JP2009215423A - Polymer containing basket-type silsesquioxane structure, and negative resist material containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer containing basket-type silsesquioxane structure and a novel negative resist material relating the same. <P>SOLUTION: The polymer has structure represented by formula (I), wherein, R is a 1-40C alkyl group, (substituted)aryl group, or (substituted)arylalkyl group, R<SP>2</SP>is a single bond, 1-40C alkylene group, or (substituted)arylene group, R<SP>3</SP>is a 1-8C alkyl group or phenyl group whose at least one hydrogen is substituted by -OR<SP>4</SP>or hydroxyl group, and n is an integer of at least 2. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polymer containing a cage silsesquioxane structure. The present invention also relates to a negative resist material containing the polymer. The negative resist material of the present invention is useful for display elements and the like.

In recent years, with the higher integration of integrated circuits, finer pattern formation is required, and chemically amplified resist materials using acid as a catalyst have been developed.
As such a resist material, Patent Document 1 reports a negative resist material made of a copolymer of hydroxystyrene and indene. In Patent Document 2, a part of hydroxy of a novolak resin or polyhydroxystyrene is acidified. A negative resist material using a resin protected with a substituent that is not decomposed by the above is disclosed. Further, Patent Document 3 discloses a negative resist material containing, as a base resin, a polymer compound containing a unit having high etching resistance and a unit for optimizing resolution in hydroxystyrene.
Further, negative resist materials containing a silsesquioxane resin are also disclosed (Patent Documents 4 and 5).
However, a new material has been demanded for clearer patterning.
JP 2003-233185 A JP-A-11-349760 JP 2006-201532 A JP 2005-266474 A Japanese Patent Laid-Open No. 2000-221687

  An object of the present invention is to provide a polymer that can form a pattern with high resolution and can be used as a negative resist material having excellent thermal stability. Another object of the present invention is to provide a negative resist material containing the polymer and a pattern forming method using the same.

  The present inventor has intensively studied to solve the above problems. As a result, we succeeded in synthesizing a polymer obtained from a monomer having a cage silsesquioxane structure represented by the formula (I), and further, using this polymer, a clear and highly heat-stable pattern. The present invention has been completed.

式（I）において、
Ｒは独立して炭素数１〜４０のアルキル、任意の水素がハロゲンもしくは炭素数２〜２０のアルキニルで置き換えられてもよいアリール、又はアリールにおける任意の水素がハロゲンもしくは炭素数１〜２０のアルキルで置き換えられてもよいアリールアルキルである。ここに、炭素数１〜４０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−又はシクロアルキレン又はフェニレンで置き換えられてもよく；アリールアルキルのアルキレンにおいて任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−又はシクロアルキレンで置き換えられてもよい。
Ｒ¹は独立して炭素数１〜８のアルキル、フェニル及びシクロヘキシルから選択される基である。
Ｒ²は単結合、炭素数１〜４０のアルキレン、又は任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよい、フェニレン、ジフェニレン、ナフタレンジイル、アントラセンジイルもしくはナフタセンジイルである。
Ｒ³は独立して炭素数１〜８のアルキル又は少なくとも一つの水素が−ＯＲ⁴（Ｒ⁴は水酸基の保護基を示す）もしくは水酸基に置き換えられ、その他の任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニルであり；Ｒ³のうち、少なくとも一方が、少なくとも一つの水素が−ＯＲ⁴もしくは水酸基に置き換えられ、その他の任意の水素がハロゲン、フェニルもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニルである。
ｎは２以上の整数を示す。
（２）Ｒ³のうち、少なくとも一方が、少なくとも一つの水素が−ＯＲ⁴に置き換えられ、その他の任意の水素がハロゲン、フェニルもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニルである、（１）に記載の重合体。
（３）Ｒ³のうち、少なくとも一方が、少なくとも一つの水素が水酸基に置き換えられ、その他の任意の水素がハロゲン、フェニルもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニルである、（１）に記載の重合体。
（４）式（II）で示されるシルセスキオキサン誘導体と、式（III）で示される化合物とを反応させて得られる、（２）に記載の重合体。

式（II）において、
Ｒは独立して炭素数１〜４０のアルキル、任意の水素がハロゲンもしくは炭素数２〜２０のアルキニルで置き換えられてもよいアリール、又はアリールにおける任意の水素がハロゲンもしくは炭素数１〜２０のアルキルで置き換えられてもよいアリールアルキルである。ここに、炭素数１〜４０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−又はシクロアルキレン又はフェニレンで置き換えられてもよく；アリールアルキルのアルキレンにおいて任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−又はシクロアルキレンで置き換えられてもよい。
Ｒ¹は独立して炭素数１〜８のアルキル、フェニル及びシクロヘキシルから選択される基である。

Ｒ³−Ｃ≡Ｃ−Ｒ²−Ｃ≡Ｃ−Ｒ³ （III）
式（III）において、
Ｒ²は単結合、炭素数１〜４０のアルキレン、又は任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニレン、ジフェニレン、ナフタレンジイル、アントラセンジイルもしくはナフタセンジイルであり；
Ｒ³は炭素数１〜８のアルキル、又は少なくとも一つの水素が−ＯＲ⁴（Ｒ⁴は水酸基の保護基を示す）に置き換えられ、その他の任意の水素がハロゲン、フェニルもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニルであり、Ｒ³のうち、少なくとも一方が、少なくとも一つの水素が−ＯＲ⁴に置き換えられ、その他の任意の水素がハロゲン、フェニルもしくは炭素数１〜４のアルキルで置き換えられてもよいフェニルである。
（５）（４）に記載の重合体を脱保護することによって得られる、（３）に記載の重合体。
（６）（１）〜（５）のいずれか一項に記載の重合体と、光酸発生剤と、架橋剤とを含むことを特徴とするネガ型レジスト材料。
（７）（６）に記載のネガ型レジスト材料を基板上に塗布する工程と、前記基板のネガレジスト材料塗布面に輻射線を照射する工程と、現像液で現像する工程を含むことを特徴とするレジストパターンの形成方法。
（８）（６）に記載のネガ型レジスト材料が塗布され、輻射線の照射および現像処理がなされたことにより、表面にレジストパターンが形成された、電子回路基板。 The present invention is as follows.
(1) A polymer represented by the formula (I).

In formula (I):
R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced by halogen or alkynyl having 2 to 20 carbon atoms, or any hydrogen in aryl is halogen or alkyl having 1 to 20 carbon atoms Is an arylalkyl which may be replaced by Here, in the alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene or phenylene; In the formula, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene.
R ¹ is a group independently selected from alkyl having 1 to 8 carbons, phenyl and cyclohexyl.
R ² is a single bond, alkylene having 1 to 40 carbon atoms, or phenylene, diphenylene, naphthalenediyl, anthracenediyl or naphthacenediyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms.
R ³ is independently an alkyl having 1 to 8 carbon atoms or at least one hydrogen is replaced by —OR ⁴ (R ⁴ is a protecting group for a hydroxyl group) or a hydroxyl group, and any other hydrogen is a halogen atom or 1 carbon atom. Phenyl, which may be replaced by ˜4 alkyl; at least one of R ³ , at least one hydrogen is replaced by —OR ⁴ or a hydroxyl group, and any other hydrogen is halogen, phenyl or carbon number 1 Phenyl optionally substituted with ~ 4 alkyls.
n represents an integer of 2 or more.
(2) At least one of R ³ is phenyl in which at least one hydrogen is replaced with —OR ⁴ and any other hydrogen may be replaced with halogen, phenyl, or alkyl having 1 to 4 carbon atoms. The polymer as described in (1).
(3) At least one of R ³ is phenyl in which at least one hydrogen is replaced with a hydroxyl group, and any other hydrogen may be replaced with halogen, phenyl, or alkyl having 1 to 4 carbon atoms. The polymer as described in 1).
(4) The polymer according to (2), obtained by reacting a silsesquioxane derivative represented by formula (II) with a compound represented by formula (III).

In formula (II):
R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced by halogen or alkynyl having 2 to 20 carbon atoms, or any hydrogen in aryl is halogen or alkyl having 1 to 20 carbon atoms Is an arylalkyl which may be replaced by Here, in the alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene or phenylene; In the formula, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene.
R ¹ is a group independently selected from alkyl having 1 to 8 carbons, phenyl and cyclohexyl.

R ³ —C≡C—R ² —C≡C—R ³ (III)
In formula (III),
R ² is a single bond, alkylene having 1 to 40 carbons, or phenylene, diphenylene, naphthalenediyl, anthracenediyl or naphthacenediyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbons;
R ³ is alkyl having 1 to 8 carbon atoms, or at least one hydrogen is replaced by —OR ⁴ (R ⁴ is a hydroxyl-protecting group), and any other hydrogen is halogen, phenyl or carbon atoms having 1 to 4 carbon atoms. And at least one of R ³ , at least one hydrogen is replaced by —OR ^4, and any other hydrogen is halogen, phenyl or an alkyl having 1 to 4 carbon atoms. It may be replaced with phenyl.
(5) The polymer according to (3), which is obtained by deprotecting the polymer according to (4).
(6) A negative resist material comprising the polymer according to any one of (1) to (5), a photoacid generator, and a crosslinking agent.
(7) The method includes a step of applying the negative resist material according to (6) onto a substrate, a step of irradiating the negative resist material application surface of the substrate with radiation, and a step of developing with a developer. A resist pattern forming method.
(8) An electronic circuit board on which a resist pattern is formed on the surface by applying the negative resist material according to (6) and performing irradiation with radiation and development treatment.

The terms used in the present invention are defined as follows. Alkyl and alkylene may both be straight-chain groups or branched groups. This is the same when any hydrogen in these groups is replaced with a halogen or a cyclic group, or when any —CH ₂ — is replaced with —O—, cycloalkylene, phenylene or the like. is there. “Arbitrary” used in the present invention indicates that not only the position but also the number is arbitrary. When a plurality of groups are replaced with another group, each group may be replaced with a different group. However, in the present invention, when it is described that any —CH ₂ — may be replaced by —O—, a plurality of consecutive —CH ₂ — is not replaced by —O—. Examples of halogen in the present invention are fluorine, chlorine and bromine.

  According to the present invention, a negative resist material containing a polymer represented by the formula (I), a photoacid generator, and a crosslinking agent is applied on a substrate, irradiated with radiation, and developed with a developer. By doing so, it is possible to create a clear and highly stable circuit pattern.

式（I）において、Ｒは独立して炭素数１〜４０のアルキル、任意の水素がハロゲンもしくは炭素数２〜２０のアルキニルで置き換えられてもよいアリール、又はアリールにおける任意の水素がハロゲンもしくは炭素数１〜２０のアルキルで置き換えられてもよいア
リールアルキルである。ここに、炭素数１〜４０のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−又はシクロアルキレン又はフェニレンで置き換えられてもよく；アリールアルキルのアルキレンにおいて任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ₂−は−Ｏ−又はシクロアルキレンで置き換えられてもよい。重合体中、Ｒ、Ｒ¹、Ｒ²、Ｒ³は、同一であっても、異なっていてもよい。 Hereinafter, the present invention will be described in more detail.
<1> Polymer of the Present Invention The polymer of the present invention is represented by the formula (I).

In the formula (I), R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced by halogen or alkynyl having 2 to 20 carbon atoms, or any hydrogen in aryl is halogen or carbon It is arylalkyl which may be substituted with alkyl of the number 1-20. Here, in the alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene or phenylene; In the formula, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene. In the polymer, R, R ¹ , R ² and R ³ may be the same or different.

  In the formula (I), it is preferable that all Rs are the same one group, but they may be composed of two or more different groups. Examples of the case where 8 Rs are composed of different groups are composed of 2 or more alkyls, are composed of 2 or more aryls, are composed of 2 or more arylalkyls, When composed of at least one alkyl and at least one aryl, composed of at least one alkyl and at least one arylalkyl, composed of at least one aryl and at least one arylalkyl, etc. It is. Combinations other than these examples may be used.

When R is alkyl, the carbon number is 1-40. A preferable carbon number is 1-20. A more preferable carbon number is 1-8. The arbitrary hydrogen may be replaced with fluorine, and the arbitrary —CH ₂ — may be replaced with —O— or cycloalkylene. Preferred examples of alkyl include unsubstituted alkyl having 1 to 20 carbons, alkoxyalkyl having 2 to 20 carbons, and a group in which one —CH ₂ — is substituted with cycloalkylene in alkyl having 1 to 8 carbons, Further, in each of the groups listed here, a group in which any hydrogen is replaced with fluorine, or the like. The preferable carbon number of cycloalkylene is 3-8.

  Examples of unsubstituted alkyl having 1 to 20 carbon atoms are methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 1,1,2-trimethyl. Propyl, heptyl, octyl, 2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and the like.

  Examples of fluorinated alkyls having 1 to 20 carbon atoms are 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonadecafluorohexyl, tridecafluoro- 1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro-1H, 1H, 2H, 2H- Such as tetradecyl.

  Examples of the alkoxyalkyl having 2 to 20 carbon atoms are 3-methoxypropyl, methoxyethoxyundecyl, 3-heptafluoroisopropoxypropyl and the like.

Examples of the group in which one —CH ₂ — in C 1-8 alkyl is replaced by cycloalkylene are cyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl, 2-bicycloheptyl, cyclooctyl and the like.

A preferred example in which R in formula (I) is an aryl in which any hydrogen is optionally substituted by halogen or alkyl having 1 to 20 carbons is an arbitrary hydrogen being halogen or alkyl having 1 to 8 carbons. Optionally substituted phenyl, and unsubstituted naphthyl. Here, preferred examples of halogen are fluorine, chlorine and bromine. In the alkyl having 1 to 8 carbon atoms which is a substituent of phenyl, arbitrary hydrogen may be replaced with fluorine, and arbitrary —CH ₂ — may be replaced with —O— or phenylene.

Preferred examples when R is aryl include unsubstituted phenyl, unsubstituted naphthyl, alkylphenyl, alkyloxyphenyl, phenyl with substituents including phenyl, and any hydrogen in each group listed herein. Is a group in which is replaced by halogen.
Examples of halogenated phenyl are pentafluorophenyl, 4-chlorophenyl, 4-bromophenyl and the like. Examples of alkylphenyl are 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl. 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 4- (1-methylethyl) phenyl, 4- (1,1-dimethylethyl) phenyl, 4- (2-ethylhexyl) phenyl, 2,4,6-tris (1-methylethyl) phenyl and the like. Examples of alkyloxyphenyl are 4-methoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-butoxyphenyl, 4-pentyloxyphenyl, 4-heptyloxyphenyl, 4-decyloxyphenyl, 4-octadecyloxyphenyl 4- (1-methylethoxy) phenyl, 4- (2-methylpropoxy) phenyl, 4- (1,1-dimethylethoxy) phenyl, and the like.

  Examples of phenyl having a substituent containing phenyl are 4-phenyloxyphenyl, 3-phenylmethylphenyl, biphenyl, terphenyl and the like.

  Examples of phenyl in which a part of hydrogen on the benzene ring is replaced by halogen and another hydrogen is replaced by alkyl or alkyloxy are 3-chloro-4-methylphenyl, 2,5-dichloro-4-methylphenyl 3,5-dichloro-4-methylphenyl, 2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl, 3-bromo-4-methylphenyl, 2,5 -Dibromo-4-methylphenyl, 3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl, 3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl, 3, 5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl, 2,3-difluoro-4-ethoxyphenyl, 2,3- Fluoro-4-propoxy phenyl, and the like.

Next, an example is given in which R in formula (I) is arylalkyl, and any hydrogen in the aryl may be replaced by halogen or alkyl having 1 to 20 carbons. In the arylalkyl alkylene, any hydrogen may be replaced with fluorine, and any —CH ₂ — may be replaced with —O— or cycloalkylene. A preferred example of arylalkyl is phenylalkyl. In this phenylalkyl, the alkylene preferably has 1 to 8 carbon atoms.
Examples of unsubstituted phenylalkyl are phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 11-phenylundecyl, 1-phenylethyl, 2-phenyl Phenylpropyl, 1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl, 1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2-phenylpropyl, 1-phenylhexyl, etc. It is.

In phenylalkyl, any hydrogen in the benzene ring may be replaced by halogen or alkyl having 1 to 8 carbon atoms. In the alkyl having 1 to 8 carbon atoms, arbitrary hydrogen may be replaced with fluorine, and arbitrary —CH ₂ — may be replaced with —O—, cycloalkylene, or phenylene.
Examples of phenylalkyl in which any hydrogen of phenyl is replaced by fluorine are 4-fluorophenylmethyl, 2,3,4,5,6-pentafluorophenylmethyl, 2- (2,3,4,5,6 -Pentafluorophenyl) ethyl, 3- (2,3,4,5,6-pentafluorophenyl) propyl, 2- (2-fluorophenyl) propyl, 2- (4-fluorophenyl) propyl and the like.

  Examples of phenylalkyl in which any hydrogen on the benzene ring is replaced by chlorine are 4-chlorophenylmethyl, 2-chlorophenylmethyl, 2,6-dichlorophenylmethyl, 2,4-dichlorophenylmethyl, 2,3,6-trichlorophenyl Methyl, 2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl, 2,3,4,6-tetrachlorophenylmethyl, 2,3,4,5,6-pentachlorophenylmethyl, 2- (2-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2,4,5-chlorophenyl) ethyl, 2- (2,3,6-chlorophenyl) ethyl, 3- (3-chlorophenyl) propyl , 3- (4-chlorophenyl) propyl, 3- (2,4,5-trichlorophenyl) propyl, 3- 2,3,6-trichlorophenyl) propyl, 4- (2-chlorophenyl) butyl, 4- (3-chlorophenyl) butyl, 4- (4-chlorophenyl) butyl, 4- (2,3,6-trichlorophenyl) Butyl, 4- (2,4,5-trichlorophenyl) butyl, 1- (3-chlorophenyl) ethyl, 1- (4-chlorophenyl) ethyl, 2- (4-chlorophenyl) propyl, 2- (2-chlorophenyl) Propyl, 1- (4-chlorophenyl) butyl and the like.

  Examples of phenylalkyl in which any hydrogen of phenyl is replaced by bromine are 2-bromophenylmethyl, 4-bromophenylmethyl, 2,4-dibromophenylmethyl, 2,4,6-tribromophenylmethyl, 2, 3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl, 2- (4-bromophenyl) ethyl, 3- (4-bromophenyl) propyl, 3- (3 -Bromophenyl) propyl, 4- (4-bromophenyl) butyl, 1- (4-bromophenyl) ethyl, 2- (2-bromophenyl) propyl, 2- (4-bromophenyl) propyl and the like.

  Examples of phenylalkyl in which any hydrogen on the benzene ring is replaced with alkyl having 1 to 8 carbon atoms include 2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl, 4-dodecylphenylmethyl, 2, 5-dimethylphenylmethyl, 2- (4-methylphenyl) ethyl, 2- (3-methylphenyl) ethyl, 2- (2,5-dimethylphenyl) ethyl, 2- (4-ethylphenyl) ethyl, 2- (3-ethylphenyl) ethyl, 1- (4-methylphenyl) ethyl, 1- (3-methylphenyl) ethyl, 1- (2-methylphenyl) ethyl, 2- (4-methylphenyl) propyl, 2- (2-methylphenyl) propyl, 2- (4-ethylphenyl) propyl, 2- (2-ethylphenyl) propyl, 2- (2,3-dimethyl) Phenyl) propyl, 2- (2,5-dimethylphenyl) propyl, 2- (3,5-dimethylphenyl) propyl, 2- (2,4-dimethylphenyl) propyl, 2- (3,4-dimethylphenyl) Propyl, 2- (2,5-dimethylphenyl) butyl, 4- (1-methylethyl) phenylmethyl, 2- (4- (1,1-dimethylethyl) phenyl) ethyl, 2- (4- (1- Methylethyl) phenyl) propyl, 2- (3- (1-methylethyl) phenyl) propyl, and the like.

An example in which any hydrogen in the benzene ring is phenylalkyl substituted with alkyl having 1 to 8 carbon atoms, and hydrogen in this alkyl is substituted with fluorine is 3-trifluoromethylphenylmethyl, 2- ( 4-trifluoromethylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) ethyl, 1- ( 3-trifluoromethylphenyl) ethyl, 1- (4-trifluoromethylphenyl) ethyl, 1- (4-nonafluorobutylphenyl) ethyl, 1- (4-tridecafluorohexylphenyl) ethyl, 1- (4 -Heptadecafluorooctylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) Propyl, 1-methyl-1- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) propyl, 1-methyl-1- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) propyl, 1-methyl-1- (4-heptadecafluorooctylphenyl) ethyl and the like.

An example in which any hydrogen of the benzene ring is phenylalkyl substituted with alkyl having 1 to 8 carbon atoms, and CH ₂ — in this alkyl is substituted with —O— is 4-methoxyphenylmethyl, 3 -Methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2- (4-methoxyphenyl) ethyl, 3- (4-methoxyphenyl) propyl, 3- (2-methoxyphenyl) propyl, 3- (3,4-dimethoxyphenyl) ) Propyl, 1- (4-methoxyphenyl) ethyl, (3-methoxymethylphenyl) ethyl and the like.

An example in which any hydrogen on the benzene ring is phenylalkyl substituted with alkyl having 1 to 8 carbon atoms, and one of CH ₂ — in this alkyl is substituted with cycloalkylene, is another —CH ₂ Examples of cases where-is replaced by -O- include cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylphenylpropyl, cyclohexyloxyphenylmethyl and the like.
An example in which any hydrogen on the benzene ring is phenylalkyl substituted with alkyl having 1 to 8 carbon atoms, and one of CH ₂ — in the alkyl is substituted with phenylene, is another example of —CH ₂ —. Examples including the case where is replaced by —O— include 2- (4-phenoxyphenyl) ethyl, 2- (4-phenoxyphenyl) propyl, 2- (2-phenoxyphenyl) propyl, and 4-biphenylylmethyl. 3-biphenylylethyl, 4-biphenylylethyl, 4-biphenylylpropyl, 2- (2-biphenylyl) propyl, 2- (4-biphenylyl) propyl, and the like.

  Examples of phenylalkyl in which at least two hydrogens on the benzene ring are replaced with different groups include 3- (2,5-dimethoxy-3,4,6-trimethylphenyl) propyl, 3-chloro-2-methylphenylmethyl, 4-chloro-2-methylphenylmethyl, 5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl, 2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl, 2,3-dichloro-4-methylphenylmethyl, 2,5-dichloro-4-methylphenylmethyl, 3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl, 2,3,4,6-tetrachloro-4-methylphenylmethyl, 2,3,4,6-tetrachloro-5-methylphenylmethyl 2,3,4,5-tetrachloro-6-methylphenylmethyl, 4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl, 2,4-dichloro-3 , 5-dimethylphenylmethyl, 2,6-dichloro-3,5-dimethylphenylmethyl, 2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl, 4-bromo 2-methylphenylmethyl, 5-bromo-2-methylphenylmethyl, 6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenylmethyl, 2 3,5-tribromo-4-methylphenylmethyl, 2,3,5,6-tetrabromo-4-methylphenylmethyl, and the like.

  The most preferred examples of phenyl in phenylalkyl are unsubstituted phenyl and phenyl having at least one of fluorine, alkyl having 1 to 4 carbon atoms and methoxy as a substituent.

Examples of phenylalkyl in which —CH ₂ — of alkylene is replaced by —O— or cycloalkylene include 3-phenoxypropyl, phenylcyclohexyl, phenoxycyclohexyl and the like.

Further preferred examples of R are unsubstituted phenyl, phenyl halide, phenyl having at least one methyl, methoxyphenyl, naphthyl, phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl, 1-methyl-2-phenyl Ethyl, pentafluorophenylpropyl, 4-ethylphenylethyl, 3-ethylphenylethyl, 4- (1,1-dimethylethyl) phenylethyl, 4-methoxyphenylpropyl, phenoxypropyl, cyclopentyl and cyclohexyl.
The most preferred examples of R are unsubstituted phenyl, cyclopentyl and cyclohexyl.

In the formula (I), R ¹ is independently a group selected from alkyl having 1 to 8 carbon atoms, phenyl and cyclohexyl. A preferred example of R ¹ is alkyl having 1 to 4 carbon atoms. The most preferred example of R ¹ is methyl.

In the formula (I), R ² represents a single bond, alkylene having 1 to 40 carbon atoms, or phenylene, diphenylene, naphthalenediyl, anthracene, in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms Diyl or naphthacene diyl.

Ｒ²が任意の水素がハロゲンもしくは炭素数１〜４のアルキルで置き換えられてもよいジフェニレンの場合、ジフェニレンに結合する２つの置換基の位置は、以下のいずれの位置でもよい。

When R ² is phenylene in which arbitrary hydrogen is replaced by halogen or alkyl having 1 to 4 carbon atoms, the positions of two substituents (groups including R ³ ) bonded to phenyl are ortho, meta, para Either of these may be used.

When R ² is diphenylene in which arbitrary hydrogen is replaced by halogen or alkyl having 1 to 4 carbon atoms, the position of the two substituents bonded to diphenylene may be any of the following positions.

When R ² is naphthalenediyl in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, the position of the two substituents bonded to naphthalene may be any of the following positions.

In addition, when R ² is anthracenediyl in which arbitrary hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, the position of the two substituents bonded to anthracene may be any of the following positions.

When R ² is naphthacenediyl in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, the position of the two substituents bonded to naphthacene may be any of the following positions.

R ³ is alkyl having 1 to 8 carbons or phenyl in which at least one hydrogen is replaced by —OR ⁴ or a hydroxyl group, and any other hydrogen may be replaced by halogen or alkyl having 1 to 4 carbons; At least one of R ³ is phenyl in which at least one hydrogen is replaced by —OR ⁴ or a hydroxyl group, and any other hydrogen may be replaced by halogen, phenyl, or alkyl having 1 to 4 carbon atoms.
Preferably, each R ³ is phenyl in which at least one hydrogen is replaced by —OR ⁴ or a hydroxyl group, and any other hydrogen may be replaced by halogen, phenyl or alkyl having 1 to 4 carbon atoms.

In —OR ⁴ , R ⁴ is a hydroxyl-protecting group.
Such a protecting group for a hydroxyl group may be a generally known protecting group, specifically, tertiary butyl, benzyl, 2,6-dichlorobenzyl, 2-bromobenzyloxycarbonyl, tetrahydropyranyl, methoxymethyl, ethoxy. Mention may be made of groups such as methyl, acetoxy, piperoyl, silyl and the like.
In order to deprotect —OR ⁴ to —OH, benzyl and the like can be deprotected by hydrogen reduction reaction or perch reduction using palladium as a catalyst, and tertiary butyl and the like are strongly acidic such as trifluoroacetic acid. The methoxymethyl, silyl and the like can be deprotected by hydrolysis under acidic conditions or neutral conditions.

式（II）で示される化合物は、国際公開03/024870号パンフレットに記載されている方法により合成することができる。 Of R ³ , at least one hydrogen is replaced with —OR ^4, and any other hydrogen is phenyl, which may be replaced with halogen, phenyl, or alkyl having 1 to 4 carbon atoms. The polymer represented by I) is obtained by polymerizing the compound represented by the formula (II) and the compound represented by the formula (III) by utilizing a hydrosilylation reaction.

The compound represented by the formula (II) can be synthesized by the method described in International Publication No. 03/024870 pamphlet.

R ³ —C≡C—R ² —C≡C—R ³ (III)

In the formula (III), R ² is a single bond, alkylene having 1 to 40 carbon atoms, or arbitrary hydrogen, which may be replaced by halogen or alkyl having 1 to 4 carbon atoms, phenylene, diphenylene, naphthalenediyl, anthracenediyl Or naphthacenediyl;
R ³ is alkyl having 1 to 8 carbon atoms, or at least one hydrogen is replaced by —OR ⁴ (R ⁴ is a hydroxyl-protecting group), and any other hydrogen is halogen, phenyl or alkyl having 1 to 4 carbon atoms. And at least one of R ³ , at least one hydrogen is replaced with —OR ^4, and any other hydrogen is replaced with halogen, phenyl, or alkyl having 1 to 4 carbon atoms. Which may be phenyl.

Examples of these compounds are shown below.

And at least one of R ³ is a compound represented by the formula (wherein at least one hydrogen is replaced by a hydroxyl group, and any other hydrogen is phenyl, which may be replaced by halogen, phenyl, or alkyl having 1 to 4 carbon atoms. The polymer of I) is obtained by hydrolyzing a polymer obtained by polymerizing the compound represented by the above formula (II) and the compound represented by the formula (III) by utilizing a hydrosilylation reaction. .

In the formula (I), n is an integer of 2 or more, and the molecular weight of the polymer of the present invention is appropriately set according to the use and is not particularly limited, but the number average molecular weight is preferably 1,400 to 1,000,000. A number average molecular weight of 1,400 to 500,000 is more preferred.
The solvent used for the polymerization reaction (hydrosilylation polymerization) is not particularly limited as long as it does not inhibit the progress of the reaction. Preferred solvents are hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF) and dioxane, methylene chloride, carbon tetrachloride, etc. Halogenated hydrocarbon solvents, and ester solvents such as ethyl acetate. These solvents may be used alone or in combination. Among these solvents, aromatic hydrocarbon solvents, and toluene is most preferable. A solvent is not necessarily required, but when used, a preferred ratio of the compound of the present invention to the solvent is 0.05 to 80% by weight based on the weight of the solvent. A more desirable ratio is 30 to 70% by weight. The proportion depends on the purpose.
The polymerization may be carried out at room temperature. Heating may be performed to promote polymerization. Cooling may be performed to control heat generation or undesirable polymerization due to polymerization.
A catalyst is preferably used for the polymerization. Examples of preferred hydrosilylation catalysts are Karstedt catalyst, Spier catalyst, hexachloroplatinic acid and the like, which are generally well known catalysts. Since these hydrosilylation catalysts are highly reactive, the reaction can proceed sufficiently if added in a small amount. The amount used is 10 ⁻⁹ to 1 mol% in terms of the ratio of the transition metal contained in the catalyst to the hydrosilyl group. A preferable addition ratio is 10 ⁻⁷ to 10 ⁻³ mol%. 10 ⁻⁹ mol% is the lower limit of the addition ratio required to allow the polymerization to proceed and be completed within an acceptable time. In consideration of keeping the manufacturing cost low, this ratio is preferably 1 mol% or less.

Next, a method for purifying the polymer will be described. This polymer is isolated and purified by efficiently removing unreacted addition polymerizable monomers. Although there are various methods, a purification method by reprecipitation operation is preferable. This purification method is performed as follows. First, in the polymerization reaction solution containing the polymer and the unreacted monomer, a solvent that does not dissolve the polymer but dissolves the unreacted monomer, a so-called precipitant is added to this solution to remove only the polymer. Precipitate. A preferred amount of the precipitating agent is 20 to 50 times based on the weight of the polymerization reaction solution.
A preferred precipitant is a solvent that is compatible with the solvent used in the polymerization, does not dissolve the polymer at all, dissolves only unreacted monomers, and has a relatively low boiling point. Examples of preferred precipitating agents are lower alcohols and aliphatic hydrocarbons. Particularly preferred precipitants are methanol and hexane. And in order to raise the removal efficiency of an unreacted monomer further, what is necessary is just to increase the repetition frequency of reprecipitation operation. By this method, only the polymer can be precipitated in a poor solvent, and the unreacted monomer and the polymer can be easily separated by a filtration operation.

  The polymer of the present invention is preferably used after being dissolved in a suitable solvent. The solvent used is not particularly limited as long as it is a solvent capable of dissolving the polymer. Specific examples include toluene, xylene, mesitylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, N-methyl-2-pyrrolidone (NMP), formamide, N, N-dimethylformamide, N, N-dimethylacetamide. N, N-dimethylimidazolidinone, hexamethylphosphoric triamide, sulfolane, γ-butyrolactone, diethyl ether, THF, dioxane, dichloromethane, chloroform, 1,2-dichloroethane, alkyl lactate, 3-methyl-3-methoxybutano- , Tetralin, isophorone, ethyl acetate, ethylene glycol monoalkyl ether (such as ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (diethylene glycol- Monoethyl ether, etc.), ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (such as propylene glycol monobutyl ether), dialkyl malonate (malon) And diethyl acid). Preferred are toluene, mesitylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, THF, ethyl acetate, and propylene glycol monomethyl ether acetate. These solvents may be used alone or in combination.

<2> Negative resist material of this invention The negative resist material of this invention contains the polymer of this invention, a photo-acid generator, and a crosslinking agent. The ratio of the polymer of the present invention, the photoacid generator, and the crosslinking agent is not particularly limited as long as it can be used as a negative resist material, but is preferably 80 to 90 wt%: 1 to 5 wt%: 5 to 15 wt%. Particularly preferred is 88.5% by weight: 1.5% by weight: 10% by weight.

Any crosslinking agent may be used as long as it has a function of crosslinking a polymer with an acid generated from a photoacid generator, and examples thereof include a compound containing an aromatic compound having at least two hydroxymethyls. Two or more kinds of such compounds may be used. The hydroxymethyl may be protected with a group such as acetyl. The following can be illustrated as such a compound.

  Examples of the photoacid generator include a photosensitizer having a function of generating an acid upon irradiation with radiation, and a photoacid generator is preferably composed of a portion that absorbs radiation and a portion that is a source of acid. Examples of such a photoacid generator include sulfonium salts, iodonium salts, and nonionic types.

The following can be mentioned as an example of a sulfonium salt.

The following can be mentioned as an example of an iodonium salt.

Nonionic photoacid generators include organic hageron compounds such as trihalomethyltriazine compounds, nitrobenzyl esters, diazosulfones, oxime sulfonates, N-sulfonyloxyimides, and the following are examples. it can.

<3> Method for Forming Resist Pattern of the Present Invention and Electronic Circuit Board Examples of a method for forming a resist pattern using the negative resist material of the present invention include the following methods.
First, the present invention is such that the coating film thickness is preferably 0.1 to 2.0 μm on a substrate by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating or the like. Apply a negative resist material.
Here, the substrate is not particularly limited as long as it is used in an electronic device, but for example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass; polycarbonate, polyester, acrylic resin, vinyl chloride resin Synthetic resin sheets, films or substrates such as aromatic polyamide resins, polyamideimides, polyimides, etc .; metal substrates such as aluminum plates, copper plates, nickel plates, stainless steel plates; ceramic plates; semiconductor substrates having photoelectric conversion elements; . The substrate may be subjected to a pretreatment such as a chemical treatment using a chemical such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum deposition.

Next, the substrate coated with the negative resist material is heated using a hot plate or the like at 110 to 150 ° C. for 3 to 20 minutes, preferably 110 to 130 ° C. for 4 to 10 minutes.
After heating, radiation selected from ultraviolet rays, far ultraviolet rays, X-rays, excimer lasers, γ rays, synchrotron radiation, etc. is emitted so that a target pattern is formed on the negative resist material application surface on the substrate. The exposure amount may be an amount suitable for the pattern is formed, but is preferably about 1 to 200 mJ / cm ^2, about 10 to 100 mJ / cm ² is more preferable.
After exposure, it is further desirable to heat at 250 to 350 ° C. for 2 to 4 hours using a hot plate or the like, and it is more preferable to heat at 300 ° C. for 3 hours.

Next, an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH) is used as a developer, and development is performed by an immersion method, a paddle method, a spray method, or the like. As a result, the exposed portion of the resist film is crosslinked with the base resin and dissolved by the developer, and the unexposed resist film is dissolved, so that a target pattern is formed on the substrate.
A substrate having a negative resist pattern formed on the surface in this manner can be suitably used as an electronic circuit substrate such as an integrated circuit (LSI) substrate.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited by a following example. In the chemical formulas in the examples, Me is methyl, Ph is phenyl, and THP is tetrahydropyranyl.
Nuclear magnetic resonance spectra (NMR) were measured with JNM-AL 300 manufactured by JEOL. The infrared absorption spectrum (IR) was measured with JASCO FT / IR-460 Plus. Average molecular weight is G from Shodex
Gel permeation chromatography (GPC) was measured with PC-101 and calculated. The standard substance is polystyrene, and two columns LF-804 manufactured by Shodex are directly connected, and the detector is RI (refractometer). The mobile phase is THF, the column temperature is 40 ° C., and the mobile phase flow rate is 1 mL / min.

300 mlナスフラスコにp-iodophenol 22.01 g (0.1 mol)、ether 200 mlを加え0 ℃に冷却した。この溶液に3,4-dihydro-2H-pyran 33.65 g (36.49 ml, 0.4 mol)、p-toluenesulfonic acid 1.25 g (6.5 mmol) を加え、室温で1 時間攪拌した。反応混合物にK₂CO₃ 8.5 g
(40 mmol)を加えて0 ℃で2 時間攪拌した後に、1 N NaOH水溶液を100 ml加えた。NaOH水溶液をetherで抽出した後に、NaCl水溶液で3回洗浄した。反応混合物をMgSO₄で乾燥し、溶媒を除去した後に、少量のNaOH水溶液を含むエタノールで再結晶を行うことにより無色の針状結晶を29.83 g得た。収率：98 %。¹H NMR (CDCl₃, 300 MHz) δ(ppm) 7.53 (d, J = 9.0 Hz, 2H), 6.81 (d, J = 9.0 Hz, 2H), 5.36 (t, J = 3.1 Hz, 1H), 3.84 (ddd, J = 11.3 Hz, J' = 9.7 Hz, J'' = 3.1 Hz, 1H), 3.57 (dtd, J = 11.3 Hz, J' = 4.0 Hz, J'' = 1.5 Hz, 1H), 1.86-2.05 (m, 1H), 1.78-1.86 (m, 2H), 1.55-1.73 (m, 3H). ¹³C NMR (CDCl₃, 75 MHz) δ(ppm) 156.9, 138.2, 118.8, 96.3, 83.9, 61.9, 30.2, 25.1, 18.6. IR (KBr, cm^-1) 3434 (br m), 2942 (m), 2870 (m), 1584 (m), 1483 (s), 1235 (s), 1200 (m), 1174 (m), 1120 (m), 1035 (m), 1019 (m), 953 (s), 917 (s), 872 (m), 822 (s), 642 (m). Synthesis example 1
4-tetrahydropyranyl iodobenzene (1)

To a 300 ml eggplant flask, 22.01 g (0.1 mol) of p-iodophenol and 200 ml of ether were added and cooled to 0 ° C. To this solution were added 33.65 g (36.49 ml, 0.4 mol) of 3,4-dihydro-2H-pyran and 1.25 g (6.5 mmol) of p-toluenesulfonic acid, and the mixture was stirred at room temperature for 1 hour. K ₂ CO ₃ 8.5 g in the reaction mixture
(40 mmol) was added and the mixture was stirred at 0 ° C. for 2 hours, and then 100 ml of 1 N NaOH aqueous solution was added. The aqueous NaOH solution was extracted with ether and then washed 3 times with aqueous NaCl solution. The reaction mixture was dried over MgSO ₄ , the solvent was removed, and recrystallization was performed with ethanol containing a small amount of NaOH aqueous solution to obtain 29.83 g of colorless needle crystals. Yield: 98%. ¹ H NMR (CDCl ₃ , 300 MHz) δ (ppm) 7.53 (d, J = 9.0 Hz, 2H), 6.81 (d, J = 9.0 Hz, 2H), 5.36 (t, J = 3.1 Hz, 1H), 3.84 (ddd, J = 11.3 Hz, J '= 9.7 Hz, J''= 3.1 Hz, 1H), 3.57 (dtd, J = 11.3 Hz, J' = 4.0 Hz, J '' = 1.5 Hz, 1H), 1.86-2.05 (m, 1H), 1.78-1.86 (m, 2H), 1.55-1.73 (m, 3H). ¹³ C NMR (CDCl ₃ , 75 MHz) δ (ppm) 156.9, 138.2, 118.8, 96.3, 83.9 , 61.9, 30.2, 25.1, 18.6.IR (KBr, cm ^-1 ) 3434 (br m), 2942 (m), 2870 (m), 1584 (m), 1483 (s), 1235 (s), 1200 ( m), 1174 (m), 1120 (m), 1035 (m), 1019 (m), 953 (s), 917 (s), 872 (m), 822 (s), 642 (m).

500 ml 3つ口フラスコに(1) 15.21 g (50.0 mmol)、dichlorobis(triphenylphosphino)palladium(II) (Pd(PPh₃)₂Cl₂) 0.35 g (0.5 mmol)、CuI 0.19 g (1.0 mmol)、diisopropylamine 300 mlを加えた。この溶液に2-methyl-3-butyn-2-ol 4.21g (50 mmol)とdiisopropylamine 20 mlの溶液を室温で滴下した後に4 時間攪拌した。溶媒を減圧下で除去した後、etherを加え、NaCl水溶液で洗浄を行った。得られた反応混合物をMgSO₄で乾燥し、溶媒を除去した後に、ethyl acetate / hexane (1:2, v/v)を展開溶媒としたカラムクロマトグラフィーによって茶色の固体を11.55 g得た。収率：89 %。¹H NMR (CDCl₃, 300 MHz)
δ(ppm) 7.30 (d, J = 8.8 Hz, 2H), 6.94 (d, J = 8.8 Hz, 2H), 5.39 (t, J = 3.1 Hz, 1H), 3.85 (ddd, J = 11.4 Hz, J' = 9.4 Hz, J'' = 3.1 Hz, 1H), 3.58 (dtd, J = 11.3 Hz, J' = 4.0 Hz, J'' = 1.3 Hz, 1H), 2.19 (s, 1H), 2.04-1.85 (m, 1H), 1.85-1.77 (m, 2H), 1.75-1.52 (m, 3H), 1.581 (s, 9H). ¹³C NMR (CDCl₃, 75 MHz) δ(ppm) 157.0, 132.9, 116.3, 115.6, 96.2, 92.4, 82.0, 65.6, 62.0, 31.5, 30.2, 25.1, 18.6. IR (KBr, cm^-1) 3400 (br m), 2931 (m), 2225 (w), 1605 (m), 1509 (s), 1358 (m), 1243 (s), 1169 (s), 1159(s), 1112 (s), 1035 (m). Synthesis example 2
2-methyl-4- (4- (tetrahydropyranyl) phenyl) but-3-yn-2-ol (2)

In a 500 ml three-necked flask (1) 15.21 g (50.0 mmol), dichlorobis (triphenylphosphino) palladium (II) (Pd (PPh ₃ ) ₂ Cl ₂ ) 0.35 g (0.5 mmol), CuI 0.19 g (1.0 mmol), 300 ml diisopropylamine was added. A solution of 4.21 g (50 mmol) of 2-methyl-3-butyn-2-ol and 20 ml of diisopropylamine was added dropwise to this solution at room temperature, followed by stirring for 4 hours. The solvent was removed under reduced pressure, ether was added, and the mixture was washed with an aqueous NaCl solution. The obtained reaction mixture was dried over MgSO ₄ and the solvent was removed. Then, 11.55 g of a brown solid was obtained by column chromatography using ethyl acetate / hexane (1: 2, v / v) as a developing solvent. Yield: 89%. ¹ H NMR (CDCl ₃ , 300 MHz)
δ (ppm) 7.30 (d, J = 8.8 Hz, 2H), 6.94 (d, J = 8.8 Hz, 2H), 5.39 (t, J = 3.1 Hz, 1H), 3.85 (ddd, J = 11.4 Hz, J '= 9.4 Hz, J''= 3.1 Hz, 1H), 3.58 (dtd, J = 11.3 Hz, J' = 4.0 Hz, J '' = 1.3 Hz, 1H), 2.19 (s, 1H), 2.04-1.85 (m, 1H), 1.85-1.77 (m, 2H), 1.75-1.52 (m, 3H), 1.581 (s, 9H). ¹³ C NMR (CDCl ₃ , 75 MHz) δ (ppm) 157.0, 132.9, 116.3 , 115.6, 96.2, 92.4, 82.0, 65.6, 62.0, 31.5, 30.2, 25.1, 18.6.IR (KBr, cm ^-1 ) 3400 (br m), 2931 (m), 2225 (w), 1605 (m), 1509 (s), 1358 (m), 1243 (s), 1169 (s), 1159 (s), 1112 (s), 1035 (m).

300 mlナスフラスコに(2) 2.34 g (9 mmol)、NaOH 0.8 g (20 mmol)、toluene 200 mlを加え2 時間加熱還流を行った。反応溶液を室温にした後に、ろ過により固体を除き、溶媒を除去した。得られた固体をCHCl₃ / hexane (1:1, v/v)を展開溶媒としたカラムクロマトグラフィーによって精製することで淡黄色の針状結晶を1.56 g得た。収率：85 %。¹H
NMR (CDCl₃, 300 MHz): δ(ppm) 7.40 (d, J = 8.9 Hz, 2H), 6.97 (d, J = 8.9 Hz, 2H), 5.41 (t, J = 3.1 Hz, 1H), 3.85 (ddd, J = 11.4 Hz, J' = 9.5 Hz, J'' = 3.1 Hz, 1H), 3.58 (dtd, J = 11.3 Hz, J' = 4.0 Hz, J'' = 1.5 Hz, 1H), 2.98 (s, 1H), 2.06-1.87 (m, 1H), 1.87-1.80 (m, 2H), 1.75-1.53 (m, 3H). ¹³C NMR (CDCl₃, 75 MHz): δ(ppm) 157.4, 133.5, 116.3, 114.9, 96.1, 92.4, 83.6, 75.8, 62.0, 30.2, 25.1, 18.6.
IR (KBr, cm^-1) 3290 (m), 3278 (m), 2940 (m), 2106 (w), 1604 (m), 1506 (s), 1355
(m), 1284 (m), 1239 (s), 1201 (m), 1170 (m), 1117 (m), 1032 (m), 960 (m), 947 (s), 916 (s), 835(s). Synthesis example 3
4-tetrahydropyranyl etynylbenzene (3)

(2) 2.34 g (9 mmol), NaOH 0.8 g (20 mmol), and toluene 200 ml were added to a 300 ml eggplant flask and heated under reflux for 2 hours. After bringing the reaction solution to room temperature, the solid was removed by filtration and the solvent was removed. The obtained solid was purified by column chromatography using CHCl ₃ / hexane (1: 1, v / v) as a developing solvent to obtain 1.56 g of pale yellow needle crystals. Yield: 85%. ¹ H
NMR (CDCl ₃ , 300 MHz): δ (ppm) 7.40 (d, J = 8.9 Hz, 2H), 6.97 (d, J = 8.9 Hz, 2H), 5.41 (t, J = 3.1 Hz, 1H), 3.85 (ddd, J = 11.4 Hz, J '= 9.5 Hz, J''= 3.1 Hz, 1H), 3.58 (dtd, J = 11.3 Hz, J' = 4.0 Hz, J '' = 1.5 Hz, 1H), 2.98 . (s, 1H), 2.06-1.87 (m, 1H), 1.87-1.80 (m, 2H), 1.75-1.53 (m, 3H) 13 C NMR (CDCl 3, 75 MHz): δ (ppm) 157.4, 133.5, 116.3, 114.9, 96.1, 92.4, 83.6, 75.8, 62.0, 30.2, 25.1, 18.6.
IR (KBr, cm ^-1 ) 3290 (m), 3278 (m), 2940 (m), 2106 (w), 1604 (m), 1506 (s), 1355
(m), 1284 (m), 1239 (s), 1201 (m), 1170 (m), 1117 (m), 1032 (m), 960 (m), 947 (s), 916 (s), 835 (s).

300 ml 3つ口フラスコに1,4-diiodobenzene 5.938 g (18 mmol)、dichlorobis(triphenylphosphino) palladium(II) (Pd(PPh₃)₂Cl₂) 0.126 g (0.18 mmol)、CuI 0.684g (0.36 mmol)、diisopropylamine 250 mlを加え、N₂置換を行った。この溶液を50 ℃に加熱した後に(3) 7.281 g (36 mmol)、diisopropylamine 20 mlの溶液を滴下して7 時間攪拌した。得られた反応混合物を室温にした後に、減圧下で溶媒を除去した。その後CHCl₃で抽出してNaCl水溶液で洗浄した。この反応混合物をMgSO₄で乾燥し、溶媒を除去した後にCHCl₃で数回再結晶を行った。収率：25 %。¹H NMR (CDCl₃, 300 MHz): δ(ppm) 7.45 (s, 4H), 7.43 (d, J = 8.6 Hz, 4H), 7.09 (d, J = 8.6 Hz, 4H), 5.43 (t, J = 3.0 Hz, 2H), 3.87 (ddd, J = 11.2 Hz, J' = 9.4 Hz, J'' = 3.0 Hz, 2H), 3.60 (dtd, J = 11.3 Hz, J' = 4.0 Hz, J'' = 1.4 Hz, 2H), 2.07-1.88 (m, 2H), 1.88-1.80 (m, 4H), 1.76-1.53 (m,
6H). ¹³C NMR(CDCl₃, 75 MHz): δ(ppm) 157.2, 133.0,131.3, 123.1, 116.4, 116.0, 96.2, 91.2, 87.9, 62.0, 30.2, 25.1, 18.6. IR (KBr, cm^-1) 2941 (m), 2875 (w), 2214
(w), 1600 (m), 1516 (m), 1236 (s), 1200 (s), 1118 (s), 1037 (s), 954 (s), 914 (s), 838 (s). Synthesis example 4
1,4-bis ((4- (tetrahydropyranyl) phenyl) ethynyl) benzene (4)

1,4-diiodobenzene 5.938 g (18 mmol), dichlorobis (triphenylphosphino) palladium (II) (Pd (PPh ₃ ) ₂ Cl ₂ ) 0.126 g (0.18 mmol), CuI 0.684 g (0.36 mmol) ), 250 ml of diisopropylamine was added to perform N ₂ substitution. After this solution was heated to 50 ° C., (7) 7.281 g (36 mmol), 20 ml of diisopropylamine was added dropwise and stirred for 7 hours. After the resulting reaction mixture was brought to room temperature, the solvent was removed under reduced pressure. Thereafter, the mixture was extracted with CHCl ₃ and washed with an aqueous NaCl solution. The reaction mixture was dried over MgSO ₄ and the solvent was removed, followed by recrystallization with CHCl ₃ several times. Yield: 25%. ¹ H NMR (CDCl ₃ , 300 MHz): δ (ppm) 7.45 (s, 4H), 7.43 (d, J = 8.6 Hz, 4H), 7.09 (d, J = 8.6 Hz, 4H), 5.43 (t, J = 3.0 Hz, 2H), 3.87 (ddd, J = 11.2 Hz, J '= 9.4 Hz, J''= 3.0 Hz, 2H), 3.60 (dtd, J = 11.3 Hz, J' = 4.0 Hz, J ''= 1.4 Hz, 2H), 2.07-1.88 (m, 2H), 1.88-1.80 (m, 4H), 1.76-1.53 (m,
^{.. 6H) 13 C NMR (} CDCl 3, 75 MHz): δ (ppm) 157.2, 133.0,131.3, 123.1, 116.4, 116.0, 96.2, 91.2, 87.9, 62.0, 30.2, 25.1, 18.6 IR (KBr, cm - ¹ ) 2941 (m), 2875 (w), 2214
(w), 1600 (m), 1516 (m), 1236 (s), 1200 (s), 1118 (s), 1037 (s), 954 (s), 914 (s), 838 (s).

50 mlシュレンクにDDPOSS（double-decker-shaped silsesquiozane） 2.296 g (1.99 m
mol)、(4) 0.957 g (2.00 mmol)を加え、Ar置換した後にtoluene 4 mlを加えた。この溶液を100℃に加熱した後に、Platinum(0)-1,3-divinyl-1,1,3,3- tetramethyldisiloxane complex (キシレンで3重量％に溶解したもの (Pt(dvs))を40 μl加え、7 時間攪拌した。得られた反応混合物を室温に戻した後に、toluene 15 mlを加え、MeOH 300 mlに対して再沈殿を行うことによって淡黄色の固体を3.161 g得た。収率：97 %。M_n = 19200, M_w = 67400, PDI = 3.51, ¹H NMR (CDCl₃, 300 MHz): δ(ppm) 7.6-6.2 (m, 54H), 5.30-5.15 (br, 2H), 3.80 (br, 2H), 3.49 (br, 2H), 1.92-1.53 (m, 12H), 0.41-0.22 (m, 6H). ¹³C
NMR (CDCl₃, 75 MHz): δ(ppm) 156.2, 139.2, 134.0, 132.8, 131.8, 131.2, 130.8, 130.3, 129.4, 128.9, 128.5, 127.7, 116.4, 115.7, 115.6, 96.4, 94.4, 62.1, 30.5, 25.1, 18.9, -1.2. IR (KBr, cm^-1) 2943 (w), 1603 (w), 1596 (w), 1506 (w), 1430 (w), 1132 (s), 1081 (s), 963 (w), 728 (m), 697 (m). Example 1
tetrahydropyranyl (THP) protected polymer (5)

50 ml Schlenk with DDPOSS (double-decker-shaped silsesquiozane) 2.296 g (1.99 m
mol), (4) 0.957 g (2.00 mmol) was added, and after Ar substitution, 4 ml of toluene was added. After heating this solution to 100 ° C, 40 μl of Platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3% by weight dissolved in xylene (Pt (dvs)) The resulting reaction mixture was allowed to warm to room temperature, 15 ml of toluene was added, and reprecipitation was performed on 300 ml of MeOH to obtain 3.161 g of a pale yellow solid. 97%, M _n = 19200, M _w = 67400, PDI = 3.51, ¹ H NMR (CDCl ₃ , 300 MHz): δ (ppm) 7.6-6.2 (m, 54H), 5.30-5.15 (br, 2H), 3.80 (br, 2H), 3.49 (br, 2H), 1.92-1.53 (m, 12H), 0.41-0.22 (m, 6H). ¹³ C
NMR (CDCl ₃ , 75 MHz): δ (ppm) 156.2, 139.2, 134.0, 132.8, 131.8, 131.2, 130.8, 130.3, 129.4, 128.9, 128.5, 127.7, 116.4, 115.7, 115.6, 96.4, 94.4, 62.1, 30.5 , 25.1, 18.9, -1.2.IR (KBr, cm ^-1 ) 2943 (w), 1603 (w), 1596 (w), 1506 (w), 1430 (w), 1132 (s), 1081 (s) , 963 (w), 728 (m), 697 (m).

500 mlナスフラスコに(5) 3.161 g (1.94 mmol)とTHF 340 mlを加える。その後、0.1 N
HCl水溶液60 mlを加え、50 ℃で12 時間加熱還流を行った。反応混合物にNaHCO₃を加えた後に、NaCl水溶液で洗浄し、MgSO₄で乾燥した。溶媒を除去した後に少量のTHFに溶解させ、H₂O / MeOH (20:1, v/v)に対して再沈殿することによって淡黄色固体を2.531 g得た。収率 89 %。M_n = 17700, M_w = 58600, PDI = 3.31, ¹H NMR (CDCl₃, 300 MHz): δ(ppm) 9.58 (br, 1H), 9.31 (br, 1H), 7.57-6.36 (m, 54H), 0.42-0.19 (m, 6H). ¹³C NMR(CDCl₃, 75 MHz): δ(ppm) 154.7, 134.0, 131.7, 131.5, 130.3, 129.3, 127.7, 115.6, 114.5, -1.1. IR (KBr, cm^-1) 3549 (br), 3422 (w), 3073 (w), 1608 (m), 1595 (m), 1509 (m), 1430 (m), 1262 (m), 1132 (s), 1081 (s), 1027 (m), 728 (m), 697 (m). Example 2
OH Polymer (6)

(5) 3.161 g (1.94 mmol) and THF 340 ml are added to a 500 ml eggplant flask. Then 0.1 N
60 ml of an aqueous HCl solution was added, and the mixture was heated to reflux at 50 ° C. for 12 hours. NaHCO ₃ was added to the reaction mixture, which was then washed with an aqueous NaCl solution and dried over MgSO ₄ . After removing the solvent, it was dissolved in a small amount of THF and reprecipitated against H ₂ O / MeOH (20: 1, v / v) to obtain 2.531 g of a pale yellow solid. Yield 89%. M _n = 17700, M _w = 58600, PDI = 3.31, ¹ H NMR (CDCl ₃ , 300 MHz): δ (ppm) 9.58 (br, 1H), 9.31 (br, 1H), 7.57-6.36 (m, 54H ), 0.42-0.19 (m, 6H). ¹³ C NMR (CDCl ₃ , 75 MHz): δ (ppm) 154.7, 134.0, 131.7, 131.5, 130.3, 129.3, 127.7, 115.6, 114.5, -1.1.IR (KBr , cm ^-1 ) 3549 (br), 3422 (w), 3073 (w), 1608 (m), 1595 (m), 1509 (m), 1430 (m), 1262 (m), 1132 (s), 1081 (s), 1027 (m), 728 (m), 697 (m).

Example 3
Patterning creation method
OH polymer (6) 88.5 wt%, 4,4'-Methylenebis [2,6-bis (hydroxymethyl) phenol] (MBHP: crosslinker) 10 wt%, (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)- 2- (methylphenyl) -acetonitrile (PTMA: photoacid generator) A mixture having a composition of 1.5% by weight was dissolved in NMP to prepare a 30% by weight solution. This solution was spin-cast on a silicon substrate and then dried at 100 ° C. for 2 minutes using a hot plate to obtain a coating film having a thickness of about 2 μm. Then, 436 nm UV light was irradiated at 50 mJ / cm ² and heated at 115 ° C. for 5 minutes using a hot plate. Development was performed by using a 1: 1 (v / v) mixed solution of 2-propanol and 2.38 wt% tetramethylammonium hydroxide aqueous solution as the developer, immersing the substrate in the developer for 30 seconds, and then rinsing with distilled water. . Furthermore, curing was carried out by heating at 250 ° C. for 3 hours on a hot plate in a N ₂ stream.
The decrease in film thickness at the exposed and unexposed areas was measured, and the decrease in film thickness (nm) divided by the development time (seconds) was taken as the dissolution rate. When the dissolution rate of the exposed portion is not observed, it means that a sufficient crosslinking reaction has occurred, and when the dissolution rate of the non-exposed portion is high, the pattern does not become blurred due to diffusion or the like.
The dissolution rate of the exposed portion was 0.1 nm / s or less, and the dissolution rate of the non-exposed portion was 100 nm / s. It was found that OH Polymer can form a clear pattern.
FIG. 1 shows a pattern actually created using OH Polymer.

Examples 4-7
Patterning was performed in the same manner as in Example 3 except that the ratios of OH polymer, MBHP, and PTMA were as follows.
Example 4 Example 5 Example 6 Example 7
OH polymer 85 wt% 90 wt% 75 wt% 87 wt%
MBHP 10% 15% 20% 10%
PTMA 5% 5% 5% 3%
Dissolution rate of exposed area <0.1 nm / s <0.1 nm / s <0.1 nm / s <0.1 nm / s
Dissolution rate of non-exposed part 40nm / s 50nm / s 100nm / s 50nm / s

Examples 8-13
Patterning was performed in the same manner as in Example 3 except that the heating temperature after irradiation on the hot plate was as follows.

Example 8 Example 9 Example 10 Example 11
Heating temperature 110 ° C 120 ° C 125 ° C 130 ° C
Dissolution rate of exposed area <0.1 nm / s <0.1 nm / s <0.1 nm / s <0.1 nm / s
Dissolution rate of non-exposed part 100nm / s 80nm / s 70nm / s 60nm / s

Example 12 Example 13
Heating temperature 135 ℃ 140 ℃
Dissolution rate of exposed area <0.1nm / s <0.1nm / s
Dissolution rate of non-exposed part 30nm / s 30nm / s

Examples 14-16
Patterning was performed in the same manner as in Example 3 except that the heating time after irradiation on the hot plate was as follows.
Example 14 Example 15 Example 16
Heating time 4 min 6 min 8 min Dissolution rate of exposed area <0.1 nm / s <0.1 nm / s <0.1 nm / s
Dissolution rate of non-exposed part 100nm / s 100nm / s 100nm / s

また、比誘電率ε_rは屈折率ｎ_avから、以下の式によって算出した。
ε_r＝ｎ_av ²
それぞれの結果は以下に示すとおりである。Δｎはそのポリマーの複屈折を示す。

この結果、このフィルムは光学的異方性を示さず、高い絶縁性があることが明らかとなった。 The same sample as in Example 3 was used as a 2 μm thick thermally crosslinked film (300 ° C., 3 h) on a silicon substrate. This film was set in a prism coupler (Metricon, PC-2000), and the refractive index n in the in-plane direction (TE) and the film thickness direction (TM) was measured at a wavelength of 632.8 nm. Further, the average refractive index n _av of the sample was obtained from the following formula.

The relative dielectric constant ε _r was calculated from the refractive index n _av by the following formula.
ε _r = n _av ²
Each result is as follows. Δn represents the birefringence of the polymer.

As a result, it was revealed that this film does not exhibit optical anisotropy and has high insulating properties.

The figure (photograph) of the pattern formation made using the negative resist material of this invention.

Claims (8)

A polymer represented by the formula (I).

In formula (I):
R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced by halogen or alkynyl having 2 to 20 carbon atoms, or any hydrogen in aryl is halogen or alkyl having 1 to 20 carbon atoms Is an arylalkyl which may be replaced by Here, in the alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene or phenylene; In the formula, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene.
R ¹ is a group independently selected from alkyl having 1 to 8 carbons, phenyl and cyclohexyl.
R ² is a single bond, alkylene having 1 to 40 carbon atoms, or phenylene, diphenylene, naphthalenediyl, anthracenediyl or naphthacenediyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms.
R ³ is independently an alkyl having 1 to 8 carbon atoms or at least one hydrogen is replaced by —OR ⁴ (R ⁴ is a protecting group for a hydroxyl group) or a hydroxyl group, and any other hydrogen is a halogen atom or 1 carbon atom. Phenyl, which may be replaced by ˜4 alkyl; at least one of R ³ , at least one hydrogen is replaced by —OR ⁴ or a hydroxyl group, and any other hydrogen is halogen, phenyl or carbon number 1 Phenyl optionally substituted with ~ 4 alkyls.
n represents an integer of 2 or more. 6. At least one of R ³ is phenyl in which at least one hydrogen is replaced with —OR ^4, and any other hydrogen is optionally substituted with halogen, phenyl, or alkyl having 1 to 4 carbons. 1. The polymer according to 1. 2. At least one of R ³ is phenyl in which at least one hydrogen is replaced with a hydroxyl group, and any other hydrogen is optionally substituted with halogen, phenyl, or alkyl having 1 to 4 carbon atoms. The polymer described. The polymer according to claim 2, obtained by reacting a silsesquioxane derivative represented by the formula (II) with a compound represented by the formula (III).

In formula (II):
R is independently alkyl having 1 to 40 carbon atoms, aryl in which arbitrary hydrogen may be replaced by halogen or alkynyl having 2 to 20 carbon atoms, or any hydrogen in aryl is halogen or alkyl having 1 to 20 carbon atoms Is an arylalkyl which may be replaced by Here, in the alkyl having 1 to 40 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene or phenylene; In the formula, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced by —O— or cycloalkylene.
R ¹ is a group independently selected from alkyl having 1 to 8 carbons, phenyl and cyclohexyl.

R ³ —C≡C—R ² —C≡C—R ³ (III)
In formula (III),
R ² is a single bond, alkylene having 1 to 40 carbons, or phenylene, diphenylene, naphthalenediyl, anthracenediyl or naphthacenediyl in which any hydrogen may be replaced by halogen or alkyl having 1 to 4 carbons;
R ³ is alkyl having 1 to 8 carbon atoms, or at least one hydrogen is replaced by —OR ⁴ (R ⁴ is a hydroxyl-protecting group), and any other hydrogen is halogen, phenyl or carbon atoms having 1 to 4 carbon atoms. And at least one of R ³ , at least one hydrogen is replaced by —OR ^4, and any other hydrogen is halogen, phenyl or an alkyl having 1 to 4 carbon atoms. It may be replaced with phenyl. The polymer according to claim 3, which is obtained by deprotecting the polymer according to claim 4. A negative resist material comprising the polymer according to claim 1, a photoacid generator, and a crosslinking agent. A resist comprising the steps of: applying a negative resist material according to claim 6 on a substrate; irradiating a negative resist material application surface of the substrate with radiation; and developing with a developer. Pattern formation method. An electronic circuit board, wherein the negative resist material according to claim 6 is applied, and a resist pattern is formed on the surface by irradiation with radiation and development processing.

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