JP4964608B2 - Antistatic agent, antistatic film and antistatic film coated article - Google Patents

Description

  The present invention relates to an antistatic agent that can be used as a coating material for a resist in lithography technology using charged particle beams such as light, electron beams, or ion beams. More specifically, when applied to a chemically amplified resist, an antistatic agent capable of effectively suppressing resist film reduction phenomenon or fogging phenomenon, an antistatic film using the antistatic agent, and an antistatic film are coated. The present invention relates to a coated article.

  Chemically amplified resists have become an indispensable material as a common lithography technology using charged particle beams such as light, electron beams, or ion beams, but they are easily affected by the usage environment and are difficult to handle. It is known that there is.

  When a chemically amplified resist is coated with a water-soluble coating material, the acid generated by exposure is neutralized by the coating material, or the acid component contained in the coating material erodes the resist surface layer even though it is not exposed. There was a problem such as being in the same state as the exposure. Thus, a slight acid component in the coating material greatly affects the sensitivity of the resist. This phenomenon appears as a film loss in a positive resist and as a hardly soluble layer or an insoluble layer in a negative resist.

  As a method for preventing such a phenomenon, a method of suppressing a decrease in pH by using a buffer solution containing a weak acid and an amine in an aqueous coating material solution (Patent Document 1; JP-A-11-189746), an aqueous coating material solution A method for preparing a composition containing a fluorinated aliphatic sulfonic acid or a fluorinated aliphatic carboxylic acid (Patent Document 2; JP-A-2003-29410) has been proposed.

  In addition, the surface after the chemically amplified resist is formed is hydrophobic, and there is a problem that it becomes difficult to apply an antistatic agent unless surface activity is imparted by a method such as adding a surfactant. is there. Since the antistatic agent is used by coating on a resist, flatness and uniformity are required. Therefore, it has been conventionally proposed to contain a surfactant or a binder polymer for the purpose of improving the coating property. For example, in Patent Document 3 (Japanese Patent Laid-Open No. 6-3813), a conductive material for pattern formation comprising a composition comprising sulfonated polyaniline and a polymer compound soluble in a solvent and / or a surfactant as components. Sex compositions have been reported. This may improve planarization, coatability, and conductivity. However, if a surfactant is used to give coatability, it adversely affects the resist properties such as the formation of a mixing layer. Therefore, as an antistatic agent for chemically amplified resists that do not use a surfactant, a proposal has been made to reduce the influence on chemically amplified resists by using a polymer compound having a nitrogen-containing functional group and a terminal hydrophobic group. (Patent Document 4; JP 2002-226721 A). Patent Document 5 (Japanese Patent Application Laid-Open No. 8-109351) shows that a water-soluble polymer as a binder polymer and a polymer compound that forms an emulsion in an aqueous system can be used in a composition having an effect of preventing charge-up. Yes.

  Since the antistatic agent for resist is used for the purpose of temporarily imparting electrical conductivity during processing, it is required that it can be easily removed with water, alkaline water or the like without being insolubilized. Among water-soluble polymers, those having an ester group are not suitable because they may generate an acid by hydrolysis or the like and affect the resist. Moreover, what has a crosslinkable terminal may become insolubilized during a process, and there exists a possibility that peeling will become impossible. A water-soluble polymer having basicity is not preferred because precipitation may occur when used in combination with a water-soluble conductive polymer having a sulfonic acid group.

  In recent years, the progress of semiconductor devices has been remarkable, and with the improvement of resist processing accuracy, the demands on the flatness and uniformity of the antistatic agent and the resist resolution performance after resist development have further increased. In the conventional method, the coating property of the antistatic agent is insufficient, and the influence on the resist shape due to the additive such as the surfactant contained in the antistatic agent that has been permitted in the past affects the quality of the semiconductor manufacturing. It has become to. That is, in recent years, in the fine processing of a resist of 100 nm or less, the resist shape is managed on the order of several nm. However, even if the antistatic agent has a slight influence on the resist, the resist shape is not improved at such a fine processing level. The rectangularity of the is significantly impaired. In addition, the resist patterned through the development process is subsequently transferred to the substrate by the dry etching process, but for the purpose of preventing collapse of the resist patterned in accordance with the miniaturization of the minimum circuit line width of the semiconductor device, The resist is becoming thinner so that the resist pattern has an appropriate aspect ratio, and the change in the resist shape greatly affects the pattern transfer during etching. In other words, with the advance of semiconductor device fabrication technology, the demand for antistatic agents for maintaining the performance of chemically amplified resists has become increasingly severe, and there is a demand for antistatic films that further reduce the impact on resists. In addition, non-chemically amplified resists may use an inorganic resist for ultrafine processing on the order of 10 nm, which may cause film loss.

JP 11-189746 A JP 2003-29410 A JP-A-6-3813 JP 2002-226721 A JP-A-8-109351

  An object of the present invention is to provide an antistatic agent excellent in prevention of fogging and film reduction phenomenon in a chemically amplified resist, an antistatic film using the antistatic agent, and a coated article.

  As a result of intensive studies to solve the above problems, the present inventors have made water-soluble polymers, particularly water-soluble polymer compounds having a polypeptide bond or specific water-soluble polymers having a polyvinyl structure, water-soluble. Even when using surfactants that can be applied to resists easily and inexpensively by using in combination with conductive polymers, the effect on resists (resist dissolution and resist development) is maintained while maintaining coatability. The inventors have found that resist fogging and film slipping phenomenon as a result can be suppressed, and the present invention has been completed based on such knowledge. In addition, an antistatic agent whose coating property is improved by containing a surfactant is not only developed not only for chemically amplified resists but also for non-chemically amplified resists for microfabrication. The antistatic agent of the present invention is not only effective in suppressing mixing for chemically amplified resists, but also effective in suppressing mixing for such non-chemically amplified resists. I found out.

（式中、Ｐ¹は、次式Ｐ¹(１）

または次式Ｐ¹(２）

を表し、Ｐ¹が前記Ｐ¹(１）のとき、Ｐ²は次式−Ｃ（＝Ｏ）−を表し、かつＺはメチレン基−ＣＨ（−Ｒ）−を表していて、このとき式（１０）は、アミノ酸残基（１０)ａ

（式中、Ｒ，Ｒ’は、アミノ酸残基を構成する置換基を表わし、Ｒ’が水素原子のときは、Ｒは独立してアミノ酸残基を構成する置換基を表し、Ｒ’が水素原子でないときは、ＲとＲ’は協力して、水酸基で置換されていてもよい含窒素環を形成して、アミノ酸残基（１０)ａはアミノ酸残基（１０)ａ’

（式中、Ｗ^aは、式−(ＣＲ^aＲ^b)ｎ−で示されるポリメチレン基を表し、置換基Ｒ^a，Ｒ^bはそれぞれ独立して水素原子、アルキル基、または水酸基を表わし、ｎは２〜８の整数を表す。）であってもよい。）で示される繰り返し構造を示し、
Ｐ¹が前記Ｐ¹(２）のとき、Ｚ＝−Ｏ−、またはＺ＝−Ｎ（−Ｑ）−であり、
前記Ｚ＝−Ｏ−のとき、Ｐ²＝アルキル基であって、式（１０）は、アルコキシエチレン残基（１０)ｂ

で示される繰り返し構造を示し、
前記Ｚ＝−Ｎ（−Ｑ）−のとき、Ｐ²とＱとは協力してラクタム環基を形成して、式（１０）は、アミドエチレン残基（１０)ｃ

（式中、Ｗ^cは式−(ＣＲ^cＲ^d)ｎ−で示されるポリメチレン基を表し、置換基Ｒ^c，Ｒ^dはそれぞれ独立して水素原子、またはアルキル基を表わし、ｎは２〜８の整数を表す。）で示される繰り返し構造を示す。）で示される化学構造を繰り返し構造として有する、前記１に記載の帯電防止剤。
４．水溶性高分子が、前記式（１０)ａ、（１０)ｂ、または（１０)ｃで示される繰り返し構造のうち、少なくとも１種を分子内に有する水溶性高分子である前記１に記載の帯電防止剤。
５．水溶性高分子がアミノ酸残基（１０)ａ

を繰り返し構造とするポリペプチド構造を有する水溶性高分子である前記１〜４のいずれか１項に記載の帯電防止剤。
６．水溶性高分子が、式（１０)’

（式中、Ｙ＝−Ｏ−のとき、Ｐ²＝アルキル基であって、式（１０)’は、アルコキシエチレン残基（１０)ｂ

で示される繰り返し構造を示し、
Ｙ＝−Ｎ（−Ｑ）−のとき、Ｐ²とＱとは協力してラクタム環基を形成して、式（１０)’は、アミドエチレン残基（１０)ｃ

（式中、Ｗ^cは式−(ＣＲ^cＲ^d)ｎ−で示されるポリメチレン基を表し、置換基Ｒ^c，Ｒ^dはそれぞれ独立して水素原子、またはアルキル基を表わし、ｎは２〜８の整数を表す。）で示される繰り返し構造を示す。）で示されるポリビニル構造を繰り返し構造として有する水溶性高分子である前記１、３または４に記載の帯電防止剤。
７．ポリペプチド構造を有する水溶性高分子が、タンパク質加水分解物である前記２〜５のいずれか１項に記載の帯電防止剤。
８．水溶性高分子が、ポリペプチド、ポリビニルピロリドン、ポリビニルカプロラクタム、ポリビニルアルキルエーテルからなる群のうち、少なくとも１種の水溶性高分子である前記１、３、または４に記載の帯電防止剤。
９．水溶性高分子が、ポリビニルピロリドンである前記８に記載の帯電防止剤。
１０．水溶性高分子が、重量平均分子量100000以上のポリビニルピロリドンである前記９に記載の帯電防止剤。
１１．更に、界面活性剤を含有する前記１〜１０のいずれか１項に記載の帯電防止剤。
１２．水溶性導電性高分子0.1〜２０質量％、ポリペプチド構造を有する水溶性高分子0.0001〜１０質量％及び溶媒70.0〜99.8質量％を含む前記１、２、３、４、５、または７に記載の帯電防止剤。
１３．水溶性導電性高分子0.1〜２０質量％、ポリビニル構造を有する水溶性高分子0.0001〜１０質量％及び溶媒70.0〜99.8質量％を含む前記１、３、４、６、８、９、または１０に記載の帯電防止剤。
１４．水溶性導電性高分子0.1〜２０質量％、ポリペプチド構造を有する水溶性高分子を0.0001〜１０質量％、界面活性剤0.0001〜２質量％及び溶媒68.0〜99.8質量％含む前記１１に記載の帯電防止剤。
１５．水溶性導電性高分子0.1〜２０質量％、ポリビニル構造を有する水溶性高分子を0.0001〜１０質量％、界面活性剤0.0001〜２質量％及び溶媒68.0〜99.8質量％含む前記１１に記載の帯電防止剤。
１６．水溶性導電性高分子がブレンステッド酸基またはその塩を有するπ共役系導電性高分子である前記１〜１５のいずれか１項に記載の帯電防止剤。
１７．ブレンステッド酸基がスルホン酸基である前記１６に記載の帯電防止剤。
１８．水溶性導電性高分子が、下記式（１）

（式中、ｍ、ｎは、それぞれ独立して、０または１を表わす。Ｘは、Ｓ、Ｎ−Ｒ¹（Ｒ¹は水素原子、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、フェニル基及び置換フェニル基からなる群から選択される基を表わす。）、またはＯのいずれかを表わし、Ａは、−Ｂ−ＳＯ₃ ^-Ｍ⁺で表わされる置換基を少なくとも１つ有し、かつその他の置換基を有していてもよい炭素数１〜４のアルキレンまたはアルケニレン基（二重結合は２つ以上有していてもよい。）を表わし、Ｂは、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐ及びｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を含む前記１７に記載の帯電防止剤。
１９．水溶性導電性高分子が、下記式（２）

（式中、Ｒ²〜Ｒ⁴は、それぞれ独立して、水素原子、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、または−Ｂ−ＳＯ₃ ^-Ｍ⁺基を表わす。Ｂは、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐ及びｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を含む前記１７に記載の帯電防止剤。
２０．水溶性導電性高分子が、下記式（３）

（式中、Ｒ⁵は、水素原子、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、または−Ｂ−ＳＯ₃ ^-Ｍ⁺基を表わし、Ｂは、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐ及びｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を含む前記１７に記載の帯電防止剤。
２１．水溶性導電性高分子が、下記式（４）

（式中、Ｒ⁶とＲ⁷は、それぞれ独立して、水素原子、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、または−Ｂ−ＳＯ₃ ^-Ｍ⁺基を表わし、Ｒ⁸は、水素原子、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、フェニル基及び置換フェニル基からなる群から選択される一価の基を表わし、Ｂは、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐ及びｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオン、または第４級アンモニウムイオンを表わす。）で示される化学構造を含む前記１７に記載の帯電防止剤。
２２．水溶性導電性高分子が、５−スルホイソチアナフテン−１，３−ジイルを含む重合体である前記１９に記載の帯電防止剤。
２３．前記１〜２２のいずれか１項に記載の帯電防止剤を用いて得られる帯電防止膜。
２４．前記２３に記載の帯電防止膜で被覆して得られる被覆物品。
２５．被覆表面が下地基板に塗布した感光性組成物もしくは感荷電粒子線組成物である前記２４に記載の被覆物品。
２６．前記２３に記載の帯電防止膜を用いることを特徴とするパターン形成方法。 That is, the present invention relates to the following antistatic agent, antistatic film and antistatic film-coated article, and a pattern forming method using the antistatic film.
1. An antistatic agent comprising a water-soluble conductive polymer, a solvent, and a water-soluble polymer.
2. 2. The antistatic agent according to 1 above, wherein the water-soluble polymer is a water-soluble polymer having a polypeptide structure.
3. The water-soluble polymer is of formula (10)

(Where P ¹ is the following formula P ¹ (1)

Or the following formula P ¹ (2)

When P ¹ is P ¹ (1), P ² represents the following formula —C (═O) —, and Z represents a methylene group —CH (—R) —, where (10) is an amino acid residue (10) a

(In the formula, R and R ′ represent a substituent constituting an amino acid residue, and when R ′ is a hydrogen atom, R independently represents a substituent constituting an amino acid residue, and R ′ represents a hydrogen atom. When not an atom, R and R ′ cooperate to form a nitrogen-containing ring optionally substituted with a hydroxyl group, and amino acid residue (10) a is converted to amino acid residue (10) a ′.

(Wherein W ^a represents a polymethylene group represented by the formula — (CR ^a R ^b ) n—, and the substituents R ^a and R ^b each independently represent a hydrogen atom, an alkyl group, or a hydroxyl group, and n Represents an integer of 2 to 8. ) Showing the repeating structure
When P ¹ is P ¹ (2), Z = —O— or Z = —N (—Q) —,
When Z = —O—, P ² = alkyl group, and the formula (10) is an alkoxyethylene residue (10) b

The repeating structure shown by
When Z = —N (—Q) —, P ² and Q cooperate to form a lactam ring group, and the formula (10) is an amidoethylene residue (10) c

Wherein W ^c represents a polymethylene group represented by the formula — (CR ^c R ^d ) n—, the substituents R ^c and R ^d each independently represent a hydrogen atom or an alkyl group, and n represents 2 to 2 Represents an integer of 8). 2. The antistatic agent according to 1 above, which has a chemical structure represented by
4). 2. The water-soluble polymer according to 1 above, wherein the water-soluble polymer is a water-soluble polymer having in the molecule at least one of the repeating structures represented by the formula (10) a, (10) b, or (10) c. Antistatic agent.
5. Water-soluble polymer is amino acid residue (10) a

5. The antistatic agent according to any one of 1 to 4, which is a water-soluble polymer having a polypeptide structure having a repeating structure.
6). The water-soluble polymer is represented by the formula (10) ′

(In the formula, when Y = —O—, P ² = alkyl group, and the formula (10) ′ represents an alkoxyethylene residue (10) b

The repeating structure shown by
When Y = —N (—Q) —, P ² and Q cooperate to form a lactam ring group, and the formula (10) ′ represents an amidoethylene residue (10) c

Wherein W ^c represents a polymethylene group represented by the formula — (CR ^c R ^d ) n—, the substituents R ^c and R ^d each independently represent a hydrogen atom or an alkyl group, and n represents 2 to 2 Represents an integer of 8). 5. The antistatic agent according to 1, 3, or 4, which is a water-soluble polymer having a polyvinyl structure represented by (2) as a repeating structure.
7). 6. The antistatic agent according to any one of 2 to 5, wherein the water-soluble polymer having a polypeptide structure is a protein hydrolysate.
8). 5. The antistatic agent according to 1, 3, or 4, wherein the water-soluble polymer is at least one water-soluble polymer from the group consisting of polypeptide, polyvinyl pyrrolidone, polyvinyl caprolactam, and polyvinyl alkyl ether.
9. 9. The antistatic agent according to 8 above, wherein the water-soluble polymer is polyvinyl pyrrolidone.
10. 10. The antistatic agent according to 9, wherein the water-soluble polymer is polyvinyl pyrrolidone having a weight average molecular weight of 100,000 or more.
11. Furthermore, antistatic agent of any one of said 1-10 containing surfactant.
12 8. The 1, 2, 3, 4, 5, or 7 comprising 0.1 to 20% by mass of a water-soluble conductive polymer, 0.0001 to 10% by mass of a water-soluble polymer having a polypeptide structure and 70.0 to 99.8% by mass of a solvent. Antistatic agent.
13. In the above 1, 3, 4, 6, 8, 9, or 10 containing 0.1 to 20% by mass of water-soluble conductive polymer, 0.0001 to 10% by mass of water-soluble polymer having a polyvinyl structure and 70.0 to 99.8% by mass of solvent The antistatic agent as described.
14 The charging according to 11 above, comprising 0.1 to 20% by mass of a water-soluble conductive polymer, 0.0001 to 10% by mass of a water-soluble polymer having a polypeptide structure, 0.0001 to 2% by mass of a surfactant and 68.0 to 99.8% by mass of a solvent. Inhibitor.
15. The antistatic material according to 11 above, comprising 0.1 to 20% by mass of a water-soluble conductive polymer, 0.0001 to 10% by mass of a water-soluble polymer having a polyvinyl structure, 0.0001 to 2% by mass of a surfactant, and 68.0 to 99.8% by mass of a solvent. Agent.
16. 16. The antistatic agent according to any one of 1 to 15, wherein the water-soluble conductive polymer is a π-conjugated conductive polymer having a Bronsted acid group or a salt thereof.
17. 17. The antistatic agent according to 16 above, wherein the Bronsted acid group is a sulfonic acid group.
18. The water-soluble conductive polymer is represented by the following formula (1)

(In the formula, m and n each independently represents 0 or 1. X represents S, N—R ¹ (R ¹ is a hydrogen atom, linear or branched saturated having 1 to 20 carbon atoms) or unsaturated hydrocarbon group, a group selected from phenyl and the group consisting of substituted phenyl group), or represents one of O, a is, -B-SO ₃ ^-. substituted represented by M ⁺ Represents an alkylene or alkenylene group having 1 to 4 carbon atoms which may have at least one group and may have other substituents (which may have two or more double bonds); Represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represent an integer of 0 or 1-3, and q represents 0 or 1 .M ⁺ represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion The antistatic agent according to the 17, including a chemical structure represented by).
19. The water-soluble conductive polymer is represented by the following formula (2)

(In the formula, R ^{2 to} R ⁴ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear structure having 1 to 20 carbon atoms. Or a branched saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group, or a —B—SO ₃ ⁻ M ⁺ group, where B is _{- (CH 2) p - (} O) q - (CH 2) r - represents, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1 .M 18. The antistatic agent according to 17 above, which comprises a chemical structure represented by: ⁺ represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.
20. The water-soluble conductive polymer is represented by the following formula (3)

(In the formula, R ⁵ represents a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched saturated or unsaturated group having 1 to 20 carbon atoms. It represents M ⁺ group, B is - ^- alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or _{-B-SO 3, (CH 2} ) p - ( O) _q — (CH ₂ ) _r —, p and r each independently represent an integer of 0 or 1 to 3, q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal 18. The antistatic agent according to 17 above, which comprises a chemical structure represented by an ion or a quaternary ammonium ion.
21. The water-soluble conductive polymer is represented by the following formula (4)

(In the formula, R ⁶ and R ⁷ are each independently a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a straight chain having 1 to 20 carbon atoms. or branched, saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or -B-SO _3, ^- represents M ⁺ group, R ⁸ is Represents a monovalent group selected from the group consisting of a hydrogen atom, a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group; (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, wherein p and r each independently represent an integer of 0 or 1-3, and q represents 0 or 1. M ⁺ Is hydrogen ion, alkali metal ion, or quaternary ammonia The antistatic agent according to the 17 containing a chemical structure represented by representing the ion.).
22. 20. The antistatic agent as described in 19 above, wherein the water-soluble conductive polymer is a polymer containing 5-sulfoisothianaphthene-1,3-diyl.
23. 23. An antistatic film obtained by using the antistatic agent according to any one of 1 to 22.
24. 24. A coated article obtained by coating with the antistatic film as described in 23 above.
25. 25. The coated article according to 24, wherein the coated surface is a photosensitive composition or a charged particle beam composition coated on a base substrate.
26. 24. A pattern forming method using the antistatic film as described in 23 above.

  The antistatic agent of the present invention is applied to the surface of a chemically amplified resist, and when a coated antistatic film is formed, the quality of the chemically amplified resist changes (for example, fogging, film reduction, T top, shoulder drop, etc.) The pattern can be formed with high accuracy because the pattern can be formed with high accuracy, and positional displacement can be prevented in the drawing process using charged particle beams due to the antistatic effect. can do. In addition, the antistatic agent of the present invention is applied to the surface of a chemically amplified resist and used to suppress mixing such as development failure and change in development time, as well as suppressing mixing of non-chemically amplified resist. Is also effective.

  The antistatic agent according to the present invention comprises a water-soluble conductive polymer, a solvent and a water-soluble polymer, particularly a water-soluble polymer compound having a polypeptide bond, particularly an amino acid residue represented by the formula (10) a A water-soluble polymer having a repeating structure, a water-soluble polymer having an alkoxyethylene residue represented by the formula (10) b as a repeating structure, and an amideethylene residue represented by the formula (10) c. A water-soluble polymer having a structure, and a water-soluble polymer having at least one of the repeating residues represented by formulas (10) a, (10) b, and (10) c as a repeating structure And a composition containing a water-soluble polymer having a structure represented by the formula (10) as a repeating structure, and may further contain a surfactant.

  If the antistatic agent of the present invention is applied to an article and then allowed to stand or dry, the solvent contained in the antistatic agent is reduced by volatilization or the like, resulting in a semi-solid or solid with no fluidity. The film body that has lost its fluidity is called an antistatic film.

(I) Water-soluble conductive polymer Examples of the water-soluble conductive polymer used in the present invention include π-conjugated conductive polymers having a Bronsted acid group or a salt thereof. The Bronsted acid group may be directly bonded to the π-electron conjugated main chain, or may be bonded via a spacer (for example, an alkylene side chain or an oxyalkylene side chain). It is not limited to the primary structure of the molecule.
Examples of the Bronsted acid group include a sulfonic acid group and a carboxylic acid group, and a sulfonic acid group is preferable.

  Specific examples of the water-soluble conductive polymer include poly (isothianaphthenesulfonic acid), poly (thiophenealkylsulfonic acid), poly (pyrrolealkylsulfonic acid), poly (anilinesulfonic acid), and poly (anilinealkanesulfonic acid). ), Poly (aniline thioalkane sulfonic acid), etc., or copolymers containing repeating units having sulfonic acid groups or salts of these polymers, or various salt structures and substituted derivatives thereof. There may be mentioned polymers.

  Moreover, the repeating unit containing a sulfonic acid group in the copolymer is preferably 50 to 100 mol%, more preferably 80 to 100 mol% of all repeating units of the polymer.

The copolymer used in the present invention may be a copolymer containing a repeating unit composed of another π-conjugated chemical structure, or may be a copolymer composition composed of 2 to 5 kinds of repeating units.
The “copolymer containing repeating units” referred to in the present invention is not necessarily limited to a copolymer containing the units continuously, as long as desired conductivity based on the π-conjugated main chain is expressed. A polymer containing a repeating unit discontinuously and discontinuously in the π-conjugated main chain such as a random copolymer may be used.

式（１）中、ｍ、ｎは、それぞれ独立して、０または１を表わす。Ｘは、Ｓ、Ｎ−Ｒ¹、またはＯのいずれかを表わし、Ｒ¹は水素原子、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、フェニル基及び置換フェニル基からなる群から選択される基を表わし、Ａは、−Ｂ−ＳＯ₃ ^-Ｍ⁺で表わされる置換基を少なくとも１つ有し、かつその他の置換基を有していてもよい炭素数１〜４のアルキレンまたはアルケニレン基（二重結合は２つ以上有していてもよい。）を表わし、Ｂは、−（ＣＨ₂）_p−（Ｏ）_q−（ＣＨ₂）_r−を表わし、ｐ及びｒは、それぞれ独立して、０または１〜３の整数を表わし、ｑは０または１を表わす。Ｍ⁺は、水素イオン、アルカリ金属イオンまたは第４級アンモニウムイオンを表わす。 Examples of the repeating unit containing a sulfonic acid group or a salt thereof in the water-soluble conductive polymer include chemical structures represented by the following formulas (1), (2), (3) and (4).

In formula (1), m and n each independently represents 0 or 1. X represents S, N—R ¹ , or O, and R ¹ represents a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, and a substituent. represents a group selected from the group consisting of phenyl group, a is, -B-SO ₃ ^- at least one having a substituent represented by M ^+, and the number of carbon atoms, which may have other substituents 1-4 alkylene or alkenylene group (. double bond which may have two or more) represents, B _{is, - (CH 2) p -} (O) q - (CH 2) r - a represents , P and r each independently represents an integer of 0 or 1 to 3, and q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion.

Other substituents for the alkylene or alkenylene group include linear or branched saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, linear or branched saturated or unsaturated groups having 1 to 20 carbon atoms. One or more selected from a saturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, and a substituted phenyl group.
Examples of the substituted phenyl group represented by R ¹ and the above substituted phenyl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a halogen atom. It is a phenyl group substituted with 1 to 5 groups selected from substituents.

式（２）中、Ｒ²〜Ｒ⁴は、それぞれ独立して、水素原子、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和のアルコキシ基、水酸基、ハロゲン原子、ニトロ基、シアノ基、トリハロメチル基、フェニル基、置換フェニル基、または−Ｂ−ＳＯ₃ ^-Ｍ⁺基を表わし、Ｂ及びＭ⁺は前記と同じ意味を表わす。

In formula (2), R ^{2 to} R ⁴ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and a straight chain having 1 to 20 carbon atoms. linear or branched, saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or -B-SO _3, ^- represents M ⁺ group, B And M ⁺ represent the same meaning as described above.

Examples of the substituent of the substituted phenyl group represented by R ² , R ^3, or R ⁴ include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, and the like. It may be.

An arbitrary ethylene group in the hydrocarbon group and alkoxy group represented by R ² , R ³ and R ⁴ is a carbonyl group (—CO—), an oxy group (—O—), a carbonyloxy group (—COO— or —OCO). −), Aminocarbonyl group (—NH ₂ —CO— or —CO—NH ₂ —), aminosulfonyl group (—NH ₂ —SO ₂ — or —SO ₂ —NH ₂ —), sulfanyl group (—S—) , A sulfinyl group (—S (O) —), a sulfonyl group (—SO ₂ —), a sulfonyloxy group (—SO ₂ —O— or —O—SO ₂ —), or an imino group (—NH—) It may be.

Specifically, alkylcarbonylalkyl group, alkoxyalkyl group, alkoxyalkoxy group, alkoxycarbonyl group, alkoxycarbonylalkyl group, acyloxy group, acyloxyalkyl group, alkylaminocarbonyl group, alkylaminocarbonylalkyl group, alkylcarbonylamino group, Alkylcarbonylaminoalkyl group, alkylaminosulfonyl group, alkylaminosulfonylalkyl group, alkylsulfonylamino group, alkylsulfonylaminoalkyl group, alkylthio group, alkylthioalkyl group, alkylsulfinyl group, alkylsulfinylalkyl group, alkylsulfonyl group, alkylsulfonyl Alkyl group, alkylsulfonyloxy group, alkylsulfonyloxyalkyl group, alkylamino , And the alkyl moiety of the above include those replaced by a phenyl group which may be substituted. The substituent for the phenyl group is the same as the substituent for the substituted phenyl group represented by R ^{2 to} R ⁴ .

式（３）中、Ｒ⁵は、前記のＲ²〜Ｒ⁴と同様の意味を表わし、Ｂ及びＭ⁺は前記と同じ意味を表わす。

In formula (3), R ⁵ represents the same meaning as R ^{2 to} R ⁴ described above, and B and M ⁺ represent the same meaning as described above.

式（４）中、Ｒ⁶とＲ⁷は、それぞれ独立して、前記のＲ²〜Ｒ⁴と同様の意味を表わし、Ｂ及びＭ⁺は前記と同じ意味を表わし、Ｒ⁸は、水素原子、炭素数１〜２０の直鎖状もしくは分岐状の飽和または不飽和の炭化水素基、フェニル基及び置換フェニル基からなる群から選択される基を表わす。Ｒ⁸が表わす置換フェニル基の置換基は、Ｒ²〜Ｒ⁴が表わす置換フェニル基の置換基と同様である。

In formula (4), R ⁶ and R ⁷ each independently represents the same meaning as R ^{2 to} R ⁴ , B and M ⁺ represent the same meaning as described above, and R ⁸ represents a hydrogen atom. Represents a group selected from the group consisting of a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, and a substituted phenyl group. The substituent of the substituted phenyl group represented by R ⁸ is the same as the substituent of the substituted phenyl group represented by R ^{2 to} R ⁴ .

  In the definitions of the formulas (1) to (4), the saturated or unsaturated hydrocarbon group means a group consisting of a carbon atom and a hydrogen atom. For example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group. Groups, cycloalkynyl groups, aromatic carbocycles and groups in which one or more hydrogen atoms in these groups have been replaced by other groups.

R ^{2 to} R ⁵ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, and a linear or branched alkoxy group having 1 to 20 carbon atoms. A linear or branched alkoxy group having 1 to 20 is more preferable. R ⁶ or R ⁷ is preferably a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, or a substituted phenyl group.

Particularly preferred examples of R ^{2 to} R ⁷ include a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, a carbonyl group-containing group, an alkoxyalkoxy group, an alkoxycarbonyl group, an acyloxy group, a phenyl group, and a substituted phenyl group. And sulfonic acid groups. Specific examples of these substituents include methyl, ethyl, propyl, allyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, alkyl groups such as dodecyl, tetradecyl, hexadecyl, vinyl, 1- Alkenyl groups such as propynyl and 1-butenyl, alkoxyalkyl groups such as ethoxyethyl, methoxyethyl and methoxyethoxyethyl, carbonyl group-containing groups such as acetonyl and phenacyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy and hexyl Alkoxy groups such as oxy, octyloxy and dodecyloxy, alkoxyalkoxy groups such as methoxyethoxy and methoxyethoxyethoxy, alkoxy such as methoxycarbonyl, ethoxycarbonyl and butoxycarbonyl Acyloxy group such as carbonyl group, acetoxy, butyroyloxy, phenyl group which may have a substituent such as halogen atom, alkyl group, alkoxy group, such as phenyl, fluorophenyl, chlorophenyl, bromophenyl, methylphenyl, methoxyphenyl Etc.

  In the formulas (1) to (4), preferable examples of B include a single bond, methylene, ethylene, propylene, butylene, pentylene, hexylene, arylene, butadienylene, oxymethylene, oxyethylene, oxypropylene, methyleneoxyethylene, And ethyleneoxyethylene. Particularly preferred B is a single bond, ethylene, propylene, oxyethylene, or ethyleneoxyethylene.

Two or more kinds of cations represented by M ⁺ may be mixed.
Examples of alkali metal ions include Na ⁺ , Li ⁺ and K ⁺ .

The quaternary ammonium ion is represented by N (R ⁹ ) (R ¹⁰ ) (R ¹¹ ) (R ¹² ) ⁺ . R ^{9 to} R ¹² each independently represents a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group, an alkoxy group, a hydroxyl group, an oxy group It may be an alkyl or aryl group containing a group containing an element other than carbon and hydrogen, such as an alkylene group, a thioalkylene group, an azo group, an azobenzene group, and a p-diphenyleneoxy group.

Examples of quaternary ammonium ions include NH ₄ ⁺ , NH (CH ₃ ) ₃ ⁺ , NH (C ₆ H ₅ ) ₃ ⁺ , N (CH ₃ ) ₂ (CH ₂ OH) (CH ₂ -Z) ^{+ and the} like. (However, Z represents an arbitrary substituent having a chemical formula weight of 600 or less, and examples thereof include a phenoxy group, p-diphenyleneoxy group, p-alkoxydiphenyleneoxy group, p-alkoxyphenylazophenoxy group, etc.) Or an unsubstituted or alkyl-substituted cation. In addition, in order to convert into a specific cation, you may use a normal ion exchange resin.

An arbitrary ethylene group in the alkyl group represented by R ^{9 to} R ¹² is a carbonyl group (—CO—), an oxy group (—O—), a carbonyloxy group (—COO— or —OCO—), an aminocarbonyl group (— NH ₂ —CO— or —CO—NH ₂ —), aminosulfonyl group (—NH ₂ —SO ₂ — or —SO ₂ —NH ₂ —), sulfanyl group (—S—), sulfinyl group (—S (O )-), A sulfonyl group (—SO ₂ —), a sulfonyloxy group (—SO ₂ —O— or —O—SO ₂ —), or an imino group (—NH—) may be substituted.

  Preferable specific examples of the chemical structure represented by the formula (1), (2) or (3) include 5- (3′-propanesulfo) -4,7-dioxycyclohexa [2,3-c] thiophene. -1,3-diyl, 5- (2′-ethanesulfo) -4,7-dioxycyclohexa [2,3-c] thiophene-1,3-diyl, 5-sulfoisothianaphthene-1,3- Diyl, 4-sulfoisothianaphthene-1,3-diyl, 4-methyl-5-sulfoisothianaphthene-1,3-diyl, 6-methyl-5-sulfoisothianaphthene-1,3-diyl, 6 -Methyl-4-sulfoisothianaphthene-1,3-diyl, 5-methyl-4-sulfoisothianaphthene-1,3-diyl, 6-ethyl-5-sulfoisothianaphthene-1,3-diyl, 6-propyl-5-sulfoiso Naphthene-1,3-diyl, 6-butyl-5-sulfoisothianaphthene-1,3-diyl, 6-hexyl-5-sulfoisothianaphthene-1,3-diyl, 6-decyl-5-sulfoiso Thianaphthene-1,3-diyl, 6-methoxy-5-sulfoisothianaphthene-1,3-diyl, 6-ethoxy-5-sulfoisothianaphthene-1,3-diyl, 6-chloro-5-sulfo Isothianaphthene-1,3-diyl, 6-bromo-5-sulfoisothianaphthene-1,3-diyl, 6-trifluoromethyl-5-sulfoisothianaphthene-1,3-diyl, 5- (sulfomethane ) Isothianaphthene-1,3-diyl, 5- (2′-sulfoethane) isothianaphthene-1,3-diyl, 5- (2′-sulfoethoxy) isothianaphthene-1,3-di 5- (2 ′-(2 ″ -sulfoethoxy) methane) -isothianaphthene-1,3-diyl, 5- (2 ′-(2 ″ -sulfoethoxy) ethane) -isothianaphthene-1, 3-diyl or the like, or lithium salt, sodium salt, ammonium salt, methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt, tetramethylammonium salt, tetraethylammonium salt, etc. Is mentioned.

  Preferred specific examples of the chemical structure represented by the formula (4) include 2-sulfo-1,4-iminophenylene, 3-methyl-2-sulfo-1,4-iminophenylene, 5-methyl-2-sulfo- 1,4-iminophenylene, 6-methyl-2-sulfo-1,4-iminophenylene, 5-ethyl-2-sulfo-1,4-iminophenylene, 5-hexyl-2-sulfo-1,4-imino Phenylene, 3-methoxy-2-sulfo-1,4-iminophenylene, 5-methoxy-2-sulfo-1,4-iminophenylene, 6-methoxy-2-sulfo-1,4-iminophenylene, 5-ethoxy 2-sulfo-1,4-iminophenylene, 2-sulfo-N-methyl-1,4-iminophenylene, 2-sulfo-N-ethyl-1,4-iminophenylene, or the like Umushio, sodium salts, ammonium salts, methyl ammonium salts, ethyl ammonium salts, dimethyl ammonium salts, diethyl ammonium salts, trimethylammonium salts, triethylammonium salts, tetramethylammonium salts, tetraethylammonium salts and the like.

  Specific examples of water-soluble conductive polymers other than the above formulas (1) to (4) that can be used in the present invention include poly (carbazole-N-alkanesulfonic acid) and poly (phenylene-oxyalkanesulfonic acid). ), Poly (phenylene vinylene-alkanesulfonic acid), poly (phenylene vinylene-oxyalkanesulfonic acid), poly (aniline-N-alkanesulfonic acid), poly (thiophenealkylcarboxylic acid), poly (thiopheneoxyalkylcarboxylic acid) , Poly (polypyrrolealkylcarboxylic acid), poly (pyrroleoxyalkylcarboxylic acid), poly (carbazole-N-alkylcarboxylic acid), poly (phenylene-oxyalkylcarboxylic acid), poly (phenylenevinylene-alkylcarboxylic acid), poly (Phenylene vinylene-oxy Alkyl carboxylic acid), poly (aniline-N-alkyl carboxylic acid) or substituted derivatives thereof, 6-sulfonaphtho [2,3-c] thiophene-1,3-diyl, etc., or lithium salts, sodium salts, ammonium salts thereof Methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, triethyl ammonium salt, tetramethyl ammonium salt, tetraethyl ammonium salt and the like.

  The molecular weight of the water-soluble conductive polymer used in the present invention is 5 to 2000, preferably 10 to 1000, in terms of the number of repeating units (degree of polymerization) constituting the main chain.

  As a particularly preferred specific example of the water-soluble conductive polymer used in the present invention, a polymer of 5-sulfoisothianaphthene-1,3-diyl, 80 mol% of 5-sulfoisothianaphthene-1,3-diyl is used. A random copolymer, a copolymer of 5-sulfoisothianaphthene-1,3-diyl and isothianaphthene-1,3-diyl, poly (3- (3-thienyl) ethanesulfonic acid), Random copolymer containing 50 mol% or more of poly (3- (3-thienyl) propanesulfonic acid), poly (2- (3-thienyl) oxyethanesulfonic acid), 2-sulfo-1,4-iminophenylene, 2 -Copolymer of sulfo-1,4-iminophenylene and 1,4-iminophenylene, or lithium salt, sodium salt, ammonium salt, triethylammonium of these polymers Moniumu salts and the like.

(II) Solvent The solvent used in the present invention is a solvent that is miscible with water and dissolves the water-soluble polymer and the water-soluble conductive polymer. Specific examples of the solvent include water, ethers such as 1,4-dioxane and tetrahydrofuran, carbonates such as dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate, nitriles such as acetonitrile and benzonitrile, methanol, ethanol, Examples include alcohols such as propanol and isopropanol, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide and N-methyl-2-pyrrolidone, mineral acids such as sulfuric acid, and organic acids such as acetic acid. These solvents can be used alone or as a mixed solvent of two or more.

（式中、Ｐ¹は、次式Ｐ¹(１）

または次式Ｐ¹(２）

を表し、Ｐ¹が前記Ｐ¹(１）のとき、Ｐ²は次式−Ｃ（＝Ｏ）−を表し、かつＺはメチレン基−ＣＨ（−Ｒ）−を表していて、このとき式（１０）は、アミノ酸残基（１０)ａ

（式中、Ｒ，Ｒ’は、アミノ酸残基を構成する置換基を表わし、Ｒ’が水素原子のときはＲは独立してアミノ酸残基を構成する置換基を表し、Ｒ’が水素原子でないときは、ＲとＲ’は協力して、水酸基で置換されていてもよい含窒素環を形成して、アミノ酸残基（１０)ａはアミノ酸残基（１０)ａ’

（式中、Ｗ^aは、式−(ＣＲ^aＲ^b)ｎ−で示されるポリメチレン基を表し、置換基Ｒ^a，Ｒ^bはそれぞれ独立して水素原子、アルキル基、または水酸基を表わし、ｎは２〜８の整数を表す。）であってもよく、式（１０)ａ’は、好ましくは式（１０)ａ”

（式中、Ｗは、いずれかの炭素原子が水酸基で置換されていてもよいエチレン基を表す。）であってもよい。）で示される繰り返し構造（ポリペプチド構造）を示し、
Ｐ¹が前記Ｐ¹(２）のとき、Ｚ＝−Ｏ−、またはＺ＝−Ｎ（−Ｑ）−であり、
前記Ｚ＝−Ｏ−のとき、Ｐ²＝アルキル基であって、式（１０）は、アルコキシエチレン残基（１０)ｂ

で示される繰り返し構造（ポリビニルアルキルエーテル構造）を示し、
前記Ｚ＝−Ｎ（−Ｑ）−のとき、Ｐ²とＱとは協力してラクタム環基を形成して、式（１０）は、アミドエチレン残基

（式中、Ｗ^cは式−(ＣＲ^cＲ^d)ｎ−で示されるポリメチレン基を表し、置換基Ｒ^c，Ｒ^dはそれぞれ独立して水素原子、またはアルキル基を表わし、ｎは２〜８の整数を表す。）で示される繰り返し構造を示し、式（１０)ｃのうち、次式（１０)ｃ’

（ただし、ｎは、１〜７の整数を表す。）で示される繰り返し構造（ポリビニルラクタム構造）が好ましい。）で示される化学構造を繰り返し構造として有する水溶性高分子が好ましい。 (III) Water-soluble polymer The water-soluble polymer used in the present invention includes a water-soluble polymer having a polypeptide structure, and a formula (10)

(Where P ¹ is the following formula P ¹ (1)

Or the following formula P ¹ (2)

When P ¹ is P ¹ (1), P ² represents the following formula —C (═O) —, and Z represents a methylene group —CH (—R) —, where (10) is an amino acid residue (10) a

(In the formula, R and R ′ represent a substituent constituting an amino acid residue. When R ′ is a hydrogen atom, R independently represents a substituent constituting an amino acid residue, and R ′ represents a hydrogen atom. Otherwise, R and R ′ cooperate to form a nitrogen-containing ring optionally substituted with a hydroxyl group, and amino acid residue (10) a is converted to amino acid residue (10) a ′.

(Wherein W ^a represents a polymethylene group represented by the formula — (CR ^a R ^b ) n—, and the substituents R ^a and R ^b each independently represent a hydrogen atom, an alkyl group, or a hydroxyl group, and n Represents an integer of 2 to 8.), and the formula (10) a ′ is preferably the formula (10) a ″.

(Wherein W represents an ethylene group in which any carbon atom may be substituted with a hydroxyl group). ) Shows a repeating structure (polypeptide structure)
When P ¹ is P ¹ (2), Z = —O— or Z = —N (—Q) —,
When Z = —O—, P ² = alkyl group, and the formula (10) is an alkoxyethylene residue (10) b

The repeating structure (polyvinyl alkyl ether structure) shown by
When Z = —N (—Q) —, P ² and Q cooperate to form a lactam ring group, and the formula (10) is an amidoethylene residue.

Wherein W ^c represents a polymethylene group represented by the formula — (CR ^c R ^d ) n—, the substituents R ^c and R ^d each independently represent a hydrogen atom or an alkyl group, and n represents 2 to 2 8 represents an integer of 8), and of formula (10) c, the following formula (10) c ′

(However, n represents the integer of 1-7.) The repeating structure (polyvinyl lactam structure) shown by this is preferable. The water-soluble polymer having a chemical structure represented by

を繰り返し構造とするポリペプチド構造を有する水溶性高分子を含み、これらは、各種タンパク質を加水分解して得る方法、任意のアミノ酸やオリゴペプチドなどから合成する方法、微生物等の生物を用い生産する方法等により得ることができる。各種タンパク質を加水分解する場合、使用するタンパク質は、天然に広く存在し容易に入手し得る天然由来物が好ましく、例えば、ケラチンやコラーゲンといったタンパク質は繊維性タンパク質で、生体を形成する構造タンパク質でもある。任意のアミノ酸からポリペプチドを合成する例としては、２個のアミノ酸分子またはその誘導体（例えば酸クロリドにしたものなど）間の縮合を繰り返して一つ一つのアミノ酸残基（例えば式（１０)ａで示されるアミノ酸残基など）をペプチド結合させる方法、精製アミノ酸Ｎ−カルボキシ無水物を重合する方法、ポリスチレンフィルムのような高分子に反応基をつけて１種類のアミノ酸を結合させ、そのアミノ酸を反応し易い構造に変えてから、また次の別のアミノ酸を結合させていくというメリーフィールドの固相合成方法が挙げられる。なお、アミノ酸残基（１０)ａとしては、グリシン（Gly）、アラニン（Ala）、バリン（Val）、ロイシン（Leu）、イソロイシン（Ile）、セリン（Ser）、トレオニン（Thr）、アスパラギン酸（Asp）、アスパラギン（Asn）、グルタミン酸（Glu）、グルタミン（Gln）、システイン（Cys）、メチオニン（Met）、リシン（Lys）、アルギニン（Arg）、ヒスチジン（His）、フェニルアラニン（Phe）、チロシン（Tyr）、トリプトファン（Trp）、プロリン（Pro）、３−ヒドロキシプロリン（3Hyp）、４−ヒドロキシプロリン（4Hyp）のアミノ酸残基（前記例示のアミノ酸について括弧内にそのアミノ酸残基の３文字略号を示した。）などが挙げられる。 [Water-soluble polymer having a polypeptide structure]
The water-soluble polymer having a polypeptide structure used in the present invention is the amino acid residue (10) a.

Water-soluble polymers having a polypeptide structure with a repeating structure, these are produced by hydrolyzing various proteins, synthesized from any amino acid, oligopeptide, etc., and produced using organisms such as microorganisms It can be obtained by a method or the like. In the case of hydrolyzing various proteins, the protein used is preferably a natural product that exists widely in nature and can be easily obtained. For example, proteins such as keratin and collagen are fibrous proteins, and are structural proteins that form living bodies. . As an example of synthesizing a polypeptide from an arbitrary amino acid, condensation between two amino acid molecules or derivatives thereof (for example, those converted into acid chlorides) is repeated to form individual amino acid residues (for example, formula (10) a A method of polymerizing purified amino acid N-carboxyanhydride, attaching a reactive group to a polymer such as a polystyrene film, and binding one type of amino acid, One example is Maryfield's solid-phase synthesis method in which the structure is changed to an easily reactive structure and then another amino acid is bound. The amino acid residue (10) a includes glycine (Gly), alanine (Ala), valine (Val), leucine (Leu), isoleucine (Ile), serine (Ser), threonine (Thr), aspartic acid ( Asp), asparagine (Asn), glutamic acid (Glu), glutamine (Gln), cysteine (Cys), methionine (Met), lysine (Lys), arginine (Arg), histidine (His), phenylalanine (Phe), tyrosine ( Tyr), tryptophan (Trp), proline (Pro), 3-hydroxyproline (3Hyp), 4-hydroxyproline (4Hyp) amino acid residues Etc.).

  Examples of protein hydrolysates include hydrolyzed collagen, which is a hydrolyzate of collagen that is abundant in cow skin-derived gelatin, pig skin-derived gelatin, fish skin-derived gelatin, fish scales, and the like, and is often contained in wool and feathers. There are hydrolysates derived from animal proteins such as hydrolyzed keratin, which is a hydrolyzate of keratin, and hydrolyzed casein, which is a hydrolyzed casein contained in milk and the like. Examples of the silk thread include hydrolysates of vegetable proteins such as hydrolyzed silk derived from silk, hydrolyzed casein derived from soybean protein, conchiolin and wheat protein.

  Since the water-soluble polymer having a polypeptide structure contains the various amino acids, chemical modification can be easily performed. In the present invention, various derivatives subjected to chemical modification can also be used. Specific examples of the chemical modification include quaternary ammonium cationization and silylation of a terminal amino group of a polypeptide and esterification of a terminal carboxyl group. Quaternary ammonium cationization can be induced not only on the terminal amino group of the polypeptide but also on the side chain of basic amino acids such as lysine and histidine. Moreover, various fatty acids can also be condensed for the purpose of solubilizing the solvent and imparting a surface active effect.

（式中、Ｙ＝−Ｏ−のとき、Ｐ²＝アルキル基であって、式（１０)’は、アルコキシエチレン残基（１０)ｂ

で示される繰り返し構造（ポリビニルアルキルエーテル構造）を示し、
Ｙ＝−Ｎ（−Ｑ）−のとき、Ｐ²とＱとは協力してラクタム環基を形成して、式（１０)’は、アミドエチレン残基

（式中、Ｗ^cは式−(ＣＲ^cＲ^d)ｎ−で示されるポリメチレン基を表し、置換基Ｒ^c，Ｒ^dはそれぞれ独立して水素原子、またはアルキル基を表わし、ｎは２〜８の整数を表す。）で示される繰り返し構造を示し、式（１０)ｃのうち、次式（１０)ｃ’

（ただし、ｎは、１〜７の整数を表す。）で示される繰り返し構造（ポリビニルラクタム構造）が好ましい。）で示される化学構造（ポリビニル構造）を繰り返し構造として有する水溶性高分子が好ましい。 [Water-soluble polymer having a polyvinyl structure as a repeating structure]
As the water-soluble polymer having a polyvinyl structure as a repeating structure used in the present invention, as the particularly preferable one, the above formula (10) ′

(In the formula, when Y = —O—, P ² = alkyl group, and the formula (10) ′ represents an alkoxyethylene residue (10) b

The repeating structure (polyvinyl alkyl ether structure) shown by
When Y = —N (—Q) —, P ² and Q cooperate to form a lactam ring group, and the formula (10) ′ is an amidoethylene residue.

Wherein W ^c represents a polymethylene group represented by the formula — (CR ^c R ^d ) n—, the substituents R ^c and R ^d each independently represent a hydrogen atom or an alkyl group, and n represents 2 to 2 8 represents an integer of 8), and of formula (10) c, the following formula (10) c ′

(However, n represents the integer of 1-7.) The repeating structure (polyvinyl lactam structure) shown by this is preferable. A water-soluble polymer having a chemical structure (polyvinyl structure) represented by () as a repeating structure is preferable.

で示されるビニル基を有するモノマーの１種または２種以上を単独でまたは複数を、前記カチオン系重合触媒を用いて重合または共重合させることによっても、式（１０)’

で示される繰り返し構造（ポリビニル構造）を有する水溶性高分子を製造することができる。 The method for producing a water-soluble polymer having a polyvinyl structure as a repeating structure according to the present invention is not particularly limited. For example, at least one monomer having a corresponding vinyl group is converted into a peroxide, a sulfite, an azo catalyst, a fluoride. The target water-soluble polymer can be obtained by polymerization using a polymerization catalyst such as boron or aluminum chloride. That is, for example, the equation (20)

It is also possible to polymerize or copolymerize one or two or more of the monomers having a vinyl group represented by the formula (10) ′ by using the cationic polymerization catalyst.

A water-soluble polymer having a repeating structure (polyvinyl structure) represented by can be produced.

（式中、Ｙ＝−Ｏ−のとき、Ｐ²＝アルキル基であって、式（２０）は、ビニルアルキルエーテル（２０)ｂ

を示し、
Ｙ＝−Ｎ（−Ｑ）−のとき、Ｐ²とＱとは協力してラクタム環基を形成して、式（２０）は、Ｎ−ビニルラクタム（２０)ｃ

（式中、Ｗ^cは式−(ＣＲ^cＲ^d)ｎ−で示されるポリメチレン基を表し、置換基Ｒ^c，Ｒ^dはそれぞれ独立して水素原子、またはアルキル基を表わし、ｎは２〜８の整数を表す。）を示し、式（２０)ｃのうち、次式（２０)ｃ’

（ただし、ｎは、１〜７の整数を表す。）が好ましい。）で示されるビニル基を有するモノマーの少なくとも１種を重合させることによっても得ることができる。得られる目的の水溶性高分子は、式（１０)’

（式中、Ｙ＝−Ｏ−のとき、Ｐ²＝アルキル基であって、式（１０)’は、アルコキシエチレン残基（１０)ｂ

で示される繰り返し構造（ポリビニルアルキルエーテル構造）を示し、
Ｙ＝−Ｎ（−Ｑ）−のとき、Ｐ²とＱとは協力してラクタム環基を形成して、式（１０)’は、
アミドエチレン残基

（式中、Ｗ^cは式−(ＣＲ^cＲ^d)ｎ−で示されるポリメチレン基を表し、置換基Ｒ^c，Ｒ^dはそれぞれ独立して水素原子、またはアルキル基を表わし、ｎは２〜８の整数を表す。）で示される繰り返し構造を示し、式（１０)ｃのうち、次式（１０)ｃ’

（ただし、ｎは、１〜７の整数を表す。）で示される繰り返し構造（ポリビニルラクタム構造）が好ましい。）で示される化学構造（ポリビニル構造）を繰り返し構造として有する水溶性高分子が好ましい。 That is, the water-soluble polymer (10) ′ having a polyvinyl structure as a repeating structure particularly preferably used in the present invention has the formula (20)

(In the formula, when Y = —O—, P ² = alkyl group, and the formula (20) is a vinyl alkyl ether (20) b

Indicate
When Y = —N (—Q) —, P ² and Q cooperate to form a lactam ring group, and the formula (20) is N-vinyllactam (20) c

Wherein W ^c represents a polymethylene group represented by the formula — (CR ^c R ^d ) n—, the substituents R ^c and R ^d each independently represent a hydrogen atom or an alkyl group, and n represents 2 to 2 Represents an integer of 8), and of the formula (20) c, the following formula (20) c ′

(However, n represents an integer of 1 to 7). It can also be obtained by polymerizing at least one monomer having a vinyl group represented by The target water-soluble polymer obtained is represented by the formula (10) ′

(In the formula, when Y = —O—, P ² = alkyl group, and the formula (10) ′ represents an alkoxyethylene residue (10) b

The repeating structure (polyvinyl alkyl ether structure) shown by
When Y = -N (-Q)-, P ² and Q cooperate to form a lactam ring group, and the formula (10) '
Amidoethylene residue

Wherein W ^c represents a polymethylene group represented by the formula — (CR ^c R ^d ) n—, the substituents R ^c and R ^d each independently represent a hydrogen atom or an alkyl group, and n represents 2 to 2 8 represents an integer of 8), and of formula (10) c, the following formula (10) c ′

(However, n represents the integer of 1-7.) The repeating structure (polyvinyl lactam structure) shown by this is preferable. A water-soluble polymer having a chemical structure (polyvinyl structure) represented by () as a repeating structure is preferable.

The alkyl groups P ² , R ^a , R ^b , R ^c , and R ^d are preferably a linear or branched chain or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples thereof include methyl Group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Linear or branched chain alkyl groups such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. A cyclic alkyl group is mentioned, Among these, a C1-C8 alkyl group is preferable, and a methyl group, an ethyl group, n-propyl group, i-propyl group, n- Butyl group, i- butyl group, sec- butyl group, more preferably a lower alkyl group having 1 to 4 carbon atoms a t- butyl group and the like. Methylene group forming the N- vinyllactam (20) c and the amidoethylene residue (10) c lactam ring - (CH ₂₎ n- of n is preferably an integer of 1 to 7, 1 to 5 An integer of is more preferable.

の具体例としては、
ｎ＝１のラクタム環基（β−プロピオラクタム基）

ｎ＝２のラクタム環基（γ−ブチロラクタム基＝ビニルピロリドンまたはその重合体のラクタム環基）

ｎ＝３のラクタム環基（δ−バレロラクタム基）

ｎ＝４のラクタム環基（ε-カプロラクタム基＝ビニルカプロラクタムまたはその重合体のラクタム環基）

ｎ＝５のラクタム環基

などが挙げられる。 Of the lactam ring groups formed by the cooperation of P ² and Q, particularly preferred lactam ring groups (n = n)

As a specific example of
n = 1 lactam ring group (β-propiolactam group)

n = 2 lactam ring group (γ-butyrolactam group = vinylpyrrolidone or a lactam ring group of a polymer thereof)

n = 3 lactam ring group (δ-valerolactam group)

n = 4 lactam ring group (ε-caprolactam group = vinyl caprolactam or polymer lactam ring group)

n = 5 lactam ring group

Etc.

  Specific examples of the particularly preferable water-soluble polymer having the polyvinyl structure as a repeating structure include polyvinyl pyrrolidone, polyvinyl caprolactam, and copolymers thereof, or polyvinyl methyl ether, polyvinyl ethyl ether, and copolymers thereof. Etc. The copolymerization ratio of the copolymer is arbitrary. The polymer to be used may be water-soluble, but the preferred range of the weight average molecular weight of the water-soluble polymer varies depending on the type of monomer, but it is usually desirable to be in the range of 1000 to 2,000,000, more preferably 5000. It is in the range of ~ 2,000,000. If the molecular weight is low, a sufficient effect may not be obtained, and the resist may be dissolved. If it exceeds 2,000,000, it may be difficult to dissolve, or application may be difficult due to an increase in viscosity of the composition after dissolution. As the polyvinyl pyrrolidone, those having a weight average molecular weight of 100,000 or more, preferably in the range of 800,000 to 2,000,000, more preferably 1,000,000 to 1,800,000 are used. If it is less than 100,000, the desired effect may not be obtained.

  The specific water-soluble polymer having the polyvinyl structure as a repeating structure according to the present invention can prevent mixing while maintaining good coatability by containing these in combination with a surfactant. These volume-dependent effects of the specific water-soluble polymer having the polyvinyl structure as a repeating structure according to the present invention have a volume dependency, and are usually in the range of 0.0001 to 10% with respect to the entire composition, more preferably. Is used in the range of 0.01 to 2% by mass. If the amount is too small, the effect of suppressing mixing may be insufficient. If the amount is too large, the ratio of the conductive polymer may decrease, leading to a decrease in conductivity. Specifically, for example, the water-soluble polymer having the polyvinyl lactam structure such as polyvinyl pyrrolidone, polyvinyl caprolactam, and their polymers and copolymers has a mixing suppressing effect. Depending on the molecular weight, the mixing suppression effect tends to increase as the molecular weight increases. Moreover, the same mixing suppression effect is recognized also by the water-soluble polymer which has the said polyvinyl alkyl ether structure. In addition, even if it contains the water-soluble polymer which has the said polyvinyl structure based on this invention, the influence on a resist is not recognized. On the other hand, when polyacrylic acid, polyacrylamide, or polystyrene sulfonic acid is used as the water-soluble polymer, mixing is not suppressed regardless of the molecular weight. That is, when a surfactant and these water-soluble polymers are contained in the conductive polymer, the coating property is improved, but mixing with the resist occurs, and in the case of a negative resist, the development time is extended. In addition, a water-soluble polymer having a basic residue such as polyvinylimidazole, polyallylamine, or polyethyleneimine is not preferable because it may cause precipitation when used in combination with a water-soluble conductive polymer having a sulfonic acid group.

  The antistatic agent of the present invention, in particular, the antistatic agent using the water-soluble polymer having the polypeptide structure or the specific water-soluble polymer having the polyvinyl structure as a repeating structure, only suppresses mixing of the chemically amplified resist. In addition, it is effective in suppressing mixing with non-chemically amplified resists. That is, for example, an antistatic agent using a water-soluble polymer having the polypeptide structure or a specific water-soluble polymer having the polyvinyl structure as a repeating structure has a mixing suppression effect on a negative chemical amplification resist. In addition to this, it also shows a mixing suppression effect for non-chemically amplified resists. Further, when an antistatic agent using a specific water-soluble polymer having the polyvinyl structure as a repeating structure or a water-soluble polymer having the polypeptide structure is used, the film thickness of the positive chemical amplification resist is reduced. small. Further, the antistatic agent of the present invention can suppress the influence of the surfactant on the resist while maintaining a low contact angle even in chemically amplified resists and non-chemically amplified resists.

  These water-soluble polymers having the polypeptide structure or specific water-soluble polymers having the polyvinyl structure as a repeating structure do not cause mixing with the chemically amplified resist. Furthermore, even if the antistatic agent contains a compound that causes mixing with a resist such as a surfactant described later, the water-soluble polymer having the polypeptide structure or the polyvinyl structure is included as a repeating structure. By including a specific water-soluble polymer, resist mixing resistance can be imparted.

(IV) Surfactant The surfactant that can be used in the present invention is not particularly limited as long as it is a compound that exhibits a surfactant effect, and is an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic interface. Any activator can be used.

  Specific examples of the anionic surfactant include alkyl ether carboxylic acid, linear alkylbenzene sulfonic acid, α-olefin sulfonic acid, alkane sulfonate, dialkyl sulfosuccinic acid, naphthalene sulfonic acid formaldehyde condensate, alkyl sulfate ester, polyoxy Examples thereof include ethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, higher alcohol phosphate, higher alcohol ethylene oxide adduct phosphate, acyl-N-methyltaurine, and salts thereof.

  Specific examples of the cationic surfactant include monoalkylammonium, dialkylammonium, ethoxylated ammonium, quaternary amine, alkylamine acetic acid and the like, and salts thereof can also be used.

  Specific examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, lauryldimethylamine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauric acid amidopropyl betaine , Lauryl hydroxysulfobetaine, alanines and the like, and salts thereof can also be used.

  Specific examples of the nonionic surfactant include glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, alkyl glyceryl ether, polyoxyethylene alkylphenyl ether Tellurium, polyoxyethylene polyoxypropylene ether, polyoxyalkylene alkyl ether, acetylene glycol, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, alkyl glyceryl ether, fatty acid alkylene oxide adduct, polyoxyethylene hydrogenated castor oil, Fatty acid alkanolamide, fatty acid amide alkylene oxide adduct, amine EO adduct, Examples include amine PO adducts.

  These surfactants can be used alone or in admixture of two or more. Preferably, the surfactant is at least one of an anionic surfactant and an amphoteric surfactant, and further, a surfactant such as an amphoteric surfactant, a nonionic surfactant, a cationic surfactant, or a water-soluble polymer. It is also possible to use a mixture of compounds having an effect.

(V) Blending amount The blending amount of each component of the antistatic agent of the present invention is a water-soluble conductive polymer of 0.1 to 20% by mass, a water-soluble polymer having the polypeptide structure, or a repeating structure of the polyvinyl structure. The specific water-soluble polymer 0.0001 to 10% by mass and 70.0 to 99.8% by mass of the solvent are preferable. More preferably, the water-soluble conductive polymer is 0.2 to 5% by mass, the water-soluble polymer having the polypeptide structure, or the specific water-soluble polymer having the polyvinyl structure as a repeating structure is 0.01 to 2% by mass and the solvent. It is 93-99.7 mass%.

  Further, in the composition containing the surfactant, 0.0001 to 20% by mass of the water-soluble conductive polymer, the water-soluble polymer having the polypeptide structure, or the specific water-soluble polymer having the polyvinyl structure as a repeating structure is 0.0001. -10 mass%, surfactant 0.0001-2 mass%, and solvent 68.0-99.8 mass% are preferable. More preferably, the water-soluble conductive polymer is 0.2 to 5% by mass, the water-soluble polymer having the polypeptide structure, or the specific water-soluble polymer having the polyvinyl structure as a repeating structure is 0.01 to 2% by mass, the surface activity. 0.0001 to 10% by mass of the agent and 83 to 99.7% by mass of the solvent.

  When the amount of the water-soluble polymer having the polypeptide structure or the specific water-soluble polymer having the polyvinyl structure as a repeating structure is less than 0.0001% by mass, the effect of suppressing the mixing layer formation on the resist cannot be expected. Moreover, since there exists a possibility that electroconductivity may fall when it exceeds 10 mass%, it is unpreferable. The water solubility of the water-soluble polymer having the polypeptide structure or the specific water-soluble polymer having the polyvinyl structure as a repeating structure used in the present invention is dissolved in an addition amount that exhibits the above effect. Say.

(VI) Applications The antistatic agent of the present invention can be used for both non-chemically amplified resists and chemically amplified resists. Further, it can be used for both positive resists and negative resists.

For non-chemically amplified resists, it is effective as an antistatic agent with excellent coating properties. Specific examples of non-chemically amplified resists include phenolic resins such as novolak resins, acrylic resins such as polymethyl methacrylate resins and polyacrylate resins, copolymer systems of α-methylstyrene and α-chloroacrylic acid, etc. An example is calix arene.
In addition, non-chemically amplified resists include inorganic resists, but specific examples include those obtained by dissolving hydrogensilsesquioxane (HSQ) in a solvent such as methyl isobutyl ketone. HSQ is used as an interlayer insulating film of a semiconductor device such as a flash memory, and the resist has a strong surface hydrophobicity. This resist may cause resist mixing by an antistatic agent.

  For a chemically amplified resist, it is more effectively recognized that the mixing layer on the contact surface between the antistatic film of the present invention and the chemically amplified resist is prevented from being formed. Specific examples of the chemically amplified resist include photosensitive resins such as phenol resin, acrylic resin, and azide compound, polymethacrylate resin, polyvinylphenol and polyhydroxystyrene, α-methylstyrene and α-chloroacryl. Examples thereof include charged particle beam resins such as a copolymer system with an acid.

  Further, additives such as a photosensitizer, an azide compound, a crosslinking agent, a dissolution inhibitor, and an acid generator may be added to the non-chemical amplification resist and the chemical amplification resist.

The antistatic agent of the present invention is M ⁺ -OH ⁻ for neutralizing Bronsted acid of water-soluble conductive polymer and other additives contained in the solution, wherein M ⁺ has the same meaning as above, Represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion). By changing the addition amount of this compound, the pH of the antistatic agent can be arbitrarily adjusted between acidic and alkaline.
The pH of the antistatic agent of the present invention is preferably pH 2-9, and more preferably pH 3-8. When a chemically amplified resist is used, if the pH is less than 2, the proton concentration is high and there is a possibility of adversely affecting the developing performance of the resist. If the pH exceeds 9, the water-soluble conductive polymer may be undoped and the electrical conductivity may be lowered.

  The antistatic agent of the present invention is applied to the resist surface to form an antistatic film. As a method of applying the antistatic agent to the resist surface, a spin coating method is preferable, but other methods such as a dipping method (dipping method), a spraying method, a bar coater method, and the like may be used. After the application, the antistatic film is formed by air-drying at room temperature or by heat-treating the substrate on which the resist is applied with an oven or a hot plate. Note that heat treatment in an inert gas atmosphere is more preferable for removing the solvent.

  Examples of the article coated with the antistatic film of the present invention include a substrate in which an antistatic film and a resist are laminated. Examples of the substrate material include a compound semiconductor wafer such as a silicon wafer, a gallium arsenide wafer, and an indium phosphide wafer, a quartz substrate, a glass substrate, and a magnetic substrate. Moreover, it can also coat | cover with the material to process, such as when shape | molding with an ion beam etc., without using a resist.

  The article of the present invention includes a substrate that temporarily exists in a semiconductor manufacturing process and a manufacturing process of a photomask, a reticle, a stencil mask, a nanoimprint template, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is further demonstrated, this invention is not restrict | limited at all by the following examples. The pH of the aqueous solution was measured with a glass electrode type hydrogen ion concentration meter pH METER F-13 (manufactured by Horiba, Ltd.).

[Water-soluble conductive polymer]
Poly (5-sulfoisothianaphthene-1,3-diyl):
Poly (5-sulfoisothianaphthene-1,3-diyl) was synthesized and purified with reference to the method described in JP-A-7-48436. The obtained water-soluble conductive polymer had a sulfonic acid substitution product composition of almost 100 mol% (1.0 mol fraction) when the substitution rate of the polymer repeating unit by the sulfonic acid group was determined by neutralization titration with alkali. It was a polymer. As for molecular weight, the number average molecular weight was 18000 from GPC measurement (in terms of sodium polystyrene sulfonate). The obtained poly (5-sulfoisothianaphthene-1,3-diyl) was prepared to be a 0.1 wt% aqueous solution and concentrated with Millipore Pericon XL (membrane type Biomax-10) so as to be 1 wt%. did. It refine | purified by repeating this operation 5 times.
Poly (3- (3-thienyl) propanesulfonic acid):
Poly (3- (3-thienyl) propanesulfonic acid) is the 39th Polymer Society of Japan Preliminary Proceedings (Vol. 39, Polymer Preprints Japan). It was synthesized using the method described on page 561 (1990). As for the molecular weight, the weight average molecular weight was 100,000 from GPC measurement (in pullulan conversion). The obtained poly (3- (3-thienyl) propanesulfonic acid) was prepared to be a 0.1 wt% aqueous solution, and concentrated with Pellicon XL (membrane type Biomax-10) manufactured by Millipore to be 1 wt%. It refine | purified by repeating this operation 5 times.
Poly (aniline-3-sulfonic acid):
Poly (aniline-3-sulfonic acid) is described in J. Org. Am. Chem. Soc. , 112.2800 pages (1990). As for the molecular weight, the weight average molecular weight was 20000 from GPC measurement (in pullulan conversion). The obtained poly (aniline-3-sulfonic acid) was prepared to be a 0.1 wt% aqueous solution, and was concentrated with Pellicon XL (membrane type Biomax-10) manufactured by Millipore so as to be 1 wt%. It refine | purified by repeating this operation 5 times.

[Water-soluble polymer having a polypeptide structure]
Hydrolyzed collagen (additive A): Promois W-42SP (Mn: 1000)
Hydrolyzed collagen (additive B): Promois W-32 (Mn: 400)
Hydrolyzed collagen (additive C): Promois W-52P (Mn: 2000)
Hydrolyzed keratin (additive D): Promois WK-H (Mn: 1000)
Hydrolyzed keratin (additive E): Promois WK-L (Mn: 4000)
Hydrolyzed silk (additive F): Promois SILK-700SP (Mn: 350)
Hydrolyzed silk (additive G): Promois SILK-1000P (Mn: 1000)
The molecular weight of each additive is shown by the number average molecular weight (Mn), the additives A to F are calculated based on the total nitrogen amount and the amino acid nitrogen amount, and the additive G is measured by gel filtration analysis. is there. All the water-soluble polymers having the above polypeptide structure are manufactured by Seiwa Kasei Co., Ltd.

[Water-soluble polymer having a polyvinyl structure as a repeating structure]
・ Polyvinyl methyl ether (additive H): 50% aqueous solution of poly (methyl vinyl ether) manufactured by Aldrich ・ Polyvinylpyrrolidone (additive I): manufactured by Aldrich (Mw 1300000)
-Vinylpyrrolidone / vinyl caprolactam copolymer (additive J): Lustec VPC55K65W manufactured by BASF
Polyvinylcaprolactam (additive K): produced by purifying Luvicap EG manufactured by BASF with an ultrafiltration membrane.
・ Polyvinylpyrrolidone (Additive L): Aldrich (Mw55,000)
Polystyrene sulfonate ammonium salt (additive M): Aldrich (Mw200,000)
・ Polyacrylamide (Additive N): Aldrich (Mw10,000)
・ Polyacrylic acid (Additive O): Aldrich (Mw250,000)
For purification using an ultrafiltration membrane, Millipore Pellicon XL (membrane type Biomax-5) is used, and BASF Luvicap EG is repeatedly diluted and concentrated with purified water to remove solvents other than purified water. This was done by removing.

[Surfactant]
・ Dodecylbenzenesulfonic acid (additive P): Perex FS manufactured by Kao Corporation
・ Alkyl diphenyl ether disulfonic acid (additive Q): Desulfurization of perex SSH (sodium alkyl diphenyl ether disulfonate) manufactured by Kao Corporation with a cationic ion exchange resin (Amberlite IR-120B manufactured by Organo Corporation) Produced by.

Example 1
By dissolving 0.6 parts by mass of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.2 parts by mass of hydrolyzed collagen (additive A) in water to make the total amount 80 parts by mass, adding ammonia water After adjusting to pH 4.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass.
Using the obtained antistatic agent, contact angle measurement with a negative chemical amplification resist (contact angle measurement A), development time measurement of a negative chemical amplification resist (measurement condition B), charging by the following methods The surface resistance of the inhibitor (measurement condition F) was measured. The results are shown in Table 1.

Example 2
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass, dodecylbenzenesulfonic acid (additive P) 0.025 parts by mass, hydrolyzed collagen (additive A) 0.1 parts by mass dissolved in water Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, contact angle measurement with a negative chemical amplification resist (contact angle measurement A), development time measurement of a negative chemical amplification resist (measurement condition B), charging by the following methods The surface resistance of the inhibitor (measurement condition F) was measured. The results are shown in Table 1.

Example 3
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass, dodecylbenzenesulfonic acid (additive P) 0.025 parts by mass, hydrolyzed collagen (additive A) 0.2 parts by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, the contact angle measurement with respect to the negative chemical amplification system resist (contact angle measurement A) and the development time measurement of the negative type chemical amplification system resist (measurement conditions B and B−) are as follows. 2) The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Tables 1 and 2.

Example 4
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 part by mass, alkyldiphenyl ether disulfonic acid (additive Q) 0.05 part by mass, hydrolyzed collagen (additive A) 0.1 part by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, contact angle measurement with a negative chemical amplification resist (contact angle measurement A), development time measurement of a negative chemical amplification resist (measurement condition B), charging by the following methods The surface resistance of the inhibitor (measurement condition F) was measured. The results are shown in Table 1.

Example 5
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 part by mass, alkyldiphenyl ether disulfonic acid (additive Q) 0.05 part by mass, hydrolyzed collagen (additive A) 0.2 part by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, contact angle measurement with a negative chemical amplification resist (contact angle measurement A) and contact angle measurement with a positive chemical amplification resist (contact angle measurement B) by the following methods The development time measurement of the negative chemical amplification resist (measurement condition B), the film loss measurement of the positive chemical amplification resist (measurement condition E), and the measurement of the surface resistance of the antistatic agent (measurement condition F) were performed. The results are shown in Tables 1 and 7.

Example 6
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass, dodecylbenzenesulfonic acid (additive P) 0.025 parts by mass, hydrolyzed collagen (additive B) 0.2 parts by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 2.

Example 7
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass, dodecylbenzenesulfonic acid (additive P) 0.025 parts by mass, hydrolyzed collagen (additive C) 0.2 parts by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 2.

Example 8
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 part by mass, dodecylbenzenesulfonic acid (additive P) 0.025 part by mass, hydrolyzed keratin (additive D) 0.2 part by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 2.

Example 9
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass, dodecylbenzenesulfonic acid (additive P) 0.025 parts by mass, hydrolyzed keratin (additive E) 0.2 parts by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 2.

Example 10
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 part by mass, dodecylbenzenesulfonic acid (additive P) 0.025 part by mass, hydrolyzed silk (additive F) 0.2 part by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 2.

Example 11
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass, dodecylbenzenesulfonic acid (additive P) 0.025 parts by mass, hydrolyzed silk (additive G) 0.2 parts by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 2.

Example 12
By dissolving 0.6 parts by mass of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.2 parts by mass of polyvinyl methyl ether (additive H) in water, the total amount is 80 parts by mass, and adding ammonia water. After adjusting to pH 4.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass.
Using the obtained antistatic agent, contact angle measurement with a negative chemical amplification resist (contact angle measurement A), development time measurement of a negative chemical amplification resist (measurement condition B), charging by the following methods The surface resistance of the inhibitor (measurement condition F) was measured. The results are shown in Table 3.

Examples 13-24
As in Example 12, an antistatic agent was prepared using a water-soluble polymer (additives H to K) having a polyvinyl structure as a repeating structure and surfactants (additives P and Q) shown in Table 3. did.
Using the obtained antistatic agent, the contact angle measurement with respect to the negative chemical amplification system resist (contact angle measurement A), the development time measurement of the negative chemical amplification system resist (measurement condition C), and charging by the following methods The surface resistance of the inhibitor (measurement condition F) was measured. The results are shown in Table 3.

Example 25
Poly (3- (3-thienyl) propanesulfonic acid)) 0.6 parts by mass, dodecylbenzenesulfonic acid (additive P) 0.025 parts by mass, hydrolyzed collagen (additive A) 0.2 parts by mass are dissolved in water, After adjusting the pH to 4.5 by adding ammonia water to 80 parts by mass, water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods Went. The results are shown in Table 4.

Example 26
Dissolve 0.6 parts by mass of sulfonated polyaniline, 0.025 parts by mass of dodecylbenzenesulfonic acid (additive P), 0.2 parts by mass of hydrolyzed collagen (additive A) in water to make the total amount 80 parts by mass, and add ammonia water. After adjusting the pH to 4.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods Went. The results are shown in Table 4.

Example 27
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 part by mass, dodecylbenzenesulfonic acid (additive P) 0.05 part by mass, hydrolyzed collagen (additive A) 0.2 part by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the resulting antistatic agent, measurement of the contact angle to the negative chemically amplified resist (contact angle measurement A-2) and development time measurement of the negative chemically amplified resist (measurement condition C) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 5.

Example 28
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass, dodecylbenzenesulfonic acid (additive P) 0.05 parts by mass, polyvinyl methyl ether (additive H) 0.2 parts by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the resulting antistatic agent, measurement of the contact angle to the negative chemically amplified resist (contact angle measurement A-2) and development time measurement of the negative chemically amplified resist (measurement condition C) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 5.

Example 29
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 part by mass, dodecylbenzenesulfonic acid (additive P) 0.1 part by mass, hydrolyzed collagen (additive A) 0.2 part by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, the contact angle measurement with respect to the negative non-chemical amplification resist (contact angle measurement A-3) and the development time measurement of the negative non-chemical amplification resist (measurement) by the following methods Condition D) was performed. The results are shown in Table 6.

Example 30
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 part by mass, dodecylbenzenesulfonic acid (additive P) 0.1 part by mass, polyvinyl methyl ether (additive H) 0.2 part by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, the contact angle measurement with respect to the negative non-chemical amplification resist (contact angle measurement A-3) and the development time measurement of the negative non-chemical amplification resist (measurement) by the following methods Condition D) was performed. The results are shown in Table 6.

Comparative Example 1
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass is dissolved in water to a total amount of 80 parts by mass, adjusted to pH 4.5 by adding aqueous ammonia, and then added with water. The antistatic agent was prepared at 100 parts by mass.
Using the obtained antistatic agent, the contact angle measurement with respect to the negative chemical amplification resist (contact angle measurement A) and the development time measurement of the negative chemical amplification resist (measurement condition B) in the same manner as in Example 1. ) And measurement of the surface resistance of the antistatic agent (measurement condition F). The results are shown in Table 1.

Comparative Example 2
By dissolving 0.6 parts by mass of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.025 parts by mass of dodecylbenzenesulfonic acid (Additive P) in water to a total amount of 80 parts by mass and adding aqueous ammonia After adjusting to pH 4.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass. Using the obtained antistatic agent, the contact angle measurement with respect to the negative chemical amplification resist (contact angle measurement A) and the development time measurement of the negative chemical amplification resist (measurement condition B) in the same manner as in Example 1. And B-2), the surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Tables 1 and 2.

Comparative Example 3
By dissolving 0.6 parts by mass of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.050 parts by mass of alkyldiphenyl ether disulfonic acid (Additive Q) in water to make 80 parts by mass, and adding ammonia water After adjusting to pH 4.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass. Using the obtained antistatic agent, the contact angle measurement with respect to the negative chemical amplification resist (contact angle measurement A) and the contact angle measurement with respect to the positive chemical amplification resist (contact angle) in the same manner as in Example 5. Measurement A-4), development time measurement of negative chemically amplified resist (measurement condition B), film loss measurement of positive chemically amplified resist (measurement condition E), measurement of surface resistance of antistatic agent (measurement condition F) ) The results are shown in Tables 1 and 7.

Comparative Examples 4-7
Instead of the additive H in Example 12, an antistatic agent was prepared using the water-soluble polymer (additives L to O) and the surfactant (additive P) shown in Table 3.
Using the obtained antistatic agent, contact angle measurement with a negative chemical amplification resist (contact angle measurement A), development time measurement of a negative chemical amplification resist (measurement condition B), charging by the following methods The surface resistance of the inhibitor (measurement condition F) was measured. The results are shown in Table 3.

Comparative Example 8
By dissolving 0.6 parts by mass of poly (3- (3-thienyl) propanesulfonic acid) and 0.025 parts by mass of dodecylbenzenesulfonic acid (additive P) in water to make the total amount 80 parts by mass, adding aqueous ammonia to pH 4 After adjusting to 0.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods Went. The results are shown in Table 4.

Comparative Example 9
0.6 parts by mass of sulfonated polyaniline and 0.025 parts by mass of dodecylbenzenesulfonic acid (additive P) are dissolved in water to make the total amount 80 parts by mass. After adjusting to pH 4.5 by adding ammonia water, water is further added. The antistatic agent was prepared in a total amount of 100 parts by mass.
Using the obtained antistatic agent, measurement of contact angle to negative chemically amplified resist (contact angle measurement A) and development time measurement of negative chemically amplified resist (measurement condition B-2) by the following methods Went. The results are shown in Table 4.

Comparative Example 10
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass and dodecylbenzenesulfonic acid (additive P) 0.05 parts by mass are dissolved in water, the total amount is 80 parts by mass, and ammonia water is added. After adjusting the pH to 4.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass.
Using the resulting antistatic agent, measurement of the contact angle to the negative chemically amplified resist (contact angle measurement A-2) and development time measurement of the negative chemically amplified resist (measurement condition C) by the following methods The surface resistance of the antistatic agent was measured (measurement condition F). The results are shown in Table 5.

Comparative Example 11
Dissolve 0.6 parts by mass of poly (5-sulfoisothianaphthene-1,3-diyl) and 0.1 parts by mass of dodecylbenzenesulfonic acid (additive P) in water to a total amount of 80 parts by mass, and add ammonia water. After adjusting the pH to 4.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass.
Using the obtained antistatic agent, the contact angle measurement with respect to the negative non-chemical amplification resist (contact angle measurement A-3) and the development time measurement of the negative non-chemical amplification resist (measurement) by the following methods Condition D) was performed. The results are shown in Table 6.

Comparative Example 12
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass is dissolved in water, the total amount is 80 parts by mass, and after adjusting to pH 4.5 by adding ammonia water, water is further added, An antistatic agent was prepared in a total amount of 100 parts by mass.
Using the obtained antistatic agent, the contact angle measurement with respect to the negative non-chemical amplification resist (contact angle measurement A-3) and the development time measurement of the negative non-chemical amplification resist (measurement) by the following methods Condition D) was performed. The results are shown in Table 6.

  The measurement method and evaluation method of each physical property are as follows. In the following, spinner 1H-III (manufactured by Kyoei Semiconductor Co., Ltd.) is used for spin coating of antistatic film and resist film, peeling of antistatic film with ultrapure water, and shaking off developer after development. Using. Further, the resist film thickness and the antistatic film thickness are obtained by digging a groove having a width of about 1 mm in each film and measuring the step with a stylus type step gauge Dektak-3030 (manufactured by Nippon Vacuum Co., Ltd.). It was.

1) Contact angle measurement for negative chemical amplification resist (contact angle measurement A)
The contact angle was measured with a DM-500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. In the contact angle measurement, the contact angle between the droplet and the resist film was read 30 seconds after the droplet of the antistatic agent was formed on the resist film surface. The resist film was dropped on a 4 × 4 cm silicon wafer by 0.2 mL of a negative chemical amplification resist, and immediately applied by spin coating at 1500 rpm using a spinner, and pre-baked on a hot plate at 105 ° C. for 90 seconds to remove the solvent. It was produced by removing. The negative chemical amplification type resist used was Microposit SAL-601-SR2 E-beam resist manufactured by Rohm and Haas Electronic Materials.

1-2) Measurement of contact angle to negative chemical amplification resist (contact angle measurement A-2)
The contact angle was measured with a DM-500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. In the contact angle measurement, the contact angle between the droplet and the resist film was read 30 seconds after the droplet of the antistatic agent was formed on the resist film surface. The resist film is 0.2 mL of a negative chemical amplification resist on a 4 × 4 cm silicon wafer, and immediately applied by spin coating at 1500 rpm using a spinner, and pre-baking is performed at 105 ° C. for 90 seconds on a hot plate. It was produced by removing. As the negative chemical amplification resist, FEN-270 resist manufactured by Fuji Film Electronics Materials Co., Ltd. was used.

1-3) Measurement of contact angle for non-chemically amplified resist (contact angle measurement A-3)
The contact angle was measured with a DM-500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. In the contact angle measurement, the contact angle between the droplet and the resist film was read 30 seconds after the droplet of the antistatic agent was formed on the resist film surface. The resist film is a 0.2 × 4 cm negative non-chemical amplification resist on a 4 × 4 cm silicon wafer, immediately spin-coated using a spinner at 1500 rpm, and prebaked at 180 ° C. for 40 minutes on a hot plate. It was produced by removing. The non-chemically amplified resist used was Fox-12 resist manufactured by Dow Corning.

1-4) Measurement of contact angle for positive chemically amplified resist (contact angle measurement A-4)
The contact angle was measured with a DM-500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. In the contact angle measurement, the contact angle between the droplet and the resist film was read 30 seconds after the droplet of the antistatic agent was formed on the resist film surface. The resist film was dropped onto a 4 × 4 cm silicon wafer by 0.2 mL of a positive chemical amplification resist, and immediately spin-coated using a spinner at 1500 rpm, pre-baked on a hot plate at 120 ° C. for 90 seconds, and the solvent was removed. It was produced by removing. As the positive chemical amplification resist, FEP-171 resist manufactured by Fuji Film Electronics Materials Co., Ltd. was used.

2) Measurement of development time of negative chemically amplified resist (measurement condition B)
The development time of the negative chemically amplified resist was evaluated by the following procedure.
(1) Resist film formation: 0.2 mL of negative chemical amplification resist is dropped on a 4 × 4 cm silicon wafer, and immediately spin-coated at 1500 rpm using a spinner, and the solvent is removed by pre-baking at 105 ° C. for 90 seconds. Thus, a resist film having a thickness of about 300 nm was obtained. The negative chemical amplification type resist used was Microposit SAL-601-SR2 E-beam resist manufactured by Rohm and Haas Electronic Materials.
(2) Antistatic film formation: 2 mL of an antistatic agent was dropped on the coated resist surface, and after 10 minutes, spin coating was performed at 800 rpm using a spinner 1H-III (manufactured by Kyoei Semiconductor Co., Ltd.). And an antistatic film having a thickness of about 20 nm was formed.
(3) Baking treatment: A substrate on which an antistatic film and a resist were laminated was heated on a hot plate at 80 ° C. for 180 seconds, and then allowed to stand at room temperature in air for 5 minutes.
(4) Detachment of antistatic film: 10 mL of ultrapure water was dropped on the surface of the antistatic film after baking, and allowed to stand for 60 seconds, and then the antistatic agent dissolved in the ultrapure water was removed with a spin coater at 800 rpm. did.
(5) Re-bake treatment: After heating for resist post-exposure baking at 110 ° C./60 seconds, the resist was left in air at room temperature for 5 minutes.
(6) Development: 2 mL of a 2.38 mass% tetramethylammonium hydroxide aqueous solution that is a developer is dropped on the resist surface obtained in (5), and the time for the resist film in contact with the developer to disappear from the substrate is set. Measured as development time.

2-2) Development time measurement of negative chemically amplified resist (measurement condition B-2)
The development time of the negative type chemically amplified resist was measured in the same manner as in the measurement condition B except that the baking time of 2) and (3) was changed to heating at 75 ° C. for 60 seconds instead of heating at 80 ° C. for 180 seconds. .

3) Development time measurement of negative chemically amplified resist (measurement condition C)
The development time of the negative chemically amplified resist was evaluated by the following procedure.
(1) Resist film formation: 0.2 mL of negative chemical amplification resist is dropped on a 4 × 4 cm silicon wafer, and then immediately spin-coated using a spinner at 1000 rpm, and the solvent is removed by pre-baking at 120 ° C. for 90 seconds. Thus, a resist film having a thickness of about 300 nm was obtained. As the negative chemical amplification resist, FEN-270 resist manufactured by Fuji Film Electronics Materials Co., Ltd. was used.
(2) Antistatic film formation: 2 mL of antistatic treatment agent was dropped on the coated resist surface, and after 10 minutes, it was rotated at 800 rpm using a spinner 1H-III (manufactured by Kyoei Semiconductor Co., Ltd.). Application was performed to form an antistatic film having a thickness of about 20 nm.
(3) Baking treatment: A substrate on which an antistatic film and a resist were laminated was heated on a hot plate at 80 ° C. for 90 seconds, and then allowed to stand at room temperature in air for 5 minutes.
(4) Re-bake treatment: After heating for resist post-exposure baking at 110 ° C. for 90 seconds, the resist was left in air at room temperature for 5 minutes.
(5) Detachment of antistatic film: 10 mL of ultrapure water was dropped onto the surface of the antistatic film after baking, and left for 60 seconds, and then the antistatic agent dissolved in the ultrapure water was removed with a spin coater at 800 rpm. did.
(6) Development: 2 mL of a 2.38 mass% tetramethylammonium hydroxide aqueous solution that is a developer is dropped on the resist surface obtained in (5), and the time for the resist film in contact with the developer to disappear from the substrate is set. Measured as development time.

4) Development time measurement of negative type non-chemical amplification resist (Measurement condition D)
The development time of the negative type non-chemical amplification resist was evaluated by the following procedure.
(1) Resist film formation: After dropping 0.2 mL of negative non-chemical amplification resist on a 4 × 4 cm silicon wafer, immediately spin-apply at 1500 rpm using a spinner and remove the solvent by prebaking at 180 ° C. for 10 minutes. As a result, a resist film having a thickness of about 200 nm was obtained. As the negative non-chemical amplification resist, Fox-12 resist manufactured by Dow Corning was used.
(2) Antistatic film formation: 2 mL of antistatic treatment agent was dropped on the coated resist surface, and after 10 minutes, it was rotated at 800 rpm using a spinner 1H-III (manufactured by Kyoei Semiconductor Co., Ltd.). Application was performed to form an antistatic film having a thickness of about 20 nm.
(3) Detachment of antistatic film: 10 mL of ultrapure water was dropped on the surface of the antistatic film after baking, left standing for 60 seconds, and then the antistatic agent dissolved in the ultrapure water was removed with a spin coater at 800 rpm. did.
(4) Development: 2 mL of a 2.38 mass% tetramethylammonium hydroxide aqueous solution, which is a developer, is dropped on the resist surface obtained in (3), and the time for the resist film in contact with the developer to disappear from the substrate is measured. Measured as development time.
When the operation (4) was performed on the resist film (1) without using the antistatic agents of Examples and Comparative Examples of this patent, the TMAH development time was 60 seconds.

5) Film thickness measurement of positive chemically amplified resist (measurement condition E)
The film slip measurement of the positive chemically amplified resist was evaluated by the following procedure.
(1) Formation of positive resist film: 0.2 mL of positive chemical amplification resist is dropped onto a 4 × 4 cm silicon wafer, and then immediately applied by spin coating at 1500 rpm using a spinner, and prebaked at 120 ° C. for 90 seconds. The resist film with a film thickness of about 300 nm was obtained by removing. As the positive chemically amplified resist, FEP-171 resist manufactured by Fuji Film Electronics Materials Co., Ltd. was used.
(2) Measurement of film thickness: The resist film thickness was measured by digging a groove having a width of about 1 mm in the resist and using a stylus type step gauge. This was the film thickness immediately after resist application.
(3) Antistatic film formation: 2 mL of an antistatic agent is dropped onto the coated resist surface, and after 1 minute, spin coating is performed at 800 rpm using a spinner to form an antistatic film having a film thickness of about 20 nm. Formed.
(4) Baking treatment: The substrate on which the antistatic film and the resist were laminated was heated on a hot plate at 80 ° C. for 90 seconds and then left in air at room temperature for 5 minutes.
(5) Re-bake treatment: After heating for resist post-exposure baking at 110 ° C./60 seconds, the resist was left in air at room temperature for 5 minutes.
(6) Detachment of antistatic agent: 10 mL of ultrapure water was dropped on the surface of the antistatic film after the re-bake treatment, left standing for 60 seconds, and then antistatic agent dissolved in ultrapure water with a spin coater at 800 rpm. Removed.
(7) Development: 2 mL of a 2.38 mass% tetramethylammonium hydroxide aqueous solution, which is a developer, is dropped on the resist surface after removal of the antistatic film, allowed to stand at room temperature for 60 seconds, and then developed with a spin coater at 200 rpm. While shaking off, 10 mL of ultrapure water was added dropwise, and water droplets remaining on the resist surface were further shaken off at 800 rpm.
(8) Re-measurement of film thickness: The resist film thickness after development was re-measured with a stylus type step gauge in a groove having a width of about 1 mm dug in the resist. This was taken as the resist film thickness after development.
(9) Measurement of film thickness value: The film thickness value of resist was obtained by subtracting the film thickness measured in (8) from the film thickness measured in (2).

6) Measurement of surface resistance of antistatic agent (measuring condition F)
2 mL of an antistatic agent was dropped onto a 60 × 60 mm square glass substrate (# 1737 manufactured by Corning), and then spin-coated at 800 rpm using a spinner to prepare an antistatic agent coating film. The resulting antistatic agent coating film was measured for surface resistance using a surface resistance measuring device Megaresta MODEL HT-301 (manufactured by Cicid Electric Co., Ltd.).

  In Example 1, the development time can be shortened compared to Comparative Example 1 by adding a water-soluble polymer having a polypeptide structure. In Examples 2 to 5, a negative chemical amplification resist development can be achieved by adding a water-soluble polymer having a polypeptide structure that can provide a low contact angle with a surfactant and give good coating properties. Time can be shortened. In Comparative Example 1, a contact angle is large and application by spin coating causes poor application, and it cannot be applied well unless the contact angle is lowered. In Comparative Examples 2 and 3, by adding a surfactant, the contact angle can be lowered and the coating property is good and the coating failure does not occur. However, the negative chemically amplified resist is not dissolved by the developer and the development failure Happened.

  Regardless of the molecular weight of the water-soluble polymer having the polypeptide structure used in Example 1 and the type of protein raw material derived therefrom, the surfactant can have a low contact angle and can impart good coatability, and The negative chemical amplification resist development time can be shortened.

添加剤Ｈ：ポリビニルメチルエーテル
添加剤Ｉ：ポリビニルピロリドン（Ｍｗ1300000）
添加剤Ｊ：ビニルピロリドン／ビニルカプロラクタム共重合体
添加剤Ｋ：ポリビニルカプロラクタム
添加剤Ｌ：ポリビニルピロリドン（Ｍｗ55,000）
添加剤Ｍ：ポリスチレンスルホン酸ＮＨ₃（Ｍｗ200,000）
添加剤Ｎ：ポリアクリルアミド（Ｍｗ10,000）
添加剤Ｏ：ポリアクリル酸（Ｍｗ250,000）

Additive H: Polyvinyl methyl ether Additive I: Polyvinylpyrrolidone (Mw 1300000)
Additive J: Vinylpyrrolidone / vinylcaprolactam copolymer additive K: Polyvinylcaprolactam additive L: Polyvinylpyrrolidone (Mw55,000)
Additive M: Polystyrenesulfonic acid NH ₃ (Mw200,000)
Additive N: Polyacrylamide (Mw10,000)
Additive O: Polyacrylic acid (Mw250,000)

In Examples 12 to 14, the negative chemical amplification resist development time can be shortened by including a specific water-soluble polymer having a polyvinyl structure as a repeating structure.
In Examples 15 to 24, by containing a specific water-soluble polymer having a low contact angle with a surfactant and imparting good coating properties and having a polyvinyl structure as a repeating structure, The amplification system resist development time can be shortened.
In Comparative Examples 4 to 7, by containing a surfactant and a water-soluble polymer, the contact angle can be reduced and the coating property is good and no coating failure occurs. Dissolving and development failure occurred.

    In Examples 25 and 26, the development time can be shortened by adding a water-soluble polymer (additive A) having a polypeptide structure. Not only poly (5-sulfoisothianaphthene-1,3-diyl) but also poly (3- (3-thienyl) propanesulfonic acid)) and sulfonated polyaniline, a water-soluble polymer having a polypeptide structure or An antistatic agent containing a specific water-soluble polymer having a polyvinyl structure as a repeating structure is unlikely to cause resist mixing. Comparative Examples 8 and 9 contained surfactant P and could be applied to a resist substrate, but the negative chemical amplification resist was not dissolved by the developer, resulting in poor development.

Examples of Fox-12, a negative non-chemical amplification resist of Examples 29 and 30, which is an antistatic agent containing a water-soluble polymer having a polypeptide structure or a specific water-soluble polymer having a polyvinyl structure as a repeating structure The TMAH development time and the TMAH development time in the case where no antistatic agent is used are substantially the same, whereas the TMAH development time in Comparative Example 11 is shortened, and the water-soluble polymer having a polypeptide structure or polyvinyl Resist mixing is suppressed by an antistatic agent containing a specific water-soluble polymer having a structure as a repeating structure.
Since Example 12 did not contain a surfactant, the contact angle with Fox-12 was as high as 79 ° and could not be applied to Fox-12. A resist that is difficult to apply such as Fox-12 requires a surfactant. In order to prevent resist mixing, a water-soluble polymer having a polypeptide structure or a specific structure having a polyvinyl structure as a repeating structure is required. An antistatic agent containing a water-soluble polymer is required.

  In the positive chemical amplification resist, the influence on the resist appears as a film reduction. When the antistatic agent of Comparative Example 3 was used, the film shear value was 20 nm, but the polypeptide structure used in Example 5 The film shear value could be reduced to 16 nm by using an antistatic agent to which a water-soluble polymer having s was added. That is, the antistatic agent of the present invention can suppress the influence of the surfactant on the resist while maintaining a low contact angle even in a positive chemical amplification resist.

Example 31
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 part by mass, alkyl diphenyl ether disulfonic acid (additive Q) 0.075 part by mass, hydrolyzed collagen (additive A) 0.2 part by mass are dissolved in water, and the total amount Was adjusted to pH 4.5 by adding ammonia water, and water was further added to prepare an antistatic agent with a total amount of 100 parts by mass.
Using the obtained antistatic agent, electron beam drawing was performed by the following method to evaluate resist pattern formation.

The resist pattern formation evaluation method by electron beam drawing is as follows.
(1) Resist film formation: A resist film was prepared by dropping 0.2 mL of a negative chemical amplification resist onto a 2 × 2 cm silicon wafer and spin-coating it at 2000 rpm for 60 seconds using a spinner. After coating, the solvent was removed by pre-baking at 105 ° C. for 60 seconds on a hot plate, and the resist film having a film thickness of about 300 nm was obtained by cooling in the atmosphere at room temperature for 5 minutes. The negative chemical amplification type resist used was Microposit SAL-601-SR2 E-beam resist manufactured by Rohm and Haas Electronic Materials.
(2) Antistatic film formation: 2 mL of an antistatic agent was dropped on the coated resist surface, and after 10 minutes, spin coating was performed at 1500 rpm using a spinner to charge the resist with a film thickness of about 20 nm. A prevention film was formed.
(3) Baking treatment: The substrate on which the antistatic film and the resist were laminated was heated on a hot plate at 75 ° C. for 180 seconds and then left in air at room temperature for 10 minutes.
(4) Electron beam drawing: Electron beam drawing was performed using JBX-6000FS manufactured by JEOL. In the electron beam exposure, thin lines of a line and space design (L / S) were drawn under the conditions of a current amount of 100 pA and a DOSE amount of 5 to 52.5 μC / cm ² . L / S was set to have a length of 50 μm, a pitch width of 200 nm, 500 nm, and 1000 nm, and a line and space having the same width.
(5) Detachment of antistatic film: The antistatic film was removed by allowing it to stand on the surface of the antistatic film after baking for 30 seconds after leaving it in pure water and drying with nitrogen gas.
(6) Re-bake treatment: After heating for resist post-exposure baking conditions at 115 ° C./60 seconds, the resist was left at room temperature in air for 5 minutes.
(7) Development: The resist-coated substrate obtained in (6) is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution as a developer for 5 minutes for development, and further immersed in pure water for 30 seconds. Rinse.
(8) Resist pattern formation evaluation by electron beam drawing was performed by SEM observation of the resist pattern obtained by development.

Comparative Example 13
Poly (5-sulfoisothianaphthene-1,3-diyl) 0.6 parts by mass and alkyl diphenyl ether disulfonic acid (additive Q) 0.075 parts by mass are dissolved in water, the total amount is 80 parts by mass, and ammonia water is added. After adjusting the pH to 4.5, water was further added to prepare an antistatic agent in a total amount of 100 parts by mass.
Using the resulting antistatic agent, electron beam drawing was performed in the same manner as in Example 31 to evaluate resist pattern formation.

As a result, when the antistatic agent obtained in Comparative Example 13 was used, in the top view observation with an optical microscope, there were many remaining resist portions in addition to the electron beam irradiated portions, and the L / S pattern There was no space in the drawing portion, and the desired resist pattern could not be obtained. On the other hand, when the antistatic agent obtained in Example 31 was used, a desired line and space resist pattern was obtained. When the resist cross section was observed by SEM, the optimum DOSE amount was 10 to 14 μC / cm ² at 250 μmL / S.

Claims (15)

A water-soluble conductive polymer, a solvent and a water-soluble polymer having a polypeptide structure, wherein the water-soluble conductive polymer is a π-conjugated conductive polymer having a Bronsted acid group or a salt thereof, The chargeable polymer is a protein hydrolyzate having a number average molecular weight of 4000 or less selected from collagen hydrolysates, keratin hydrolysates, casein hydrolysates, silk hydrolysates, conchiolin hydrolysates and gluten hydrolysates Inhibitor.   The antistatic agent according to claim 1, wherein the Bronsted acid group is a sulfonic acid group. The water-soluble polymer is represented by the formula (10) a

(In the formula, R and R ′ represent a substituent constituting an amino acid residue, and when R ′ is a hydrogen atom, R independently represents a substituent constituting an amino acid residue, and R ′ represents a hydrogen atom. When not an atom, R and R ′ cooperate to form a nitrogen-containing ring optionally substituted with a hydroxyl group, and amino acid residue (10) a is converted to amino acid residue (10) a ′.

(Wherein W ^a represents a polymethylene group represented by the formula — (CR ^a R ^b ) n—, and the substituents R ^a and R ^b each independently represent a hydrogen atom, an alkyl group, or a hydroxyl group, and n Represents an integer of 2 to 8. The antistatic agent of Claim 1 or 2 which has a chemical structure shown by this as a repeating structure.   Furthermore, the antistatic agent in any one of Claims 1-3 containing surfactant.   The antistatic agent according to any one of claims 1 to 3, comprising 0.1 to 20% by mass of a water-soluble conductive polymer, 0.0001 to 10% by mass of a water-soluble polymer having a polypeptide structure, and 70.0 to 99.8% by mass of a solvent.   The water-soluble conductive polymer is 0.1 to 20% by mass, the water-soluble polymer having a polypeptide structure is 0.0001 to 10% by mass, the surfactant is 0.0001 to 2% by mass, and the solvent is 68.0 to 99.8% by mass. Antistatic agent. The water-soluble conductive polymer is represented by the following formula (1)

(In the formula, m and n each independently represents 0 or 1. X represents S, N—R ¹ (R ¹ is a hydrogen atom, linear or branched saturated having 1 to 20 carbon atoms) or unsaturated hydrocarbon group, a group selected from phenyl and the group consisting of substituted phenyl group), or represents one of O, a is, -B-SO ₃ ^-. substituted represented by M ⁺ Represents an alkylene or alkenylene group having 1 to 4 carbon atoms which may have at least one group and may have other substituents (which may have two or more double bonds); Represents — (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, p and r each independently represent an integer of 0 or 1-3, and q represents 0 or 1 .M ⁺ represents a hydrogen ion, an alkali metal ion or a quaternary ammonium ion The antistatic agent according to claim 2 comprising a chemical structure represented by). The water-soluble conductive polymer is represented by the following formula (2)

(In the formula, R ^{2 to} R ⁴ each independently represent a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear structure having 1 to 20 carbon atoms. Or a branched saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group, or a —B—SO ₃ ⁻ M ⁺ group, where B is _{- (CH 2) p - (} O) q - (CH 2) r - represents, p and r each independently represents 0 or an integer of 1 to 3, q represents 0 or 1 .M ^{+ Represents} a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.) The antistatic agent according to any one of claims 2 to 6, comprising a chemical structure represented by: The water-soluble conductive polymer is represented by the following formula (3)

(In the formula, R ⁵ represents a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a linear or branched saturated or unsaturated group having 1 to 20 carbon atoms. It represents M ⁺ group, B is - ^- alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or _{-B-SO 3, (CH 2} ) p - ( O) _q — (CH ₂ ) _r —, p and r each independently represent an integer of 0 or 1 to 3, q represents 0 or 1. M ⁺ represents a hydrogen ion, an alkali metal The antistatic agent according to any one of claims 2 to 6, comprising a chemical structure represented by an ion or a quaternary ammonium ion. The water-soluble conductive polymer is represented by the following formula (4)

(In the formula, R ⁶ and R ⁷ are each independently a hydrogen atom, a linear or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a straight chain having 1 to 20 carbon atoms. or branched, saturated or unsaturated alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or -B-SO _3, ^- represents M ⁺ group, R ⁸ is Represents a monovalent group selected from the group consisting of a hydrogen atom, a straight-chain or branched saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group; (CH ₂ ) _p — (O) _q — (CH ₂ ) _r —, wherein p and r each independently represent an integer of 0 or 1-3, and q represents 0 or 1. M ⁺ Is hydrogen ion, alkali metal ion, or quaternary ammonia The antistatic agent according to claim 2 comprising a chemical structure represented by representing the ion.).   The antistatic agent according to claim 8, wherein the water-soluble conductive polymer is a polymer containing 5-sulfoisothianaphthene-1,3-diyl.   The antistatic film | membrane obtained using the antistatic agent of any one of Claims 1-11.   A coated article obtained by coating with the antistatic film according to claim 12.   The coated article according to claim 13, wherein the coated surface is a photosensitive composition or a charged particle beam composition coated on a base substrate.   A pattern forming method using the antistatic film according to claim 12.