JP5083528B2 - Novel photoacid generator, resist material and pattern forming method using the same - Google Patents

Description

  The present invention relates to a novel photoacid generator suitably used as a photoacid generator for a resist material, a resist material using the same, and a pattern forming method.

  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 higher 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 that can exhibit sufficient resolution with a small exposure amount is required. It is most common to select a highly transparent material at a wavelength of 193 nm. For example, with respect to the base resin, polyacrylic acid and its derivatives, norbornene-maleic anhydride alternating polymer, polynorbornene and 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. When a photoacid generator that generates alkane or arenesulfonic acid as 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. It has been found that the acid strength for cleaving the acid labile group of the resin is not sufficient, 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, acids that generate perfluoroalkyl ether sulfonic acids in Patent Documents 3 to 5: Japanese Patent Application Laid-Open Nos. 2002-214774, 2003-140332, and US 2002/0197558 are disclosed. Generators have been proposed.

  On the other hand, perfluorooctane sulfonic acid, or its derivative, is known as PFOS after its acronym, and is an eco-concentration derived from stability (non-degradable) derived from C—F bond, hydrophobicity, and lipophilicity. And accumulation are problems. The US Environment Agency (EPA) has enacted 13 PFOS-related substances in the Significant New Use Rule, and the 75 substances are exempted from use in the photoresist field. . Furthermore, the application of the most important new usage rule has been proposed for 183 substances of perfluoroalkanesulfonic acid or its derivatives.

  In order to cope with such problems related to PFOS, partial fluorine-substituted alkanesulfonic acids having a reduced fluorine substitution rate have been developed by various companies. 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 to light. A resist material containing an agent, specifically, di (4-tert-butylphenyl) iodonium = 1,1-difluoro-2- (1-naphthyl) ethanesulfonate is disclosed, and Patent Document 7: Special 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. In addition, Patent Document 3: JP-A-2002-214774 does not describe a synthesis method, but in the specification, difluorosulfoacetic acid alkyl ester (1- (alkoxycarbonyl) -1,1-difluoromethanesulfonate) , A photoacid generator having difluorosulfoacetamide (1-carbamoyl-1,1-difluoromethanesulfonate) and the like are disclosed, and further, JP-A-2005-266766 discloses perfluoroalkylene disulfonyl. A photosensitive composition containing a compound that generates a partially fluorinated alkanesulfonic acid having a sulfonylamide structure derived from difluoride is disclosed.

  However, both of the substances in the above-mentioned patent documents are hydrocarbon skeletons in which the basic skeleton is difficult to decompose, although the fluorine substitution rate is lowered, and since there is no easily decomposable substituent such as an ester group, the substance is easily decomposable. However, the molecular design for changing the size of the alkanesulfonic acid is limited, and the fluorine-containing starting material is expensive.

  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 immersion lithography, there is a need for a pattern forming method that can provide a good resist pattern after development.

  Furthermore, when a fine pattern is to be formed, the problem of sparse patterns with different optical contrasts and dimensional differences (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.

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

The acid generated by the photoacid generator is such that it has sufficient acid strength to cleave acid labile groups in the resist material, good storage stability in the resist material, and suitable in the resist material. Diffusion, low volatility, little elution into water, little foreign matter after development and peeling, good degradability without impacting the environment after the end of lithography use, etc. However, acids generated from conventional photoacid generators do not satisfy these requirements.
Furthermore, conventional resist materials using photoacid generators do not degrade resolution, and cannot solve the problems of density dependence and line edge roughness.

  The present invention solves the above-mentioned problems of the conventional photoacid generator, can suppress elution into water particularly during ArF immersion exposure, and suppresses the generation of foreign substances peculiar to immersion exposure, To provide a novel photoacid generator suitable as a photoacid generator for resist materials, such as density dependency dependency and line edge roughness, which can be effectively used, a resist material using the same, and a pattern forming method With the goal.

  As a result of intensive studies on the above problems, the present inventors have made 1,1,1,3,3,3-hexafluoro-2-propanol, which is industrially easily available, a starting material, a carbonyl group, 1,1,3,3,3-pentafluoro-2-acyloxypropane-1-sulfonate or 1,1,3,3,3-pentafluoro-2-arylcarbonyl having a carboxyl group, a carboxylate ester or a lactone structure The inventors have found that compounds represented by onium salts, oximes, and imides having oxypropane-1-sulfonate are effective as photoacid generators for chemically amplified resist materials, and have made the present invention.

（式中、点線は結合位置を示す。）
で示される二価の基から選択され、又はＲ ¹ とＲは相互に結合してＣ（＝Ｏ）と共に下記の基

（式中、点線は結合位置を示す。）
のいずれかを形成してもよい。）
請求項２：
下記一般式（２）で示されるスルホニウム塩。
ＲＣ（＝Ｏ）−Ｒ¹−ＣＯＯＣＨ（ＣＦ₃）ＣＦ₂ＳＯ₃ ^- Ｒ²Ｒ³Ｒ⁴Ｓ⁺ （２）
（式中、Ｒ、Ｒ ¹ は上記の通り。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（２ａ）で示されるスルホニウム塩。
ＲＣ（＝Ｏ）−Ｒ¹−ＣＯＯＣＨ（ＣＦ₃）ＣＦ₂ＳＯ₃ ^- （Ｒ⁵（Ｏ）_n）_mＰｈ’Ｓ⁺Ｐｈ₂
（２ａ）
（式中、Ｒ、Ｒ ¹ は上記の通り。Ｒ⁵は置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアルケニル基、又は置換もしくは非置換の炭素数６〜１４のアリール基を示す。ｍは１〜５の整数、ｎは０（零）又は１を示す。Ｐｈはフェニル基を示す。Ｐｈ’はフェニル基の水素原子ｍ個をＲ⁵（Ｏ）_n−基に置換した基を示す。）
請求項４：
下記一般式（２ｂ）で示されるヨードニウム塩。
ＲＣ（＝Ｏ）−Ｒ¹−ＣＯＯＣＨ（ＣＦ₃）ＣＦ₂ＳＯ₃ ^- （（Ｒ⁵（Ｏ）_n）_mＰｈ’）₂Ｉ⁺
（２ｂ）
（式中、Ｒ、Ｒ ¹ は上記の通り。Ｒ⁵は置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基又はアルケニル基、又は置換もしくは非置換の炭素数６〜１４のアリール基を示す。ｍは１〜５の整数、ｎは０（零）又は１を示す。Ｐｈ’はフェニル基の水素原子ｍ個をＲ⁵（Ｏ）_n−基に置換した基を示す。）
請求項５：
ベース樹脂、酸発生剤及び有機溶剤を含有してなるレジスト材料において、前記酸発生剤が、請求項１記載の式（１ａ）で示されるスルホン酸を発生する光酸発生剤であることを特徴とするレジスト材料。
請求項６：
ベース樹脂が、ポリ（メタ）アクリル酸及びその誘導体、シクロオレフィン誘導体−無水マレイン酸交互重合体、シクロオレフィン誘導体と無水マレイン酸とポリアクリル酸又はその誘導体との３あるいは４元以上の共重合体、シクロオレフィン誘導体−α−トリフルオロメチルアクリル酸誘導体共重合体、ポリノルボルネン、開環メタセシス重合体、並びに開環メタセシス重合体水素添加物から選択される１種又は２種以上の高分子重合体であることを特徴とする請求項５記載のレジスト材料。
請求項７：
ベース樹脂が、珪素原子を含有する高分子構造体であることを特徴とする請求項５記載のレジスト材料。
請求項８：
ベース樹脂が、フッ素原子を含有する高分子構造体であることを特徴とする請求項５記載のレジスト材料。
請求項９：
請求項６、７又は８記載のベース樹脂、請求項１記載の一般式（１ａ）で示されるスルホン酸を発生する光酸発生剤及び溶剤を含有し、上記ベース樹脂が現像液に不溶あるいは難溶であって、酸の作用によって現像液に可溶となる化学増幅ポジ型レジスト材料。
請求項１０：
更に、クエンチャーを添加してなることを特徴とする請求項９記載の化学増幅ポジ型レジスト材料。
請求項１１：
更に、溶解阻止剤を含有することを特徴とする請求項９又は１０記載の化学増幅ポジ型レジスト材料。
請求項１２：
請求項５乃至１１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波長３００ｎｍ以下の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１３：
波長１９３ｎｍのＡｒＦエキシマレーザーを用い、レジスト材料が塗布された基板と投影レンズの間に水を挿入する液浸リソグラフィー法であることを特徴とする請求項１２記載のパターン形成方法。 That is, the present invention provides the following novel photoacid generator, a resist material and a pattern forming method using the same.
Claim 1:
Sensitive to high energy rays of ultraviolet rays, far ultraviolet rays, electron beams, EUV, X-rays, excimer lasers, γ rays, or synchrotron radiation, and generates sulfonic acid represented by the following general formula (1a) Photoacid generator for chemically amplified resist materials.
^{RC (= O) R 1 -COOCH} (CF 3) CF 2 SO 3 - H + (1a)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents methylene, ethylene, 1,3-propylene, 1,2-propylene, isopropylidene, 1,4-butylene, 1,6-hexylene, o-phenylene, m-phenylene, p-phenylene, the following formula

(In the formula, the dotted line indicates the bonding position.)
Or R ¹ and R are bonded to each other to form the following group together with C (═O):

(In the formula, the dotted line indicates the bonding position.)
Either of these may be formed . )
Claim 2:
A sulfonium salt represented by the following general formula (2).
^{RC (= O) -R 1 -COOCH} (CF 3) CF 2 SO 3 - R 2 R 3 R 4 S + (2)
(Wherein R ¹ , R ¹ are as described above. R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C 1-10 linear or branched alkyl group, 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 any two or more of R ² , R ³ and R ⁴ are mutually It may combine to form a ring with the sulfur atom in the formula.)
Claim 3:
A sulfonium salt represented by the following general formula (2a).
RC (═O) —R ¹ —COOCH (CF ₃ ) CF ₂ SO ₃ ⁻ (R ⁵ (O) _n ) _m Ph ′S ⁺ Ph ₂
(2a)
(Wherein R ¹ and R ¹ are as described above. R ⁵ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number. 6 to 14 represents an aryl group, m represents an integer of 1 to 5, n represents 0 (zero) or 1, Ph represents a phenyl group, Ph ′ represents m hydrogen atoms of the phenyl group, R ⁵ (O ) Indicates a group substituted with _n -group.)
Claim 4:
An iodonium salt represented by the following general formula (2b).
RC (═O) —R ¹ —COOCH (CF ₃ ) CF ₂ SO ₃ ⁻ ((R ⁵ (O) _n ) _m Ph ′) ₂ I ⁺
(2b)
(Wherein R ¹ and R ¹ are as described above. R ⁵ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number. 6 to 14 represents an aryl group, m represents an integer of 1 to 5, n represents 0 (zero) or 1, Ph ′ represents m hydrogen atoms of a phenyl group substituted with an R ⁵ (O) _n — group. Group.)
Claim 5 :
A resist material comprising a base resin, an acid generator, and an organic solvent, wherein the acid generator is a photoacid generator that generates a sulfonic acid represented by the formula (1a) according to claim 1. Resist material.
Claim 6 :
Base resin is poly (meth) acrylic acid and derivatives thereof, cycloolefin derivative-maleic anhydride alternating polymer, copolymer of cycloolefin derivative, maleic anhydride and polyacrylic acid or derivative thereof. , Cycloolefin derivative-α-trifluoromethylacrylic acid derivative copolymer, polynorbornene, ring-opening metathesis polymer, and one or more polymer polymers selected from hydrogenated ring-opening metathesis polymers The resist material according to claim 5 , wherein:
Claim 7 :
6. The resist material according to claim 5 , wherein the base resin is a polymer structure containing silicon atoms.
Claim 8 :
6. The resist material according to claim 5 , wherein the base resin is a polymer structure containing fluorine atoms.
Claim 9 :
A base resin according to claim 6 , 7 or 8, a photoacid generator for generating a sulfonic acid represented by the general formula (1a) according to claim 1, and a solvent, wherein the base resin is insoluble or difficult to develop in a developer. A chemically amplified positive resist material that is soluble and becomes soluble in a developer by the action of an acid.
Claim 10 :
The chemically amplified positive resist composition according to claim 9 , further comprising a quencher.
Claim 11 :
The chemically amplified positive resist composition according to claim 9 or 10 , further comprising a dissolution inhibitor.
Claim 12 :
The process of apply | coating the resist material of any one of Claim 5 thru | or 11 on a board | substrate, the process of exposing with a high energy ray with a wavelength of 300 nm or less through a photomask after heat processing, and heat processing as needed And a step of developing using a developing solution.
Claim 13 :
13. The pattern forming method according to claim 12, which is an immersion lithography method using an ArF excimer laser with a wavelength of 193 nm and inserting water between a substrate coated with a resist material and a projection lens.

  Since the photoacid generator of the present invention has a carbonyl group, a carboxyl group, a carboxylate structure or a lactone structure in addition to the β-position acyloxy group or arylcarbonyloxy group, the resin in the resist material It has good compatibility with other materials and can control acid diffusion. Moreover, these photo-acid generators which generate | occur | produce sulfonic acid can be used without a problem in the process of application | coating in a device preparation process, baking before exposure, exposure, baking after exposure, and image development. Furthermore, not only elution into water during ArF immersion exposure can be suppressed, but also 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 β-position acyloxy group or arylcarbonyloxy group is alkali-hydrolyzed, so it can be converted to a lower molecular weight, low-accumulation compound, Combustibility is high because the fluorine substitution rate is low during disposal.

Photoacid generator The photoacid generator of the present invention is a compound represented by a sulfonium salt, an iodonium salt, an oxime sulfonate, and a sulfonyloxyimide. Responsible for high energy rays of γ-rays or synchrotron radiation, generates sulfonic acid represented by the following general formula (1a), and is used as a photoacid generator for chemically amplified resist materials .
^{RC (= O) R 1 -COOCH} (CF 3) CF 2 SO 3 - H + (1a)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents a heteroaryloxy group, R ¹ represents a C 1-20 divalent organic group which may have a substituent having a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom; Alternatively, a plurality of ring structures may be formed.)

R in the above formula (1a) is a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or a carbon number. A heteroaryl group having 4 to 15 carbon atoms, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 carbon atoms Represents -15 heteroaryloxy groups; R ¹ represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent having a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, and forms a single or plural cyclic structure together with R You may do it. Examples of the substituent for R include a hydroxyl group, an alkoxyl group, an aryloxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a carboxyl group, an alkoxycarbonyl group, an amide group, a carbonyl group, and an ether-bonded oxygen atom. It is done. In this case, when R is an alkyl group, one or more of its hydrogen atoms may be substituted with an aryl group, and when R is an aryl group, one or more of its hydrogen atoms are substituted with an alkyl group. Also good.

  More specifically, R represents hydroxyl group, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl. Group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, 1-adamantyl group, 2-adamantyl group, bicyclo [2.2.1] heptene-2- Yl group, 1-adamantanemethyl group, 2-adamantanemethyl group, phenyl group, 4-methoxyphenyl group, 4-tert-butylphenyl group, 4-biphenyl group, 1-naphthyl group, 2-naphthyl group, 10-anthranyl Group, 2-furanyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropyloxy group, n-buto Si group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyl Oxy group, 1-adamantyloxy group, 2-adamantyloxy group, bicyclo [2.2.1] hepten-2-yloxy group, 1-adamantanemethoxy group, 2-adamantanemethoxy group, phenoxy group, 4-methoxyphenyloxy Group, 4-tert-butylphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 10-anthranyloxy group, 2-furanyloxy group, 2,2,2-trifluoroethoxy, 1,1,1,3,3,3-hexafluoro-2-propyl Alkoxy group, a 2,2,3,3-tetrafluoro-propoxy group. Of these, hydroxyl group, methoxy group, cyclohexyloxy group, and 1-adamantanemethoxy group are preferably used.

R ¹ represents a C 1-20 divalent organic group which may have a substituent having a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, and may form a cyclic structure together with R Good. Examples of the substituent for R ¹ include a hydroxyl group, an alkoxy group, an aryloxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a carboxyl group, an alkoxycarbonyl group, an amide group, a carbonyl group, and an ether-bonded oxygen atom. It is done. Specific examples of R ¹ include methylene, ethylene, 1,3-propylene, 1,2-propylene, isopropylidene, 1,4-butylene, 1,6-hexylene, o-phenylene, m-phenylene, and p-phenylene. Further, those having the following structure can be mentioned. In the following structural formula, the bonding position is indicated by a dotted line.

Of these, ethylene, 1,3-propylene and those having the following structures are preferably used.

When R and R ¹ are bonded to each other, the following structures are exemplified.

Specific sulfonic acids are shown below.

Sulfonium salt The sulfonium salt according to the present invention is represented by the following general formula (2).
^{RC (= O) -R 1 -COOCH} (CF 3) CF 2 SO 3 - R 2 R 3 R 4 S + (2)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents a heteroaryloxy group, R ¹ represents a C 1-20 divalent organic group which may have a substituent having a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom; Alternatively, R ² , R ³ and R ⁴ may be independently substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, alkenyl group or An oxoalkyl group, or Or unsubstituted aryl group having 6 to 18 carbon atoms, aralkyl or aryloxoalkyl group, or R ^2, 2 or more any of the R ³ and R ⁴ in the formula are bonded to each other A ring may be formed with a sulfur atom.)

R and R ¹ in the general formula (2) are as described above. R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group, alkenyl group or oxoalkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon number of 6 -18 aryl group, aralkyl group or aryloxoalkyl group, or any two or more of R ² , R ³ and R ⁴ are bonded to each other to form a ring together with the sulfur atom in the formula May be. Specifically, as the 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 -N-butylphenyl group, alkylphenyl group such as 2,4-dimethylphenyl group, alkylnaphthyl group such as methylnaphthyl group, ethylnaphthyl group, alkoxynaphthyl group such as methoxynaphthyl group, ethoxynaphthyl group, dimethylnaphthyl 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. As the aryloxoalkyl group, 2-aryl-2-oxoethyl group such as 2-phenyl-2-oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group and the like 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 via a sulfur atom, the groups forming these cyclic structures are: , 4-butylene, 3-oxa-1,5-pentylene, and the like. Furthermore, aryl groups having polymerizable substituents such as an acryloyloxy group and a methacryloyloxy group can be mentioned as a substituent. Specifically, 4-acryloyloxyphenyl group, 4-methacryloyloxyphenyl group, 4-acryloyloxy- Examples include 3,5-dimethylphenyl group, 4-methacryloyloxy-3,5-dimethylphenyl group, 4-vinyloxyphenyl group, 4-vinylphenyl group and the like.

  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 preferable examples include triphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, 4-tert-butoxyphenyldiphenylsulfonium, tris (4-tert-butylphenyl) sulfonium, 4-tert-butoxycarbonylmethyloxyphenyldiphenylsulfonium, and the like. It is done. Furthermore, 4-methacryloyloxyphenyldiphenylsulfonium, 4-acryloyloxyphenyldiphenylsulfonium, 4-methacryloyloxyphenyldimethylsulfonium, 4-acryloyloxyphenyldimethylsulfonium, (4-methacryloyloxy-3,5-dimethylphenyl) diphenylsulfonium, (4-acryloyloxy-3,5-dimethylphenyl) diphenylsulfonium and the like. With respect to these polymerizable sulfonium cations, reference can be made to JP-A-4-230645, JP-A-2005-84365, etc., and these polymerizable sulfonium salts can be used as monomers of the constituents of the high molecular weight compounds described later. Can be used.

In this case, examples of the sulfonium salt include those represented by the following general formula (2a).
RC (═O) —R ¹ —COOCH (CF ₃ ) CF ₂ SO ₃ ⁻ (R ⁵ (O) _n ) _m Ph ′S ⁺ Ph ₂
(2a)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents a heteroaryloxy group, R ¹ represents a C 1-20 divalent organic group which may have a substituent having a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom; R ⁵ may be a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number. 6-14 ants M represents an integer of 1 to 5, n represents 0 (zero) or 1. Ph represents a phenyl group, and Ph ′ represents m hydrogen atoms of the phenyl group as R ⁵ (O). _n represents a group substituted on the group.)

R and R ¹ in the general formula (2a) are as described above, and the substitution position of the R ^5- (O) _n -group is not particularly limited, but the 4-position or 3-position of the phenyl group is preferable. More preferably, it is the 4th position. R ⁵ is methyl group, ethyl group, n-propyl group, sec-propyl group, cyclopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group. N-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, phenyl group, 4-methoxyphenyl group, 4-tert-butylphenyl group, and n = 1 In this case, an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group may be mentioned. m is an integer of 1 to 5, preferably 1. n is 0 (zero) or 1.

  Specific examples of the sulfonium cation include 4-methylphenyldiphenylsulfonium, 4-ethylphenyldiphenylsulfonium, 4-tert-butylphenyldiphenylsulfonium, 4-cyclohexylphenyldiphenylsulfonium, 4-n-hexylphenyldiphenylsulfonium, 4-n -Octylphenyldiphenylsulfonium, 4-methoxyphenyldiphenylsulfonium, 4-ethoxyphenyldiphenylsulfonium, 4-tert-butoxyphenyldiphenylsulfonium, 4-cyclohexyloxyphenyldiphenylsulfonium, 4-n-hexyloxyphenyldiphenylsulfonium, 4-n -Octyloxyphenyldiphenylsulfonium, 4-dodecyloxyphenyldiphenylsulfone 4-trifluoromethylphenyldiphenylsulfonium, 4-trifluoromethyloxyphenyldiphenylsulfonium, 4-tert-butoxycarbonylmethyloxyphenyldiphenylsulfonium, 4-methacryloyloxyphenyldiphenylsulfonium, 4-acryloyloxyphenyldiphenylsulfonium, 4-n-hexyloxy-3,5-dimethylphenyl) diphenylsulfonium), (4-methacryloyloxy-3,5-dimethylphenyl) diphenylsulfonium, (4-acryloyloxy-3,5-dimethylphenyl) diphenylsulfonium, etc. Is mentioned.

Iodonium Salt The present invention also provides an iodonium salt. The iodonium salt of the present invention is represented by the following general formula (2b).
RC (═O) —R ¹ —COOCH (CF ₃ ) CF ₂ SO ₃ ⁻ ((R ⁵ (O) _n ) _m Ph ′) ₂ I ⁺
(2b)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents a heteroaryloxy group, R ¹ represents a C 1-20 divalent organic group which may have a substituent having a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom; R ⁵ may be a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number. 6-14 ants M represents an integer of 1 to 5, n represents 0 (zero) or 1. Ph ′ is as described above.)

R, R ¹ , R ⁵ , n, and m in the general formula (2b) are as described above. The substitution position of the R ⁵ — (O) _n — group is not particularly limited, but the 4-position or 3-position of the phenyl group is preferred. More preferably, it is the 4th position. Specific iodonium cations include bis (4-methylphenyl) iodonium, bis (4-ethylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (4- (1,1-dimethylpropyl) phenyl. ) Iodonium, 4-methoxyphenylphenyliodonium, 4-tert-butoxyphenylphenyliodonium, 4-acryloyloxyphenylphenyliodonium, 4-methacryloyloxyphenylphenyliodonium, among others, bis (4-tert-butylphenyl) Iodonium is preferably used.

（式中、Ｒは水酸基、置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、置換もしくは非置換の炭素数６〜１５のアリール基又は炭素数４〜１５のヘテロアリール基、置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルコキシ基、又は置換もしくは非置換の炭素数６〜１５のアリールオキシ基又は炭素数４〜１５のヘテロアリールオキシ基を示す。Ｒ¹は酸素原子、窒素原子又は硫黄原子などのヘテロ原子を持つ置換基を有していてもよい炭素数１〜２０の二価の有機基を示し、Ｒと共に単数もしくは複数の環状構造を形成していてもよい。Ｘ、Ｙは相互に独立に水素原子又は置換もしくは非置換の炭素数１〜６のアルキル基を示すか、あるいはＸ及びＹが相互に結合してそれらが結合している炭素原子と共に飽和もしくは不飽和の炭素数６〜１２の環を形成してもよい。Ｚは単結合、二重結合、メチレン基、又は酸素原子を示す。） N-sulfonyloxyimide compound The present invention also provides an N-sulfonyloxyimide compound represented by the following general formula (3a).

(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents a heteroaryloxy group, R ¹ represents a C 1-20 divalent organic group which may have a substituent having a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom; Alternatively, a plurality of cyclic structures may be formed, X and Y each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other. And they are combined May form a ring of 6 to 12 carbon atoms, saturated or unsaturated with the carbon atoms .Z represents a single bond, double bond, methylene group, or an oxygen atom.)

X and Y in the general formula (3a) each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or X and Y are bonded to each other to bond them. A saturated or unsaturated ring having 6 to 12 carbon atoms may be formed together with the carbon atoms. Z represents a single bond, a double bond, a methylene group, or an oxygen atom. R and R ¹ are the same as described above. The imide skeleton excluding the sulfonate part is specifically shown below. JP-A 2003-252855 can be referred to for the imide skeleton.

（式中、Ｒは水酸基、置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、置換もしくは非置換の炭素数６〜１５のアリール基又は炭素数４〜１５のヘテロアリール基、置換もしくは非置換の炭素数１〜２０の直鎖状、分岐状又は環状のアルコキシ基、又は置換もしくは非置換の炭素数６〜１５のアリールオキシ基又は炭素数４〜１５のヘテロアリールオキシ基を示す。Ｒ¹は酸素原子、窒素原子又は硫黄原子などのヘテロ原子を持つ置換基を有していてもよい炭素数１〜２０の二価の有機基を示し、Ｒと共に単数もしくは複数の環状構造を形成していてもよい。ｑは０又は１を示すが、ｑが０の場合、ｐは置換もしくは非置換の炭素数１〜２０のアルキル基、又は置換もしくは非置換の炭素数６〜１５のアリール基を示し、ｑが１の場合には、ｐは単結合、置換もしくは非置換の炭素数１〜２０のアルキレン基、又は置換もしくは非置換の炭素数６〜１５のアリーレン基を示す。ＥＷＧはシアノ基、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、５Ｈ−パーフルオロペンチル基、６Ｈ−パーフルオロヘキシル基、ニトロ基又はメチル基を示し、ｑが１の場合、互いのＥＷＧが相互に結合してそれらが結合している炭素原子と共に炭素数６の環を形成してもよい。） Oxime sulfonate compound The present invention also provides an oxime sulfonate compound represented by the following general formula (3b).

(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents a heteroaryloxy group, R ¹ represents a C 1-20 divalent organic group which may have a substituent having a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom; Alternatively, a plurality of cyclic structures may be formed, and q represents 0 or 1, and when q is 0, p represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted group. Aryl having 6 to 15 carbon atoms In the case where q is 1, p represents a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms. Group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, 5H-perfluoropentyl group, 6H-perfluorohexyl group, nitro group or methyl group, and when q is 1, mutual EWGs are mutually To form a ring having 6 carbon atoms together with the carbon atom to which they are bonded.)

R and R ¹ in the general formula (3b) are the same as above, but when q is 0, p is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon number. 6 to 15 aryl group, and when q is 1, p is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms. Indicates. EWG represents cyano group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, 5H-perfluoropentyl group, 6H-perfluorohexyl group, nitro group or methyl group. EWG may be bonded to each other to form a ring of 6 carbon atoms together with the carbon atom to which they are bonded. The skeletons of these oxime sulfonates are disclosed in US Pat. No. 6,261,738, JP-A-9-95479, JP-A-9-208554, JP-A-9-230588, JP-A-2906999, JP-A-9-301948. No. 2000, Japanese Patent Laid-Open No. 2000-314956, Japanese Patent Laid-Open No. 2001-233842, and International Publication No. 2004/074242.

A more specific skeleton of oxime sulfonate excluding the sulfonate moiety is shown below.

  Here, a method for synthesizing the sulfonium salt represented by the general formula (2) will be described as one example of the photoacid generator for generating the sulfonic acid represented by the general formula (1a) of the present invention.

  Triphenylsulfonium 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate synthesized as described below is converted into an aliphatic carboxylic acid halide or aliphatic carboxylic acid having a carboxylic acid ester structure or a lactone structure. By reacting with anhydride, aromatic carboxylic acid halide, aromatic carboxylic acid anhydride, aliphatic dicarboxylic acid anhydride, or aromatic dicarboxylic acid anhydride under basic conditions, carboxylic acid ester structure or lactone structure or carbonyl A sulfonium salt of the above general formula (2) having a group and a carboxyl group can be obtained.

  The sulfonium salt and iodonium salt of the general formulas (2a) and (2b) of the present invention can be synthesized in the same manner as described above.

  When synthesizing the imide sulfonate and oxime sulfonate represented by the above general formulas (3a) and (3b) of the present invention, an imide having a 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate moiety Sulfonates and oxime sulfonates are converted into aliphatic carboxylic acid halides or aliphatic carboxylic acid anhydrides, aromatic carboxylic acid halides or aromatic carboxylic acid anhydrides, aliphatic dicarboxylic acid anhydrides, or aromatics having a carboxylic acid ester structure or a lactone structure. An imide sulfonate or oxime sulfonate having a carboxylic acid ester structure, a lactone structure, a carbonyl group, or a carboxyl group can be obtained by reacting with an aromatic dicarboxylic acid anhydride under basic conditions.

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 and iodonium other than triphenylsulfonium can be carried out in the same manner.

In addition, the synthesis of imide sulfonate and oxime sulfonate having a 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate moiety will be described.
1,1,3,3,3-pentafluoro-2-acyloxypropane sulfonate or 1,1,3,3,3-pentafluoro-2-arenecarbonyloxypropane sulfonate is converted to thionyl chloride, phosphorus oxychloride By reacting with a chlorinating agent such as phosphorus pentachloride, the corresponding sulfonyl chloride or sulfonic acid anhydride is obtained and reacted with N-hydroxydicarboxylimide or an oxime by a conventional method to obtain 1,1,3,3 , 3-pentafluoro-2-acyloxypropane sulfonate or 1,1,3,3,3-pentafluoro-2-arenecarbonyloxypropane sulfonate. Subsequent hydrolysis of the acyloxy group or arenecarbonyloxy group yields the desired intermediate raw material imide sulfonate or oxime sulfonate having a 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate moiety. be able to.

  The raw material sulfonium salt and iodonium salt are described in The Chemistry of sulfone group Part 1 John-Wiley & Sons (1981), Advanced Photochemistry, vol. 17 John-Wiley & Sons (1992); Org. Chem. , 1988.8.53.5571-5573, or JP-A-8-311018, JP-A-9-15848, JP-A-2001-122850, JP-A-7-25846, JP-A-2001-181221, The compound can be synthesized with reference to Japanese Unexamined Patent Publication No. 2002-193887 and Japanese Patent Application Laid-Open No. 2002-193925. In addition, an onium cation having an acryloyloxy group or a methacryloyloxy group as a polymerizable substituent can be obtained by converting an existing hydroxyphenyldiphenylsulfonium halide by a method described in JP-A-4-230645, JP-A-2005-84365, or the like. It can be synthesized by reacting with acryloyl chloride or methacryloyl chloride under basic conditions.

  The synthesis of imide sulfonate and oxime sulfonate is described in JP-A No. 2003-252855, US Pat. No. 6,261,738, JP-A No. 9-95479, JP-A No. 9-208554, and JP-A No. 9-230588. No. 2,906,999, JP-A-9-301948, JP-A-2000-314956, JP-A-2001-233842, and WO 2004/074242.

  The present invention firstly provides a photoacid generator for a chemically amplified resist material that generates the sulfonic acid represented by the general formula (1a) by high energy ray irradiation. Secondly, sulfonium salts, iodonium salts, dicarboxylimide sulfonates and oxime sulfonates useful as photoacid generators for chemically amplified resist materials are provided, and thirdly, the above general formula ( Provided is a resist material containing a photoacid generator for a chemically amplified resist material that generates a sulfonic acid represented by 1a) and a resin whose solubility in an alkaline developer is changed by the action of an acid.

Here, the resist material of the present invention is:
(A) the photoacid generator (that is, the photoacid generator that generates the sulfonic acid of formula (1a)),
(B) an organic solvent,
(C) a base resin whose solubility in an alkaline developer is changed by the action of an acid,
(D) quencher, if necessary
If necessary, (E) a photoacid generator other than the photoacid generator,
If necessary, (F) an organic acid derivative and / or a fluorine-substituted alcohol,
Furthermore, (G) a chemically amplified positive resist material characterized by containing a dissolution inhibitor having a weight average molecular weight of 3,000 or less, if necessary,
Or (A) the photoacid generator,
(B) an organic solvent,
(C ′) an alkali-soluble resin, which is hardly soluble in alkali by a crosslinking agent,
(H) a crosslinking agent that crosslinks with an acid,
(D) quencher, if necessary
If necessary, (E) a chemically amplified negative resist material containing a photoacid generator other than the photoacid generator.

  The photoacid generator of the component (A) of the present invention is as described above. More specifically, the compound of the general formula (2), (2a), (2b), (3a) or (3b) is The compounding quantity is 0.1-10 parts with respect to 100 parts (parts by mass, the same applies hereinafter) of the base resin in the resist material, particularly 1-7 parts.

  The organic solvent of the component (B) 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, cyclohexanone and a mixed solvent thereof, which have the highest solubility of the acid generator in the resist component, are preferably used. Is done.

  The amount of the organic solvent used is preferably 200 to 3,000 parts, particularly 400 to 2,000 parts, based on 100 parts of the base resin.

The base resin of component (C) or component (C ′) used in the present invention is polyhydroxystyrene (PHS), PHS and styrene, (meth) acrylic acid ester, and other polymerizations for KrF excimer laser resist materials. Copolymers with functional olefin compounds, ArF excimer laser resist materials, poly (meth) acrylic acid esters, alternating copolymers of cycloolefin and maleic anhydride, and further vinyl ethers or (meth) acrylic acid Examples include ester-containing copolymer systems, polynorbornene systems, cycloolefin ring-opening metathesis polymerization systems, cycloolefin ring-opening metathesis polymer hydrogenated products, etc., and fluorine of the above KrF and ArF polymers for F ₂ excimer laser resist materials Substituents, etc. are mentioned, but these polymerized poly It is not limited to chromatography. Furthermore, the sulfonium salt and iodonium salt of the present invention having a polymerizable substituent, specifically, (4-acryloyloxyphenyl) diphenylsulfonium cation, (4-methacryloyloxyphenyl) diphenylsulfonium cation, (4-acryloyloxyphenyl) Sulfonium salts, iodonium by combinations of onium cations such as phenyliodonium cation and (4-methacryloyloxyphenyl) phenyliodonium cation and anions such as hydrogen cyclohexanedicarboxylate 1- (difluorosulfomethyl) -2,2,2-trifluoroethyl Salts can be used as polymerization components for these base resins. The base resins can be used alone or in combination of two or more. In the case of a positive resist material, the dissolution rate of unexposed areas is generally reduced by substituting phenol or carboxyl groups or hydroxyl groups of fluorinated alkyl alcohols with acid labile groups.

  Although these base resins are not particularly limited, JP 2000-159758 A, JP 2000-186118 A, JP 2000-309611 A, JP 2000-327633 A, JP 2000-2000 A. 330283, JP 2001-329052, JP 2002-202609, JP 2002-161116, JP 2003-2883, JP 2003-20313, JP 2003-26728 Gazette, JP-A-2003-34706, JP-A-2003-64134, JP-A-2003-66612, JP-A-2003-113213, JP-A-2003-316027, JP-A-2003-321466, Japanese Unexamined Patent Application Publication Nos. 2004-143153 and 2004-2004 24082, JP 2004-115486 and JP include those described in JP-A-2004-62175.

  In this case, in particular, the base resin is poly (meth) acrylic acid and derivatives thereof, cycloolefin derivative-maleic anhydride alternating polymer, cycloolefin derivative, maleic anhydride, polyacrylic acid or derivatives thereof, or three or four or more elements. One or more selected from the following copolymers, cycloolefin derivatives-α-trifluoromethylacrylic acid derivative copolymer, polynorbornene, ring-opening metathesis polymer, and ring-opening metathesis polymer hydrogenated product A high molecular polymer is preferred.

The base resin is preferably a polymer structure containing a silicon atom or a polymer structure containing a fluorine atom.
These are disclosed in JP-A-2005-8765, JP-A-2004-354417, JP-A-2004-352743, JP-A-2004-331854, JP-A-2004-331853, and JP-A-2004-292781. JP-A-2004-252405, JP-A-2004-190036, JP-A-2004-115762, JP-A-2004-83873, JP-A-2004-59844, JP-A-2004-35671, JP-A-2004-83900, JP-A-2004-99689, JP-A-2004-145048, JP-A-2004-217533, JP-A-2004-231815, JP-A-2004-244439, JP-A-2004 JP-A-256562, JP-A-2004-30744 , JP 2004-323422, JP 2005-29527 JP include those described, for example, in JP-A-2005-29539.

  As described above, in the case of a chemically amplified positive resist material, the base resin has an acid labile group, is insoluble or hardly soluble in the developer, and the acid labile group is decomposed by the acid. Those that are soluble in the developer are used. In this case, the acid labile group of the base resin is variously selected. In particular, the acetal group having 2 to 30 carbon atoms and the tertiary alkyl group having 4 to 30 carbon atoms represented by the following formulas (C1) and (C2): Etc.

In the above formulas (C1) and (C2), R ²⁰¹ and R ²⁰² are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a heteroatom such as oxygen, sulfur, nitrogen or fluorine. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ may be a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a 7 to 10 carbon atom. An aralkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen and fluorine. R ²⁰¹ and R ²⁰² , R ²⁰¹ and R ²⁰³ , R ²⁰² and R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ , R ²⁰⁴ and R ²⁰⁶ , R ²⁰⁵ and R ²⁰⁶ are bonded to each other. A ring having 3 to 30 carbon atoms may be formed together with oxygen atoms.

  Specific examples of the acetal group represented by the formula (C1) include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, isopropoxymethyl group, t-butoxymethyl group, 1-methoxyethyl group, 1 -Methoxypropyl group, 1-methoxybutyl group, 1-ethoxyethyl group, 1-ethoxypropyl group, 1-ethoxybutyl group, 1-propoxyethyl group, 1-propoxypropyl group, 1-propoxybutyl group, 1-cyclopentyl Oxyethyl group, 1-cyclohexyloxyethyl group, 2-methoxyisopropyl group, 2-ethoxyisopropyl group, 1-phenoxyethyl group, 1-benzyloxyethyl group, 1-phenoxypropyl group, 1-benzyloxypropyl group, 1 -Adamantyloxyethyl group, 1-adamantyloxy Propyl group, 2-tetrahydrofuryl group, 2-tetrahydro-2H-pyranyl group, 1- (2-cyclohexanecarbonyloxyethoxy) ethyl group, 1- (2-cyclohexanecarbonyloxyethoxy) propyl group, 1- [2- ( Examples thereof include, but are not limited to, 1-adamantylcarbonyloxy) ethoxy] ethyl group and 1- [2- (1-adamantylcarbonyloxy) ethoxy] propyl group.

Specific examples of the tertiary alkyl group represented by the above formula (C2) include t-butyl group, t-pentyl group, 1-ethyl-1-methylpropyl group, 1,1-diethylpropyl group, 1,1, 2-trimethylpropyl group, 1-adamantyl-1-methylethyl group, 1-methyl-1- (2-norbornyl) ethyl group, 1-methyl-1- (tetrahydrofuran-2-yl) ethyl group, 1-methyl- 1- (7-oxanalbornan-2-yl) ethyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-propylcyclopentyl group, 1-cyclopentylcyclopentyl group, 1-cyclohexylcyclopentyl group, 1- (2 -Tetrahydrofuryl) cyclopentyl group, 1- (7-oxanalbornan-2-yl) cyclopentyl group, 1-methylcyclo Xyl group, 1-ethylcyclohexyl group, 1-cyclopentylcyclohexyl group, 1-cyclohexylcyclohexyl group, 2-methyl-2-norbornyl group, 2-ethyl-2-norbornyl group, 8-methyl-8-tricyclo [5.2 .1.0 ^2,6 ] decyl group, 8-ethyl-8-tricyclo [5.2.1.0 ^2,6 ] decyl group, 3-methyl-3-tetracyclo [4.4.0.1 ^{2, 5,} 1 ^7,10] dodecyl group, 3-ethyl-3-tetracyclo [4.4.0.1 ^{2, 5,} 1 ^7,10] dodecyl group, 2-methyl-2-adamantyl group, 2-ethyl - 2-adamantyl group, 1-methyl-3-oxo-1-cyclohexyl group, 1-methyl-1- (tetrahydrofuran-2-yl) ethyl group, 5-hydroxy-2-methyl-2-adamantyl group, 5-hydroxy -2-ethyl Although a 2-adamantyl group can be illustrated, it is not limited to these.

  Further, 1 mol% or more of the hydrogen atoms of the hydroxyl group of the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the following general formula (C3a) or (C3b).

In said formula, R ^<207> , R ^<208> shows a hydrogen atom or a C1-C8 linear, branched or cyclic alkyl group. R ²⁰⁷ and R ²⁰⁸ may be bonded to form a ring together with the carbon atom to which they are bonded. In the case of forming a ring, R ²⁰⁷ and R ²⁰⁸ are linear or branched having 1 to 8 carbon atoms. An alkylene group is shown. ^R209 is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and b is 0 or an integer of 1 to 10. A represents an a + 1 valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may intervene a heteroatom, or A part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—. a is an integer of 1-7.

  Specific examples of the crosslinked acetal represented by the general formulas (C3a) and (C3b) include the following formulas (C3-1) to (C3-8), but are not limited thereto.

  The polystyrene-based weight average molecular weight of the base resin by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, and if it is less than 2,000, the film formability and resolution are poor. If it exceeds 100,000, the resolution may be inferior, or foreign matter may be generated during pattern formation.

  The ratio of the monomer unit containing an acid labile group to the monomer unit (structural unit) of these base resins is 1 to 70%, preferably 20 to 60% as a molar ratio in the base resin for ArF excimer laser resist material. In the base resin for the KrF excimer laser resist material, it is 1 to 50%, preferably 20 to 40%.

  As monomer units other than the above-mentioned monomer units containing acid labile groups, base resins for ArF excimer laser resist materials include polar resins such as alcohols, fluorine-substituted alcohols, ethers, lactones, esters, acid anhydrides, and carboxylic acids. It is preferable that a monomer unit containing a group is introduced. Further, styrene, indene, 4-acetoxystyrene or the like may be introduced into the base resin for the KrF excimer laser resist material in addition to the 4-hydroxystyrene unit into which no acid labile group has been introduced. These monomer units are preferably introduced in one kind or two or more kinds.

  As the quencher of the component (D), a compound capable of suppressing the diffusion rate when the acid generated from the photoacid generator diffuses into the resist film is suitable. By blending such a quencher, In addition to easy adjustment of resist sensitivity, the diffusion rate of acid in the resist film is suppressed to improve resolution, suppress sensitivity changes after exposure, reduce substrate and environmental dependence, and expose A margin, a pattern profile, etc. 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, amide derivatives, imide derivatives, carbamate derivatives, 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 and the like, secondary aliphatic amines include 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 include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like can be mentioned. It is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives such as 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, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 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, 1 H-indazole derivatives, indoline derivatives, quinoline derivatives (eg, 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-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, examples of nitrogen-containing compounds having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like, Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, 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, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Can be mentioned.

  Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, maleimide and the like. Examples of the carbamate derivative include N-tert-butoxycarbonyl-N, N-dicyclohexylamine, N-tert-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-triisopropylbenzenesulfonate, tetrabutyl Ammonium = 2,4,6-triisopropylbenzenesulfonate, benzyltrimethylammonium = 2,4,6-triisopropylbenzenesulfonate, tetramethylammonium acetate, tetrabutylammonium acetate, benzyltrimethylammonium acetate, tetramethylammonium = Benzoate, tetrabutylammonium benzoate And benzyl trimethylammonium = benzoate and the like.

（式中、ｋは１、２又は３である。側鎖Ｒｘは同一でも異なっていてもよく、下記一般式（Ｒｘ−１）、（Ｒｘ−２）又は（Ｒｘ−３）で表すことができる。側鎖Ｒｙは同一又は異種の、水素原子、又は直鎖状、分岐状又は環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炭素数１〜２０のアルキル基を示し、エーテル基もしくはヒドロキシル基を含んでもよい。また、Ｒｘ同士が結合して環を形成してもよい。） Furthermore, 1 type, or 2 or more types chosen from the amine compound shown by the following general formula (Am-1) can also be added.

(In the formula, k is 1, 2 or 3. The side chains Rx may be the same or different and may be represented by the following general formula (Rx-1), (Rx-2) or (Rx-3). The side chain Ry can be the same or different, a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms in which some or all of linear, branched or cyclic hydrogen atoms may be substituted with fluorine atoms. And may contain an ether group or a hydroxyl group, and Rx may combine with each other to form a ring.)

（式中、Ｒ³⁰¹、Ｒ³⁰³、Ｒ³⁰⁶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、Ｒ³⁰²、Ｒ³⁰⁵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、エステル基又はラクトン環を１あるいは複数含んでいてもよい。Ｒ³⁰⁴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、Ｒ³⁰⁷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、エステル基又はラクトン環を１あるいは複数含んでいてもよい。）

(In the formula, R ³⁰¹ , R ³⁰³ , and R ³⁰⁶ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰² and R ³⁰⁵ are hydrogen atoms, and some or all of the hydrogen atoms are fluorine atoms. in substituted carbon atoms and optionally 1 to 20 linear, branched or cyclic alkyl group, hydroxy group, an ether group, an ester group, or may contain one or more lactone rings .R ³⁰⁴ Is a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁷ is a linear chain having 1 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms. A branched, cyclic or cyclic alkyl group, which may contain one or a plurality of hydroxy groups, ether groups, ester groups or lactone rings.)

  Specific examples of the compound represented by the general formula (Am-1) include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, and tris {2- (2-methoxy). Ethoxymethoxy) 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- Azabicyclooctadecane, 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, tri [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-methoxyethoxycarbo) Nyl) 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 Bis (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-formylo) Ciethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2- Acetoxyethyl) 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-butyl Bis [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, but are not limited to, carbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone. Not.

（式中、Ｒｘは前述の通り、Ｒ³⁰⁸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, 1 type, or 2 or more types of the amine compound which has the cyclic structure shown by the following general formula (Am-2) can also be added.

(In the formula, Rx is as described above, and R ³⁰⁸ 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, and a carbonyl group. , One or more ether groups, ester groups or sulfides may be included.)

  Specific examples of the compound represented by the general formula (Am-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} Tylmorpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, methoxyacetate 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-morpho Ethyl nopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 3- (1-pyrrolidinyl) propionic acid 2 -Oxotetrahydrofuran-3-yl, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-pyrrolidinyl) propionic acid 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-pyro Methyl lysinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate, 2-morpholinoethyl 2-methoxyacetate, 2- (2-methoxyethoxy) acetic acid 2- Morpholinoethyl, 2- [2- (2-methoxyethoxy) ethoxy] acetate 2-morpholinoethyl, 2-morpholinoethyl hexanoate, 2-morpholinoethyl octoate, 2-morpholinoethyl decanoate, 2-morpholinoethyl laurate, Examples include 2-morpholinoethyl myristate, 2-morpholinoethyl palmitate, 2-morpholinoethyl stearate, 2-morpholinoethyl cyclohexanecarboxylate, and 2-morpholinoethyl adamantanecarboxylate.

（式中、Ｒｘ、Ｒ³⁰⁸、ｋは前述の式（Ａｍ−１）の通り、Ｒ³⁰⁹、Ｒ³¹⁰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, an amine compound containing a cyano group represented by the following general formulas (Am-3) to (Am-6) can be added.

(Wherein, Rx, R ^308, k is the aforementioned formula (Am-1 as), R ^309, R ³¹⁰ represents a linear or branched alkylene group of 1 to 4 carbon atoms the same or different. )

  Specific examples of amine compounds containing a cyano group include 3- (diethylamino) propiononitrile, 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-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3 Methyl 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-formyloxyethyl) -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-aminopropiononitrile, 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] aminoacetonitrile, N-cyanomethyl-N- (2-me Methyl toxiethyl) -3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate, 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) aminoacetonitrile N- (3-acetoxy-1-propyl Pyr) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1- Piperidine propiononitrile, 4-morpholine propiononitrile, 1-pyrrolidine acetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) -3-aminopropion Cyanomethyl acid, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2- Meto Cyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 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), cyanomethyl 1-pyrrolidinepropionate, 1-piperidinepropiate Examples thereof include cyanomethyl onate, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), and 4-morpholine propionic acid (2-cyanoethyl).

（式中、Ｒ³¹¹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、アセタール基のいずれかを１個あるいは複数個含む。Ｒ³¹²、Ｒ³¹³、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。） Furthermore, an amine compound having an imidazole skeleton and a polar functional group represented by the following general formula (Am-7) can be added.

(In the formula, R ³¹¹ 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; The polar functional group includes one or more of a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, a cyano group, and an acetal group, wherein R ³¹² , R ³¹³ and R ³¹⁴ are a hydrogen atom, (It is a linear, branched or cyclic alkyl group, aryl group or aralkyl group having 1 to 10 carbon atoms.)

（式中、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、カーボネート基のいずれかを一つ以上含んでいてもよい。Ｒ³¹⁶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 a benzimidazole skeleton and a polar functional group represented by the following general formula (Am-8) can be added.

(Wherein R ³¹⁵ is an alkyl group having a linear, branched or cyclic polar functional group having 1 to 20 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms, and polar functional group as an ester group, an acetal group includes cyano group one or more other a hydroxyl group, a carbonyl group, an ether group, a sulfide group, an .R ³¹⁶ also include one or more of any of the carbonate groups is a hydrogen atom A linear, branched or cyclic alkyl group, aryl group or aralkyl group having 1 to 10 carbon atoms.)

（式中、Ｊは窒素原子又は≡Ｃ−Ｒ³²³である。Ｋは窒素原子又は≡Ｃ−Ｒ³²⁴である。Ｒ³¹⁷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。Ｒ³¹⁸、Ｒ³¹⁹、Ｒ³²⁰、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か、又はＲ³¹⁸とＲ³¹⁹、Ｒ³²⁰とＲ³²¹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。Ｒ³²²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。Ｒ³²³、Ｒ³²⁴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とＲ³²⁴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, a nitrogen-containing heterocyclic compound having a polar functional group represented by the following general formulas (Am-9) and (Am-10) can be added.

(Wherein J is a nitrogen atom or ≡C—R ^323. K is a nitrogen atom or ≡C—R ^324. R ³¹⁷ may have a hydrogen atom partially or entirely substituted with a fluorine atom. An alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms, and the polar functional group includes a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, and a cyano group. Or at least one acetal group, wherein R ³¹⁸ , R ³¹⁹ , R ³²⁰ , and R ³²¹ are a hydrogen atom, a linear, branched or cyclic alkyl group or aryl group having 1 to 10 carbon atoms, or R ³¹⁸ and R ³¹⁹ , R ³²⁰ and R ³²¹ may be bonded to each other to form a benzene ring, naphthalene ring or pyridine ring, and R ³²² is a hydrogen atom, a linear, branched or cyclic group having 1 to 10 carbon atoms. an alkyl or aryl group .R ³²³ R ³²⁴ is a hydrogen atom, a straight, branched or cyclic alkyl group or .R ³²² and R ³²⁴ is an aryl group may form a benzene or naphthalene ring. )

（式中、Ｒ³²⁵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。Ｒ³²⁶はＣＯ₂Ｒ³²⁷、ＯＲ³²⁸又はシアノ基である。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のアルキル基である。Ｒ³²⁸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。Ｒ³²⁹は単結合、メチレン基、エチレン基、硫黄原子又は−Ｏ（ＣＨ₂ＣＨ₂Ｏ）_h−基である。ｈ＝０，１，２，３又は４である。Ｒ³³⁰は水素原子、メチル基、エチル基又はフェニル基である。Ｔは窒素原子又はＣＲ³³¹である。Ｕは窒素原子又はＣＲ³³²である。Ｖは窒素原子又はＣＲ³³³である。Ｒ³³¹、Ｒ³³²、Ｒ³³³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Ｒ³³¹とＲ³³²又はＲ³³²とＲ³³³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, an amine compound having an aromatic carboxylic acid ester structure represented by the following general formulas (Am-11) to (Am-14) can be added.

(In the formula, R ³²⁵ is an aryl group having 6 to 20 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms, and part or all of the hydrogen atoms are halogen atoms, straight chain having 1 to 20 carbon atoms. , Branched or cyclic alkyl group, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkoxy group having 1 to 10 carbon atoms, acyloxy group having 1 to 10 carbon atoms, or carbon number R ³²⁶ may be CO ₂ R ³²⁷ , OR ³²⁸ or cyano group, and R ³²⁷ may be a carbon number in which some methylene groups may be substituted with oxygen atoms. R ³²⁸ is an alkyl group having 1 to 10 carbon atoms or an acyl group in which some methylene groups may be substituted with oxygen atoms, R ³²⁹ is a single bond, a methylene group, ethylene, sulfur atom or _{-O (CH 2 CH 2 O)} h -Group, h = 0, 1, 2, 3 or 4. R ³³⁰ is a hydrogen atom, methyl group, ethyl group or phenyl group, T is a nitrogen atom or CR ³³¹ , U is a nitrogen atom Or CR ³³² , V is a nitrogen atom or CR ^333. R ³³¹ , R ³³² and R ³³³ are each independently a hydrogen atom, a methyl group or a phenyl group, or R ³³¹ and R ³³² or R ³³² and R ³³³ may combine to form an aromatic ring having 6 to 20 carbon atoms or a heteroaromatic ring having 2 to 20 carbon atoms.

（式中、Ｒ³³⁴は水素又は炭素数１〜１０の直鎖状、分枝状又は環状のアルキル基である。Ｒ³³⁵及びＲ³³⁶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。Ｒ³³⁵とＲ³³⁶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 (Am-15) can be added.

Wherein R ³³⁴ is hydrogen or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. R ³³⁵ and R ³³⁶ 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 ³³⁵ and R ³³⁶ may combine with each other to form a C 2-20 heterocycle or heteroaromatic ring.

  In addition, these quenchers can be used individually by 1 type or in combination of 2 or more types, and a compounding quantity is 0.001-2 parts with respect to 100 parts of base resins, Especially 0.01-1 part is preferable. If the blending amount is less than 0.001 part, there is no blending effect, and if it exceeds 2 parts, the sensitivity may be too low.

  In addition to the photoacid generator of the formula (1a) of the present invention, when the photoacid generator of component (E) is added, ultraviolet rays, far ultraviolet rays, electron beams, EUV, X-rays, excimer lasers, γ rays Any compound that generates an acid upon irradiation with high energy rays such as synchrotron radiation may be used. Suitable photoacid generators include photoacid generators such as sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxydicarboximide, O-arylsulfonyloxime, O-alkylsulfonyloxime, and the like. Although described in detail below, these can be used alone or in admixture 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, bis (substituted alkylsulfonyl) imide, or tris (substituted alkylsulfonyl) methide. As the iodonium cation, diphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4-tert- Examples include butoxyphenylphenyliodonium, 4-methoxyphenylphenyliodonium, and the sulfonates include trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, tridecafluorohexanesulfonate, and perfluoro (4-ethyl). Cyclohexane) sulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroe 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, dodecylbenzenesulfate Nate, 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 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) 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 tris (substituted alkylsulfonyl) methides. And tris (trifluoromethylsulfonyl) methide, and combinations of these iodonium salts.

  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 dicarboximide, phthalic imide, cyclohexyl dicarboximide, 5-norbornene-2,3-dicarboximide, 7-oxabicyclo [ 2.2.1] Imido skeletons such as -5-heptene-2,3-dicarboximide and 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 trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, 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 Phonate, 2- (1-adamantanecarbonylcarbonyl) -1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 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-pentafluoropropanesulfonate, 2- (1-adamantanecarbonylcarbonyl) -1,1,3,3,3-pentafluoropropanesulfonate, 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, and a bisoxime sulfonate type.

  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) ) Oxiimino-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、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 or halobenzenesulfonyl group having 1 to 10 carbon atoms. 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- Pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 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-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 And acetonitrile, bis (α- (4-methoxybenzenesulfonyloxy) imino) -m-phenylene diacetonitrile, and the like, and 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate 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 (E) is used as a resist material for KrF excimer laser, sulfonium salts, bissulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate are preferred. 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 (E) component as a resist material for ArF excimer lasers, 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 (E) component as an ArF immersion resist material, 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 addition amount of the photoacid generator of the component (E) in 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, but is 0 with respect to 100 parts of the base resin in the resist material. -10 parts, and when blended, it is 0.1 to 10 parts, preferably 0.1 to 5 parts. When the proportion of the photoacid generator of the component (E) 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 (E) 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 addition.

When two or more photoacid generators are used in combination, and one of the photoacid generators is an onium salt that generates a so-called weak acid, a function of acid diffusion control can be provided. That is, when a photoacid generator that generates a strong acid (for example, fluorine-substituted sulfonic acid) and an onium salt that generates a weak acid (for example, a sulfonic acid or carboxylic acid that is not fluorine-substituted) are mixed and used, When a strong acid generated from a photoacid generator upon irradiation 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 for 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.

  In addition, a compound capable of decomposing with an acid to generate an acid (acid-growing compound) may be added to the resist material of the present 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 and 2-phenyl-2- (2-tosyloxyethyl) -1,3-dioxolane. 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 the diffusion, resulting in degradation of resolution and pattern shape.

  Examples of the organic acid derivative as the component (F) are not particularly limited, but specifically, phenol, cresol, catechol, resorcinol, pyrogallol, phloroglysin, bis (4-hydroxyphenyl) methane, 2, 2-bis (4′-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-hydroxyphenyl) ) Ethane, hydroxybenzophenone, 4-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 2-hydroxyphenylacetic acid, 3- (4-hydroxyphenyl) propionic acid, 3- (2-hydroxyphenyl) propionic acid, 2,5- Dihydroxyphenylacetic acid, 3,4-dihydroxyphenylacetic acid, 1 2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, 1,2-phenylenedioxydiacetic acid, 1,4-phenylenedipropanoic acid, benzoic acid, salicylic acid, 4,4- Bis (4′-hydroxyphenyl) valeric acid, 4-tert-butoxyphenylacetic acid, 4- (4-hydroxyphenyl) butyric acid, 3,4-dihydroxymandelic acid, 4-hydroxymandelic acid, and the like. Among them, salicylic acid, 4,4-bis (4′-hydroxyphenyl) valeric acid is preferred. These can be used alone or in combination of two or more.

  In addition, as the fluorine-substituted alcohol, a compound in which other than the α-position of the alcohol is substituted with fluorine can be used, and is not particularly limited. A compound having a 2-propanol end is desirable. Specifically, the following compounds can be exemplified.

  However, R ′ in the above formula is an acetal group having 2 to 30 carbon atoms, a tertiary alkyl group having 4 to 30 carbon atoms, or the like represented by the formulas (C1) and (C2) described in the above base resin. is there.

  The addition amount of the organic acid derivative or fluorine-substituted alcohol in the chemically amplified resist material of the present invention is 5 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 more than 5 parts, resolution may be deteriorated. The organic acid derivative or the like may not be added depending on the combination of the compositions in the resist.

  (G) As a compound (dissolution inhibitor) having a weight average molecular weight of 3,000 or less whose solubility in an alkali developer is changed by the action of an acid, a low molecular weight phenol or carboxylic acid derivative of 2,500 or less, A compound in which some or all of the hydrogen atoms of the hydroxyl group of the fluorine-substituted alcohol are substituted with an acid-labile substituent can be added.

  The phenol or carboxylic acid derivative having a weight average molecular weight of 2,500 or less includes bisphenol A, bisphenol H, bisphenol S, 4,4-bis (4′-hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1 , 1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-hydroxyphenyl) ethane, phenolphthalein, thymolphthalein, cholic acid, deoxycholic acid, lithocholic acid, etc. Examples of the fluorine-substituted alcohol include the same compounds as those specifically exemplified as the compounds having 1,1,1,3,3,3-hexafluoro-2-propanol ends. Examples of the acid labile substituent include those exemplified as the acid labile group of the polymer.

  Examples of suitably used dissolution inhibitors include bis (4- (2′-tetrahydropyranyloxy) phenyl) methane, bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert -Butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1'-ethoxyethoxy) phenyl) methane, bis ( 4- (1′-ethoxypropyloxy) phenyl) methane, 2,2-bis (4 ′-(2 ″ -tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 ″-) Tetrahydrofuranyloxy) phenyl) propane, 2,2-bis (4′-tert-butoxyphenyl) propane, 2 2-bis (4′-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) ) Phenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) valeric acid tert-butyl, 4-tert-butyl 4,4-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) valerate, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, Tert-Butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate, 4,4-bis (4′-tert-butyl) Xycarbonylmethyloxyphenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 ″) -Ethoxypropyloxy) phenyl) tert-butylvalerate, tris (4- (2'-tetrahydropyranyloxy) phenyl) methane, tris (4- (2'-tetrahydrofuranyloxy) phenyl) methane, tris (4- tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1, 1,2-tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1 , 2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyl) Methyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane And cholic acid tert-butyl ester, deoxycholic acid tert-butyl ester, lithocholic acid tert-butyl ester, and the like. Or the compound of Unexamined-Japanese-Patent No. 2003-107706 is mentioned.

  The addition amount of the dissolution inhibitor of the component (G) in the resist material of the present invention is 20 parts or less, preferably 15 parts or less with respect to 100 parts of the base resin in the resist material. If it exceeds 20 parts, the monomer component increases, so the heat resistance of the resist material decreases.

  The (C ′) component alkali-soluble resin used in the negative resist material of the present invention, which is hardly alkali-soluble by a crosslinking agent, includes an acid labile group of the above-mentioned resin (C). It is preferable to use a base resin before substitution.

  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.

  Moreover, in order to give various functions, you may introduce | transduce a substituent into a part of phenolic hydroxyl group of the said acid labile group protection polymer, and a carboxyl group. For example, a substituent for improving adhesion to the substrate and a substituent for improving etching resistance, particularly an acid for controlling the dissolution rate in an alkaline developer of an unexposed part and a low-exposed part to be not too high. It is preferable to introduce a relatively stable substituent into alkali or alkali. Examples of the substituent include, for example, 2-hydroxyethyl group, 2-hydroxypropyl group, methoxymethyl group, methoxycarbonyl group, ethoxycarbonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 4-methyl-2-oxo-4 -Oxolanyl group, 4-methyl-2-oxo-4-oxanyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, acetyl group, pivaloyl group, adamantyl group, Examples thereof include, but are not limited to, an isobornyl group and a cyclohexyl group. In addition, an acid-decomposable substituent such as a tert-butoxycarbonyl group, a tert-butyl group, or a tert-butoxycarbonylmethyl group can be introduced.

  The addition amount of the resin of the component (C ′) in the resist material of the present invention is arbitrary, but it is 65 to 99 parts, preferably 65 to 98 parts with respect to 100 parts of the total solid content in the resist material.

  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 acid crosslinking agent as the component (H) 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.

  In the chemically amplified resist material of the present invention, additives such as a surfactant for improving coatability and a light-absorbing material for reducing irregular reflection from the substrate can be added.

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, Sorbitan fatty acid esters such as polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers, 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, Surfynol E1004, KH-20, and KH-30 are preferred. 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.

  Furthermore, an ultraviolet absorber can be blended with the chemically amplified resist material of the present invention. Although not particularly limited, those described in JP-A-11-190904 can be used, and preferably bis (4-hydroxyphenyl) sulfoxide, bis (4-tert-butoxyphenyl) sulfoxide, bis (4 -Tert-butoxycarbonyloxyphenyl) sulfoxide, diaryl sulfoxide derivatives such as bis [4- (1-ethoxyethoxy) phenyl] sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-tert-butoxyphenyl) sulfone, bis Diarylsulfone derivatives such as (4-tert-butoxycarbonyloxyphenyl) sulfone, bis [4- (1-ethoxyethoxy) phenyl] sulfone, bis [4- (1-ethoxypropoxy) phenyl] sulfone, benzoquinonediazide, Diazo compounds such as phtoquinone diazide, anthraquinone diazide, diazofluorene, diazotetralone, diazophenanthrone, complete or partial naphthoquinone-1,2-diazide-5-sulfonic acid chloride and 2,3,4-trihydroxybenzophenone Ester compounds, quinonediazide group-containing compounds such as complete or partial ester compounds of naphthoquinone-1,2-diazide-4-sulfonic acid chloride and 2,4,4′-trihydroxybenzophenone, etc., tert-butyl 9-anthracenecarboxylate , 9-anthracenecarboxylic acid tert-amyl, 9-anthracenecarboxylic acid tert-methoxymethyl, 9-anthracenecarboxylic acid tert-ethoxyethyl, 9-anthracenecarboxylic acid 2-tert-tetrahydropyra Le, can be mentioned 9-anthracene carboxylic acid 2-tert-tetrahydrofuranyl and the like.

  The blending amount of the ultraviolet absorber may or may not be added depending on the type of the resist material, but when added, it is 0 to 10 parts, more preferably 0.5 to 10 parts with respect to 100 parts of the base resin. Parts, more preferably 1 to 5 parts.

In order to form a pattern using the chemically amplified resist material of the present invention, a known lithography technique can be employed, for example, a substrate for manufacturing an integrated circuit (Si, SiO ₂ , SiN, SiON, TiN). , WSi, BPSG, SOG, organic antireflective coating, etc.) or substrate for mask circuit production (Cr, CrO, CrON, MoSi, etc.), spin coat, roll coat, flow coat, dip coat, spray coat, doctor coat It is applied so as to have a coating film thickness of 0.1 to 2.0 μm by an appropriate application method such as 60 to 150 ° C. for 1 to 10 minutes, preferably 80 to 140 ° C. for 1 to 5 minutes on a hot plate. Pre-bake. Next, the target pattern is exposed through a predetermined mask at a light source selected from ultraviolet rays, far ultraviolet rays, electron beams, EUV, X-rays, excimer lasers, γ rays, synchrotron radiation, etc., preferably at an exposure wavelength of 300 nm or less. .

Among these, more preferable light sources include excimer lasers, particularly KrF excimer lasers, deep ultraviolet rays of 245 to 255 nm, and ArF excimer lasers. It is preferable to expose so that the exposure amount is about 1 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² . Post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably at 80 to 140 ° C. for 1 to 3 minutes.

  Further, 0.1 to 5% by weight, preferably 2 to 3% by weight, using an aqueous developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes The target pattern is formed on the substrate by development by a conventional method such as a dip method, a paddle method, or a spray method.

The resist material of the present invention is particularly suitable for fine patterning by far ultraviolet rays of 254 to 193 nm, vacuum ultraviolet rays of 157 nm, electron beams, X-rays, excimer lasers, γ rays and synchrotron radiation among high energy rays. . In addition, when deviating from the upper limit and the lower limit of the above range, the target pattern may not be obtained.
In the present invention, in particular, an immersion lithography method in which an ArF excimer laser having a wavelength of 193 nm is used during exposure and a liquid such as water, glycerin, or ethylene glycol is inserted between the substrate and the projection lens is suitably employed.

  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.

[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 Same as Synthesis Example 1 except that 4-tert-butylbromobenzene was used instead of chlorobenzene of Synthesis Example 1 and the amount of water was increased during extraction. 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 Bis (4-methylphenyl) sulfoxide was used in place of diphenyl sulfoxide in Synthesis Example 1, and 4-chlorotoluene was used in place of chlorobenzene. 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, aging was carried out at room temperature for 3 hours, ice-cooled 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 this 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. It was used for 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 a target aqueous solution of phenacyltetrahydrothiophenium bromide.

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 hydrogen sulfite 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 [white 5.85 g of 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 2-hydroxy-1,1,3,3,3-pentafluoropropane-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 sulfonium salts prepared in Synthesis Examples 2 to 8 were used. These onium salts (PAG2 to PAG8) are shown below.

[Synthesis Example 19] Synthesis of hydrogen of triphenylsulfonium cyclohexane-1,2-dicarboxylate 1- (difluorosulfomethyl) -2,2,2-trifluoroethyl [PAG A]
4.9 g (0.01 mol) of triphenylsulfonium 2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate of Synthesis Example 11 1.0 g (0.01 mol) of triethylamine, N , N-dimethylaminopyridine (0.24 g, 0.002 mol) is dissolved in acetonitrile (20 g), and cis-cyclohexane-1,2-dicarboxylic anhydride (1.85 g, 0.012 mol) is added thereto at 50 ° C. The mixture was heated and stirred for 24 hours. A diluted hydrochloric acid aqueous solution prepared from 2 g of 12 N hydrochloric acid and 20 g of water was added, and then acetonitrile was distilled off under reduced pressure. 50 g of dichloromethane and 20 g of water were added to the residue to separate the organic layer. The organic layer was then washed with 20 g of water, and dichloromethane was distilled off under reduced pressure. Recrystallization purification was performed by adding ether to the residue, followed by filtration and drying to obtain the desired product. 3.8 g of white crystals (59% yield)
The spectrum data of the obtained target object are shown. Nuclear magnetic resonance spectra ( ¹ H-NMR, ¹⁹ F-NMR / DMSO-d ₆ ) are shown in FIGS.

Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
3066, 2940, 2859, 1768, 1733, 1477, 1448, 1371, 1326, 1276, 1251, 1232, 1189, 1166, 1145, 1112, 1074, 995, 750, 682, 642, 503
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
_{^{NEGATIVE M - 383 (CF 3 CH}} (OCO-C 6 H 10 -CO 2 H) CF 2 SO 3 - equivalent)

Synthesis Example 20 Synthesis of triphenylsulfonium bicyclo [2.2.1] heptane-2,3-dicarboxylate cyclohexyl 1- (difluorosulfomethyl) -2,2,2-trifluoroethyl [PAG B]
4.9 g (0.01 mol) of triphenylsulfonium 2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate of Synthesis Example 11 1.0 g (0.01 mol) of triethylamine, N , N-dimethylaminopyridine (0.24 g, 0.002 mol) was dissolved in 20 g of acetonitrile and cooled on ice. 3.4 g (0.012 mol) of 3-cyclohexyloxycarbonylbicyclo [2.2.1] heptane-2-carbonyl chloride was added at a temperature not exceeding 5 ° C., and the mixture was stirred at room temperature for 1 hour. A diluted hydrochloric acid aqueous solution prepared from 1 g of 12 N hydrochloric acid and 10 g of water was added, and then acetonitrile was distilled off under reduced pressure. 100 g of dichloromethane and 20 g of water were added to the residue to separate the organic layer, and then the organic layer was washed with 20 g of water, and dichloromethane was distilled off under reduced pressure. Ether was added to the residue and the separated oil was decanted three times. The oil was dried under reduced pressure to obtain 5.8 g of the desired product as a glassy solid (yield 82%).
The spectrum data of the obtained target object are shown. Nuclear magnetic resonance spectra ( ¹ H-NMR, ¹⁹ F-NMR / DMSO-d ₆ ) are shown in FIGS.

Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
2940, 1762, 1720, 1477, 1448, 1371, 1265, 1251, 1214, 1184, 1116, 1087, 1072, 995, 750, 684, 642, 530
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
NEGATIVE M ^- 383 (equivalent to CF ₃ CH (OCO—C ₇ H ₁₀ —CO ₂ C ₆ H ₁₁ ) CF ₂ SO ₃ ^— )

Synthesis Example 21 Synthesis of triphenylsulfonium hexahydro-3,5-methano-2H-cyclopenta [b] furan-2-oxo-7-carboxylic acid = 1-difluorosulfomethyl-2,2,2-trifluoroethyl [PAG C]
Hexahydro-3,5-methano-2-oxo-2H-cyclopenta [b] furan-7-carboxylic acid instead of 3-cyclohexyloxycarbonylbicyclo [2.2.1] heptane-2-carbonyl chloride of Synthesis Example 20 The target product was obtained as a glassy solid in the same manner as in Synthesis Example 20 except that 2.0 g (0.01 mol) of chloride was used.
The spectrum data of the obtained target object are shown. Nuclear magnetic resonance spectra ( ¹ H-NMR, ¹⁹ F-NMR / DMSO-d ₆ ) are shown in FIGS.

Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
2993, 179, 1477, 1448, 1369, 1315, 1253, 1216, 1186, 1166, 1135, 1101, 1087, 1070, 1035, 995, 983, 950, 840, 750, 684, 640, 578, 551, 522, 501
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
NEGATIVE M ^- 393 (corresponding to CF ₃ CH (OCO—C ₈ H ₉ O ₂ ) CF ₂ SO ₃ ^— )

The structures of [PAG A], [PAG B], and [PAG C] are shown below.

  The cyclohexane-1,2-dicarboxylic acid derivative in the anion part of [PAG A] includes cis and trans. The bicyclo [2.2.1] heptane-2,3-dicarboxylic acid derivative in the anion part of [PAG B] has two endo- and exo, and [PAG C] hexahydro-3,5-methano- The 2H-cyclopenta [b] furan-2-oxo-7-carboxylic acid derivative also has one endo- and exo. From the analysis results, [PAG A], [PAG B], and [PAG C] were all isomer mixtures.

  The photoacid generator of the present invention may be composed of only a single compound or an isomer mixture.

[Synthesis Examples 22 to 42]
[PAG D] to [PAG X] were synthesized in the same manner as in Synthesis Examples 19 to 21 using PAG2 to PAG8 synthesized in Synthesis Examples 12 to 18.

[Synthesis Example 43] Synthesis of triphenylsulfonium 4-adamantanone-1-carboxylic acid = 1- (difluorosulfomethyl) -2,2,2-trifluoroethyl [PAG Y]
4-Adamantanone-1-carboxylic acid synthesized by a reaction with 5-hydroxy-2-adamantanone, sulfuric acid and formic acid was converted to the corresponding carboxylic acid chloride with oxalyl chloride.
4.9 g (0.01 mol) of triphenylsulfonium 2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate of Synthesis Example 11 1.0 g (0.01 mol) of triethylamine, N , N-dimethylaminopyridine (0.24 g, 0.002 mol) was dissolved in 20 g of acetonitrile and cooled on ice. 2.6 g (0.012 mol) of the 4-adamantanone-1-carbonyl chloride described above was added at a temperature not exceeding 5 ° C., and the mixture was stirred at room temperature for 1 hour. A diluted hydrochloric acid aqueous solution prepared from 1 g of 12 N hydrochloric acid and 10 g of water was added, and then acetonitrile was distilled off under reduced pressure. 50 g of dichloromethane, 50 g of methyl isobutyl ketone and 20 g of water were added to the residue, and the organic layer was separated. The organic layer was then washed with 20 g of water, and the solvent was distilled off under reduced pressure. Ether was added to the residue and the separated oil was decanted three times. The oily product was dried under reduced pressure to obtain 4.3 g of the oily desired product (yield 65%).
The spectrum data of the obtained target object are shown. Nuclear magnetic resonance spectra ( ¹ H-NMR, ¹⁹ F-NMR / DMSO-d ₆ ) are shown in FIGS. In ¹ H-NMR, a slight residue of dichloromethane and methyl isobutyl ketone was observed.

Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
2937, 2861, 1758, 1724, 1687, 1477, 1448, 1373, 1326, 1251, 1218, 1186, 1162, 1089, 1074, 1033, 995, 917, 750, 684, 640, 574, 551, 516, 503
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
_{^{NEGATIVE M - 405 ((C 10}} H 13 O-COO) CH (CF 3) CF 2 SO 3 - equivalent)

The structure of [PAG Y] is shown below.

[Synthesis Example 44] Synthesis of triphenylsulfonium phthalate = hydrogen 1- (difluorosulfomethyl) -2,2,2-trifluoroethyl [PAG Z1]
4.9 g (0.01 mol) of triphenylsulfonium 2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate of Synthesis Example 11 was dissolved in 20 g of tetrahydrofuran, and the solution was dissolved in a dry ice / methanol bath. Cooled down. n-Butyllithium hexane solution (0.01 mol) was added, and then 3.0 g (0.02 mol) of phthalic anhydride was added at a temperature not exceeding 5 ° C. and stirred at room temperature for 1 hour. Next, 0.1 g (0.001 mol) of N, N, N ′, N′-tetramethylethylenediamine was added, and the mixture was further stirred for 1 hour. After adding a diluted hydrochloric acid aqueous solution prepared from 1 g of 12 N hydrochloric acid and 10 g of water, tetrahydrofuran was distilled off under reduced pressure. 50 g of dichloromethane, 50 g of methyl isobutyl ketone and 20 g of water were added to the residue, and the organic layer was separated. The organic layer was then washed with 20 g of water, and the solvent was distilled off under reduced pressure. Ether was added to the residue for crystallization, and 3.4 g of the target product was obtained as white crystals (yield 50%).
The spectrum data of the obtained target object are shown. Nuclear magnetic resonance spectra ( ¹ H-NMR, ¹⁹ F-NMR / DMSO-d ₆ ) are shown in FIGS.

Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
3064, 2969, 2935, 1772, 1727, 1477, 1448, 1394, 1371, 1324, 1280, 1259, 1228, 1193, 1168, 1135, 1110, 1079, 993, 906, 777, 754, 748, 684, 642, 580, 553, 522, 503
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
_{^{NEGATIVE M - 377 ((C 7}} H 5 O 2 -COO) CH (CF 3) CF 2 SO 3 - equivalent)

The structure of [PAG Z1] is shown below.

Synthesis Example 45 Synthesis of triphenylsulfonium succinic acid = hydrogen 1- (difluorosulfomethyl) -2,2,2-trifluoroethyl [PAG Z2]
The target product was obtained as white crystals (yield 76%) in the same manner as in Synthesis Example 19 except that succinic anhydride was used in place of the cyclohexane-1,2-dicarboxylic acid anhydride of Synthesis Example 19.
The spectrum data of the obtained target object are shown. Nuclear magnetic resonance spectra ( ¹ H-NMR, ¹⁹ F-NMR / DMSO-d ₆ ) are shown in FIGS.

Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
3093, 3068, 1776, 1733, 1477, 1448, 1421, 1373, 1321, 1276, 1238, 1184, 1170, 1128, 1076, 995, 948, 906, 838, 752, 684, 642, 512, 503
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
_{^{NEGATIVE M - 329 ((C 3}} H 5 O 2 -COO) CH (CF 3) CF 2 SO 3 - equivalent)

The structure of [PAG Z2] is shown below.

[Synthesis Example 46] Synthesis of triphenylsulfonium 3-cyclohexene-1,2-dicarboxylic acid = hydrogen 1- (difluorosulfomethyl) -2,2,2-trifluoroethyl [PAG Z3]
The target product was obtained as white crystals in the same manner as in Synthesis Example 19 except that 3-cyclohexene-1,2-dicarboxylic acid anhydride was used instead of cyclohexane-1,2-dicarboxylic acid anhydride of Synthesis Example 19. Yield 70%).
The spectrum data of the obtained target object are shown. Nuclear magnetic resonance spectra ( ¹ H-NMR, ¹⁹ F-NMR / DMSO-d ₆ ) are shown in FIGS.

Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
3064, 2971, 1768, 1735, 1477, 1448, 1371, 1324, 1274, 1249, 1224, 1189, 1135, 1072, 995, 750, 684, 642, 503
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
_{^{NEGATIVE M - 381 ((C 7}} H 9 O 2 -COO) CH (CF 3) CF 2 SO 3 - equivalent)

The structure of [PAG Z3] is shown below.

[Synthesis Example 47]
Synthesis of triphenylsulfonium 4-cyclohexanonecarboxylic acid = 1- (difluorosulfomethyl) -2,2,2-trifluoroethyl [PAG Z4]
The target product was obtained as an oily substance (yield 69%) in the same manner as in Synthesis Example 43 except that 4-cyclohexanone carbonyl chloride was used instead of 4-adamantanone-1-carbonyl chloride in Synthesis Example 43.
The spectrum data of the obtained target object are shown. Nuclear magnetic resonance spectra ( ¹ H-NMR, ¹⁹ F-NMR / DMSO-d ₆ ) are shown in FIGS. 15 and 16.

Infrared absorption spectrum (IR (KBr); cm ⁻¹ )
1766, 1712, 1477, 1448, 1373, 1324, 1251, 1216, 1186, 1116, 1072, 995, 925, 875, 838, 750, 684, 642
Time-of-flight mass spectrometry (TOFMS; MALDI)
POSITIVE M ⁺ 263 (equivalent to (C ₆ H ₅ ) ₃ S ⁺ )
_{^{NEGATIVE M - 353 ((C 6}} H 9 O-COO) CH (CF 3) CF 2 SO 3 - equivalent)

The structure of [PAG Z4] is shown below.

[Examples 1 to 11 and Comparative Examples 1 and 2]
Evaluation of Resolution of Resist Material Using the photoacid generator shown in the above synthesis example and a polymer represented by the following formula (Polymer 1 to Polymer 8) as a base resin, a quencher with a composition shown in Table 1 with KH-20 (Seimi Chemical Co., Ltd.) A resist solution is prepared by dissolving in a solvent containing 0.01% by mass, and the resist material is filtered through a 0.2 μm Teflon (registered trademark) filter to obtain a resist solution. Were prepared respectively.

  An antireflection film solution (Nissan Chemical Industry Co., Ltd., ARC-29A) is applied on a silicon substrate and baked at 200 ° C. for 60 seconds. Coating was performed and baking was performed at 100 ° C. for 60 seconds using a hot plate to prepare a resist film having a thickness of 120 nm. This was exposed using an ArF excimer laser microstepper (manufactured by Nikon Corporation, NSR-S307E, NA = 0.85, 4/5 annular illumination, Cr mask), and the temperature shown in Table 2 for 60 seconds. Bake (PEB) was applied and developed with an aqueous solution of 2.38 mass% tetramethylammonium hydroxide for 60 seconds.

The resist is evaluated by taking the exposure amount for resolving the line and space of the 80 nm group at 1: 1 as the optimum exposure amount (Eop, mJ / cm ² ) and separating the minimum line and space line at this exposure amount. The width (nm) was taken as the resolution of the evaluation resist. As an evaluation of the density dependency, the actual dimension on the wafer of the isolated line pattern with the mask size of 130 nm (1:10 isolated line pattern) is measured at the optimum exposure amount, and the mask fidelity (the dimension on the wafer and the dimension is larger). Good).
Table 1 shows the composition of each resist material, and Table 2 shows the evaluation results.

In Table 1, the photoacid generators used in the solvents, quenchers and comparative examples are as follows.
Solvent A: Propylene glycol monomethyl ether acetate Solvent B: Cyclohexanone quencher A: Triethanolamine quencher B: Trismethoxymethoxyethylamine TPS-NfO: Triphenylsulfonium perfluoro-1-butanesulfonate TPS-BzOPFPS: Triphenylsulfonium 2- Benzoyloxy-1,1,3,3,3-pentafluoropropane-1-sulfonate

Next, pseudo immersion exposure was performed using the resist materials of Examples 1, 4, 9 and Comparative Example 1. Specifically, a 125 nm resist film was formed by the same process as described above, and exposed using an ArF excimer laser microstepper (manufactured by Nikon Corporation, S307E, dipole). Immediately after the exposure, pure water was added to the entire surface of the wafer, and the resist exposure surface was immersed in pure water for 60 seconds (paddle). After pure water was shaken off by wafer spin, the PEB process as usual was followed by development. The number of defects in the pattern formed after development was inspected by a defect inspection apparatus WINWIN 50-1200L (manufactured by Tokyo Seimitsu Co., Ltd.), and the defect density was determined according to the following formula. The results are shown in Table 3.
Defect density (pieces / cm ² ) = total number of detected defects / inspection area formed pattern:
80 nm / pitch 160 nm line and space repetitive pattern defect inspection conditions:
Light source UV, inspection pixel size 0.125 μm, cell-to-cell mode Further, the shape of the resist cross-section pattern was observed using a scanning electron microscope. The results are shown in Table 3.

  From the results of Tables 2 and 3, the resist material of the present invention has high sensitivity and high resolution, low density dependency, and shape change and appearance of defects even with long-term rinsing with water compared to conventional products. In other words, it was confirmed that it could sufficiently cope with immersion exposure.

₁₆ is a diagram showing ¹ H-NMR / DMSO-d ₆ of [PAG A] in Synthesis Example 19. FIG. 19 is a diagram showing ¹⁹ F-NMR / DMSO-d ₆ of [PAG A] in Synthesis Example 19. FIG. FIG. ₆ shows ¹ H-NMR / DMSO-d ₆ of [PAG B] in Synthesis Example 20. 14 is a diagram showing ¹⁹ F-NMR / DMSO-d ₆ of [PAG B] in Synthesis Example 20. FIG. FIG. ¹⁴ shows ¹ H-NMR / DMSO-d ₆ of [PAG C] in Synthesis Example 21. 14 is a diagram showing ¹⁹ F-NMR / DMSO-d ₆ of [PAG C] in Synthesis Example 21. FIG. FIG. ¹⁴ shows ¹ H-NMR / DMSO-d ₆ of [PAG Y] in Synthesis Example 43. FIG. 14 shows ¹⁹ F-NMR / DMSO-d ₆ of [PAG Y] in Synthesis Example 43. FIG. ₆ shows ¹ H-NMR / DMSO-d ₆ of [PAG Z1] in Synthesis Example 44. 14 is a diagram showing ¹⁹ F-NMR / DMSO-d ₆ of [PAG Z1] in Synthesis Example 44. FIG. FIG. ₆ shows ¹ H-NMR / DMSO-d ₆ of [PAG Z2] in Synthesis Example 45. FIG. 14 shows ¹⁹ F-NMR / DMSO-d ₆ of [PAG Z2] in Synthesis Example 45. FIG. 5 shows ¹ H-NMR / DMSO-d ₆ of [PAG Z3] in Synthesis Example 46. FIG. 14 shows ¹⁹ F-NMR / DMSO-d ₆ of [PAG Z3] in Synthesis Example 46. FIG. ¹⁴ shows ¹ H-NMR / DMSO-d ₆ of [PAG Z4] in Synthesis Example 47. FIG. 14 shows ¹⁹ F-NMR / DMSO-d ₆ of [PAG Z4] in Synthesis Example 47.

Claims (13)

Sensitive to high energy rays of ultraviolet rays, far ultraviolet rays, electron beams, EUV, X-rays, excimer lasers, γ rays, or synchrotron radiation, and generates sulfonic acid represented by the following general formula (1a) Photoacid generator for chemically amplified resist materials.
^{RC (= O) R 1 -COOCH} (CF 3) CF 2 SO 3 - H + (1a)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents methylene, ethylene, 1,3-propylene, 1,2-propylene, isopropylidene, 1,4-butylene, 1,6-hexylene, o-phenylene, m-phenylene, p-phenylene, the following formula

(In the formula, the dotted line indicates the bonding position.)
Or R ¹ and R are bonded to each other to form the following group together with C (═O):

(In the formula, the dotted line indicates the bonding position.)
Either of these may be formed . ) A sulfonium salt represented by the following general formula (2).
^{RC (= O) -R 1 -COOCH} (CF 3) CF 2 SO 3 - R 2 R 3 R 4 S + (2)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents methylene, ethylene, 1,3-propylene, 1,2-propylene, isopropylidene, 1,4-butylene, 1,6-hexylene, o-phenylene, m-phenylene, p-phenylene, the following formula

(In the formula, the dotted line indicates the bonding position.)
Or R ¹ and R are bonded to each other to form the following group together with C (═O):

(In the formula, the dotted line indicates the bonding position.)
Either of these may be formed . R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group, alkenyl group or oxoalkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon number of 6 -18 aryl group, aralkyl group or aryloxoalkyl group, or any two or more of R ² , R ³ and R ⁴ are bonded to each other to form a ring together with the sulfur atom in the formula May be. ) A sulfonium salt represented by the following general formula (2a).
RC (═O) —R ¹ —COOCH (CF ₃ ) CF ₂ SO ₃ ⁻ (R ⁵ (O) _n ) _m Ph ′S ⁺ Ph ₂
(2a)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents methylene, ethylene, 1,3-propylene, 1,2-propylene, isopropylidene, 1,4-butylene, 1,6-hexylene, o-phenylene, m-phenylene, p-phenylene, the following formula

(In the formula, the dotted line indicates the bonding position.)
Or R ¹ and R are bonded to each other to form the following group together with C (═O):

(In the formula, the dotted line indicates the bonding position.)
Either of these may be formed . R ⁵ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. m represents an integer of 1 to 5, and n represents 0 (zero) or 1. Ph represents a phenyl group. Ph ′ represents a group in which m hydrogen atoms of a phenyl group are substituted with R ⁵ (O) _n — groups. ) An iodonium salt represented by the following general formula (2b).
RC (═O) —R ¹ —COOCH (CF ₃ ) CF ₂ SO ₃ ⁻ ((R ⁵ (O) _n ) _m Ph ′) ₂ I ⁺
(2b)
(In the formula, R represents a hydroxyl group, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or 4 to 15 carbon atoms. A heteroaryl group, a substituted or unsubstituted linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms or 4 to 15 carbon atoms R ¹ represents methylene, ethylene, 1,3-propylene, 1,2-propylene, isopropylidene, 1,4-butylene, 1,6-hexylene, o-phenylene, m-phenylene, p-phenylene, the following formula

(In the formula, the dotted line indicates the bonding position.)
Or R ¹ and R are bonded to each other to form the following group together with C (═O):

(In the formula, the dotted line indicates the bonding position.)
Either of these may be formed . R ⁵ represents a substituted or unsubstituted linear, branched or cyclic alkyl group or alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 14 carbon atoms. m represents an integer of 1 to 5, and n represents 0 (zero) or 1. Ph ′ represents a group in which m hydrogen atoms of a phenyl group are substituted with R ⁵ (O) _n — groups. )   A resist material comprising a base resin, an acid generator, and an organic solvent, wherein the acid generator is a photoacid generator that generates a sulfonic acid represented by the formula (1a) according to claim 1. Resist material. Base resin is poly (meth) acrylic acid and derivatives thereof, cycloolefin derivative-maleic anhydride alternating polymer, copolymer of cycloolefin derivative, maleic anhydride and polyacrylic acid or derivative thereof. , Cycloolefin derivative-α-trifluoromethylacrylic acid derivative copolymer, polynorbornene, ring-opening metathesis polymer, and one or more polymer polymers selected from hydrogenated ring-opening metathesis polymers The resist material according to claim 5 , wherein: 6. The resist material according to claim 5 , wherein the base resin is a polymer structure containing silicon atoms. 6. The resist material according to claim 5 , wherein the base resin is a polymer structure containing fluorine atoms. A base resin according to claim 6 , 7 or 8, a photoacid generator for generating a sulfonic acid represented by the general formula (1a) according to claim 1, and a solvent, wherein the base resin is insoluble or difficult to develop in a developer. A chemically amplified positive resist material that is soluble and becomes soluble in a developer by the action of an acid. The chemically amplified positive resist composition according to claim 9 , further comprising a quencher. The chemically amplified positive resist composition according to claim 9 or 10 , further comprising a dissolution inhibitor. The process of apply | coating the resist material of any one of Claim 5 thru | or 11 on a board | substrate, the process of exposing with a high energy ray with a wavelength of 300 nm or less through a photomask after heat processing, and heat processing as needed And a step of developing using a developing solution. 13. The pattern forming method according to claim 12, which is an immersion lithography method using an ArF excimer laser with a wavelength of 193 nm and inserting water between a substrate coated with a resist material and a projection lens.

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