JP2008133448A - Sulfonium salt and polymer compound having polymerizable anion, resist material and pattern forming method - Google Patents

Abstract

（Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基。）
【選択図】なしProvided are a polymer compound and a monomer for producing a base resin of a radiation-sensitive resist material, and a resist material having high resolution, density dependency and excellent exposure margin.
A polymer compound which generates a sulfonic acid having a repeating unit represented by the general formula (1a) in response to high energy rays or heat.

(R ¹ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)
[Selection figure] None

Description

The present invention includes (1) a polymer compound that is sensitive to high energy rays, heat, etc., and generates sulfonic acid, (2) a sulfonium salt having a polymerizable anion useful as a raw material for a photoacid generator and a sulfonic acid polymer, The present invention relates to (3) a polymer compound containing the sulfonium salt as a monomer, (4) a resist material containing the polymer compound, and (5) a pattern forming method using the resist material.
In the present invention, high energy rays include ultraviolet rays, far ultraviolet rays, electron beams, EUV, X-rays, excimer lasers, γ rays, and synchrotron radiation.

  In recent years, with the high integration and high speed of LSIs, miniaturization of pattern rules is demanded, and far ultraviolet lithography and vacuum ultraviolet lithography are promising as next-generation fine processing techniques. Among them, photolithography using ArF excimer laser light as a light source is an indispensable technique for ultrafine processing of 0.13 μm or less.

ArF lithography began to be used in part from the fabrication of 130 nm node devices and became the main lithography technology from 90 nm node devices. As lithography technology for the next 45nm node, initially 157nm lithography using F ₂ laser is promising, its development was retarded by several problems have been pointed out, water between the projection lens and the wafer, ethylene glycol, glycerin, etc. ArF immersion lithography that can design the numerical aperture (NA) of the projection lens to 1.0 or more and achieve high resolution by inserting a liquid having a higher refractive index than air has rapidly emerged (for example, Non-patent literature 1: Journal of photopolymer Science and Technology Vol. 17, No. 4, p587 (2004)).

  In ArF lithography, in order to prevent deterioration of precise and expensive optical system materials, a resist material with high sensitivity capable of exhibiting sufficient resolution with a small amount of exposure is required. It is most common to select a highly transparent one at a wavelength of 193 nm. For example, for the base resin, polyacrylic acid and its derivatives, norbornene-maleic anhydride alternating polymer, polynorbornene, ring-opening metathesis polymer, ring-opening metathesis polymer hydrogenated product, etc. have been proposed. Some achievements have been achieved in terms of raising the nature.

  Various studies have also been made on photoacid generators. In this case, a photoacid generator that generates alkane or arene sulfonic acid, which has been used in a chemically amplified resist material using a conventional KrF excimer laser beam as a light source, is used as a component of the ArF chemically amplified resist material. In such a case, it is known that the acid strength for cleaving the acid labile group of the resin is not sufficient, and the resolution is not possible at all, or the sensitivity is low and it is not suitable for device production.

  For this reason, as the photoacid generator for the ArF chemically amplified resist material, one that generates perfluoroalkanesulfonic acid with high acid strength is generally used. These photoacid generators that generate perfluoroalkanesulfonic acid have already been developed as KrF resist materials. For example, Patent Document 1: Japanese Patent Application Laid-Open No. 2000-122296 and Patent Document 2: Japanese Patent Application Laid-Open No. Hei 11-. Japanese Patent No. 282168 describes a photoacid generator that generates perfluorohexanesulfonic acid, perfluorooctanesulfonic acid, perfluoro-4-ethylcyclohexanesulfonic acid, and perfluorobutanesulfonic acid. Further, as novel acid generators, perfluoroalkyl ether sulfonic acids are generated in Patent Documents 3 to 5: Japanese Patent Application Laid-Open No. 2002-214774, Japanese Patent Application Laid-Open No. 2003-140332, and US Patent Application Publication No. 2002/0197558. An acid generator has been proposed.

  Among the above, perfluorooctane sulfonic acid derivative (PFOS) has environmental problems such as non-degradability and concentration in the environment. Acid development is underway. For example, Patent Document 6: JP-T-2004-531749 discloses that an α, α-difluoroalkanesulfonate is developed from an α, α-difluoroalkene and a sulfur compound, and this sulfonic acid is generated by exposure. A resist material containing an agent, specifically, di (4-tert-butylphenyl) iodonium = 1,1-difluoro-2- (1-naphthyl) ethanesulfonate has been disclosed. No. 2004-2252 discloses the development of α, α, β, β-tetrafluoroalkane sulfonate using α, α, β, β-tetrafluoro-α-iodoalkane and a sulfur compound and generates this sulfonic acid. A photoacid generator and a resist material are disclosed. Moreover, although the above-mentioned patent document 3 does not describe the synthesis method, difluorosulfoacetic acid alkyl ester, difluorosulfoacetic acid amide and the like are disclosed in the text, and further, patent document 8: Discloses a photosensitive composition containing a compound that generates a partially fluorinated alkanesulfonic acid having a sulfonylamide structure derived from perfluoroalkylene disulfonyldifluoride.

  However, when a fine pattern having a pitch of less than 200 nm is to be formed, a problem of a sparse pattern having a different optical contrast or a dimensional difference (dense / dense dependency) between dense patterns has been increasing. The improvement of the density dependency can be achieved to some extent by using a photoacid generator that generates a low-diffusibility acid, but none is satisfactory. While further refinement of pattern rules is required, in addition to exhibiting excellent performance in sensitivity, substrate adhesion, and etching resistance, measures to improve the fundamental density dependence without degradation of resolution Is needed.

  Under such circumstances, a polymer compound having an acroyloxyphenyldiphenylsulfonium salt as a monomer for the purpose of improving sensitivity (Patent Document 9: JP-A-4-230645) or a line edge of a polyhydroxystyrene resin. For the purpose of improving roughness, the above monomer is incorporated into a base resin (Patent Document 10: JP-A-2005-84365). However, since the cation side is bonded to the polymer compound in these, the sulfonic acid generated by irradiation with high energy rays is not different from the sulfonic acid generated from the conventional photoacid generator, and is not satisfactory for the above problems. . In addition, for the purpose of improving sensitivity and resist pattern shape, a sulfonium salt in which an anion side such as polystyrene sulfonic acid is incorporated in a polymer main chain is disclosed (Patent Document 11: Japanese Patent No. 3613491). Both are arene sulfonic acid and alkyl sulfonic acid derivatives, and since the acid strength of the generated acid is low, it is insufficient for cleaving acid labile groups, particularly acid labile groups of ArF chemically amplified resists.

  In addition, in the liquid immersion exposure, there are problems such as a defective resist pattern shape due to a defect due to a minute water droplet remaining on the exposed resist wafer, a collapse of the resist pattern after development, and a T-top shape. Also in liquid immersion lithography, there is a need for a pattern forming method that can provide a good resist pattern after development.

Furthermore, as exposure techniques after ArF lithography, electron beam (EB) lithography, F ₂ lithography, EUV (extreme ultraviolet light) lithography, X-ray lithography, etc. are promising, but under vacuum (under reduced pressure) Since exposure must be performed, sulfonic acid generated during exposure volatilizes, and there is a possibility that a good pattern shape cannot be obtained, and volatilized sulfonic acid may cause damage to the exposure apparatus.

JP 2000-122296 A JP-A-11-282168 JP 2002-214774 A JP 2003-140332 A US Patent Application Publication No. 2002/0197558 JP-T-2004-531749 Japanese Patent Laid-Open No. 2004-2252 JP 2005-266766 A JP-A-4-230645 JP 2005-84365 A Japanese Patent No. 3613491 Journal of photopolymer Science and Technology Vol. 17, no. 4, p587 (2004)

  The present invention has been made in view of the above circumstances, and a monomer for a base resin of a resist material having high resolution and excellent mask fidelity in photolithography using a high energy beam such as ArF excimer laser light as a light source. It is an object of the present invention to provide a sulfonium salt having a polymerizable anion useful as a polymer, a polymer compound obtained from the sulfonium salt, a resist material containing the polymer compound, and a pattern forming method using the resist material.

  As a result of intensive studies to achieve the above object, the present inventors have found that sulfonium salts having a polymerizable anion represented by the following general formula (1) can be obtained from inexpensive industrial raw materials, high energy rays, heat Resist materials using a polymer compound that generates a repeating unit of a sulfonic acid represented by the following general formula (1a) as a base resin, a polymer compound in which a sulfonium salt having this polymerizable anion is introduced as a repeating unit, It has been found that the polymer compound is excellent in various properties such as exposure dose dependency, density dependency, and mask fidelity, and this polymer compound is extremely effective as a resist material for precise microfabrication.

（式中、Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を示す。）
請求項２：
下記一般式（１）で示される重合性アニオンを有するスルホニウム塩。

（式中、Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を示す。Ｒ²、Ｒ³及びＲ⁴は相互に独立に置換もしくは非置換の炭素数１〜１０の直鎖状又は分岐状のアルキル基、アルケニル基又はオキソアルキル基、又は置換もしくは非置換の炭素数６〜１８のアリール基、アラルキル基又はアリールオキソアルキル基を示すか、あるいはＲ²、Ｒ³及びＲ⁴のうちのいずれか２つ以上が相互に結合して式中の硫黄原子と共に環を形成してもよい。）
請求項３：
下記一般式（２）で示される繰り返し単位を含有することを特徴とする高分子化合物。

（式中、Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を示す。Ｒ²、Ｒ³及びＲ⁴は相互に独立に置換もしくは非置換の炭素数１〜１０の直鎖状又は分岐状のアルキル基、アルケニル基又はオキソアルキル基、又は置換もしくは非置換の炭素数６〜１８のアリール基、アラルキル基又はアリールオキソアルキル基を示すか、あるいはＲ²、Ｒ³及びＲ⁴のうちのいずれか２つ以上が相互に結合して式中の硫黄原子と共に環を形成してもよい。）
請求項４：
更に、下記一般式（３）〜（６）で表される繰り返し単位のいずれか１種以上を含有することを特徴とする請求項３記載の高分子化合物。

（式中、Ｒ¹は上記と同様である。Ｒ⁶及びＲ⁷はそれぞれ独立に水素原子又は水酸基を示す。Ｘは酸不安定基を示す。Ｙはラクトン構造を有する置換基を示す。Ｚは水素原子、炭素数１〜１５のフルオロアルキル基、又は炭素数１〜１５のフルオロアルコール含有置換基を示す。）
請求項５：
更に、下記一般式（７）〜（１０）で表される繰り返し単位のいずれか１種以上を含有することを特徴とする請求項３又は４記載の高分子化合物。

（式中、Ｒ¹、Ｘは上記と同様である。Ｇは酸素原子又はカルボニルオキシ基（−Ｃ（＝Ｏ）Ｏ−）を示す。）
請求項６：
請求項３乃至５のいずれか１項記載の高分子化合物をベース樹脂として含有することを特徴とするレジスト材料。
請求項７：
請求項３乃至５のいずれか１項記載の高分子化合物及び上記一般式（２）を含まない高分子化合物をベース樹脂として含有することを特徴とするレジスト材料。
請求項８：
更に、水に不溶でアルカリ現像液に可溶な界面活性剤を含む請求項６又は７記載のレジスト材料。
請求項９：
請求項６乃至８のいずれか１項記載のレジスト材料を基板上に塗布する工程と、加熱処理後フォトマスクを介して高エネルギー線で露光する工程と、必要に応じて加熱処理した後、現像液を用いて現像する工程とを含むことを特徴とするパターン形成方法。
請求項１０：
請求項６乃至８のいずれか１項記載のレジスト材料を基板上に塗布する工程と、加熱処理後、水に不溶でアルカリ現像液に可溶な保護膜を塗布する工程と、当該基板と投影レンズの間に水を挿入しフォトマスクを介して高エネルギー線で露光する工程と、必要に応じて加熱処理した後、現像液を用いて現像する工程とを含むことを特徴とするパターン形成方法。
請求項１１：
請求項６乃至８のいずれか１項記載のレジスト材料を基板上に塗布する工程と、加熱処理後電子線で描画する工程と、必要に応じて加熱処理した後、現像液を用いて現像する工程とを含むことを特徴とするパターン形成方法。 That is, the present invention provides the following sulfonium salt and polymer compound having a polymerizable anion, a resist material, and a pattern forming method.
Claim 1:
A polymer compound which generates a sulfonic acid having a repeating unit represented by the following general formula (1a) in response to high energy rays or heat.

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)
Claim 2:
A sulfonium salt having a polymerizable anion represented by the following general formula (1).

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted straight chain of 1 to 10 carbon atoms. Or a branched alkyl group, an alkenyl group or an oxoalkyl group, or a substituted or unsubstituted aryl group, aralkyl group or aryloxoalkyl group having 6 to 18 carbon atoms, or R ² , R ³ and R ⁴ . Any two or more of them may be bonded to each other to form a ring together with the sulfur atom in the formula.)
Claim 3:
A polymer compound comprising a repeating unit represented by the following general formula (2).

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted straight chain of 1 to 10 carbon atoms. Or a branched alkyl group, an alkenyl group or an oxoalkyl group, or a substituted or unsubstituted aryl group, aralkyl group or aryloxoalkyl group having 6 to 18 carbon atoms, or R ² , R ³ and R ⁴ . Any two or more of them may be bonded to each other to form a ring together with the sulfur atom in the formula.)
Claim 4:
Furthermore, the high molecular compound of Claim 3 containing any 1 or more types of the repeating unit represented by following General formula (3)-(6).

(In the formula, R ¹ is the same as described above. R ⁶ and R ⁷ each independently represents a hydrogen atom or a hydroxyl group. X represents an acid labile group. Y represents a substituent having a lactone structure. Z Represents a hydrogen atom, a C1-C15 fluoroalkyl group, or a C1-C15 fluoroalcohol-containing substituent.
Claim 5:
Furthermore, the high molecular compound of Claim 3 or 4 containing any 1 or more types of the repeating unit represented by the following general formula (7)-(10).

(Wherein R ¹ and X are the same as described above. G represents an oxygen atom or a carbonyloxy group (—C (═O) O—)).
Claim 6:
A resist material comprising the polymer compound according to claim 3 as a base resin.
Claim 7:
A resist material comprising the polymer compound according to any one of claims 3 to 5 and a polymer compound not containing the general formula (2) as a base resin.
Claim 8:
The resist material according to claim 6 or 7, further comprising a surfactant that is insoluble in water and soluble in an alkaline developer.
Claim 9:
A step of applying the resist material according to any one of claims 6 to 8 on a substrate, a step of exposing with a high energy beam through a photomask after heat treatment, a heat treatment if necessary, and a development And a step of developing using a liquid.
Claim 10:
A step of applying the resist material according to any one of claims 6 to 8 on a substrate, a step of applying a protective film insoluble in water and soluble in an alkaline developer after the heat treatment, the substrate and the projection A pattern forming method comprising the steps of: inserting water between lenses and exposing with high energy rays through a photomask; and developing with a developer after heat treatment as necessary .
Claim 11:
A step of applying the resist material according to any one of claims 6 to 8 on a substrate, a step of drawing with an electron beam after heat treatment, a heat treatment as necessary, and then developing using a developer. A pattern forming method comprising the steps of:

  The resist material of the present invention can also be applied to immersion lithography. In immersion lithography, exposure is performed by inserting an immersion medium between the pre-baked resist film and the projection lens. In ArF immersion lithography, pure water is mainly used as an immersion medium. It is an important technique for extending the life of ArF lithography to the 65 nm node and beyond by combining with a projection lens having an NA of 1.0 or more, and development is accelerated.

  Further, the resist material of the present invention can reduce the pattern size after development by various shrink methods. For example, the hole size can be shrunk by a known method such as thermal flow, RELACS, SAFIRE, or WASOOM. Particularly when a hydrogenated ROMP polymer (cycloolefin ring-opening metathesis polymer hydrogenated product) having a low polymer Tg is blended, the hole size can be effectively reduced by thermal flow.

  Since the sulfonium salt having a polymerizable anion of the present invention has fluorine atoms at the α-position and γ-position of the sulfonic acid, a very strong sulfonic acid is generated when an acid is generated by irradiation with high energy rays. The acid labile group in the resist material can be efficiently cleaved, and is very useful as a monomer for producing the base resin of the radiation sensitive resist material. In addition, when the polymer compound of the present invention is used as a base resin for a radiation-sensitive resist material, it has high resolution, high density dependency and excellent exposure margin, and this polymer compound is extremely effective for precise fine processing as a resist material. It is. Furthermore, elution into water at the time of ArF immersion exposure can be suppressed, and the influence of water remaining on the wafer is small, and defects can be suppressed. When the resist waste solution is processed after device fabrication, the (meth) acrylic acid ester moiety is alkali-hydrolyzed, so it can be converted to a lower molecular weight, low-accumulation compound, and discarded by combustion. Since the fluorine substitution rate is low, the combustibility is high.

（式中、Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を示す。） The polymer compound that generates sulfonic acid in response to high energy rays or heat of the ultraviolet ray, far ultraviolet ray, electron beam, EUV, X-ray, excimer laser, γ ray, or synchrotron radiation of the present invention is represented by the following general formula ( The repeating unit represented by 1a) is generated.

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)

（式中、Ｒ¹は水素原子、フッ素原子、メチル基又はトリフルオロメチル基を示す。Ｒ²、Ｒ³及びＲ⁴は相互に独立に置換もしくは非置換の炭素数１〜１０の直鎖状又は分岐状のアルキル基、アルケニル基又はオキソアルキル基、又は置換もしくは非置換の炭素数６〜１８のアリール基、アラルキル基又はアリールオキソアルキル基を示すか、あるいはＲ²、Ｒ³及びＲ⁴のうちのいずれか２つ以上が相互に結合して式中の硫黄原子と共に環を形成してもよい。） The sulfonium salt having a polymerizable anion of the present invention is represented by the following general formula (1).

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted straight chain of 1 to 10 carbon atoms. Or a branched alkyl group, an alkenyl group or an oxoalkyl group, or a substituted or unsubstituted aryl group, aralkyl group or aryloxoalkyl group having 6 to 18 carbon atoms, or R ² , R ³ and R ⁴ . Any two or more of them may be bonded to each other to form a ring together with the sulfur atom in the formula.)

In the above formula (1), R ² , R ³ and R ⁴ are each independently substituted or unsubstituted C 1-10 linear or branched alkyl group, alkenyl group or oxoalkyl group, or substituted Or an unsubstituted aryl group having 6 to 18 carbon atoms, an aralkyl group, or an aryloxoalkyl group, or any two or more of R ² , R ^3, and R ⁴ are bonded to each other in the formula You may form a ring with a sulfur atom.
Specifically, as an alkyl group, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group Cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group and the like. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, 2-oxopropyl group, 2-oxoethyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2- ( And 4-methylcyclohexyl) -2-oxoethyl group. As the aryl group, phenyl group, naphthyl group, thienyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-tert- Alkoxyphenyl group such as butoxyphenyl group and 3-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butylphenyl group, 4 -Alkyl phenyl groups such as n-butylphenyl group and 2,4-dimethylphenyl group, alkyl naphthyl groups such as methyl naphthyl group and ethyl naphthyl group, alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dimethyl naphthyl group, Dialkylnaphthyl group such as diethylnaphthyl group, dimethoxy Fuchiru group, dialkoxy naphthyl group such as diethoxy naphthyl group. Examples of the aralkyl group include a benzyl group, a 1-phenylethyl group, and a 2-phenylethyl group. Examples of the aryloxoalkyl group include 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, and 2- (2-naphthyl) -2-oxoethyl group. Groups and the like. In addition, when any two or more of R ² , R ^3, and R ⁴ are bonded to each other to form a cyclic structure together with a sulfur atom, a group represented by the following formula is exemplified.

（式中、Ｒ⁴は上記と同様である。）

(In the formula, R ⁴ is the same as above.)

  More specifically, the sulfonium cation is represented by triphenylsulfonium, 4-hydroxyphenyldiphenylsulfonium, bis (4-hydroxyphenyl) phenylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4-tert-butoxyphenyldiphenylsulfonium, bis (4-tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, 3-tert-butoxyphenyldiphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxy Phenyl) sulfonium, 3,4-di-tert-butoxyphenyldiphenylsulfonium, bis (3,4-di-tert-butoxyphenyl) phenyls Honium, tris (3,4-di-tert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, 4-tert-butoxycarbonylmethyloxyphenyldiphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) ) Sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, (4-hydroxy-3,5-dimethylphenyl) diphenyl Sulfonium, (4-n-hexyloxy-3,5-dimethylphenyl) diphenylsulfonium, dimethyl (2-naphthyl) sulfonium, 4-hydroxyphenyldimethylsulfo , 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, diphenylmethylsulfonium, dimethylphenylsulfonium, 2-oxo-2-phenylethylthiacyclopentanium, diphenyl 2-thienylsulfonium, 4-n-butoxynaphthyl-1-thiacyclopentanium, 2-n-butoxynaphthyl-1-thiacyclopentanium, 4-methoxynaphthyl-1-thiacyclopentanium, 2-methoxynaphthyl- 1-thiacyclopentanium and the like can be mentioned. More preferably, triphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, 4-tert-butoxyphenyldiphenylsulfonium, tris (4-tert-butylphenyl) sulfonium, tris (4-tert-butoxyphenyl) sulfonium, dimethylphenylsulfonium Etc.

Specific examples of the compound represented by the general formula (1) include the following.

  The sulfonium salt having a polymerizable anion represented by the above general formula (1) of the present invention is an example, and an iodonium salt having a polymerizable anion, an ammonium salt, etc. can be synthesized by the same method as the present invention. The present invention can also be applied to a polymer compound, a resist material, a pattern forming method, and the like described later.

  As more specific iodonium cations, for example, diphenyliodonium, bis (4-methylphenyl) iodonium, bis (4- (1,1-dimethylethyl) phenyl) iodonium, bis (4- (1,1-dimethylpropyl) phenyl ) Iodonium, (4- (1,1-dimethylethoxy) phenyl) phenyliodonium, and the like. Examples of ammonium salts include tertiary ammonium salts such as trimethylammonium, triethylammonium, tributylammonium, and N, N-dimethylanilinium. And quaternary ammonium salts such as tetramethylammonium, tetraethylammonium, and tetrabutylammonium. The above-described iodonium salt having a polymerizable anion and a polymer compound having this as a repeating unit can be used as having a photoacid generating effect or a thermal acid generating effect, and an ammonium salt having a polymerizable anion and this as a repeating unit. The polymer compound can be used as a thermal acid generator.

A method for synthesizing a sulfonium salt having a polymerizable anion represented by the general formula (1) of the present invention will be described.
Triphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate synthesized by the present inventors was subjected to basic conditions with (meth) acryloyl chloride or (meth) acrylic anhydride, By reacting, the sulfonium salt of the general formula (1) having a polymerizable anion can be obtained.

The synthesis of triphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate is briefly described.
Represented by 1,1,3,3,3-pentafluoropropen-2-ylbenzoate developed by Nakai et al. Using 1,1,1,3,3,3-hexafluoro-2-propanol as a starting material 1,1,3,3,3-pentafluoropropen-2-yl aliphatic carboxylic acid ester or aromatic carboxylic acid ester with radical initiation such as sodium bisulfite or sodium sulfite and azobisisobutyronitrile or benzoyl peroxide By reacting in water or alcohol as a solvent and a mixture thereof in the presence of an agent, the corresponding 1,1,3,3,3-pentafluoro-2-acyloxypropane sulfonate or 1,1,3,3, After obtaining 3-pentafluoro-2-arenecarbonyloxypropanesulfonate, sulfonium is used as appropriate Ion exchange with triphenylsulfonium 1,1,3,3,3-pentafluoro-2-acyloxypropane sulfonate or triphenylsulfonium 1,1,3,3,3-pentafluoro-2-arenecarbonyloxy Propanesulfonate can be obtained, and the carboxylic acid ester moiety of the sulfonate is hydrolyzed with an alkali such as sodium hydroxide or potassium hydroxide or solvolyzed with an alcohol and a base to obtain the target triphenyl. Sulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate can be obtained. Synthesis of sulfonium salts other than triphenylsulfonium can be performed in the same manner.

  The reaction for synthesizing the polymerizable anion proceeds easily by a known method. A sulfonium salt such as triphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate is converted into methylene chloride, tetrahydrofuran, Dissolve in a solvent such as acetonitrile, base such as triethylamine, pyridine, 4-dimethylaminopyridine and acryloyl chloride, acrylic anhydride, methacryloyl chloride, methacrylic anhydride, 2-fluoroacryloyl chloride, 2-fluoroacrylic acid Add acid chloride or acid anhydride such as anhydride, α, α, α-trifluoromethacrylic chloride, α, α, α-trifluoromethacrylic anhydride sequentially or simultaneously, and cool or heat as necessary. It is good to do.

The polymer compound of the present invention contains a repeating unit obtained from a sulfonium salt having a polymerizable anion represented by the general formula (1).
Specific examples of the repeating unit obtained from the sulfonium salt having a polymerizable anion represented by the general formula (1) include the following general formula (2).

（式中、Ｒ¹〜Ｒ⁴は上記と同様である。）

(Wherein R ^{1 to} R ⁴ are the same as above)

  The polymer compound of the present invention contains any one or more of repeating units represented by the following general formulas (3) to (6) in addition to the repeating unit of the compound represented by the general formula (2). can do.

（式中、Ｒ¹は上記と同様である。Ｒ⁶及びＲ⁷はそれぞれ独立に水素原子又は水酸基を示す。Ｘは酸不安定基を示す。Ｙはラクトン構造を有する置換基を示す。Ｚは水素原子、炭素数１〜１５のフルオロアルキル基、又は炭素数１〜１５のフルオロアルコール含有置換基を示す。）

(In the formula, R ¹ is the same as described above. R ⁶ and R ⁷ each independently represents a hydrogen atom or a hydroxyl group. X represents an acid labile group. Y represents a substituent having a lactone structure. Z Represents a hydrogen atom, a C1-C15 fluoroalkyl group, or a C1-C15 fluoroalcohol-containing substituent.

  The polymer containing the repeating unit represented by the general formula (3) is decomposed by the action of an acid to generate a carboxylic acid, thereby giving a polymer that becomes alkali-soluble. The acid labile group X can be variously used, specifically, groups represented by the following general formulas (L1) to (L4), tertiary alkyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, Examples of each alkyl group include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

Here, a broken line shows a bond (hereinafter the same).
In the formula (L1), R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group, Ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, norbornyl group, tricyclodecanyl group, tetra Examples thereof include a cyclododecanyl group and an adamantyl group. R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, a linear, branched or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may be bonded to each other to form a ring with the carbon atom or oxygen atom to which they are bonded, and in the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each represents a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

In the formula (L2), R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and oxoalkyl having 4 to 20 carbon atoms. Group or a group represented by the above general formula (L1), and as the tertiary alkyl group, specifically, tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 2-cyclopentylpropane-2 -Yl group, 2-cyclohexylpropan-2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propan-2 -Yl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1- Examples thereof include an ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group and the like. Specific examples of the trialkylsilyl group include trimethylsilyl group, triethylsilyl group, dimethyl- Examples thereof include tert-butylsilyl group, and specific examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, 5-methyl-2-oxooxolane-5- Il group can be exemplified. y is an integer of 0-6.

In the formula (L3), R ^L05 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms which may be substituted or an aryl group having 6 to 20 carbon atoms which may be substituted; Specific examples of the optionally substituted alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, and an n-pentyl group. Group, n-hexyl group, cyclopentyl group, cyclohexyl group and other linear, branched or cyclic alkyl groups, and some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy groups, alkoxycarbonyl groups, oxo groups, amino groups Group, an alkylamino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group, etc. can be exemplified, and as an optionally substituted aryl group Specifically, a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group and the like can be exemplified. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.

In the formula (L4), R ^L06 represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms which may be substituted, or an aryl group having 6 to 20 carbon atoms which may be substituted; Specifically, the same thing as R ^L05 can be illustrated. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- Butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl Group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, etc., linear, branched or cyclic alkyl groups, and some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy groups, alkoxycarbonyl groups Oxo group, amino group, alkylamino group, cyano group, mercapto group, alkylthio group, Or the like can be exemplified those substituted in sulfo group. R ^{L07 to} R ^L16 may be bonded to each other to form a ring together with the carbon atom to which they are bonded (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 and R ^L14, etc.), in which case those involved in the bond represent a C 1-15 divalent hydrocarbon group, specifically Can be exemplified by those obtained by removing one hydrogen atom from those exemplified for the monovalent hydrocarbon group. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).

Of the acid labile groups represented by the above formula (L1), specific examples of the linear or branched groups include the following groups.

  Among the acid labile groups represented by the above formula (L1), specific examples of cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated.

  Specific examples of the acid labile group of the above formula (L2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethyl. Propyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 Examples include -cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec- Butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopentene Examples include -3-yl, 3-methyl-1-cyclohexen-3-yl, and 3-ethyl-1-cyclohexen-3-yl.

As the acid labile group of the above formula (L4), groups represented by the following formulas (L4-1) to (L4-4) are particularly preferable.

In the general formulas (L4-1) to (L4-4), a broken line indicates a coupling position and a coupling direction. R ^L41 each independently represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples include n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.

  In the general formulas (L4-1) to (L4-4), enantiomers and diastereomers may exist, but the general formulas (L4-1) to (L4-4) may exist. Represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

For example, the general formula (L4-3) represents one or a mixture of two selected from the groups represented by the following general formulas (L4-3-1) and (L4-3-2). To do.

The general formula (L4-4) represents one or a mixture of two or more selected from groups represented by the following general formulas (L4-4-1) to (L4-4-4). And

  The above general formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) Enantioisomers and enantioisomer mixtures are also shown representatively.

  The bonding directions of (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) are respectively By being on the exo side with respect to the bicyclo [2.2.1] heptane ring, high reactivity in the acid-catalyzed elimination reaction is realized (see JP 2000-336121 A). In the production of a monomer having a tertiary exo-alkyl group having a bicyclo [2.2.1] heptane skeleton as a substituent, the following general formulas (L4-1-endo) to (L4-4-endo) are used. In some cases, a monomer substituted with the indicated endo-alkyl group may be included, but in order to achieve good reactivity, the exo ratio is preferably 50 mol% or more, and the exo ratio is 80 mol% or more. More preferably.

（特開２０００−３３６１２１号公報参照）

(See JP 2000-336121 A)

Specific examples of the acid labile group of the above formula (L4) include the following groups.

Further, tertiary alkyl groups having 4 to 20 carbon atoms, trialkylsilyl groups each having 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms are specifically exemplified as R ^L04 . The thing similar to a thing etc. can be illustrated.

  Specific examples of the repeating unit represented by the general formula (3) include the following, but are not limited thereto.

Specific examples of the repeating unit represented by the general formula (4) are as follows.

Specific examples of the repeating unit represented by the general formula (5) are as follows.

Specific examples of the repeating unit represented by the general formula (6) include the following.

The polymer compound of the present invention is a repeating unit obtained from a monomer containing a carbon-carbon double bond other than the above, for example, a substituted acrylic such as methyl methacrylate, methyl crotonic acid, dimethyl maleate, dimethyl itaconate, etc. Acid esters, unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid, norbornene, norbornene derivatives, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] may contain cyclic olefins such as dodecene derivatives, unsaturated acid anhydrides such as itaconic anhydride, and repeating units obtained from other monomers.

  The polymer compound of the present invention can also be applied to lithography other than ArF exposure, such as KrF lithography, electron beam lithography, EUV lithography and the like.

（式中、Ｒ¹、Ｘは上記と同様である。Ｇは酸素原子又はカルボニルオキシ基（−Ｃ（＝Ｏ）Ｏ−）を示す。） That is, the polymer compound of the present invention includes any one of the repeating units represented by the following general formulas (7) to (10) in addition to the repeating unit of the compound represented by the general formula (2). The above may be contained, and may further contain any one or more of the repeating units represented by the general formulas (3) to (6) described above.

(Wherein R ¹ and X are the same as described above. G represents an oxygen atom or a carbonyloxy group (—C (═O) O—)).

  The polymer containing the repeating unit represented by the general formula (7) is decomposed by the action of an acid to generate a phenolic hydroxyl group and / or a carboxylic acid, thereby giving a polymer that becomes alkali-soluble. The acid labile group X can be used in various ways. Specifically, the groups represented by the above general formulas (L1) to (L4), a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms. , Each alkyl group may be a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the like.

Specific examples of the repeating unit represented by the general formula (7) include the following, but are not limited thereto.

  The substitution position of hydroxyvinylnaphthalene represented by the general formula (10) is arbitrary, and examples thereof include 6-hydroxy-2-vinylnaphthalene and 4-hydroxy-1-vinylnaphthalene. Vinyl naphthalene is preferably used.

  Furthermore, among the repeating units represented by the general formulas (3) to (6) in addition to any one of the repeating units represented by the general formulas (7) to (10), the general formula (3) The thing containing the repeating unit shown by this can be used preferably.

The polymer compound containing the sulfonium salt having a polymerizable anion of the present invention as a repeating unit and containing any one or more of the repeating units represented by the general formulas (7) to (10) is not limited to the above. Repeating units obtained from monomers containing carbon-carbon double bonds, for example, substituted acrylic esters such as methyl methacrylate, methyl crotonic acid, dimethyl maleate, dimethyl itaconate, maleic acid, fumaric acid, itacon Unsaturated carboxylic acids such as acids, norbornene, norbornene derivatives, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecene derivatives, cyclic olefins such as norbornadiene, unsaturated acid anhydrides such as itaconic anhydride, styrene, acenaphthylene, vinylnaphthalene, and other repeating units obtained from other monomers may be included. .

  In addition, the weight average molecular weight of the high molecular compound of this invention is 1,000-500,000, Preferably it is 3,000-100,000. If it is out of this range, the etching resistance may be extremely lowered, or the difference in dissolution rate before and after the exposure cannot be ensured and the resolution may be lowered. Examples of the method for measuring the molecular weight include gel permeation chromatography (GPC) in terms of polystyrene and a light scattering method.

  In the polymer compound of the present invention, a preferable content ratio of each repeating unit obtained from each monomer can be set, for example, in the following range (mol%), but is not limited thereto.

(I) One or more of the structural units represented by the formula (2) based on the monomer of the formula (1) is more than 0 mol% and not more than 100 mol%, preferably 1 to 30 mol%, Preferably it contains 5-20 mol%,
(II) One or more of the structural units represented by the above formulas (3) to (6) and / or (7) to (10) are 0 mol% or more and less than 100 mol%, preferably 70 to 99. Mol%, more preferably 80-95 mol%, if necessary,
(III) One to two or more structural units based on other monomers may be contained in an amount of 0 to 80 mol%, preferably 0 to 70 mol%, more preferably 0 to 50 mol%.

The polymer compound of the present invention is prepared by using a compound represented by the general formula (1) as the first monomer and a compound containing a polymerizable double bond as the second and subsequent monomers. Performed by polymerization reaction.
Various copolymerization reactions for producing the polymer compound of the present invention can be exemplified, and radical polymerization, anionic polymerization or coordination polymerization is preferred.

  The reaction conditions for the radical polymerization reaction are as follows: (a) As a solvent, hydrocarbons such as benzene, ethers such as tetrahydrofuran, alcohols such as ethanol, or ketones such as methyl isobutyl ketone, and (b) as a polymerization initiator Using an azo compound such as 2,2′-azobisisobutyronitrile or a peroxide such as benzoyl peroxide or lauroyl peroxide, (c) maintaining the reaction temperature at about 0 to 100 ° C., and (d) reaction The time is preferably about 0.5 to 48 hours, but this does not exclude the case where the time is out of this range.

  The reaction conditions for the anionic polymerization reaction are as follows: (a) hydrocarbons such as benzene, ethers such as tetrahydrofuran, or liquid ammonia as the solvent; (a) metals such as sodium and potassium as the polymerization initiator, n-butyllithium , Using an alkyl metal such as sec-butyllithium, ketyl, or Grignard reagent, (c) keeping the reaction temperature at about -78 to 0 ° C., and (d) setting the reaction time to about 0.5 to 48 hours, E) It is preferable to use a proton-donating compound such as methanol, a halide such as methyl iodide, and other electrophilic substances as the terminator, but this does not exclude the case where it is outside this range.

  The reaction conditions for coordination polymerization are as follows: (a) hydrocarbons such as n-heptane and toluene as the solvent, and (a) Ziegler-Natta catalyst comprising transition metal such as titanium and alkylaluminum as the catalyst, chromium and nickel compounds. (C) the reaction temperature is kept at about 0 to 100 ° C., and (d) the reaction time is set at 0. 0 ° C. Although it is preferable to set it as about 5 to 48 hours, the case where it remove | deviates from this range is not excluded.

  In addition, some or all of the acid labile groups of the polymer compound produced by the above polymerization method can be deprotected and used in negative materials described later. Furthermore, an acid labile group can be introduced again into the polymer compound from which the acid labile group has been deprotected, and a substituent different from the acid labile group introduced during polymerization can be introduced.

  For example, 4-ethoxyethoxystyrene and a sulfonium salt having a polymerizable anion represented by the general formula (1) of the present invention are converted into a high molecular compound by the radical polymerization described above, and then the ethoxyethoxy group is removed by acetic acid, pyridinium tosylate or the like. Or a copolymer with polyhydroxystyrene. This can be used as a base resin for a negative resist material. In addition, by reacting the hydroxystyrene unit of the copolymer with ditert-butyl dicarbonate, tert-butyl chloroacetate, various vinyl ethers, etc., an acid labile group different from the acid labile group (ethoxyethoxy group) at the time of polymerization is obtained. Can be introduced.

The polymer compound of the present invention is suitably used as a base polymer of a resist material, particularly a chemically amplified positive resist material, and the present invention provides a resist material containing the above polymer compound, particularly a positive resist material.
In this case, as a positive resist material,
(A) a base resin containing the polymer compound,
(C) If an organic solvent is required, (B) an acid generator,
(D) Quencher,
(E) What contains surfactant is preferable.

The polymer compound of the present invention can also be used as a base polymer for a chemically amplified negative resist material.
In this case, as a negative resist material,
(A) a base resin containing the polymer compound,
(C) an organic solvent,
(H) a cross-linking agent that cross-links with an acid, if necessary,
(D) Quencher,
(E) What contains surfactant is preferable.

  In the case of constituting the positive resist material, as the base resin of the component (A), in addition to the polymer compound of the present invention, if necessary, other resins whose dissolution rate in an alkaline developer is increased by the action of an acid. May be added. Examples include i) poly (meth) acrylic acid derivatives, ii) copolymers of norbornene derivatives-maleic anhydride, iii) hydrogenated ring-opening metathesis polymers, iv) vinyl ether-maleic anhydride- (meth). Examples include, but are not limited to, copolymers of acrylic acid derivatives, and v) polyhydroxystyrene derivatives.

  The poly (meth) acrylic acid derivative of i) is a polymer compound by a combination such as the above general formulas (3) to (6), and the polyhydroxystyrene derivative of v) is a compound of the above general formulas (7) to (10). It is a high molecular compound by a combination and the combination of (3)-(10). The content ratio of units relating to acid labile groups of these polymer compounds, for example, one or more monomer units of the above general formulas (3) and / or (7) exceeds 0 mol% and is 80 mol. %. Preferably it is 1-50 mol%, More preferably, it is 10-40 mol%.

  Among these, a method for synthesizing a hydrogenated product of a ring-opening metathesis polymer is specifically described in Examples of JP-A No. 2003-66612. Specific examples include those having the following repeating units, but are not limited thereto.

The blending ratio of the polymer compound of the present invention to another polymer compound is preferably in the range of mass ratio of 100: 0 to 10:90, particularly 100: 0 to 20:80. When the compounding ratio of the polymer compound of the present invention is less than this, a preferable performance as a resist material may not be obtained. The performance of the resist material can be adjusted by appropriately changing the blending ratio.
The polymer compound is not limited to one type, and two or more types can be added. The performance of the resist material can be adjusted by using a plurality of types of polymer compounds.

  When a photoacid generator is added as the acid generator of the component (B) used as necessary in the present invention, any compound may be used as long as it generates an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generators, and the like. Although described in detail below, these may be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate or bis (substituted alkylsulfonyl) imide or tris (substituted alkylsulfonyl) methide. As the sulfonium cation, triphenylsulfonium, 4-tert-butoxyphenyldiphenylsulfonium, bis (4-tert -Butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, 3-tert-butoxyphenyldiphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, 3,4-di-tert-butoxyphenyldiphenylsulfonium, bis (3,4-di-tert-butoxyphenyl) phenylsulfonium, Lis (3,4-di-tert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, 4-tert-butoxycarbonylmethyloxyphenyldiphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium , (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 4-methylphenyldiphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, bis (4-methyl Phenyl) phenylsulfonium, bis (4-tet-butylphenyl) phenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-tert-butyl) Phenyl) sulfonium, tris (phenylmethyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl (2-naphthyl) sulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, Trinaphthylsulfonium, tribenzylsulfonium, diphenylmethylsulfonium, dimethylphenylsulfonium, 2-oxopropylthiacyclopentanium, 2-oxobutylthiacyclopentanium, 2-oxo-3,3-dimethylbutylthiacyclopentanium, 2 -Oxo-2-phenylethylthiacyclopentanium, 4-n-butoxynaphthyl-1-thiacyclopentanium, 2 -N-butoxynaphthyl-1-thiacyclopentanium and the like. Examples of the sulfonate include trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, tridecafluorohexanesulfonate, perfluoro (4 -Ethylcyclohexane) sulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4- (trifluoromethyl) benzenesulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4 , 6-Triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (P-toluenesulfonyloxy) Benzenesulfonate, 6- (P-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, 8- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthylethanesulfonate, 1,1,2, 2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-en-8-yl) ethanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro -2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3 Pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2- (1-a Nanthanecarbonyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3 -Pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-tosyloxyethane sulfonate, adamantane methoxycarbonyl difluoromethane sulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-6-yloxycarbonyl Examples include difluoromethanesulfonate, 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate, and bis (substituted alkylsulfonyl) imide includes bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, bis ( Heptafluoropropylsulfonyl) imide, perfluoro (1,3-propylenebissulfonyl) imide and the like, and tris (substituted alkylsulfonyl) methide includes tris (trifluoromethylsulfonyl) methide, and sulfonium of these combinations Salt.

The iodonium salt is a salt of an iodonium cation and a sulfonate or bis (substituted alkylsulfonyl) imide or tris (substituted alkylsulfonyl) methide. Examples of the iodonium cation include diphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4-tert. -Butoxyphenyl phenyl iodonium, 4-methoxyphenyl phenyl iodonium and the like. Examples of the sulfonate include trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, tridecafluorohexane sulfonate, perfluoro (4- Ethylcyclohexane) sulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoro Tan sulfonate, pentafluorobenzene sulfonate, 4- (trifluoromethyl) benzene sulfonate, 4-fluorobenzene sulfonate, mesitylene sulfonate, 2,4,6-triisopropylbenzene sulfonate, toluene sulfonate, benzene sulfonate, 4- (P-toluene) Sulfonyloxy) benzenesulfonate, 6- (P-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (P-toluenesulfonyloxy) naphthalene-1-sulfonate 8- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenes Phonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthylethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2 - tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-en-8-yl) ethanesulfonate, 2-benzoyloxy -1,1,3,3 , 3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivalo Yloxypropanesulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3 , 3-Pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) -1,1 , 3,3,3-pentafluoropropane sulfonate, 2- (1-adamantanecarbonylcarbonyl) -1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3 , 3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1 -Difluoro-2-tosyloxyethane sulfonate, adamantane methoxycarbonyl difluorometa Sulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-6-yloxy Carbonyl) difluoromethanesulfonate, 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate, and the like. Examples of bis (substituted alkylsulfonyl) imide include bis (trifluoromethylsulfonyl) imide, bis (pentafluoroethylsulfonyl) imide, Examples include bis (heptafluoropropylsulfonyl) imide, perfluoro (1,3-propylenebissulfonyl) imide, and the like as tris (substituted alkylsulfonyl) methide. Includes tris (trifluoromethylsulfonyl) methide, and an iodonium salt of a combination of these.

  As the sulfonyldiazomethane, bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane Bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-acetyloxyphenylsulfonyl) diazomethane, Bis (4- (methanesulfonyloxy) phenylsulfonyl) diazomethane, bis (4- (P-toluenesulfonyloxy) phenylsulfonyl) dia Methane, bis (4-n-hexyloxyphenylsulfonyl) diazomethane, bis (2-methyl-4-n-hexyloxyphenylsulfonyl) diazomethane, bis (2,5-dimethyl-4-n-hexyloxyphenylsulfonyl) diazomethane Bis (3,5-dimethyl-4-n-hexyloxyphenylsulfonyl) diazomethane, bis (2-methyl-5-isopropyl-4-n-hexyloxy) phenylsulfonyldiazomethane, bis (2-naphthylsulfonyl) diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane Methylsulphonyl benzoyl diazomethane, and a bis-sulfonyl diazomethane and sulfonyl carbonyl diazomethane such as tert- butoxycarbonyl-4-methylphenyl sulfonyl diazomethane.

Examples of the N-sulfonyloxydicarboximide photoacid generator include succinimide, naphthalene dicarboxyimide, phthalic imide, cyclohexyl dicarboximide, 5-norbornene-2,3-dicarboximide, 7-oxabicyclo [ 2.2.1] Imido skeletons such as -5-heptene-2,3-dicarboximide, trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, tridecafluorohexanesulfonate, perfluoro (4-ethylcyclohexane) sulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4- (trifluoromethyl) benzene Zensulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (P-toluenesulfonyloxy) benzenesulfonate, 6- (P-toluenesulfonyloxy) Naphthalene-2-sulfonate, 4- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, 8- (P-toluenesulfonyloxy) naphthalene-1-sulfonate , Naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1-difluoro-2-naphthyl Tan sulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^{2 ,} 5.1 ^7,10] dodeca-3-en-8-yl) ethanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3 -Pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3 3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy 1,1,3,3,3-pentafluoropropane sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2- (1-adamantanecarbonyl Oxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro 2-hydroxypropanesulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropanesulfonate, 1,1-difluoro-2-tosyloxyethanesulfonate, adamantanemethoxycarbonyldifluoromethanesulfonate, 1- ( 3-hydroxymethyladamantane) methoxycarbonyldifluoro Tansulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-6-yloxycarbonyl) difluoromethanesulfonate, 4-oxo-1-adamantyloxy Combination compounds such as carbonyldifluoromethanesulfonate are exemplified.

  Examples of the benzoin sulfonate photoacid generator include benzoin tosylate, benzoin mesylate, and benzoin butane sulfonate.

Pyrogallol trisulfonate photoacid generators include pyrogallol, phloroglysin, catechol, resorcinol, all hydroquinone hydroxyl groups trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, tridecafluorohexane Sulfonate, perfluoro (4-ethylcyclohexane) sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4- (trifluoromethyl) benzene sulfonate, 4-fluorobenzene sulfonate, Mesitylene sulfonate, 2,4,6-triisopropylbenzene sulfonate, toluene sulfonate Benzenesulfonate, 4- (P-toluenesulfonyloxy) benzenesulfonate, 6- (P-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, 5- (P- Toluenesulfonyloxy) naphthalene-1-sulfonate, 8- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 1,1-difluoro- 2-naphthylethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyl) B [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-en-8-yl) ethanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2- Cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1, 3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanes Honate, 2- (1-adamantanecarbonylcarbonyl) -1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1, 1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-tosyloxyethane sulfonate, Adamantane methoxycarbonyldifluoromethanesulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan − - yl oxycarbonyl) difluoromethane sulfonate, compounds substituted with 4-oxo-1-adamantyloxycarbonyl difluoromethane sulfonate, and the like.

Examples of the nitrobenzyl sulfonate photoacid generator include 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and 2,6-dinitrobenzyl sulfonate. Specific examples of the sulfonate include trifluoromethane sulfonate and pentafluoroethane. Sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, tridecafluorohexane sulfonate, perfluoro (4-ethylcyclohexane) sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4- (trifluoromethyl) benzenesulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-trii Propylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (P-toluenesulfonyloxy) benzenesulfonate, 6- (P-toluenesulfonyloxy) naphthalene-2-sulfonate, 4- (P-toluenesulfonyloxy) naphthalene-1- Sulfonate, 5- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, 8- (P-toluenesulfonyloxy) naphthalene-1-sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate 1,1-difluoro-2-naphthylethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate DOO, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-en-8-yl) ethanesulfonate, 2-benzoyl Oxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3 3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- Furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoylo Ii) -1,1,3,3,3-pentafluoropropane sulfonate, 2- (1-adamantanecarbonyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1 1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxy Propanesulfonate, 1,1-difluoro-2-tosyloxyethanesulfonate, adamantanemethoxycarbonyldifluoromethanesulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2 -Oki 3,5-methano -2H- cyclopenta [b] furan-6-yl-oxycarbonyl) difluoromethanesulfonate, 4-oxo-1-adamantyloxycarbonyl difluoromethane sulfonate, and the like. A compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used.

  Examples of the sulfone photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2-bis (phenylsulfonyl) propane, 2, 2-bis (4-methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2- (cyclohexylcarbonyl) -2- (P-toluenesulfonyl) propane, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one and the like can be mentioned.

  O-arylsulfonyl oxime compound or O-alkyl sulfonyl oxime compound (oxime sulfonate) type photoacid generator includes glyoxime derivative type, long conjugated oxime sulfonate type via thiophene or cyclohexadiene, trifluoromethyl group, etc. Examples include an oxime sulfonate type in which the stability of the compound is increased by a simple electron withdrawing group, phenylacetonitrile, an oxime sulfonate type using a substituted acetonitrile derivative, a bisoxime sulfonate type, and the like.

  Examples of the photoacid generator of the glyoxime derivative type include bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- ( p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione = dioxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis -O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis- O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (2,2,2-trif Fluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (10-camphorsulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (4 -Fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (4-trifluoromethylbenzenesulfonyl) -α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-O -(Trifluoromethanesulfonyl) -nioxime, bis-O- (2,2,2-trifluoroethanesulfonyl) -nioxime, bis-O- (10-camphorsulfonyl) -nioxime, bis-O- (benzenesulfonyl)- Nioxime, bis-O- (4-fluorobenzenesulfonyl) -nioki Bis-O- (4- (trifluoromethyl) benzenesulfonyl) -nioxime, bis-O- (xylenesulfonyl) -nioxime and the like, and 2-benzoyloxy-1,1,3 3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pi Valoyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2- Naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert- Tylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2- (1-adamantanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyloxy -1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-sulfonate Tosyloxypropane sulfonate, 1,1-difluoro-2-tosyloxyethane sulfonate, adamantane methoxycarbonyl difluoromethane sulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyl difluoromethane sulfonate, methoxycarbonyl difluoromethane sulfonate, 1- (hexa Hydro-2-oxo-3,5-methano-2H-cyclopenta [b] furan-6-yloxycarbonyl) difluoromethanesulfonate, compounds substituted with 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

  As a long conjugated oxime sulfonate photoacid generator via thiophene or cyclohexadiene, (5- (P-toluenesulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (10-camphorsulfonyl) ) Oximino-5H-thiophen-2-ylidene) phenylacetonitrile, (5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (P-toluenesulfonyl) oxyimino-5H-thiophene 2-Ilidene) (2-methylphenyl) acetonitrile, (5- (10-camphorsulfonyl) oxyimino-5H-thiophen-2-ylidene) (2-methylphenyl) acetonitrile, (5-n-octanesulfonyloxy) Mino-5H-thiophen-2-ylidene) (2-methylphenyl) acetonitrile, (5- (4- (P-toluenesulfonyloxy) benzenesulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (2,5-bis (P-toluenesulfonyloxy) benzenesulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile and the like, and 2-benzoyloxy-1,1,3,3 3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyl Oxypropane sulfonate, 2-cyclohexanecarbonyloxy- , 1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3 -Pentafluoropropane sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2- (1-Adamantanecarbonyloxy) -1,1,3 3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1, 1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-tosyloxy Sietanesulfonate, adamantane methoxycarbonyldifluoromethanesulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [B] Furan-6-yloxycarbonyl) difluoromethanesulfonate, compounds substituted with 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

  2,2,2-trifluoro-1-phenylethanone = O- (methylsulfonyl) oxime, which is an oxime sulfonate type acid generator whose compound stability is increased by an electron withdrawing group such as trifluoromethyl group, , 2,2-trifluoro-1-phenylethanone = O- (10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1-phenylethanone = O- (4-methoxybenzenesulfonyl) oxime, 2,2,2-trifluoro-1-phenylethanone = O- (1-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1-phenylethanone = O- (2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1-phenylethanone = O- (2,4,6-trimethylphenylsulfonyl) oxime, 2,2,2-to Fluoro-1- (4-methylphenyl) ethanone = O- (10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylphenyl) ethanone = O- (methylsulfonyl) oxime, 2 , 2,2-trifluoro-1- (2-methylphenyl) ethanone = O- (10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1- (2,4-dimethylphenyl) ethanone = O -(10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1- (2,4-dimethylphenyl) ethanone = O- (1-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1 -(2,4-dimethylphenyl) ethanone = O- (2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1- (2,4,6- Limethylphenyl) ethanone = O- (10-camphorsulfonyl) oxime, 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) ethanone = O- (1-naphthylsulfonyl) oxime, 2 , 2,2-trifluoro-1- (2,4,6-trimethylphenyl) ethanone = O- (2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methoxyphenyl) ethanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylthiophenyl) ethanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (3 4-dimethoxyphenyl) ethanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methoxyphenyl) ethanone = O- (4-methylphenylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methoxyphenyl) ethanone = O- (4-methoxyphenylsulfonyl) oxime, 2,2,2-trifluoro- 1- (4-methoxyphenyl) ethanone = O- (4-dodecylphenylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methoxyphenyl) ethanone = O- (octylsulfonyl) oxime, 2, 2,2-trifluoro-1- (4-thiomethylphenyl) ethanone = O- (4-methoxyphenylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-thiomethylphenyl) ethanone = O -(4-dodecylphenylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-thiomethylphenyl) ethanone = O (Octylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-thiomethylphenyl) ethanone = O- (2-naphthylsulfonyl) oxime, 2,2,2-trifluoro-1- (2- Methylphenyl) ethanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylphenyl) ethanone = O- (phenylsulfonyl) oxime, 2,2,2-trifluoro-1 -(4-chlorophenyl) ethanone = O- (phenylsulfonyl) oxime, 2,2,3,3,4,4,4-heptafluoro-1-phenylbutanone = O- (10-camphorsulfonyl) oxime, 2, 2,2-trifluoro-1- (1-naphthyl) ethanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (2 Naphthyl) ethanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-benzylphenyl) ethanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (4- (Phenyl-1,4-dioxa-but-1-yl) phenyl) ethanone = O- (methylsulfonyl) oxime, 2,2,2-trifluoro-1- (1-naphthyl) ethanone = O— (Propylsulfonyl) oxime, 2,2,2-trifluoro-1- (2-naphthyl) ethanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-benzylphenyl) ethanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylsulfonylphenyl) ethanone = O- (propylsulfonyl) Oxime, 2,2,2-trifluoro-1- (4-methylsulfonyloxyphenylethanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-methylcarbonyloxy) Phenyl) ethanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (6H, 7H-5,8-dioxonaphth-2-yl) ethanone = O- (propylsulfonyl) oxime, 2, 2,2-trifluoro-1- (4-methoxycarbonylmethoxyphenyl) ethanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4- (methoxycarbonyl)-(4-amino -1-oxa-pent-1-yl) phenyl) ethanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro 1- (3,5-dimethyl-4-ethoxyphenyl) ethanone = O- (propylsulfonyl) oxime, 2,2,2-trifluoro-1- (4-benzyloxyphenyl) ethanone = O- (propylsulfonyl) Oxime, 2,2,2-trifluoro-1- (2-thiophenyl) ethanone = O- (propylsulfonate) oxime, and 2,2,2-trifluoro-1- (1-dioxathiophen-2-yl ) Ethanone = O- (propyl sulfonate) oxime, 2,2,2-trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (trifluoromethanesulfonyloxyimino)) Ethyl) phenoxy) propoxy) phenyl) ethanone = O- (trifluoromethanesulfonyl) oxime, 2,2,2-trifluoro-1 (4- (3- (4- (2,2,2-trifluoro-1- (1-propanesulfonyloxyimino) ethyl) phenoxy) propoxy) phenyl) ethanone = O- (propylsulfonyl) oxime, 2,2 , 2-trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (1-butanesulfonyloxyimino) ethyl) phenoxy) propoxy) phenyl) ethanone = O- ( Butylsulfonyl) oxime, 2,2,2-trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (4- (4-methylphenylsulfonyloxy) phenylsulfonyl) Oxyimino) ethyl) phenoxy) propoxy) phenyl) ethanone = O- (4- (4-methylphenylsulfonyloxy) phenylsulfonyl) oxime, 2 , 2,2-trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) phenyl) Sulfonyloxyimino) ethyl) phenoxy) propoxy) phenyl) ethanone = O- (2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) phenylsulfonyl) oxime and the like, and 2-benzoyl Oxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3 3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1 1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3- Pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2- (1-adamantanecarbonyloxy) -1,1,3,3 , 3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1 , 3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-tosyloxy Ethanesulfonate, adamantane methoxycarbonyldifluoromethanesulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [ b] Furan-6-yloxycarbonyl) difluoromethanesulfonate, compounds substituted with 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

（上記式中、Ｒ⁴⁰¹は置換又は非置換の炭素数１〜１０のハロアルキルスルホニル又はハロベンゼンスルホニル基を表す。Ｒ⁴⁰²は炭素数１〜１１のハロアルキル基を表す。Ａｒ⁴⁰¹は置換又は非置換の芳香族基又はヘテロ芳香族基を表す。） Moreover, the oxime sulfonate shown by a following formula (Ox-1) is mentioned.

(In the above formula, R ⁴⁰¹ represents a substituted or unsubstituted haloalkylsulfonyl group having 1 to 10 carbon atoms or a halobenzenesulfonyl group. R ⁴⁰² represents a haloalkyl group having 1 to 11 carbon atoms. Ar ⁴⁰¹ is substituted or unsubstituted. Represents an aromatic group or a heteroaromatic group.)

  Specifically, 2- (2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) pentyl) fluorene, 2- (2,2,3, 3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) butyl) fluorene, 2- (2,2,3,3,4,4,5,5,6,6-decafluoro-1 -(Nonafluorobutylsulfonyloxyimino) hexyl) fluorene, 2- (2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) pentyl) -4- Biphenyl, 2- (2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) butyl) -4-biphenyl, 2- (2,2,3,3,4, 4, 5, 5 6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) hexyl) -4-biphenyl and the like, and 2-benzoyloxy-1,1,3,3,3-pentafluoropropane in the above skeleton Sulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2 Cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1 , 3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2- (1-adamantanecarbonylcarbonyl) -1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1 , 3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate 1,1-difluoro-2-tosyloxyethane sulfonate, adamantane methoxycarbonyl difluoromethane sulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyl difluoromethane sulfonate, methoxycarbonyl difluoromethane sulfonate, 1- (hexahydro-2-oxo -3 , 5-methano-2H-cyclopenta [b] furan-6-yloxycarbonyl) difluoromethanesulfonate, and a compound in which 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate is substituted.

  As an oxime sulfonate type using a substituted acetonitrile derivative, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (p-chlorobenzenesulfonyloxyimino) -phenylacetonitrile, α- (4-nitrobenzenesulfonyloxyimino)- Phenylacetonitrile, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -4-chlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4 -Dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -4-methoxyphenyla Cetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (benzenesulfonyloxyimino) -2-thienylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -phenylacetonitrile, α- ((4-toluenesulfonyloxyimino) -4-methoxyphenyl) acetonitrile, α-((dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl) acetonitrile, α- (tosyloxyimino) -3-thienylacetonitrile, α- (Methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cycl Pentenyl acetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile and the like, and 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3 , 3,3-pentafluoro-2- (4-phenylbenzoyloxy) propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1, 1,3,3,3- Pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2- ( 4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2- (1-adamantanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-penta Fluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-tosyloxyethane sulfonate , Adamantane methoxycarbonyldifluoromethanesulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, methoxycarbonyldifluoromethanesulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H-cyclopenta [b] Furan-6-yloxycarbonyl) difluoromethanesulfonate, compounds substituted with 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

  Further, bis (α- (p-toluenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (benzenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- ( Methanesulfonyloxy) imino) -p-phenylenediacetonitrile bis (α- (butanesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (10-camphorsulfonyloxy) imino) -p-phenylenediacetonitrile, Bis (α- (trifluoromethanesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (4-methoxybenzenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (p-toluenesulfonyloxy) ) Imi F) -m-phenylenediacetonitrile, bis (α- (benzenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (methanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- ( Butanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (10-camphorsulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (trifluoromethanesulfonyloxy) imino) -m-phenylenedi Acetonitrile, bis (α- (4-methoxybenzenesulfonyloxy) imino) -m-phenylene diacetonitrile and the like, and 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate in the above skeleton 1,1,3,3,3-pe Tafluoro-2- (4-phenylbenzoyloxy) propanesulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3 3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2 -(4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2- (1-adamantanecarbonyloxy) -1,1,3,3,3-pentafluoropropane Sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfone 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2- Tosyloxyethane sulfonate, adamantane methoxycarbonyl difluoromethane sulfonate, 1- (3-hydroxymethyladamantane) methoxycarbonyl difluoromethane sulfonate, methoxycarbonyl difluoromethane sulfonate, 1- (hexahydro-2-oxo-3,5-methano-2H- And cyclopenta [b] furan-6-yloxycarbonyl) difluoromethanesulfonate and compounds substituted with 4-oxo-1-adamantyloxycarbonyldifluoromethanesulfonate.

  When the photoacid generator of component (B) is used as necessary as a resist material for a KrF excimer laser, sulfonium salts, bissulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate are preferable. Specifically, triphenylsulfonium = p-toluenesulfonate, triphenylsulfonium = camphorsulfonate, triphenylsulfonium = pentafluorobenzenesulfonate, triphenylsulfonium = nonafluorobutanesulfonate, triphenylsulfonium = 4- (p-toluenesulfonyloxy) ) Benzenesulfonate, triphenylsulfonium = 2,4,6-triisopropylbenzenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium = p-toluenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium = camphorsulfonate, 4-tert-butoxy Phenyldiphenylsulfonium = 4- (p-toluenesulfonyloxy) benzenesulfonate, 4- tert-butylphenyldiphenylsulfonium = camphorsulfonate, tris (4-methylphenyl) sulfonium = camphorsulfonate, tris (4-tert-butylphenyl) sulfonium = camphorsulfonate, bis (tert-butylsulfonyl) diazomethane, bis (cyclohexyl) Sulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-n-hexyloxyphenylsulfonyl) diazomethane, bis (2-methyl-4-n-hexyloxyphenylsulfonyl) diazomethane, bis (2, 5-dimethyl-4-n-hexyloxyphenylsulfonyl) diazomethane, bis (3,5-dimethyl-4-n-hexyloxyphenylsulfonyl) diazomethane, bis ( -Methyl-5-isopropyl-4-n-hexyloxy) phenylsulfonyldiazomethane, bis (4-tert-butylphenylsulfonyl) diazomethane, N-camphorsulfonyloxy-5-norbornene-2,3-dicarboxylic imide, N- p-toluenesulfonyloxy-5-norbornene-2,3-dicarboxylic imide, (5- (10-camphorsulfonyl) oxyimino-5H-thiophen-2-ylidene) (2-methylphenyl) acetonitrile, (5- (p -Toluenesulfonyl) oxyimino-5H-thiophen-2-ylidene) (2-methylphenyl) acetonitrile and the like.

  Moreover, when using the photoacid generator of the said (B) component as a resist material for ArF excimer lasers as needed, a sulfonium salt or oxime-O-sulfonate is preferable. Specifically, triphenylsulfonium = trifluoromethanesulfonate, triphenylsulfonium = pentafluoroethanesulfonate, triphenylsulfonium = heptafluoropropanesulfonate, triphenylsulfonium = nonafluorobutanesulfonate, triphenylsulfonium = tridecafluorohexanesulfonate, Phenylsulfonium = heptadecafluorooctanesulfonate, triphenylsulfonium = perfluoro (4-ethylcyclohexane) sulfonate, 4-methylphenyldiphenylsulfonium = nonafluorobutanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium = nonafluoro Butanesulfonate, 4-tert-butylphenyldiphenylsulfonium = Nonafluorobutanesulfonate, 4-tert-butylphenyldiphenylsulfonium = perfluoro (4-ethylcyclohexane) sulfonate, 4-tert-butylphenyldiphenylsulfonium = heptafluorooctanesulfonate, triphenylsulfonium = 1,1-difluoro-2 -Naphthylethanesulfonate, triphenylsulfonium = 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, triphenylsulfonium = 2-benzoyloxy-1,1,3,3,3 -Pentafluoropropanesulfonate, triphenylsulfonium = 1,1,3,3,3-pentafluoro-2- (pivaloyloxy) propanesulfonate, triphenylsulfonium = 2- (cyclo Xanthacarbonyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, triphenylsulfonium = 2- (2-naphthoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, tri Phenylsulfonium = 2- (1-adamantanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, Triphenylsulfonium = 2-hydroxy-1,1,3,3,3-pentafluoropropanesulfonate , Triphenylsulfonium = adamantanemethoxycarbonyldifluoromethanesulfonate, triphenylsulfonium = 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, triphenylsulfonium = methoxycarbonyldiflu Oromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 1,1,3,3 3-pentafluoro-2- (pivaloyloxy) propanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 2- (cyclohexanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 4-tert-butyl Phenyldiphenylsulfonium = 2- (2-naphthoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 2- (1-adamantanecarbonyloxy) 1,1,3,3,3-pentafluoropropanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 2-hydroxy-1,1,3,3,3-pentafluoropropanesulfonate, 4-tert-butylphenyldiphenyl Sulfonium = adamantane methoxycarbonyldifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium = methoxycarbonyldifluoromethanesulfonate, 2- Oxo-2-phenylethylthiacyclopentanium = 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, -Oxo-2-phenylethylthiacyclopentanium-2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, triphenylsulfonium = perfluoro (1,3-propylenebissulfonyl) imide, Triphenylsulfonium = bis (pentafluoroethylsulfonyl) imide, 2- (2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) pentyl) fluorene, 2 -(2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) butyl) fluorene, 2- (2,2,3,3,4,4,5,5, 6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) hexyl) fluorene, 2- (2,2,3,3,4,4,5,5-octafluoro-1- (2- (cyclohexanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonyloxyimino) Pentyl) fluorene, 2- (2,2,3,3,4,4-pentafluoro-1- (2- (cyclohexanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonyloxyimino) Butyl) fluorene, 2- (2,2,3,3,4,4,5,5,6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) hexyl) fluorene and the like.

  Moreover, when using the photoacid generator of the said (B) component as an ArF immersion resist material as needed, a sulfonium salt or oxime-O-sulfonate is preferable. Specifically, triphenylsulfonium = nonafluorobutanesulfonate, triphenylsulfonium = tridecafluorohexanesulfonate, triphenylsulfonium = heptadecafluorooctanesulfonate, triphenylsulfonium = perfluoro (4-ethylcyclohexane) sulfonate, 4-methyl Phenyldiphenylsulfonium = nonafluorobutanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium = nonafluorobutanesulfonate, 4-tert-butylphenyldiphenylsulfonium = nonafluorobutanesulfonate, 4-tert-butylphenyldiphenylsulfonium = Perfluoro (4-ethylcyclohexane) sulfonate, 4-tert-butylphenyldiphenyl Rufonium = heptafluorooctane sulfonate, triphenylsulfonium = 1,1-difluoro-2-naphthylethane sulfonate, triphenylsulfonium = 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethane sulfonate, Triphenylsulfonium = 2-benzoyloxy-1,1,3,3,3-pentafluoropropane sulfonate, triphenylsulfonium = 1,1,3,3,3-pentafluoro-2- (pivaloyloxy) propane sulfonate, tri Phenylsulfonium = 2- (cyclohexanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, triphenylsulfonium = 2- (2-naphthoyloxy) -1,1,3,3,3- Pentafluoropropa Sulfonate, triphenylsulfonium = 2- (1-adamantanecarbonyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, triphenylsulfonium = 2-hydroxy-1,1,3,3,3-penta Fluoropropanesulfonate, triphenylsulfonium = adamantanemethoxycarbonyldifluoromethanesulfonate, triphenylsulfonium = 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, triphenylsulfonium = methoxycarbonyldifluoromethanesulfonate, 4-tert-butylphenyl Diphenylsulfonium = 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 4-tert-butylpheny Rudiphenylsulfonium = 1,1,3,3,3-pentafluoro-2- (pivaloyloxy) propanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 2 (cyclohexanecarbonyloxy) -1,1,3,3 3-pentafluoropropanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 2- (2-naphthoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 2- (1-adamantanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 2-hydroxy-1,1,3,3,3-pentafluoro Propanesulfonate 4-tert-butylphenyldiphenylsulfonium = adamantanemethoxycarbonyldifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium = 1- (3-hydroxymethyladamantane) methoxycarbonyldifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium = methoxy Carbonyl difluoromethanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium = 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2-oxo-2-phenylethylthiacyclopentanium = 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, triphenylsulfonium = perfluoro B (1,3-propylenebissulfonyl) imide, triphenylsulfonium bis (pentafluoroethylsulfonyl) imide, 2- (2,2,3,3,4,4,5,5-octafluoro-1- ( Nonafluorobutylsulfonyloxyimino) pentyl) fluorene, 2- (2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) butyl) fluorene, 2- (2,2, 3,3,4,4,5,5,6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) hexyl) fluorene, 2- (2,2,3,3,4,4,5, 5-octafluoro-1- (2- (cyclohexanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonyloxyimino) pentyl) full Orene, 2- (2,2,3,3,4,4-pentafluoro-1- (2- (cyclohexanecarbonyloxy) -1,1,3,3,3-pentafluoropropanesulfonyloxyimino) butyl) Fluorene, 2- (2,2,3,3,4,4,5,5,6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) hexyl) fluorene and the like.

  The amount of the (B) component photoacid generator added to the chemically amplified resist material of the present invention may be any as long as it does not interfere with the effects of the present invention. , The same applies hereinafter) to 0.1 to 10 parts, preferably 0.1 to 5 parts. When the proportion of the component (B) of the photoacid generator is too large, there is a possibility that the resolution is deteriorated and a foreign matter problem occurs during development / resist peeling. The photoacid generator of the above component (B) can be used alone or in combination of two or more. Furthermore, a photoacid generator having a low transmittance at the exposure wavelength can be used, and the transmittance in the resist film can be controlled by the amount of the photoacid generator added.

In addition, when the photoacid generator is an onium salt that generates a so-called weak acid, a function of acid diffusion control can be provided. That is, since the polymer compound of the present invention generates a strong acid, when an onium salt that generates a weak acid (for example, a sulfonic acid or a carboxylic acid not substituted with fluorine) is mixed and used, the high energy beam irradiation results in a high energy beam irradiation. When a strong acid generated from a molecular compound collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion. In this process, since the strong acid is exchanged with a weak acid having a lower catalytic ability, the acid is apparently deactivated and the acid diffusion can be controlled.
Here, when a mixture of an onium salt generating a strong acid and an onium salt generating a weak acid is used, the strong acid can be exchanged for a weak acid as described above, but the weak acid is an onium salt that generates an unreacted strong acid. It is not possible to exchange salt by collision. These are due to the phenomenon that the onium cation is more likely to form an ion pair with the anion of the strong acid.

  Moreover, you may add the compound (acid propagation compound) which decomposes | disassembles with an acid and generate | occur | produces an acid to the resist material of this invention. For these compounds, see J. et al. Photopolym. Sci. and Tech. , 8.43-44, 45-46 (1995), J. Am. Photopolym. Sci. and Tech. , 9.29-30 (1996).

  Examples of the acid-proliferating compound include tert-butyl-2-methyl-2-tosyloxymethyl acetoacetate, 2-phenyl-2- (2-tosyloxyethyl) -1,3-dioxolane, and the like. It is not limited to. Of the known photoacid generators, compounds that are inferior in stability, particularly thermal stability, often exhibit the properties of acid-proliferating compounds.

  The addition amount of the acid multiplication compound in the resist material of the present invention is 2 parts or less, preferably 1 part or less, relative to 100 parts of the base resin in the resist material. When the addition amount is too large, it is difficult to control diffusion, resulting in degradation of resolution and pattern shape.

  The organic solvent of component (C) used in the present invention may be any organic solvent that can dissolve the base resin, acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and methyl amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and the like. Alcohols, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxypropio Examples include esters such as ethyl acid, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. These are used alone or in combination of two or more. However, it is not limited to these. In the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, and mixed solvents thereof, which have the highest solubility of the acid generator in the resist component, are preferably used. .

  The amount of the organic solvent used is preferably 200 to 1,000 parts, particularly 400 to 800 parts, based on 100 parts of the base resin.

Furthermore, 1 type, or 2 or more types of quencher (D) can be mix | blended with the resist material of this invention.
A quencher is a term that is widely used in this technical field, and refers to a compound that can suppress the diffusion rate when an acid generated from an acid generator diffuses into a resist film. In addition to facilitating adjustment of resist sensitivity by adding a quencher, the acid diffusion rate in the resist film is suppressed to improve resolution, suppress changes in sensitivity after exposure, and depend on the substrate and environment. The exposure margin and the pattern profile can be improved.

  Such quenchers include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and sulfonyl groups. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamates, ammonium salts and the like.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified as secondary aliphatic amines. Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, disi Lopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepenta The tertiary aliphatic amines are exemplified by trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Examples include cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, N, N-bis (hydroxy Ethyl) aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, dimethylaniline, 2,6-diisopropylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4- Nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine , Naphthylamine, diamino Phthalene, pyrrole derivatives (eg pyrrole-2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole Derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1- Pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethyl Rupyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzyl Pyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinopyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives , Piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (examples) Quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10- Examples include phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and as the nitrogen-containing compound having a sulfonyl group, 3-pyridinesulfonic acid and the like are exemplified, and a nitrogen-containing compound having a hydroxyl group, Nitrogen-containing compounds having a hydroxyphenyl group and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine Tanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino- 1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidine Ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxy Yurolidine, 3-cuincridinol, 3-to Propanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2- hydroxyethyl) phthalimide, N- (2- hydroxyethyl) isonicotinamide. Examples of amides include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, 1-cyclohexylpyrrolidone and the like. Examples of imides include phthalimide, succinimide, maleimide and the like. Examples of carbamates include Nt-butoxycarbonyl-N, N-dicyclohexylamine, Nt-butoxycarbonylbenzimidazole, oxazolidinone, and the like.

  As ammonium salts, pyridinium = p-toluenesulfonate, triethylammonium = p-toluenesulfonate, trioctylammonium = p-toluenesulfonate, triethylammonium = 2,4,6-triisopropylbenzenesulfonate, trioctylammonium = 2,4,6-triisopropylbenzenesulfonate, triethylammonium = camphorsulfonate, trioctylammonium = camphorsulfonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide , Tetramethylammonium = p-toluenesulfonate, tetrabutylammonium = p-to Ensulfonate, benzyltrimethylammonium = p-toluenesulfonate, tetramethylammonium = camphorsulfonate, tetrabutylammonium = camphorsulfonate, benzyltrimethylammonium = camphorsulfonate, tetramethylammonium = 2,4,6-triisopropyl Benzenesulfonate, tetrabutylammonium = 2,4,6-triisopropylbenzenesulfonate, benzyltrimethylammonium = 2,4,6-triisopropylbenzenesulfonate, acetic acid = tetramethylammonium, acetic acid = tetrabutylammonium, acetic acid = Benzyltrimethylammonium, benzoic acid = tetramethylammonium, benzoic acid = tetrabutylammonium, benzoic acid = benzyltrime Le ammonium and the like.

Furthermore, the amine compound shown by the following general formula (B) -1 is illustrated.
N (X) _n (Y) _3-n (B) -1
(In the above formula, n is 1, 2 or 3. The side chains X may be the same or different and are represented by the following general formula (X) -1, (X) -2 or (X) -3. The side chain Y represents the same or different hydrogen atom or a linear, branched or cyclic hydrogen atom, or a C 1-20 alkyl group in which some or all of the hydrogen atoms may be substituted with fluorine atoms. And may contain an ether group or a hydroxyl group, and X may be bonded to form a ring.)

（上記式中、Ｒ³⁰⁰、Ｒ³⁰²、Ｒ³⁰⁵は炭素数１〜４の直鎖状又は分岐状のアルキレン基であり、Ｒ³⁰¹、Ｒ³⁰⁴は水素原子、水素原子の一部又は全部がフッ素原子で置換されていてもよい炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、ヒドロキシ基、エーテル基、エステル基、ラクトン環を１個あるいは複数個含んでいてもよい。Ｒ³⁰³は単結合、炭素数１〜４の直鎖状又は分岐状のアルキレン基であり、Ｒ³⁰⁶は水素原子の一部又は全部がフッ素原子で置換されていてもよい炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、ヒドロキシ基、エーテル基、エステル基、ラクトン環を１個あるいは複数個含んでいてもよい。）

(In the above formula, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms, and part or all of the hydrogen atoms are fluorine. It is a C1-C20 linear, branched or cyclic alkyl group which may be substituted with an atom, and may contain one or more hydroxy groups, ether groups, ester groups and lactone rings. R ³⁰³ is a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is a carbon atom having 1 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms A linear, branched or cyclic alkyl group, which may contain one or a plurality of hydroxy groups, ether groups, ester groups and lactone rings.)

  Specific examples of the compound represented by the general formula (B) -1 include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, and tris {2- (2- Methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7 , 13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 1,4,10,13-tetraoxa-7,16-di Zabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) ) Amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2 -Pivaloyloxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) Amine, tris [2- (2-oxopropoxy) ethyl] amine, tris 2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) Amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(2-methoxyethoxycarboni ) Ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2 -Acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2 -(2-oxopropoxycarbonyl) ethylamine, N, N- (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) ) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis ( 2-formyloxyethyl) 2- (2-formyloxy) Ethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxy) Ethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) Ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbi [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine N-methylbis (2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxy Examples include carbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone.

（上記式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状又は分岐状の水素原子の一部又は全部がフッ素原子で置換されていてもよいアルキレン基であり、カルボニル基、エーテル基、エステル基又はスルフィドを１個あるいは複数個含んでいてもよい。） Furthermore, the amine compound which has a cyclic structure shown by the following general formula (B) -2 is illustrated.

(In the above formula, X is as described above, and R ³⁰⁷ is an alkylene group in which part or all of a linear or branched hydrogen atom having 2 to 20 carbon atoms may be substituted with a fluorine atom, One or more groups, ether groups, ester groups or sulfides may be included.)

  Specific examples of the general formula (B) -2 include 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl. ] Morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) ) Methoxy] ethyl] morpholine, 2- [2- (2-methoxyethoxy) ethoxy] ethylmorpholine, 2- [2- (2-butoxyethoxy) ethoxy] ethylmorpholine, 2- {2- [2- (2- Methoxyethoxy) ethoxy] ethoxy} ethylmorpholine, 2- {2- [2- (2-butoxyethoxy) ethoxy] ethoxy} ethylmorpholine, 2- (1-pyrrolidinyl) ethyl acid, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, 2- (1 -Pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] Morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, 2-methyl-3- (1-pyrrolidinyl) Methyl propionate, 3-morpholinopropionic acid , Methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran 3- (1-pyrrolidinyl) propionate 3-yl, 3-morpholinopropionate tetrahydrofurfuryl, 3-piperidinopropionate glycidyl, 2-morpholinopropionate 2-methoxyethyl, 3- (1-pyrrolidinyl) propionate 2- (2-methoxyethoxy) Ethyl, butyl 3-morpholinopropionate, cyclohexyl 3-piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, 1- Methyl pyrrolidinyl acetate Methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate, 2-morpholinoethyl 2-methoxyacetate, 2-morpholinoethyl 2- (2-methoxyethoxy) acetate, 2- [2- (2-methoxyethoxy) ethoxy] acetic acid 2-morpholinoethyl, 2-morpholinoethyl hexanoate, 2-morpholinoethyl octoate, 2-morpholinoethyl decanoate, 2-morpholinoethyl laurate, myristic acid 2 Examples include -morpholinoethyl, 2-morpholinoethyl palmitate, 2-morpholinoethyl stearate, 2-morpholinoethyl cyclohexanecarboxylate, and 2-morpholinoethyl adamantanecarboxylate.

（上記式中、Ｘ、Ｒ³⁰⁷、ｎは前述の通り、Ｒ³⁰⁸、Ｒ³⁰⁹は同一又は異種の炭素数１〜４の直鎖状又は分岐状のアルキレン基である。） Furthermore, the amine compound containing the cyano group represented by the following general formula (B) -3 to (B) -6 is illustrated.

(In the above formula, X, R ³⁰⁷ and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of amine compounds containing a cyano group represented by the general formulas (B) -3 to (B) -6 include 3- (diethylamino) propiononitrile and N, N-bis (2-hydroxyethyl). -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N -Bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2 -Methoxyethyl) -3-aminopropionate methyl, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionate methyl, N- (2-acetate) Methyl) -N- (2-cyanoethyl) -3-aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2- Hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxy Ethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ) Ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononi Ril, N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl)- 3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N , N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2- Methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl] aminoacetate Tonitrile, N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate methyl, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N -(3-Hydroxy-1-propyl) amino Tonitrile, N- (3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) amino Acetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis Cyanomethyl (2-hydroxyethyl) -3-aminopropionate, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-formyloxyethyl) -3-aminopropiate Cyanomethyl acid, cyanomethyl N, N-bis (2-methoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl) ), N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N , N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), 1-pyrrolidine pro Cyanomethyl pionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl) Is exemplified.

（上記式中、Ｒ³¹⁰は水素原子の一部又は全部がフッ素原子で置換されていてもよい炭素数２〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基としては水酸基、カルボニル基、エステル基、エーテル基、スルフィド基、カーボネート基、シアノ基、アセタール基を１個あるいは複数個含む。Ｒ³¹¹、Ｒ³¹²、Ｒ³¹³は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、アリール基又はアラルキル基である。） Furthermore, an amine compound having an imidazole skeleton and a polar functional group represented by the following general formula (B) -7 is exemplified.

(In the above formula, R ³¹⁰ is an alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms, hydroxyl group as the polar functional group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, a cyano group, containing one or a plurality of acetal group .R ^311, R ^312, R ³¹³ is a hydrogen atom, C 1 -C 10 to 10 linear, branched or cyclic alkyl groups, aryl groups or aralkyl groups.)

（上記式中、Ｒ³¹⁴は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、アリール基又はアラルキル基である。Ｒ³¹⁵は水素原子の一部又は全部がフッ素原子で置換されていてもよい炭素数１〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基としてエステル基、アセタール基、シアノ基を一つ以上含み、その他に水酸基、カルボニル基、エーテル基、スルフィド基、カーボネート基を一つ以上含んでいてもよい。） Furthermore, an amine compound having a benzimidazole skeleton and a polar functional group represented by the following general formula (B) -8 is exemplified.

(In the above formula, R ³¹⁴ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group. R ³¹⁵ is a fluorine atom in which part or all of the hydrogen atom is a fluorine atom. Is an alkyl group having a linear, branched or cyclic polar functional group having 1 to 20 carbon atoms which may be substituted with, including at least one ester group, acetal group or cyano group as the polar functional group, In addition, one or more hydroxyl groups, carbonyl groups, ether groups, sulfide groups, and carbonate groups may be contained.)

（上記式中、Ａは窒素原子又は≡Ｃ−Ｒ³²²である。Ｂは窒素原子又は≡Ｃ−Ｒ³²³である。Ｒ³¹⁶は水素原子の一部又は全部がフッ素原子で置換されていてもよい炭素数２〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基としては水酸基、カルボニル基、エステル基、エーテル基、スルフィド基、カーボネート基、シアノ基又はアセタール基を一つ以上含む。Ｒ³¹⁷、Ｒ³¹⁸、Ｒ³¹⁹、Ｒ³²⁰は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基又はアリール基であるか、又はＲ³¹⁷とＲ³¹⁸、Ｒ³¹⁹とＲ³²⁰はそれぞれ結合してベンゼン環、ナフタレン環あるいはピリジン環を形成してもよい。Ｒ³²¹は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基又はアリール基である。Ｒ³²²、Ｒ³²³は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基又はアリール基である。Ｒ³²¹とＲ³²³は結合してベンゼン環又はナフタレン環を形成してもよい。） Furthermore, the nitrogen-containing heterocyclic compound which has a polar functional group shown by the following general formula (B) -9 and (B) -10 is illustrated.

(In the above formula, A is a nitrogen atom or ≡C—R ^322. B is a nitrogen atom or ≡C—R ^323. R ³¹⁶ may be a hydrogen atom partially or entirely substituted with a fluorine atom. It is a good alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms, and examples of the polar functional group include a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, and a cyano group. Or one or more acetal groups, wherein R ³¹⁷ , R ³¹⁸ , R ³¹⁹ , and R ³²⁰ are a hydrogen atom, a linear, branched or cyclic alkyl group or aryl group having 1 to 10 carbon atoms, or R ³¹⁷ and R ³¹⁸ , R ³¹⁹ and R ³²⁰ may be bonded to each other to form a benzene ring, a naphthalene ring or a pyridine ring, and R ³²¹ is a hydrogen atom, linear, branched or cyclic having 1 to 10 carbon atoms. An alkyl group or an aryl group of R ^{32. 2} and R ³²³ are a hydrogen atom, a linear, branched or cyclic alkyl group or aryl group having 1 to 10 carbon atoms, R ³²¹ and R ³²³ may be bonded to form a benzene ring or a naphthalene ring. Good.)

（上記式中、Ｒ³²⁴は炭素数６〜２０のアリール基又は炭素数４〜２０のヘテロ芳香族基であって、水素原子の一部又は全部が、ハロゲン原子、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のアシルオキシ基、又は、炭素数１〜１０のアルキルチオ基で置換されていてもよい。Ｒ³²⁵はＣＯ₂Ｒ³²⁶、ＯＲ³²⁷又はシアノ基である。Ｒ³²⁶は一部のメチレン基が酸素原子で置換されていてもよい炭素数１〜１０のアルキル基である。Ｒ³²⁷は一部のメチレン基が酸素原子で置換されていてもよい炭素数１〜１０のアルキル基又はアシル基である。Ｒ³²⁸は単結合、メチレン基、エチレン基、硫黄原子又は−Ｏ（ＣＨ₂ＣＨ₂Ｏ）_n−基である。ｎ＝０，１，２，３又は４である。Ｒ³²⁹は水素原子、メチル基、エチル基又はフェニル基である。Ｘは窒素原子又はＣＲ³³⁰である。Ｙは窒素原子又はＣＲ³³¹である。Ｚは窒素原子又はＣＲ³³²である。Ｒ³³⁰、Ｒ³³¹、Ｒ³³²はそれぞれ独立に水素原子、メチル基又はフェニル基であるか、あるいはＲ³³⁰とＲ³³¹又はＲ³³¹とＲ³³²が結合して、炭素数６〜２０の芳香環又は炭素数２〜２０のヘテロ芳香環を形成してもよい。） Furthermore, the nitrogen-containing organic compound which has an aromatic carboxylic acid ester structure shown by the following general formula (B) -11- (B) -14 is illustrated.

(In the above formula, R ³²⁴ is an aryl group having 6 to 20 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms, and a part or all of the hydrogen atoms are halogen atoms, straight carbon atoms having 1 to 20 carbon atoms. A chain, branched or cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or carbon R ³²⁵ may be CO ₂ R ³²⁶ , OR ³²⁷ or cyano group, and R ³²⁶ may be a carbon in which some methylene groups may be substituted with oxygen atoms. R ³²⁷ is an alkyl group or acyl group having 1 to 10 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom, R ³²⁸ is a single bond or a methylene group. , an ethylene group, a sulfur atom or -O (CH ₂ CH ₂ ) _N - is a .n = 0, 1, 2, 3 or 4 is a radical .R ³²⁹ is a hydrogen atom, a methyl group, .X an ethyl group or a phenyl group is a nitrogen atom or CR ³³⁰ .Y is A nitrogen atom or CR ^331. Z is a nitrogen atom or CR ^332. R ³³⁰ , R ³³¹ and R ³³² are each independently a hydrogen atom, a methyl group or a phenyl group, or R ³³⁰ and R ³³¹ or R ³³¹ and R ³³² may combine to form an aromatic ring having 6 to 20 carbon atoms or a heteroaromatic ring having 2 to 20 carbon atoms.)

（上記式中、Ｒ³³³は水素又は炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基である。Ｒ³³⁴及びＲ³³⁵はそれぞれ独立に、エーテル、カルボニル、エステル、アルコール、スルフィド、ニトリル、アミン、イミン、アミドなどの極性官能基を一つ又は複数含んでいてもよい炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基であって水素原子の一部がハロゲン原子で置換されていてもよい。Ｒ³³⁴とＲ³³⁵は互いに結合して、炭素数２〜２０のヘテロ環又はヘテロ芳香環を形成してもよい。） Furthermore, an amine compound having a 7-oxanorbornane-2-carboxylic acid ester structure represented by the following general formula (B) -15 is exemplified.

(In the above formula, R ³³³ is hydrogen or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. R ³³⁴ and R ³³⁵ are each independently ether, carbonyl, ester, alcohol, sulfide, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, which may contain one or more polar functional groups such as nitrile, amine, imine and amide. A part of the hydrogen atoms may be substituted with a halogen atom, and R ³³⁴ and R ³³⁵ may combine with each other to form a C 2-20 heterocycle or heteroaromatic ring.

  The quencher is preferably added in an amount of 0.001 to 2 parts, particularly 0.01 to 1 part, based on 100 parts of the base resin. When the blending amount is less than 0.001 part, there is no blending effect, and when it exceeds 2 parts, the sensitivity may be excessively lowered.

  To the resist material of the present invention, a surfactant (E) conventionally used for improving the coating property as an optional component can be added in addition to the above components. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  Examples of surfactants include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene olein ether, Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate and sorbitan monostearate Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan mono Nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as stearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, F-top EF301, EF303, EF352 (manufactured by Gemco), MegaFuck F171 , F172, F173, R08, R30 (manufactured by Dainippon Ink and Chemicals), Florard FC-430, FC-431, FC-4430, FC-4432 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon Fluorine series such as S-381, S-382, SC101, SC102, SC103, SC104, SC105, SC106, Surfynol E1004, KH-10, KH-20, KH-30, KH-40 (Asahi Glass Co., Ltd.) Surface activity Organosiloxane polymer KP341, X-70-092, (manufactured by Shin-Etsu Chemical (Co.)) X-70-093, acrylic acid or methacrylic acid Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), among which FC-430, Surflon S-381, Surfinol E1004, KH-20, and KH-30 are preferable. These can be used alone or in combination of two or more.

  The addition amount of the surfactant in the chemically amplified resist material of the present invention is 2 parts or less, preferably 1 part or less with respect to 100 parts of the base resin in the resist material.

  The resist material used in the practice of the present invention has a function of reducing water penetration and leaching by orienting on the resist surface after spin coating, particularly when a resist protective film is not used in immersion exposure using water. A surfactant having can be added. This surfactant is a polymer type surfactant, and has a property of not dissolving in water but dissolving in an alkaline developer, and is particularly preferably one having high water repellency and improving water slidability. Such polymeric surfactants can be shown below.

（式中、Ｒ¹は、それぞれ同一でも異なってもよく水素原子、フッ素原子、メチル基又はトリフルオロメチル基、Ｒ⁸は、それぞれ同一でも異なってもよく、水素原子、又は炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はフッ素化アルキル基を示し、あるいは同一単量体内のＲ⁸はそれぞれ結合してこれらが結合する炭素原子と共に環を形成してもよく、その場合、合計して炭素数２〜２０の直鎖状、分岐状又は環状のアルキレン基又はフッ素化アルキレン基を示す。Ｒ⁹はフッ素原子又は水素原子を示し、あるいは、Ｒ¹⁰と結合してこれらが結合する炭素原子と共に炭素数の和が３〜１０の環、特に脂環を形成してもよい。
Ｒ¹⁰は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基で、１つ以上の水素原子がフッ素原子で置換されていてもよい。
Ｒ¹¹は１つ以上の水素原子がフッ素原子で置換された炭素数１〜１０の直鎖状又は分岐状のアルキル基で、Ｒ¹⁰とＲ¹¹が結合してこれらが結合する炭素原子と共に環を形成していてもよく、その場合、炭素数の総和が２〜１２の三価の有機基、特にアルキレン基から水素原子が１個脱離した基で、１つ以上の水素原子がフッ素原子で置換されていてもよい。
Ｒ¹²は単結合又は炭素数１〜４のアルキレン基、Ｒ¹³は同一でも異なってもよく単結合又は−Ｏ−、−ＣＲ¹Ｒ¹−である。
Ｒ¹⁴は炭素数１〜４の直鎖状又は分岐状のアルキレン基であり、同一単量体内のＲ⁸と結合してこれらが結合する炭素原子と共に炭素数４〜７の環、特に脂環を形成してもよい。
Ｒ¹⁶は１，２−エチレン基、１，３−プロピレン基、１，４−ブチレン基を示し、Ｒｆは炭素数３〜６の直鎖のパーフルオロアルキル基あるいは３Ｈ−パーフルオロプロピル基、４Ｈ−パーフルオロブチル基、５Ｈ−パーフルオロペンチル基又は６Ｈ−パーフルオロヘキシル基を示す。
Ｘ²はそれぞれ同一でも異なってもよく−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−、又は−Ｃ（＝Ｏ）−Ｒ¹⁵−Ｃ（＝Ｏ）−Ｏ−であり、Ｒ¹⁵は炭素数１〜１０の直鎖状、分岐状又は環状のアルキレン基である。
０≦（ａ−１）＜１、０≦（ａ−２）＜１、０≦（ａ−３）＜１、０＜（ａ−１）＋（ａ−２）＋（ａ−３）＜１、０≦ｂ＜１、０≦ｃ＜１であり、０＜（ａ−１）＋（ａ−２）＋（ａ−３）＋ｂ＋ｃ≦１である。）

(In the formula, R ^{1 s} may be the same or different and each may be a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R ⁸ may be the same or different; A linear, branched or cyclic alkyl group or a fluorinated alkyl group, or R ^{8 in the} same monomer may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. In total, a linear, branched or cyclic alkylene group or fluorinated alkylene group having 2 to 20 carbon atoms, R ⁹ represents a fluorine atom or a hydrogen atom, or is bonded to R ¹⁰ to form A ring having 3 to 10 carbon atoms, particularly an alicyclic ring, may be formed together with the carbon atoms to be bonded.
R ¹⁰ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, and one or more hydrogen atoms may be substituted with fluorine atoms.
R ¹¹ is a linear or branched alkyl group having 1 to 10 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and R ¹⁰ and R ¹¹ are bonded to each other to form a ring together with the carbon atoms to which these are bonded. In that case, a trivalent organic group having 2 to 12 carbon atoms in total, particularly a group in which one hydrogen atom is eliminated from an alkylene group, and one or more hydrogen atoms are fluorine atoms. May be substituted.
R ¹² is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ¹³ may be the same or different and is a single bond or —O— or —CR ¹ R ¹ —.
R ¹⁴ is a linear or branched alkylene group having 1 to 4 carbon atoms, and is bonded to R ^{8 in} the same monomer and together with the carbon atom to which these are bonded, a ring having 4 to 7 carbon atoms, particularly an alicyclic ring May be formed.
R ¹⁶ represents a 1,2-ethylene group, a 1,3-propylene group, or a 1,4-butylene group, and Rf represents a linear perfluoroalkyl group having 3 to 6 carbon atoms or a 3H-perfluoropropyl group, 4H -Represents a perfluorobutyl group, a 5H-perfluoropentyl group or a 6H-perfluorohexyl group.
X ^{2 s} may be the same or different and are —C (═O) —O—, —O—, or —C (═O) —R ¹⁵ —C (═O) —O—, wherein R ¹⁵ is carbon. It is a linear, branched or cyclic alkylene group of formula 1-10.
0 ≦ (a-1) <1, 0 ≦ (a-2) <1, 0 ≦ (a-3) <1, 0 <(a-1) + (a-2) + (a-3) < 1, 0 ≦ b <1, 0 ≦ c <1, and 0 <(a−1) + (a−2) + (a−3) + b + c ≦ 1. )

  The addition amount is in the range of 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the resist base resin.

  When the polymer compound of the present invention is used for a chemically amplified negative resist, it may have a repeating unit having a substituent that can be crosslinked by an acid crosslinking agent in addition to the repeating unit represented by the general formula (2). is necessary. More specifically, examples include, but are not limited to, repeating units derived from acrylic acid, methacrylic acid, hydroxystyrene (substitution positions are arbitrary), and hydroxyvinylnaphthalene (substitution positions are arbitrary). is not.

In addition to the above polymer compound, an alkali-soluble resin may be added.
For example, poly (p-hydroxystyrene), poly (m-hydroxystyrene), poly (4-hydroxy-2-methylstyrene), poly (4-hydroxy-3-methylstyrene), poly (α-methyl-p- Hydroxystyrene), partially hydrogenated poly (p-hydroxystyrene) copolymer, poly (p-hydroxystyrene-α-methyl-p-hydroxystyrene) copolymer, poly (p-hydroxystyrene-α-methylstyrene) copolymer, poly ( p-hydroxystyrene-styrene) copolymer, poly (p-hydroxystyrene-m-hydroxystyrene) copolymer, poly (p-hydroxystyrene-styrene) copolymer, poly (p-hydroxystyrene-acrylic acid) copolymer, poly (p- Hydroxystyrene-methacrylic acid) Mer, poly (p-hydroxystyrene-methyl acrylate) copolymer, poly (p-hydroxystyrene-acrylic acid-methyl methacrylate) copolymer, poly (p-hydroxystyrene-methyl acrylate) copolymer, poly (p-hydroxystyrene-methyl acrylate) copolymer -Methyl methacrylate) copolymer, polymethacrylic acid, polyacrylic acid, poly (acrylic acid-methyl acrylate) copolymer, poly (methacrylic acid-methyl methacrylate) copolymer, poly (acrylic acid-maleimide) copolymer, poly (methacrylic acid-maleimide) Copolymer, poly (p-hydroxystyrene-acrylic acid-maleimide) copolymer, poly (p-hydroxystyrene-methacrylic acid-maleimide) copolymer, and the like. The present invention is not limited to the mating seen.

  The blending ratio of the polymer compound of the present invention to the other alkali-soluble resin is preferably in the range of mass ratio of 100: 0 to 10:90, particularly 100: 0 to 20:80. When the compounding ratio of the polymer compound of the present invention is less than this, a preferable performance as a resist material may not be obtained. The performance of the resist material can be adjusted by appropriately changing the blending ratio.

  The alkali-soluble resin is not limited to one type, and two or more types can be added. The performance of the resist material can be adjusted by using a plurality of types of polymer compounds.

  Examples of the acid crosslinking agent that forms a crosslinked structure by the action of the acid of component (H) include compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups, or vinyl ether groups in the molecule. Glycouril derivatives, urea derivatives, hexa (methoxymethyl) melamine and the like are suitably used as the acid crosslinking agent for the chemically amplified negative resist material of the present invention. Tetraalkoxymethyl substituted glycolurils, such as N, N, N ′, N′-tetramethoxymethylurea and hexamethoxymethylmelamine, tetrahydroxymethyl substituted glycolurils and tetramethoxymethylglycolurils, substituted and unsubstituted bis -Condensates such as epichlorohydrin and phenolic compounds such as hydroxymethylphenols and bisphenol A. Particularly suitable crosslinking agents are 1,3,5,7-tetraalkoxymethylglycoluril such as 1,3,5,7-tetramethoxymethylglycoluril or 1,3,5,7-tetrahydroxymethylglycoluril, 2,6-dihydroxymethyl p-cresol, 2,6-dihydroxymethylphenol, 2,2 ′, 6,6′-tetrahydroxymethyl-bisphenol A and 1,4-bis- [2- (2-hydroxypropyl) ] -Benzene, N, N, N ′, N′-tetramethoxymethylurea, hexamethoxymethylmelamine and the like.

  The addition amount of the (H) component acid crosslinking agent in the chemically amplified resist material of the present invention is arbitrary, but is 1 to 20 parts, preferably 5 to 15 parts, relative to 100 parts of the base resin in the resist material. . These crosslinking agents may be used alone or in combination of two or more.

  The basic components of the resist material of the present invention are the above-described polymer compound (base resin), acid generator, organic solvent, and quencher. Other components such as inhibitors, acidic compounds, stabilizers, pigments may be added. In addition, the addition amount of these arbitrary components can be made into a normal amount in the range which does not prevent the effect of this invention.

A pattern can be formed using the resist material of the present invention by employing a known lithography technique, for example, a substrate for manufacturing an integrated circuit (Si, SiO ₂ , SiN, SiON, TiN, WSi). , BPSG, SOG, organic antireflection film, etc.) or a mask circuit manufacturing substrate (Cr, CrO, CrON, MoSi, etc.) so that the film thickness becomes 0.05 to 2.0 μm by a technique such as spin coating. It is applied and prebaked on a hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to 140 ° C. for 1 to 5 minutes. Next, a mask for forming a target pattern is placed over the resist film, and a high energy beam such as deep ultraviolet light, excimer laser, or X-ray, or an electron beam is applied in an exposure amount of 1 to 200 mJ / cm ² , preferably 10 to 100 mJ. Irradiate to / cm ² . Alternatively, an electron beam is directly drawn without using a mask for pattern formation. In addition to the normal exposure method, exposure may be performed by an immersion method in which a mask and a resist are immersed. In that case, it is possible to use a protective film insoluble in water. Next, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 140 ° C. for 1 to 3 minutes. Further, 0.1 to 5% by mass, preferably 2 to 3% by mass of an aqueous developer solution such as tetramethylammonium hydroxide (TMAH) is used for 0.1 to 3 minutes, preferably 0.5 to 2%. The target pattern is formed on the substrate by developing by a conventional method such as a dip method, a paddle method, or a spray method for a minute. The resist material of the present invention is particularly suitable for fine patterning using deep ultraviolet rays of 250 to 190 nm or excimer laser, X-rays and electron beams among high energy rays. Moreover, when the said range remove | deviates from an upper limit or a minimum, the target pattern may be unable to be obtained.

The above-mentioned protective film insoluble in water is used to prevent elution from the resist film and increase the water slidability of the film surface. One type is an organic solvent peeling type that requires peeling before alkali development with an organic solvent that does not dissolve the resist film, and the other type is soluble in an alkali developer and can be used to remove the resist film soluble part and remove the protective film. It is a molten type.
The latter is based on a polymer compound having a 1,1,1,3,3,3-hexafluoro-2-propanol residue which is insoluble in water and soluble in an alkaline developer, and is an alcohol solvent having 4 or more carbon atoms. , A C8-C12 ether solvent, and a material dissolved in a mixed solvent thereof are preferable.
The above-mentioned surfactant that is insoluble in water and soluble in an alkaline developer may be made into a material in which it is dissolved in an alcohol solvent having 4 or more carbon atoms, an ether solvent having 8 to 12 carbon atoms, or a mixed solvent thereof. it can.
Also, as a pattern forming method, after forming a photoresist film, pure water rinsing (post-soak) may be performed to extract an acid generator or the like from the film surface, or to wash away particles. You may perform the rinse (post-soak) for removing the water which remained on the top.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Example 1]
The sulfonium salt having a polymerizable anion of the present invention was synthesized according to the following formulation.
[Synthesis Example 1] Synthesis of triphenylsulfonium chloride 40 g (0.2 mol) of diphenylsulfoxide was dissolved in 400 g of dichloromethane and stirred under ice cooling. 65 g (0.6 mol) of trimethylsilyl chloride was added dropwise at a temperature not exceeding 20 ° C., and further aging was performed at this temperature for 30 minutes. Subsequently, Grignard reagent separately prepared from 14.6 g (0.6 mol) of metal magnesium, 67.5 g (0.6 mol) of chlorobenzene, and 168 g of tetrahydrofuran (THF) was added dropwise at a temperature not exceeding 20 ° C. After aging the reaction for 1 hour, 50 g of water was added at a temperature not exceeding 20 ° C. to stop the reaction, and 150 g of water, 10 g of 12 N hydrochloric acid and 200 g of diethyl ether were further added.
The aqueous layer was separated and washed with 100 g of diethyl ether to obtain an aqueous triphenylsulfonium chloride solution. This was used in the next reaction as an aqueous solution without further isolation.

[Synthesis Example 2] Synthesis of 4-tert-butylphenyldiphenylsulfonium bromide The same as Synthesis Example 1 except that 4-tert-butylbromobenzene was used instead of chlorobenzene of Synthesis Example 1 and the amount of water during extraction was increased. The desired product was obtained.

[Synthesis Example 3] Synthesis of 4-tert-butoxyphenyldiphenylsulfonium chloride Using 4-tert-butoxychlorobenzene in place of chlorobenzene of Synthesis Example 1 and a dichloromethane solvent containing 5% by mass of triethylamine as a solvent, extraction was performed. The target product was obtained in the same manner as in Synthesis Example 1 except that the amount of water was increased.

[Synthesis Example 4] Synthesis of tris (4-methylphenyl) sulfonium chloride The target product was obtained in the same manner as in Synthesis Example 1 except that the amount of water was increased.

[Synthesis Example 5] Synthesis of tris (4-tert-butylphenyl) sulfonium bromide Bis (4-tert-butylphenyl) sulfoxide was used instead of diphenyl sulfoxide of Synthesis Example 1, and 4-tert-butylbromobenzene was used instead of chlorobenzene. Was used in the same manner as in Synthesis Example 1 except that the amount of water during extraction was increased.

Synthesis Example 6 Synthesis of bis (4-tert-butylphenyl) iodonium hydrogen sulfate A mixture of 84 g (0.5 mol) of tert-butylbenzene, 53 g (0.25 mol) of potassium iodate, and 50 g of acetic anhydride was prepared. The mixture was stirred under ice cooling, and a mixture of 35 g of acetic anhydride and 95 g of concentrated sulfuric acid was added dropwise at a temperature not exceeding 30 ° C. Next, the mixture was aged at room temperature for 3 hours, cooled on ice again, and 250 g of water was added dropwise to stop the reaction. This reaction solution was extracted with 400 g of dichloromethane, and 6 g of sodium bisulfite was added to the organic layer for decolorization. Further, washing the organic layer with 250 g of water was repeated three times. The washed organic layer was concentrated under reduced pressure to obtain the desired crude product. The product was used in the next reaction without further purification.

Synthesis Example 7 Synthesis of phenacyltetrahydrothiophenium bromide 88.2 g (0.44 mol) of phenacyl bromide and 39.1 g (0.44 mol) of tetrahydrothiophene were dissolved in 220 g of nitromethane and stirred at room temperature for 4 hours. Went. 800 g of water and 400 g of diethyl ether were added to the reaction solution, and the separated aqueous layer was separated to obtain the desired aqueous phenacyltetrahydrothiophenium bromide solution.

Synthesis Example 8 Synthesis of Dimethylphenylsulfonium Sulfate 6.2 g (0.05 mol) of thioanisole and 6.9 g (0.055 mol) of dimethylsulfuric acid were stirred at room temperature for 12 hours. 100 g of water and 50 ml of diethyl ether were added to the reaction solution, and the aqueous layer was separated to obtain the desired aqueous dimethylphenylsulfonium sulfate solution.

[Synthesis Example 9] Synthesis of sodium 2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate 1,1,3,3,3-pentafluoro-2 synthesized by a conventional method -Propan-2-ylbenzoate 10.0g was disperse | distributed to water 72g, sodium hydrogensulfite 12.0g and benzoyl peroxide 1.24g were added, and it reacted at 85 degreeC for 65 hours. The reaction solution was allowed to cool, and toluene was added to carry out a liquid separation operation. A saturated aqueous sodium chloride solution was added to the collected aqueous layer, and the precipitated white crystals were separated by filtration. The crystals were washed with a small amount of saturated sodium chloride solution and then dried under reduced pressure to obtain the target sodium 2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate [ 5.85 g of white crystals (43% yield)].

[Synthesis Example 10] Synthesis of triphenylsulfonium 2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate Synthesis with an aqueous solution equivalent to 0.011 mol of triphenylsulfonium chloride aqueous solution of Synthesis Example 1 3.6 g (0.01 mol) of sodium 2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate synthesized in Example 9 was stirred in 50 g of dichloromethane. The organic layer was separated, and the organic layer was washed 3 times with 50 g of water. The organic layer was concentrated, and 25 g of diethyl ether was added to the residue for crystallization. The target product was obtained by filtering and drying the crystals [4.5 g of white crystals (yield 75%)].

[Synthesis Example 11] Synthesis of triphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonate (PAG1)
34.4 g of triphenylsulfonium-2-benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate of Synthesis Example 10 was dissolved in 72 g of methanol and stirred under ice cooling. Thereto, 54.0 g of 5% aqueous sodium hydroxide solution was added dropwise at a temperature not exceeding 10 ° C. After aging at this temperature for 4 hours, 6.8 g of 12N hydrochloric acid was added at a temperature not exceeding 10 ° C. to stop the reaction, and methanol was removed under reduced pressure. After adding 270 g of dichloromethane and washing the organic layer 3 times with 40 g of water, the organic layer was concentrated, and 60 g of diethyl ether was added to the residue for crystallization. The target product was obtained by filtering and drying the crystals [24.3 g (85% yield) of white crystals].

[Synthesis Examples 12 to 18]
The target product was synthesized in the same manner as in Synthesis Examples 10 and 11 except that the onium salts prepared in Synthesis Examples 2 to 8 were used. These onium salts (PAG2 to PAG8) are shown below.

[Synthesis Example 19] Synthesis of triphenylsulfonium 1,1,3,3,3-pentafluoro-2-methacryloyloxypropane-1-sulfonate [Monomer 1]
49.0 g (0.1 mol) of triphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonate of Synthesis Example 11 was dissolved in 200 g of dichloromethane, and 10.1 g (0 .10 mol) and 2.4 g (0.2 mol) of N, N-dimethylaminopyridine were added and stirred under ice cooling. Methacrylic anhydride 10.0 g (0.10 mol) was added dropwise at a temperature not exceeding 10 ° C. After further aging for 15 minutes, dilute hydrochloric acid was added for liquid separation, and the organic layer was washed with 200 g of water three times. The organic layer was then concentrated, and diethyl ether was added to the residue for crystallization. The crystals were filtered and purified by silica gel column chromatography (eluent: dichloromethane-methanol mixed solvent), recrystallized again with diethyl ether, filtered and dried to obtain the desired product [29 g of white crystals (yield 51%)]. Nuclear Magnetic Resonance spectrum of the target compound ^{(1 H-NMR, 19 F} -NMR) is shown in FIGS. Moreover, the result of an infrared absorption spectrum (IR) and a time-of-flight mass spectrometry spectrum (TOF-MS) is described below.

Infrared absorption spectrum (KBr: cm ^-1 )
1737, 1477, 1448, 1375, 1334, 1257, 1213, 1186, 1170, 1137, 1068, 993, 902, 769, 755, 748, 686, 640, 520, 512, 503
Time-of-flight mass spectrometry spectrum (TOF-MS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
_{^{NEGATIVE M - 297 (CF 3 CH}} (OCOC (CH 3) = CH 2) CF 2 SO 3 - equivalent)

Synthesis Example 20 Triphenylsulfonium 2-acryloyloxy-1,1,3,3,3-pentafluoro-1-propanesulfonate [Synthesis of Monomer 2]
Triphenylsulfonium 2-acryloyloxy-1,1,3,3,3-pentafluoro-1-propanesulfonate was prepared in the same manner as in Synthesis Example 19 except that acryloyl chloride was used instead of methacrylic anhydride in Synthesis Example 19. Synthesized.

[Synthesis Examples 21 to 34] [Synthesis of Monomers 3 to 16]
Instead of triphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonate used in Synthesis Examples 19 and 20, onium salts of Synthesis Examples 12 to 18 (PAG2 to PAG8) are used. In the same manner, an onium salt having the following polymerizable anion was synthesized.
The structural formulas of monomers 1 and 2 and monomers 3 to 16 are shown below.

[Example 2]
The polymer compound of the present invention was synthesized according to the formulation shown below.
Example 2-1 Synthesis of Polymer 1 7.60 g of triphenylsulfonium 1,1,3,3,3-pentafluoro-2-methacryloyloxypropane-1-sulfonate, 8.49 g in a flask with a nitrogen atmosphere 1- (7-oxanorbornan-2-yl) cyclopentyl methacrylate, 8.01 g 3-hydroxy-1-adamantyl methacrylate, 9.12 g 4,8-dioxatricyclomethacrylate [4.2. ^1.03,7 ] nonan-5-on-2-yl, 6.78 g 3,5-bis (hexafluoro-2-hydroxy-2-propyl) cyclohexyl methacrylate, 1.11 g 2,2 ' -Azobisisobutyronitrile, 70.0 g of MEK (methyl ethyl ketone) was taken to prepare a monomer solution. After taking 23.3 g of MEK into another flask in a nitrogen atmosphere and heating to 80 ° C. with stirring, the monomer solution was added dropwise over 4 hours. After completion of dropping, stirring was continued for 2 hours while maintaining the temperature of the polymerization solution at 80 ° C., and then cooled to room temperature. The obtained polymerization solution was dropped into 400 g of hexane which was vigorously stirred, and the precipitated copolymer was separated by filtration. The copolymer was washed twice with a mixed solvent of 45.4 g of MEK and 194.6 g of hexane, and then dried in a vacuum at 50 ° C. for 20 hours to obtain 38.7 g of a white powdery copolymer. When the copolymer was analyzed by ¹³ C-NMR, the copolymer composition ratio was 10/25/22/33/10 mol% in the order of the above monomers.

[Examples 2-2 to 35, Examples 2-42 and 43, Comparative Synthesis Examples 1-1 to 4] Synthesis of polymers 2-35, polymers 42, 43, and polymers 45-48 Resins shown in Table 1 were produced by the same procedure as in Example 2-1, except that the ratio was changed. In Table 1, the structure of each unit is shown in Tables 2-6. In Table 1 below, the introduction ratio indicates a molar ratio.
[Examples 2-36 to 40, Example 2-44, Comparative Synthesis Example 1-5] Synthesis of Polymers 36 to 40 and Polymer 46 Polymers 36 to 40 and Polymer 44 obtained by the above-described formulation were mixed with methanol and tetrahydrofuran. After dissolving in a solvent, oxalic acid was added and deprotection reaction was performed at 40 ° C. After neutralizing with pyridine, normal reprecipitation purification was performed to obtain a polymer compound having a hydroxystyrene unit.
[Example 2-41, comparative synthesis example 1-6] Synthesis of polymer 41 and polymer 50 Polymer 36 and polymer 46 were reacted with 1-chloro-1-methoxy-2-methylpropane under basic conditions to obtain the desired polymer. 41, polymer 50 was obtained.
Details regarding deprotection and protection of the polyhydroxystyrene derivatives of Examples 2-36 to 41-41 are described in JP-A Nos. 2004-115630 and 2005-8766.

Preparation of resist material [Examples 3-1 to 35, Comparative examples 2-1 to 4]
Resin of the present invention produced above [Polymer 1-30, Polymer 41, Polymer 42, Polymer 44 (P-01-30, P-41, P-42, P-44)] and Resin for Comparative Example [Polymer 45-47, polymer 50 (P-45-47, P-50)] as a base resin, an acid generator, a quencher (base), and a solvent were added in the composition shown in Table 7, and after mixing and dissolution, they were added. Was filtered with a Teflon (registered trademark) filter (pore size 0.2 μm) to obtain a resist material (R-01 to 35) and a resist material for comparison (R-60 to 63). In addition, all the solvents used 0.01% by mass of KH-20 (Asahi Glass Co., Ltd.) as a surfactant.

In Table 7, the acid generator, quencher (base), and solvent indicated by abbreviations are as follows.
PAG-1: Triphenylsulfonium Nonafluorobutanesulfonate Base-1: Tri (2-methoxymethoxyethyl) amine PGMEA: Acetic acid 1-methoxyisopropyl CyHO: Cyclohexanone EL: Ethyl lactate

Evaluation of resolution and mask fidelity: ArF exposure [Examples 4-1 to 33, Comparative examples 3-1 to 3]
The resist material of the present invention (R-01-31, R-33-34) and the resist material for comparison (R-60, 61) are coated with an antireflection film (manufactured by Nissan Chemical Industries, ARC29A, 78 nm). It spin-coated on the apply | coated silicon wafer, and heat-processed at 100 degreeC for 60 second, and formed the resist film with a thickness of 170 nm. This was exposed using an ArF excimer laser stepper (Nikon Corporation, 307E, NA = 0.85, σ0.93 / 0.70, 3/4 annular illumination, 6% halftone mask), 110 ° C. , After 60 seconds heat treatment (PEB), paddle development with 2.38 mass% tetramethylammonium hydroxide aqueous solution for 30 seconds, 1: 1 line and space pattern and 1:10 isolated line A pattern was formed. The prepared wafer with a pattern is observed with an overhead SEM (scanning electron microscope), and an exposure amount for resolving 80 nm 1: 1 line and space at 1: 1 is defined as an optimum exposure amount (mJ / cm ² ). The minimum dimension of the 1: 1 line-and-space pattern separated and resolved at the optimum exposure dose was defined as the critical resolution (dimension on the mask, in increments of 5 nm, the smaller the dimension, the better). In addition, an isolated line pattern of 1:10 is observed at the optimum exposure amount, and an actual dimension on the wafer of an isolated line pattern having a dimension on the mask of 130 nm is measured, and mask fidelity (the dimension on the wafer, the larger the dimension, the better). did.
Table 8 shows the evaluation results (limit resolution and mask fidelity) of the resist material of the present invention and the evaluation results (limit resolution and mask fidelity) of the resist material for comparison.

From the results of the examples in Table 8, it was confirmed that the resist material of the present invention had excellent resolution performance and excellent mask fidelity in ArF excimer laser exposure. On the other hand, in the result of the comparative example in Table 8, the resist material according to the conventional technique satisfies only one of the resolution performance and the mask fidelity, or neither of them can be satisfied. It is shown that it is.
As described above, the resist material based on the polymer compound containing the sulfonium salt having a polymerizable anion of the present invention as a repeating unit as a base resin has characteristics as a resist material as compared with those constructed by conventional techniques. It was confirmed that it was excellent.

Evaluation of resolution: EB exposure [Examples 4-34 and 35, Comparative Example 3-4]
The resist material (R-32, R-35) of the present invention and the resist material for comparison (R-63) are coated with an organic antireflection film (DUV-44, manufactured by Brewer Science Co., Ltd.) on 610 mm. A wafer was spin-coated and heat-treated at 100 ° C. for 60 seconds to form a resist film having a thickness of 2,000 mm. Further, exposure was performed using an electron beam exposure apparatus (manufactured by Hitachi High-Technologies Corporation, HL-800D, acceleration voltage 50 keV), and a heat treatment (PEB: post exposure bake) was performed at 120 ° C. for 60 seconds to obtain 2.38 mass. When development was performed with an aqueous solution of 1% tetramethylammonium hydroxide, positive patterns (Examples 4-35 and 36, Comparative Example 3-4) could be obtained.

The obtained resist pattern was evaluated as follows.
The exposure amount for resolving the top and bottom of a 0.12 μm line and space at 1: 1 is the optimum exposure amount (sensitivity: Eop), and the minimum line width of the separated line and space at this exposure amount is evaluated. Resolution. Moreover, the resist cross section was observed for the shape of the resolved resist pattern using a scanning electron microscope.
In order to evaluate the PED (post exposure delay) in a vacuum, after exposure by an electron beam exposure apparatus, it was left in an apparatus that was evacuated for 24 hours, after which PEB and development were performed. The dimensional change rate of the line part of the obtained 0.12 μm line and space pattern is shown. For example, when it increases by 0.012 μm, it is described as + 10%. The smaller this change, the better the stability. Table 9 shows the evaluation results.

  From the results in Table 9, it was confirmed that the resist material of the present invention was excellent in resolution performance and PED in vacuum even in EB exposure. Accordingly, it can be expected that EUV lithography, KrF lithography and the like using a polyhydroxystyrene derivative function in the same manner.

Measurement of dissolution amount of resist film [Examples 5-1 to 4, Comparative examples 4-1 to 3]
The resist materials prepared above (R-01, R-03, R-33, R-34 and Comparative Examples R-60 to 62) were each applied onto a silicon substrate by spin coating, and baked at 120 ° C. for 60 seconds. Then, a photoresist film having a thickness of 120 nm was produced. The entire surface of the photoresist film was irradiated with energy of 50 mJ / cm ^{2 with} an open frame using a Nikon ArF scanner S305B.
Next, a perfectly circular Teflon (registered trademark) ring having an inner diameter of 10 cm is placed on the irradiated photoresist film, 10 mL of pure water is carefully poured therein, and the resist film and pure water are contacted at room temperature for 60 seconds. I let you.
Then, pure water was collect | recovered and the anion component density | concentration of the photo-acid generator (PAG) in pure water was quantified with the LC-MS analyzer by Agilent.
From the measured anion concentration, the measurement results of the anion elution amount for 60 seconds are shown in Table 10 below.

  From this result, it was confirmed that the resist material of the present invention did not elute the generated acid even during immersion exposure using water. It is expected that there is little change in the pattern shape due to immersion exposure and there is little damage to the exposure machine.

1 is a diagram showing ¹ H-NMR of [Monomer 1] in Synthesis Example 19. FIG. 19 is a diagram showing ¹⁹ F-NMR of [Monomer 1] in Synthesis Example 19. FIG.

Claims (11)

A polymer compound which generates a sulfonic acid having a repeating unit represented by the following general formula (1a) in response to high energy rays or heat.

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.) A sulfonium salt having a polymerizable anion represented by the following general formula (1).

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted straight chain of 1 to 10 carbon atoms. Or a branched alkyl group, an alkenyl group or an oxoalkyl group, or a substituted or unsubstituted aryl group, aralkyl group or aryloxoalkyl group having 6 to 18 carbon atoms, or R ² , R ³ and R ⁴ . Any two or more of them may be bonded to each other to form a ring together with the sulfur atom in the formula.) A polymer compound comprising a repeating unit represented by the following general formula (2).

(In the formula, R ¹ represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted straight chain of 1 to 10 carbon atoms. Or a branched alkyl group, an alkenyl group or an oxoalkyl group, or a substituted or unsubstituted aryl group, aralkyl group or aryloxoalkyl group having 6 to 18 carbon atoms, or R ² , R ³ and R ⁴ . Any two or more of them may be bonded to each other to form a ring together with the sulfur atom in the formula.) Furthermore, the high molecular compound of Claim 3 containing any 1 or more types of the repeating unit represented by following General formula (3)-(6).

(In the formula, R ¹ is the same as described above. R ⁶ and R ⁷ each independently represents a hydrogen atom or a hydroxyl group. X represents an acid labile group. Y represents a substituent having a lactone structure. Z Represents a hydrogen atom, a C1-C15 fluoroalkyl group, or a C1-C15 fluoroalcohol-containing substituent. Furthermore, the high molecular compound of Claim 3 or 4 containing any 1 or more types of the repeating unit represented by the following general formula (7)-(10).

(Wherein R ¹ and X are the same as described above. G represents an oxygen atom or a carbonyloxy group (—C (═O) O—)).   A resist material comprising the polymer compound according to claim 3 as a base resin.   A resist material comprising the polymer compound according to any one of claims 3 to 5 and a polymer compound not containing the general formula (2) as a base resin.   The resist material according to claim 6 or 7, further comprising a surfactant that is insoluble in water and soluble in an alkaline developer.   A step of applying the resist material according to any one of claims 6 to 8 on a substrate, a step of exposing with a high energy beam through a photomask after heat treatment, a heat treatment if necessary, and a development And a step of developing using a liquid.   A step of applying the resist material according to any one of claims 6 to 8 on a substrate, a step of applying a protective film insoluble in water and soluble in an alkaline developer after the heat treatment, the substrate and the projection A pattern forming method comprising: a step of inserting water between lenses and exposing with high energy rays through a photomask; and a step of developing with a developer after heat treatment as necessary .   A step of applying the resist material according to any one of claims 6 to 8 on a substrate, a step of drawing with an electron beam after heat treatment, a heat treatment as necessary, and then developing with a developer. A pattern forming method comprising the steps of:

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