in the general formula (II) described above.

Examples of the substituent that the above-described alkyl group, monovalent aliphatic hydrocarbon ring group, alkoxycarbonyl group, alkylene group, and divalent aromatic ring group may have include R _{51 to} R ₅₃ in the above general formula (V). Specific examples similar to the substituents which each group represented by can have are given.

  m is preferably 1 or 2, and more preferably 1.

  m Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of m represents a group that is eliminated by the action of an acid.

Examples of the group Y leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). _{), - C (R 01)} (R 02) (OR 39), - C (R 01) (R 02) -C (= O) -O-C (R 36) (R 37) (R 38), —CH (R ₃₆ ) (Ar) and the like can be mentioned. R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar in these formulas have the same meanings as the groups described above.

  As the group Y leaving by the action of an acid, a structure represented by the following general formula (VI-A) is more preferable.

Here, L ₁ and L ₂ are each independently a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, or a group in which an alkylene group and a monovalent aromatic ring group are combined. Represents.

  M represents a single bond or a divalent linking group.

  Q is an alkyl group, a monovalent aliphatic hydrocarbon ring group that may contain a hetero atom, a monovalent aromatic ring group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, or a cyano group. Or represents an aldehyde group.

At least two of Q, M, and L ₁ may combine to form a ring (preferably a 5-membered or 6-membered ring).

The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a hexyl group. An octyl group can be preferably mentioned.

The monovalent aliphatic hydrocarbon ring group as L ₁ and L ₂ is, for example, an aliphatic hydrocarbon ring group having 3 to 15 carbon atoms, and specifically includes a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group. Groups and the like can be mentioned as preferred examples.

The monovalent aromatic ring group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specifically, a phenyl group, a tolyl group, a naphthyl group, an anthryl group, and the like are preferable examples. be able to.

Group formed by combining an alkylene group and a monovalent aromatic ring group as L ₁ and L ₂ are, for example, a 6 to 20 carbon atoms, a benzyl group, an aralkyl group such as a phenethyl group.

The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), a divalent aliphatic hydrocarbon ring group (for example, cyclohexane). Pentylene group, cyclohexylene group, adamantylene group, etc.), alkenylene group (eg, ethylene group, propenylene group, butenylene group, etc.), divalent aromatic ring group (eg, phenylene group, tolylene group, naphthylene group, etc.), -S -, - O -, - CO -, - SO 2 -, - N (R 0) -, and a divalent linking group formed by combining a plurality of these. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group). Octyl group, etc.).

The alkyl group as Q is the same as each of the groups as L ₁ and L ₂ described above.

The monovalent aliphatic hydrocarbon ring group which may contain a hetero atom as Q and the aliphatic hydrocarbon ring group which does not contain a hetero atom in a monovalent aromatic ring group which may contain a hetero atom Examples of the monovalent aromatic ring group not containing a hetero atom include the above-described monovalent aliphatic hydrocarbon ring groups as L ₁ and L ₂ , and monovalent aromatic ring groups. It is C3-C15.

  Examples of the monovalent aliphatic hydrocarbon ring group containing a hetero atom and the monovalent aromatic ring group containing a hetero atom include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, and imidazole. , Benzimidazole, triazole, thiadiazole, thiazole, pyrrolidone, and other groups having a heterocyclic structure, but generally called a heterocyclic ring (a ring formed of carbon and a heteroatom, or a ring formed of a heteroatom ), It is not limited to these.

Q, M, as a ring which may be formed by combining at least two L _1, Q, M, by combining at least two L _1, for example, a propylene group, to form a butylene group, an oxygen atom In the case of forming a 5-membered or 6-membered ring containing.

Each group represented by L ₁ , L ₂ , M, and Q in the general formula (VI-A) may have a substituent, for example, R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ described above. And those exemplified as the substituent that Ar may have, and the number of carbon atoms of the substituent is preferably 8 or less.

  The group represented by -MQ is preferably a group composed of 1 to 30 carbon atoms, more preferably a group composed of 5 to 20 carbon atoms.

  Specific examples of the repeating unit represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

The content of the repeating unit (B) in the resin (P) of the present invention is preferably from 3 to 90 mol%, more preferably from 5 to 80 mol%, more preferably from 7 to 70, based on all repeating units. A range of mol% is particularly preferred.
The ratio of the repeating unit (A) to the repeating unit (B) in the resin (number of moles of A / number of moles of B) is preferably 0.04 to 1.0, and preferably 0.05 to 0.9. More preferred is 0.06 to 0.8.

  The resin (P) of the present invention preferably has a repeating unit having an aromatic ring group, which is different from the repeating unit (A) and the repeating unit (B). Examples of such a repeating unit having an aromatic ring group include a repeating unit represented by the following general formula (VII).

In the formula, R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to Q to form a ring (preferably a 5-membered or 6-membered ring), and R ₄₂ in this case represents an alkylene group.

  Q represents a group containing an aromatic ring group.

General formula (VII) will be described in more detail.
Specific examples of the alkyl group, monovalent aliphatic hydrocarbon ring group, monovalent aliphatic hydrocarbon ring group, halogen atom and alkoxycarbonyl group of R ₄₁ , R ₄₂ and R ₄₃ in formula (VII) include R ₅₁ and R in the general formula (V). Examples similar to the specific examples described in ₅₂ and R ₅₃ can be given.

In the case where R ₄₂ represents an alkylene group, the alkylene group, preferably methylene group, ethylene group, propylene group, butylene group, hexylene group, and an alkylene group having 1 to 8 carbon atoms such as octylene group. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.

R ₄₁ and R ₄₃ in Formula (VII) are more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₃ ). _2- OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferable. R ₄₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with Q), and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group ( —CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), a fluorine atom (—F), a methylene group (forming a ring with Q), and an ethylene group (forming a ring with Q) are particularly preferable.

  In general formula (VII), Q is preferably a substituted or unsubstituted aromatic group having 1 to 20 carbon atoms. Examples of the aromatic group represented by Q include the following.

  Phenyl group, naphthyl group, anthranyl group, phenanthryl group, fluorenyl group, triphenylenyl group, naphthacenyl group, biphenyl group, pyrrolinyl group, furanyl group, thiophenyl group, imidazolyl group, oxazolyl group, thiazolyl group, pyridyl group, pyrazinyl group, pyrimidyl group , Pyridazyl group, indoridyl group, benzofuranyl group, benzothiophenyl group, isobenzofuranyl group, quinolidyl group, quinolinyl group, phthalazyl group, naphthyridyl group, quinoxalyl group, quinoxazolyl group, isoquinolinyl group, carbazolyl group, acridyl group, phenanthryl group , Thiantenyl group, chromenyl group, xanthenyl group, phenoxatilyl group, phenothiazyl group, phenazyl group. Among these, an aromatic hydrocarbon ring is preferable, and a phenyl group, a naphthyl group, an anthranyl group, and a phenanthryl group are more preferable, and a phenyl group is more preferable.

In one form, the general formula (VII) is preferably such that R ₄₁ , R ₄₂ and R ₄₃ are hydrogen atoms, and a repeating unit represented by the following general formula (VII-1) is preferable.

  Q represents a group containing an aromatic ring group.

  The repeating unit represented by the general formula (VII) is more preferable than the repeating unit represented by the following general formula (IV) (hereinafter also referred to as the repeating unit (C)).

Here, R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to Ar ₄ to form a ring, in which case R ₄₂ represents an alkylene group.
X ₁ represents a single bond or a divalent linking group.

Ar ₄ represents a divalent aromatic ring group, and represents a trivalent aromatic ring group when bonded to R ₄₂ to form a ring.
n represents an integer of 1 to 4.

Specific examples of the alkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in formula (IV), a monovalent aliphatic hydrocarbon ring group, a halogen atom, an alkoxycarbonyl group, and a substituent that these groups may have include: Specific examples similar to the respective groups in general formula (VII) are given.

X ₁ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by X ₁ include —COO—, —CONH—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, — NH-, an alkylene group, a cycloalkylene group and an alkenylene group may be mentioned. Among them, —COO—, —CONH—, —OCO—, —CO—, —S—, —SO— or —SO ₂ — is preferable, —COO—, —CONH—, —SO ₂ — or —SO ₃ —. Is more preferable.

Ar ₄ represents a divalent aromatic ring group. The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or, for example, thiophene, furan, Preferred examples include divalent aromatic ring groups containing heterocycles such as pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Preferable substituents in each of the above groups include alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, etc., aryl groups such as phenyl groups, and the like mentioned for R _{11 to} R _13. Groups.

Ar ₄ is more preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a phenylene group, a naphthylene group, or a biphenylene group.

  The method for synthesizing the monomer corresponding to the repeating unit represented by the general formula (VII) is not particularly limited. Med. Chem. , Vol. 34 (5), 1675-1692 (1991), vol. 35 (25), 4665-4675 (1992), J. MoI. Org. Chem. vol. 45 (18), 3657-3664 (1980), Adv. Synth. Catal. vol. 349 (1-2), 152-156 (2007), J. MoI. Org. Chem. vol. 28, 1921- 1922 (1963), Synth. Commun. vol. 28 (15), 2677-2682 (1989) and the literature cited therein, etc., and can be synthesized with reference to the synthesis method of the polymerizable carbon-carbon double bond-containing aromatic compound.

  Although the specific example of the repeating unit represented by general formula (VII) in resin (P) is shown below, this invention is not limited to this. In formula, a represents the integer of 0-2.

  It is preferable to contain the repeating unit content rate represented by general formula (VII) in resin (P) in the range of 5-90 mol% with respect to all the repeating units, More preferably, it is 10-80 mol%. More preferably, it is the range of 20-70 mol%. One type of repeating unit represented by the general formula (VII) may be used, or two or more types may be used in combination, but it is preferable that at least the repeating unit represented by the general formula (IV) is included. .

  In this invention, it is preferable that the content rate (mol%) of the repeating unit represented by general formula (VII) is equivalent to or more than the content rate of the said repeating unit (B).

[Repeating unit (D)]
The resin (P) preferably further has a repeating unit (D) having a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer.

  Examples of the group that decomposes by the action of an alkali developer and increases the dissolution rate in the alkali developer include a lactone structure and a phenyl ester structure.

  As the repeating unit (D), a repeating unit represented by the following general formula (AII) is more preferable.

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).

Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic aliphatic hydrocarbon ring structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. . Preferably a single _bond, -Ab 1 -CO ₂ - is a divalent linking group represented by.

Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic aliphatic hydrocarbon ring group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

  V represents a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer. A group having an ester bond is preferable, and a group having a lactone structure is more preferable.

  As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and (LC1-17).

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent aliphatic hydrocarbon ring group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkyl group having 2 to 8 carbon atoms. Examples include an alkoxycarbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

  The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

  The content of the repeating unit (D) in the resin (P) is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 60 mol% with respect to all the repeating units. Yes, more preferably in the range of 2-40 mol%. One type of repeating unit (D) may be used, or two or more types may be used in combination. By using a specific lactone structure, line edge roughness and development defects are improved.

Although the specific example of the repeating unit (D) in resin (P) is shown below, this invention is not limited to this. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The form of the resin (P) of the present invention may be any of random type, block type, comb type, and star type.

  The resin (P) can be synthesized, for example, by radical, cation, or anionic polymerization of an unsaturated monomer corresponding to each structure. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.

For example, as a general synthesis method, an unsaturated monomer and a polymerization initiator are dissolved in a solvent, and a batch polymerization method in which polymerization is performed by heating, a solution of an unsaturated monomer and a polymerization initiator in a heating solvent for 1 to 10 hours. The dropping polymerization method etc. which are dropped and added over are mentioned, and the dropping polymerization method is preferable.
Examples of the solvent used for the polymerization include a solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition described below, and more preferably the composition of the present invention. Polymerization is preferably carried out using the same solvent as used in the above. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester bond, a cyano group, and a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If necessary, the polymerization may be performed in the presence of a chain transfer agent (for example, alkyl mercaptan).
The reaction concentration is 5 to 70% by mass, preferably 10 to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 40 ° C to 100 ° C.
The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, more preferably 1 to 12 hours.
After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
In addition, once the resin is precipitated and separated, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).

  The molecular weight of the resin (P) according to the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and in the range of 2000 to 30000. It is particularly preferred. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

  The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50.

  Further, for the purpose of improving the performance of the resin according to the present invention, it may further have repeating units derived from other polymerizable monomers as long as the dry etching resistance is not significantly impaired. The content of repeating units derived from other polymerizable monomers in the resin is generally 50 mol% or less, preferably 30 mol% or less, based on all repeating units. Other polymerizable monomers that can be used include those shown below. For example, it is a compound having one addition polymerizable unsaturated bond selected from (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters and the like. .

  Specifically, (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Amyl acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid-t-octyl, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid 2 -Hydroxyethyl, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate and the like.

  (Meth) acrylamides include, for example, (meth) acrylamide, N-alkyl (meth) acrylamide, (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl Group, t-butyl group, heptyl group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-aryl (meth) acrylamide (as aryl groups, for example, phenyl group, tolyl group , A nitrophenyl group, a naphthyl group, a cyanophenyl group, a hydroxyphenyl group, a carboxyphenyl group, etc.), N, N-dialkyl (meth) acrylamide (R is an alkyl group having 1 to 10 carbon atoms, For example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, A hexyl group), N, N-aryl (meth) acrylamide (the aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide. N-2-acetamidoethyl-N-acetylacrylamide and the like.

Examples of allyl compounds include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyl Examples include oxyethanol.
Examples of vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl aryl ethers (eg vinyl phenyl ether, vinyl tolyl ether, vinyl chloride) Phenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether) and the like.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Examples thereof include vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.
Examples of the crotonic acid esters include alkyl crotonic acid (for example, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.).

  Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of the dialkyl esters of maleic acid or fumaric acid include dimethyl maleate and dibutyl fumarate.
In addition, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilonitrile, and the like can be given. In general, any addition-polymerizable unsaturated compound copolymerizable with the repeating unit according to the present invention can be used without any particular limitation.

  Resin (P) of this invention can be used individually by 1 type or in combination of 2 or more types. The content of the resin (P) is preferably from 30 to 99.99 mass%, preferably from 50 to 99.97 mass%, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Is more preferable, and 70 to 99.95% by mass is particularly preferable.

  Preferred specific examples of the resin (P) include, for example, one or more repeating units (A) selected from the specific examples of the repeating units represented by the general formulas (I) to (III) / the general formula ( IV) One or more types of repeating units selected from specific examples of repeating units represented by formula (V) / one type selected from specific examples of repeating units represented by the general formulas (V) to (VI) Resin having the above repeating unit (B), one or more repeating units (A) selected from specific examples of the repeating units represented by the general formulas (I) to (III) / the general formula (IV) One or more repeating units (C) selected from the specific examples of the repeating units represented by the formula (V) to one or more selected from the specific examples of the repeating units represented by the general formulas (V) to (VI). Repeating unit (B) / in the general formula (AII) It may be mentioned a resin having one or more repeating units (D) is selected from the specific examples of the repeating units.

  Although the more preferable specific example of resin (P) is shown below, this invention is not limited to these.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further include a basic compound, a resin that decomposes by the action of an acid to increase the dissolution rate in an aqueous alkaline solution, and a conventional photoacid generator. An agent, a surfactant, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a dissolution promoting compound for a developer, a compound having a proton acceptor functional group, and the like can be contained.

[2] Compound (B) which is different from the resin (P) and generates bis (alkylsulfonyl) amide upon irradiation with actinic rays or radiation
The compound (B) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention generates bis (alkylsulfonyl) amide upon irradiation with actinic rays or radiation. That is, the compound (B) is a photoacid generator. Here, the compound (B) is different from the resin (P).
The compound (B) is preferably a low molecular compound having a molecular weight of 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and preferably a low molecular compound having a molecular weight of 900 or less. Here, the low molecular weight compound in the present invention refers to a compound having an unsaturated bond (so-called polymerizable monomer) by cleaving the unsaturated bond using an initiator and growing the bond in a chain manner. It is not a so-called polymer or oligomer obtained, but a compound having a constant molecular weight of 2000 or less (more preferably 1500 or less, more preferably 900 or less) (a compound having substantially no molecular weight distribution). The molecular weight is usually 100 or more.

  Among the compounds that generate bis (alkylsulfonyl) amide upon irradiation with actinic rays or radiation, compounds represented by the following general formula (ZI ′) or (ZII ′) can be exemplified.

In the general formula (ZI ′),
R ₂₀₁ ′, R ₂₀₂ ′ and R ₂₀₃ ′ each independently represents an organic group.
X ^- represents a bis (alkylsulfonyl) amide anion.

  Examples of the bis (alkylsulfonyl) amide anion include organic anions represented by the following general formula (AN1).

In the general formula (AN1),
R ₁₆ and R ₁₇ each independently represents an alkyl group.

The alkyl group of R ₁₆ and _{R 17,} for example, those having 1 to 30 carbon atoms. Here, the alkyl group as R ₁₆ and R ₁₇ may further have a substituent. Examples of such a further substituent include a hydroxyl group and an alkyl group (preferably having 1 to 20 carbon atoms). , Cycloalkyl group (preferably having 3 to 20 carbon atoms), halogen atom (fluorine, chlorine, bromine, iodine), aryl group, nitro group, cyano group, carboxyl group, —O—, —CO—, —CO ₂ —. , —S—, —SO ₂ —, —SO ₃ —, —SO ₂ N (Rd ₁ ) —, —CO ₂ N (Rd ₂ ) —, and a group in which two or more of these are combined. Can be mentioned. Rd ₁ and Rd ₂ each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms).
In addition, the alkyl group as R ₁₆ and R ₁₇ may have one or more of the above-described further substituents.

Each of R ₁₆ and R ₁₇ preferably contains at least one fluorine atom. As a result, the reactivity of the bis (alkylsulfonyl) amide anion generated from the compound (B) as an acid can be further increased. As a result, the sensitivity and resolution can be further improved, and the exposure latitude is further improved. Can be a thing.
Further, each of R ₁₆ and R ₁₇ containing at least one fluorine atom means that the compound (B) contains at least one fluorine atom, but the fluorine atom has a low surface free energy, thereby The compound (B) tends to be unevenly distributed on the surface of the resist film. Therefore, the reaction of the bis (alkylsulfonyl) amide anion as an acid generated from the compound (B) can be more reliably performed on the surface of the resist film. As a result, it is possible to obtain a pattern having an excellent pattern shape by suppressing problems such as the T-top shape of the cross section of the pattern obtained.

The alkyl group for R ₁₆ and R ₁₇ is more preferably an alkyl group substituted with a fluorine atom or a fluoroalkyl group.
A particularly preferred embodiment of R ₁₆ and R ₁₇ is a group represented by the following general formula.

In the above general formula,
R ₁₈ represents a perfluoroalkylene group (preferably having a carbon number of 4 or less, more preferably 2 to 4, still more preferably 2 or 3).
Ax represents a single bond or a divalent linking group (preferably —O—, —CO ₂ —, —S—, —SO ₃ —, —SO ₂ N (Rd ₁ ) —). Rd ₁ represents a hydrogen atom or an alkyl group, and may combine with R ₁₉ to form a ring structure.
R ₁₉ represents a hydrogen atom, a fluorine atom, an optionally substituted linear or branched alkyl group, an optionally substituted monocyclic or polycyclic cycloalkyl group, or an optionally substituted aryl group. . The optionally substituted alkyl group, cycloalkyl group, and aryl group preferably do not have a fluorine atom as a substituent.
* Represents a bond bonded to the sulfonyl group.

R ₁₆ and R ₁₇ may be bonded to each other to form a ring.
Examples of the group formed by combining R ₁₆ and R ₁₇ with each other include an alkylene group. Preferably, it is a C2-C20 perfluoroalkylene group. By combining R ₁₆ and R ₁₇ to form a ring, the reactivity of the bis (alkylsulfonyl) amide anion generated from the compound (B) as an acid can be further increased. As a result, sensitivity, resolution can be improved. The exposure latitude can be improved and the exposure latitude can be improved.

Carbon number of the organic group as R ₂₀₁ ′, R ₂₀₂ ′ and R ₂₀₃ ′ is generally 1 to 30, preferably 1 to 20.
Two of R ₂₀₁ ′ to R ₂₀₃ ′ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
Examples of the group formed by combining two of R ₂₀₁ ′ to R ₂₀₃ ′ include an alkylene group (for example, a butylene group or a pentylene group).
Specific examples of the organic group as R ₂₀₁ ′, R ₂₀₂ ′ and R ₂₀₃ ′ include corresponding groups in the compounds (ZI′-1), (ZI′-2) and (ZI′-3) described later. be able to.

In addition, the compound which has two or more structures represented by general formula (ZI ') may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI ′) is bonded to at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (ZI ′). It may be a compound having a structure.

  More preferred (ZI ′) components include compounds (ZI′-1), (ZI′-2), and (ZI′-3) described below.

The compound (ZI′-1) is an arylsulfonium compound in which at least one of R ₂₀₁ ′ to R ₂₀₃ ′ of the general formula (ZI ′) is an aryl group, that is, a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R ₂₀₁ ′ to R ₂₀₃ ′ may be an aryl group, or a part of R ₂₀₁ ′ to R ₂₀₃ ′ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ ′ to R ₂₀₃ ′ are an alkyl group (eg, having 1 to 15 carbon atoms), a cycloalkyl group (eg, having 3 to 15 carbon atoms), an aryl group (eg, having 6 to 6 carbon atoms). 14), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group may be substituted. Preferred substituents are straight chain, branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and straight chain, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and particularly preferably. They are a C1-C4 alkyl group and a C1-C4 alkoxy group. The substituent may be substituted with any one of three R ₂₀₁ ′ to R ₂₀₃ ′, or may be substituted with all three. Further, when R ₂₀₁ ′ to R ₂₀₃ ′ are aryl groups, the substituent is preferably substituted at the p-position of the aryl group.

  The compound (ZI′-1) is preferably a compound represented by the following general formula (ZI′-1-1).

R _{1 to} R ₁₅ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acyloxy group, or an aryl group. R ₁ and R ₁₅ may be bonded to each other to form a ring. In this case, R ₁ and R ₁₅ form a single bond or a divalent linking group.
R ₁₆ and R ₁₇ each independently represents an alkyl group. R ₁₆ and R ₁₇ may be bonded to each other to form a ring.

Examples of the halogen atom of R ₁ to R _15, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a fluorine atom is particularly preferred.
Examples of the alkyl group for R _{1 to} R ₁₅ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. -20 alkyl group is mentioned, More preferably, a C1-C8 alkyl group, Most preferably, a C1-C3 alkyl group is mentioned.
As the alkyl group contained in the alkoxy group of R _{1 to} R _15, the same alkyl group as in the above R _{1 to} R ₁₅ is preferable.
As the alkyl group contained in the alkylcarbonyloxy group R ₁ to R _15, the same alkyl groups represented by _R 1 _{to R 15} are preferred.
The aryl group of R _{1 to} R ₁₅ is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

R _{1 to} R ₁₅ are preferably a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom or a halogen atom, and still more preferably a hydrogen atom.

When R ₁ and R ₁₅ are bonded to each other to form a ring, such a ring is preferably a 5- to 7-membered ring, and more preferably a 5- or 6-membered ring. Examples of the divalent linking group R ₁ and _{R 15} forms an alkylene group (preferably an alkylene group having 1 to 3 carbon _{atoms), - O -, - CO} 2 -, - S -, - SO 2 -, - Examples include SO ₃ — and a group formed by combining two or more of these.
When R ₁ and R ₁₅ are bonded to each other to form a ring, R ₁ and R ₁₅ preferably form a single bond, an alkylene group, —O—, —CO ₂ — or —S—. More preferably, it forms a group or -O-.

R _{1 to} R ₁₅ may further have a substituent. Examples of such a further substituent include a hydroxyl group, an alkyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, A cyano group, an amide group, a sulfonamide group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a carboxy group, and the like can be given.

Specific examples and preferred examples of the alkyl group as R ₁₆ and R ₁₇ are the same as those described in the general formula (AN1).

Next, the compound (ZI′-2) will be described.
The compound (ZI′-2) is a compound in the case where R ₂₀₁ ′ to R ₂₀₃ ′ in the general formula (ZI ′) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ ′ to R ₂₀₃ ′ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ₂₀₁ ′ to R ₂₀₃ ′ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, an alkoxycarbonylmethyl group, Particularly preferred is a linear or branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ ′ to R ₂₀₃ ′ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group). Group, butyl group, pentyl group). The alkyl group as R ₂₀₁ ′ to R ₂₀₃ ′ is more preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.
Preferable examples of the cycloalkyl group as R ₂₀₁ ′ to R ₂₀₃ ′ include cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group). The cycloalkyl group as R ₂₀₁ ′ to R ₂₀₃ ′ is more preferably a cyclic 2-oxoalkyl group.
The 2-oxoalkyl group as R ₂₀₁ ′ to R ₂₀₃ ′ may be linear, branched or cyclic, and preferably> C═O at the 2-position of the above alkyl group or cycloalkyl group. The group which has can be mentioned.
The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ ′ to R ₂₀₃ ′ preferably includes an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group). .
R ₂₀₁ ′ to R ₂₀₃ ′ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (ZI′-3) is a compound represented by the following general formula (ZI′-3), which is a compound having a phenacylsulfonium salt structure.

In the general formula (ZI′-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
Any two or more of R _{1c to} R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom, an ester bond, and an amide bond. May be included. Examples of the group formed by combining any two or more of R _{1c to} R _7c and R _x and R _y include a butylene group and a pentylene group.
X ⁻ represents a bis (alkylsulfonyl) amide anion, and examples thereof include the same as the bis (alkylsulfonyl) amide anion of X ⁻ in formula (ZI ′).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched group having 1 to 12 carbon atoms. An alkyl group (for example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group) can be mentioned.
Examples of the cycloalkyl group as R _{1c to} R _7c include a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group). Can do.
The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).
Preferably, any one of R _{1c to} R _5c is a linear, branched alkyl group, cycloalkyl group, or a linear, branched, or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _{1c to} R _7c . The alkyl group as R _x and R _y is more preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.
_Examples of the cycloalkyl group as R _x and R _y include the same cycloalkyl groups as R _{1c to} R _7c . The cycloalkyl group as R _x and R _y is more preferably a cyclic 2-oxoalkyl group.
Examples of the linear, branched, or cyclic 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
The alkoxy group in the alkoxycarbonylmethyl group may be the same as the alkoxy group as R _1c to R _5c.
R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

In the general formula (ZII ′),
R ₂₀₄ ′ and R ₂₀₅ ′ each independently represents an aryl group which may have a substituent, an alkyl group which may have a substituent, or an cycloalkyl group which may have a substituent. .
The aryl group for R ₂₀₄ ′ and R ₂₀₅ ′ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
The alkyl group as R ₂₀₄ ′ and R ₂₀₅ ′ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, pentyl group).
The cycloalkyl group as R ₂₀₄ ′ and R ₂₀₅ ′ preferably includes a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
Examples of the substituent that R ₂₀₄ ′ and R ₂₀₅ ′ may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, a carbon number). 6-15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.
X ⁻ represents a bis (alkylsulfonyl) amide anion, and examples thereof include the same as the bis (alkylsulfonyl) amide anion of X ⁻ in formula (ZI ′).

  Of the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by general formulas (ZI ′) to (ZIII ′) are more preferable, and compounds represented by (ZI ′) are more preferable. Particularly preferred are compounds represented by (ZI′-1) to (ZI′-3).

  The compound (B) described above is preferably a compound that generates an acid (bis (alkylsulfonyl) amide) represented by the following general formula (AC1) upon irradiation with actinic rays or radiation.

In the general formula (AC1), R ₁₆ and R ₁₇ each independently represents an alkyl group, and specific examples and preferred examples of the organic group as R ₁₆ and R ₁₇ are those described in the general formula (AN1). It is the same.

  Specific examples of the compound (B) are shown below, but the present invention is not limited thereto.

A compound (B) can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.
The content of the compound (B) in the composition is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 15% by mass, and still more preferably from 1 to 20% by mass, based on the total solid content of the resist composition. 10% by mass.

  The compound (B) may be used in combination with a photoacid generator other than the compound (B) (hereinafter also referred to as the compound (B ′)).

  The compound (B ′) is not particularly limited as long as it is a known compound, and preferred examples include compounds represented by the following general formula (ZI ″) or (ZII ″).

In the above general formula (ZI ′),
R ₂₀₁ ′, R ₂₀₂ ′ and R ₂₀₃ ′ each independently represents an organic group. _{R 201 ',} R _202' and _{R 203} 'Specific examples and preferred examples of the general formula (ZI' _{R 201} of) _{', R 202'} are similar to those described in and _{R 203} '.
Z ⁻ represents a non-nucleophilic anion other than the bis (alkylsulfonyl) imide anion (an anion having an extremely low ability to cause a nucleophilic reaction).

Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), a sulfonylimide anion, a tris (alkylsulfonyl) methide anion, and the like.

  The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, and the like.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

Examples of other Z ⁻ include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Z ^- The at least α-position by an aliphatic sulfonate anion substituted with a fluorine atom, a fluorine atom or a fluorine atom is substituted with a group having a aromatic sulfonate anion of a sulfonic acid, an alkyl group substituted with a fluorine atom Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred. More preferably, the non-nucleophilic anion is a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, perfluoro An octane sulfonate anion, a pentafluorobenzene sulfonate anion, and a 3,5-bis (trifluoromethyl) benzene sulfonate anion. From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

In general formula (ZII ″), R ₂₀₄ ′ and R ₂₀₅ ′ each independently represents an aryl group, an alkyl group or a cycloalkyl group. Specific examples and preferred examples of R ₂₀₄ ′ and R ₂₀₅ ′ This is the same as that described for R ₂₀₄ ′ and R ₂₀₅ ′ in formula (ZII ′).

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} the general formula (ZI ″).

  Among the compounds (B ′), particularly preferred examples are given below.

  The total amount of the photoacid generator (including a photoacid generator when a photoacid generator other than the compound (B) is used in combination) is 0.1 to 0.1 on the basis of the total solid content of the resist composition. 20 mass% is preferable, 0.5-17 mass% is more preferable, 1-12 mass% is still more preferable, 2.5-9 mass% is especially preferable.

  When the compound (B) and the compound (B ′) are used in combination, the photoacid generator is used in a molar ratio (compound (B) / compound (B ′)), usually 99/1 to 20/80, Preferably it is 99/1-40/60, More preferably, it is 99/1-50/50.

[3] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound.
The basic compound is preferably a nitrogen-containing organic basic compound.

  Although the basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.

(1) Compound represented by the following general formula (BS-1)

In general formula (BS-1),
Each R is independently a hydrogen atom, an alkyl group (straight or branched), a monovalent aliphatic hydrocarbon ring group (monocyclic or polycyclic), a monovalent aromatic ring group, an alkylene group and a monovalent aromatic It represents one of the groups combined with a cyclic group. However, not all three Rs are hydrogen atoms.

  Although carbon number of the alkyl group as R is not specifically limited, Usually, 1-20, Preferably it is 1-12.

  The number of carbon atoms of the monovalent aliphatic hydrocarbon ring group as R is not particularly limited, but is usually 3 to 20, preferably 5 to 15.

  Although carbon number of the monovalent | monohydric aromatic ring group as R is not specifically limited, Usually, 6-20, Preferably it is 6-10. Specifically, aryl groups, such as a phenyl group and a naphthyl group, are mentioned.

  Although carbon number of the group which combined the alkylene group and monovalent | monohydric aromatic ring group as R is not specifically limited, Usually, 7-20, Preferably it is 7-11. Specific examples include aralkyl groups such as a benzyl group.

  An alkyl group as R, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, or a group in which an alkylene group and a monovalent aromatic ring group are combined may have a hydrogen atom substituted by a substituent. Good. Examples of the substituent include an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, a hydroxyl group, a carboxyl group, and an alkoxy group. Group, aryloxy group, alkylcarbonyloxy group, alkyloxycarbonyl group and the like.

  In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are not hydrogen atoms.

  Specific examples of the compound of the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N- Examples include dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline.

  In addition, a compound in which at least one R in the general formula (BS-1) is an alkyl group substituted with a hydroxyl group can be mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

The alkyl group as R may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 of US Pat. No. 6,040,112.

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure (N-hydroxyethylpiperidine, bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) sebacate), compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. Examples of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. It may have a substituent.

More preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007/0224539. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt Ammonium salts are also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

  In addition, compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in paragraph 0108 of JP-A No. 2007-298869, and the like can also be used.

A basic compound is used individually or in combination of 2 or more types.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of the total solid of actinic-ray-sensitive or radiation-sensitive resin composition, Preferably it is 0.01-5 mass%.

  The molar ratio of photoacid generator / basic compound is preferably 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

  The photoacid generator in the above molar ratio is the total amount of the repeating unit (A) contained in the resin (P), the compound (B), and the compound (B ′).

[4] Resin that decomposes by the action of an acid and increases the dissolution rate in an alkaline aqueous solution The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is decomposed by the action of an acid to be alkaline You may contain resin which the melt | dissolution rate with respect to aqueous solution increases.

  Resins that decompose due to the action of an acid and increase the dissolution rate in an alkaline aqueous solution (hereinafter also referred to as “acid-decomposable resins”) are not included in the main chain or side chain of the resin, It is a resin having a group (acid-decomposable group) that decomposes by the action of and produces an alkali-soluble group. Among these, a resin having an acid-decomposable group in the side chain is more preferable.

  The acid-decomposable resin is decomposed with an acid into an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It can be obtained by reacting a precursor of a group capable of being reacted or copolymerizing an alkali-soluble resin monomer having an acid-decomposable group bonded thereto with various monomers.

  As the acid-decomposable group, for example, in a resin having an alkali-soluble group such as —COOH group or —OH group, a group in which a hydrogen atom of the alkali-soluble group is substituted with a group capable of leaving by the action of an acid is preferable.

  Specifically, the acid-decomposable group is preferably the same group as the acid-decomposable group described in the above-described resin of the present invention (for example, the acid-decomposable group described as the repeating unit (B) in the resin (P)). As an example.

  The resin having an alkali-soluble group is not particularly limited. For example, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene) and copolymers thereof, hydrogenated poly (Hydroxystyrene), poly (hydroxystyrene) s having a substituent represented by the following structure, and resins having phenolic hydroxyl groups, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers, hydrogen An alkali-soluble resin having a hydroxystyrene structural unit such as a modified novolak resin, and an alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

  The alkali dissolution rate of these alkali-soluble resins is preferably at least 170 kg / second as measured with 2.38 mass% tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 Å / second or more.

  The content of the group capable of decomposing with an acid is the number of repeating units (X) having a group decomposable with an acid in the resin and the number of repeating units having an alkali-soluble group not protected with a group capable of leaving with an acid. With (Y), it is represented by X / (X + Y). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  The weight average molecular weight of the acid-decomposable resin is preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000 as a polystyrene conversion value by the GPC method.

  The dispersity (Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.1 to 1.7.

  Two or more acid-decomposable resins may be used in combination.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain an acid-decomposable resin excluding the resin (P), but when it is contained, the acid-decomposable excluding the resin (P). The blending amount of the resin in the composition is preferably 0.1 to 70% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.1 to 30% by mass in the total solid content of the composition. is there.

[5] Solvent The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent. Examples of such a solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and a ring. Organic solvents such as a good monoketone compound (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate and the like can be mentioned.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate And propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene Preferred is glycol monoethyl ether.

  Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

  Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. Particularly preferred solvents include propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether.
In the present invention, the above solvents may be used alone or in combination of two or more.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent having a normal pressure (760 mmHg) and a boiling point of 150 ° C. or lower.
The said solvent may be used independently and may use 2 or more types together. Moreover, you may use together the solvent whose boiling point exceeds 150 degreeC at a normal pressure. In the composition of the present invention, the content of the solvent having a boiling point of 150 ° C. or less is preferably 50% by mass or more, and more preferably 65% by mass or more based on the total amount of the solvent. Most preferably, it is 70 mass%-100 mass%.
The solvent having a boiling point of 150 ° C. or lower preferably has a boiling point of 50 to 150 ° C., more preferably 80 to 150 ° C.

The solvent having a boiling point of 150 ° C. or lower is preferably an organic solvent, and may contain, for example, an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate ester, an alkyl alkoxypropionate, a cyclic lactone, or a ring. It can be selected from organic solvents such as good monoketone compounds, alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates.
For example, from the solvents shown below, a solvent having a boiling point of 150 ° C. or lower at normal pressure is selected, alone or in combination of two or more, and a solvent having a boiling point exceeding 150 ° C. at normal pressure is used in combination. be able to.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane) (bp = 146 ° C.), propylene glycol monoethyl ether acetate (bp). = 164-165 ° C.), propylene glycol monopropyl ether acetate (bp = 173-174 ° C./740 mmHg), ethylene glycol monomethyl ether acetate (bp = 143 ° C.), ethylene glycol monoethyl ether acetate (b P. = 156 ° C.).
Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol) (bp = 119 ° C.), propylene glycol monoethyl ether (bp = 130-131 ° C.). ), Propylene glycol monopropyl ether (bp = 148 ° C.), propylene glycol monobutyl ether (bp = 169-170 ° C.), ethylene glycol monomethyl ether (bp = 124-125 ° C.), ethylene Preferred examples include glycol monoethyl ether (bp = 134-135 ° C.).

  Examples of the alkyl lactate ester include methyl lactate (bp = 145 ° C.), ethyl lactate (bp = 154 ° C.), propyl lactate (bp = 169-172 ° C.), butyl lactate (b (P. = 185-187 ° C.).

  Examples of the alkyl alkoxypropionate include, for example, ethyl 3-ethoxypropionate (bp = 169-170 ° C.), methyl 3-ethoxypropionate (bp = 138-141 ° C.), 3-methoxypropionic acid Preferred is ethyl (bp = 156-158 ° C.).

  Examples of the cyclic lactone include β-propiolactone (bp = 162 ° C.), β-butyrolactone (bp = 71-73 ° C./29 mmHg), and γ-butyrolactone (bp = 204−). 205 ° C.), α-methyl-γ-butyrolactone (bp = 78-81 ° C./10 mmHg), β-methyl-γ-butyrolactone (bp = 87-88 ° C./10 mmHg), γ-valerolactone (Bp = 82-85 ° C./10 mmHg), γ-caprolactone (bp = 219 ° C.), γ-octanoic lactone (bp = 234 ° C.), α-hydroxy-γ-butyrolactone (Bp = 133 ° C./10 mmHg) is preferable.

As a monoketone compound which may contain a ring, for example, 2-butanone (bp = 80 ° C.)
3-methylbutanone (bp = 94-95 ° C.), pinacolone (bp = 106 ° C.), 2-pentanone (bp = 101-105 ° C.), 3-pentanone (bp) = 102 ° C), 3-methyl-2-pentanone (bp = 118 ° C), 4-methyl-2-pentanone (bp = 117-118 ° C), 2-methyl-3-pentanone ( bp = 113 ° C.), 4,4-dimethyl-2-pentanone (bp = 125-130 ° C.), 2,4-dimethyl-3-pentanone (bp = 124 ° C.), 2 2,4,4-tetramethyl-3-pentanone (bp = 152-153 ° C.), 2-hexanone (bp = 127 ° C.), 3-hexanone (bp = 123 ° C.) , 5-methyl-2-hexanone (bp = 145 ° C.), 2-heptanone (b.p. = 145 ° C.) = 149-150 ° C.), 3-heptanone (bp = 146-148 ° C.), 4-heptanone (bp = 145 ° C.), 2-methyl-3-heptanone (bp = 158) -160 ° C), 5-methyl-3-heptanone (bp = 161-162 ° C), 2,6-dimethyl-4-heptanone (bp = 165-170 ° C), 2-octanone (b P. = 173 ° C.), 3-octanone (bp = 167-168 ° C.), 2-nonanone (bp = 192 ° C./743 mmHg), 3-nonanone (bp = 187-188) ° C), 5-nonanone (bp = 186-187 ° C.), 2-decanone (bp = 211 ° C.), 3-decanone (bp = 204-205 ° C.), 4-decanone ( b.p. = 206-207 ° C.), 5-hexen-2-one (b. = 128-129 ° C.), 3-penten-2-one (bp = 121-124 ° C.), cyclopentanone (bp = 130-131 ° C.), 2-methylcyclopentanone (b P. = 139 ° C.), 3-methylcyclopentanone (bp = 145 ° C.), 2,2-dimethylcyclopentanone (bp = 143-145 ° C.), 2,4,4- Trimethylcyclopentanone (bp = 160 ° C.), cyclohexanone (bp = 157 ° C.), 3-methylcyclohexanone (bp = 169-170 ° C.), 4-methylcyclohexanone (bp) = 169-171 ° C.), 4-ethylcyclohexanone (bp = 192-194 ° C.), 2,2-dimethylcyclohexanone (bp = 169-170 ° C.), 2,6-dimethylcyclohexanone (b . p. = 174-176 ° C), 2,2,6-trimethylcyclohexanone (bp = 178-179 ° C), cycloheptanone (bp = 179 ° C), 2-methylcycloheptanone (bp) . = 182-185 ° C.) and 3-methylcycloheptanone (bp = 100 ° C./40 mmHg).

  Examples of the alkylene carbonate include propylene carbonate (bp = 240 ° C.), vinylene carbonate (bp = 162 ° C.), ethylene carbonate (bp = 243-244 ° C./740 mmHg), butylene carbonate ( (b.p. = 88 / 0.8 mmHg.degree. C.)).

  Examples of the alkyl alkoxyacetate include, for example, 2-methoxyethyl acetate (bp = 145 ° C.), 2-ethoxyethyl acetate (bp = 155-156 ° C.), acetic acid-2- (2-ethoxy Preferred are ethoxy) ethyl (bp = 219 ° C.) and 1-methoxy-2-propyl acetate (bp = 145-146 ° C.).

  As the alkyl pyruvate, for example, methyl pyruvate (bp = 134-137 ° C.), ethyl pyruvate (bp = 144 ° C.), and propyl pyruvate (bp = 166 ° C.) are preferable. Can be mentioned.

  Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. From the viewpoint of reducing outgas, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl A solvent having a boiling point at atmospheric pressure of 150 ° C. or lower, such as ether, is particularly preferable.

  The amount of the solvent (including those having a boiling point of 150 ° C. or higher) in the total amount of the composition of the present invention can be appropriately adjusted depending on the desired film thickness, etc. The total solid content concentration of the composition is 0.5-30% by mass, preferably 1.0-20% by mass, more preferably 1.5-10% by mass.

[6] Surfactant The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.

  Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include those described in [0273] et seq. Of US Patent Application Publication No. 2008/0248425.

Surfactants may be used alone or in combination of two or more.
The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

[7] Acid-decomposable dissolution inhibiting compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention decomposes by the action of an acid to increase the dissolution rate in an alkali developer, and has a molecular weight of 3000 or less. A compound (hereinafter, also referred to as “dissolution inhibiting compound”) can be contained.

  The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996). . Examples of the acid-decomposable group and alicyclic structure are the same as those described for the acid-decomposable resin.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with an electron beam or EUV light, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.
The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

[8] Other components The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a dye. Suitable dyes include oily dyes and basic dyes.

  In order to improve the acid generation efficiency by exposure, the following photosensitizers can be added.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable. Examples of such a phenol compound having a molecular weight of 1000 or less include those described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent 219294.

  In addition, compounds having a proton acceptor functional group described in JP-A No. 2006-208781 and JP-A No. 2007-286574 can be suitably used for the composition of the present application.

[9] Pattern Forming Method The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is applied on a support such as a substrate to form a film. The thickness of this resist film is preferably 0.02 to 0.1 μm.
As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

  For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon, silicon / silicon dioxide coating, silicon nitride) used in the manufacture of precision integrated circuit elements, photomasks, imprint molds, and the like. A quartz substrate having a Cr layer, etc.) is coated and dried by a suitable coating method such as a spinner or a coater to form a film. In addition, a known antireflection film can be applied in advance.

  The film is irradiated with actinic rays or radiation, preferably electron beam (EB), X-ray or EUV light, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

  In the development step, an alkali developer is usually used. Examples of the alkaline developer of the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide Alkaline aqueous solutions of cyclic amines such as quaternary ammonium salts such as pyrrole and pihelidine can be used.

Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

  For details on producing an imprint mold structure by applying the composition of the present invention, for example, the basics of nanoimprint and technological development / application development-Nanoimprint substrate technology and latest technological development-Editing : Yoshihiko Hirai Frontier Publishing (issued in June 2006), Japanese Patent No. 4109085, Japanese Unexamined Patent Application Publication No. 2008-162101, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

  <Synthesis of monomer>

Synthesis Example (Synthesis of M-II-2)
100.00 parts by mass of p-acetoxystyrene was dissolved in 400 parts by mass of ethyl acetate, cooled to 0 ° C., 47.60 parts by mass of sodium methoxide (28% methanol solution) was added dropwise over 30 minutes, For 5 hours. Ethyl acetate was added and the organic layer was washed three times with distilled water and then dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 131.70 parts by mass of p-hydroxystyrene (54% ethyl acetate solution). It was.

  p-Hydroxystyrene (54% ethyl acetate solution) 18.52 parts by mass is dissolved in ethyl acetate 56.00 parts by mass to obtain 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyl. 31.58 parts by mass of difluoride was added and cooled to 0 ° C. A solution prepared by dissolving 12.63 parts by mass of triethylamine in 25.00 parts by mass of ethyl acetate was added dropwise over 30 minutes, and the mixture was stirred at 0 ° C. for 4 hours. Ethyl acetate was added, and the organic layer was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 32.90 parts by mass of Compound A.

  35.00 parts by mass of Compound A was dissolved in 315 parts by mass of methanol, cooled to 0 ° C., 245 parts by mass of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off, ethyl acetate was added, and the organic layer was washed three times with saturated brine, and then dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 34.46 parts by mass of Compound B. .

  28.25 parts by mass of Compound B was dissolved in 254.25 parts by mass of methanol, 23.34 parts by mass of triphenylsulfonium bromide was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off, distilled water was added, and the mixture was extracted 3 times with chloroform. The obtained organic layer was washed three times with distilled water, and then the solvent was distilled off to obtain 42.07 parts by mass of the target compound (M-II-2).

<Synthesis of Resin (P)>
Synthesis Example 1 (Synthesis of P-1)
9.3 parts by mass of 1-methoxy-2-propanol was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, 5.39 parts by mass of the monomer (M-II-2) obtained in the above synthesis example, 9.05 parts by mass of styrene, 7.77 parts by mass of tert-butyl methacrylate, biphenyl methacrylate 1 .36 parts by mass, 17.3 parts by mass of 1-methoxy-2-propanol, dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] 1.95 parts by mass (for the total amount of monomers) The mixed solution was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 4 hours. The reaction solution was allowed to cool and then reprecipitated and vacuum dried with a large amount of hexane / ethyl acetate (mass ratio 60:40) to obtain 10.8 parts by mass of a resin (P-1).

  The weight average molecular weight (Mw: polystyrene conversion) obtained from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) of the obtained resin was Mw = 7000, and the dispersity was Mw / Mn = 1.56. It was.

  Thereafter, resins P-2 to P-5 were synthesized in the same manner. The structure, composition ratio (molar ratio), weight average molecular weight, and dispersity of each synthesized resin are shown in the table below.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in the following table are dissolved in a solvent, and a solution with a solid content of 1.8% by mass is prepared for each, and this is filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm, and is sensitive to radiation. A resin composition (positive resist solution) was prepared. The actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in the following table. The concentration (% by mass) of each component described in the table below is based on the total solid content of the radiation-sensitive resin composition. The results are shown in the same table.

<Resist evaluation>
Examples 1-14, Comparative Examples 1-6
The prepared radiation-sensitive resin composition is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 90 seconds to obtain a film thickness of 50 nm. A radiation sensitive film was formed.

  This radiation sensitive film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 keV). Immediately after irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Furthermore, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern. Was evaluated by the following method.

<Resist evaluation>
〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).

[Resolution]
The resolving power was defined as the limiting resolving power (line and space were separated and resolving) at the irradiation dose showing the above sensitivity. It means that it is excellent in the resolution, so that the value of resolution is small.

[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and the T-top shape was evaluated. More specifically, in the cross-sectional shape of the line pattern, “L1 is the maximum value of the line width in the region from the pattern surface to the depth direction of 10 nm”, “10 nm point from the pattern surface to the depth direction. From this, the value represented by L1 / L2 when the minimum value of the line width in the region up to the point of 50 nm in the same depth direction is L2 ″ was obtained as the T-top ratio. The closer the T-top ratio is to 1, the better the pattern shape.

[Exposure latitude (EL)]
A dose width that allowed a pattern size of 60 nm ± 10% when the dose showing the sensitivity was changed was determined, and this value was divided by the sensitivity and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

  Hereinafter, abbreviations in the table are shown.

  [Photoacid generator]

[Basic compounds]
TPI: Triphenylimidazole [Surfactant]
W-1: Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
〔solvent〕
S1: Propylene glycol monomethyl ether acetate (PGMEA)
S2: Propylene glycol monomethyl ether (PGME)

As can be seen from Table 1, compared with the actinic ray-sensitive or radiation-sensitive resin composition of the comparative example not containing the compound (B) of the present invention, the actinic ray-sensitive or radiation-sensitive resin composition of the examples. Therefore, high sensitivity, high resolution, and excellent exposure latitude can be satisfied at the same time.
Further, the actinic ray-sensitive or radiation-sensitive resin of the present invention can provide the same effect even when exposed to EUV light.

Claims (10)

Repeating unit (A) having an ionic structure site that decomposes by irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin and repeating unit (B) that decomposes by the action of an acid to generate a phenolic hydroxyl group And a resin (P) having
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (B) different from the resin (P) that generates bis (alkylsulfonyl) amide upon irradiation with actinic rays or radiation.   Repeating unit (A) having an ionic structure site that decomposes by irradiation with actinic rays or radiation to generate an acid anion in the side chain of the resin, repeating unit (B) that decomposes by the action of an acid to generate an alkali-soluble group ), And a resin (P) having a repeating unit having an aromatic ring group different from the repeating unit (A) and the repeating unit (B);
  A compound (B) different from the resin (P) that generates bis (alkylsulfonyl) amide upon irradiation with actinic rays or radiation;
An actinic ray-sensitive or radiation-sensitive resin composition containing The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein the resin (P) further has a repeating unit (C) represented by the following general formula (IV).

In the general formula (IV), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to Ar ₄ to form a ring, in which case R ₄₂ represents an alkylene group.
X ₁ represents a single bond or a divalent linking group.
Ar ₄ represents a divalent aromatic ring group, and represents a trivalent aromatic ring group when bonded to R ₄₂ to form a ring.
n represents an integer of 1 to 4. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the compound (B) is represented by the following general formula (ZI'-1-1).

R _{1 to} R ₁₅ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylcarbonyloxy group, or an aryl group. R ₁ and R ₁₅ may be bonded to each other to form a ring. In this case, R ₁ and R ₁₅ form a single bond or a divalent linking group.
R ₁₆ and R ₁₇ each independently represents an alkyl group. R ₁₆ and R ₁₇ may be bonded to each other to form a ring. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4 , wherein in the general formula (ZI′-1-1), each of R ₁₆ and R ₁₇ contains at least one fluorine atom. In formula _{(ZI'-1-1), R 16} and _{R 17} are each independently an alkyl group substituted with a fluorine atom or a fluoroalkyl group, actinic according to claim 4 or 5 A light-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 4 to 6 , wherein R ₁₆ and R ₁₇ are bonded to each other to form a ring. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7 , wherein the repeating unit (B) is a repeating unit represented by the following general formula ( VI).

In one general formula _{(VI), R 61, R} 62, R 63 each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents an alkylene group.
Ar ₆ represents a divalent aromatic ring group, and represents a trivalent aromatic ring group when bonded to R ₆₂ to form a ring.
Y represents a hydrogen atom or a group capable of leaving by the action of an acid. When a plurality of Y are present, the plurality of Y may be the same or different. However, at least one of Y represents a group capable of leaving by the action of an acid.
m represents an integer of 1 to 4.   The resist film formed using the actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-8.   The pattern formation method which has the process of exposing and developing the resist film of Claim 9.