JP2002194085A - Polysiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polysiloxane which is excellent as a resin component of a resist material which has excellent dry etching resistance and also has excellent basic physical properties as a resist such as transparency to radiation, sensitivity, resolution and developability. I will provide a. SOLUTION: The structural unit (I) represented by the following general formula (1)
And / or a polysiloxane having a structural unit (II) and a weight average molecular weight in terms of polystyrene of 500 to 1,000,000. Embedded image [In the general formula (1), each R independently represents a hydrogen atom or a methyl group, R ′ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and X represents a hydrogen atom or a monovalent acid dissociation. R '' is a hydrogen atom, having 1 to 1 carbon atoms.
20 represents a monovalent hydrocarbon group, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a primary, secondary or tertiary amino group, and n is an integer of 0 to 3. . ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polysiloxane useful as, for example, a resin component of a radiation-sensitive resin composition suitable for fine processing using radiation.

[0002]

2. Description of the Related Art In recent years, demands for higher density and higher integration of LSIs (highly integrated circuits) have been increasing, and accordingly, miniaturization of wiring patterns has been rapidly progressing. As one of means that can cope with such miniaturization of wiring patterns, there is a method of shortening the wavelength of exposure light used in a lithography process.
m) or i-rays (wavelength 365 nm)
rF excimer laser (wavelength 248 nm) or Ar
Far ultraviolet rays typified by F excimer laser (wavelength 193 nm), electron beam, being adapted to X-rays or the like is used, also the use of F ₂ excimer laser (wavelength 157 nm) has been studied. By the way, novolak resin, poly (vinylphenol) and the like have been used as resin components in conventional resist compositions, but these materials contain an aromatic ring in the structure and have strong absorption at a wavelength of 193 nm. Therefore, for example, in a lithography process using an ArF excimer laser, high accuracy corresponding to high sensitivity, high resolution, and high aspect ratio cannot be obtained. So, 193
There is a need for a resist resin component which is transparent to a wavelength of not more than nm, particularly 157 nm, and has a dry etching resistance equal to or higher than that of an aromatic ring. One such example is a siloxane-based polymer. MIT RRKunz et al. Have shown that polysiloxane-based polymers have excellent transparency at wavelengths of 193 nm or less, particularly at 157 nm. It is reported to be suitable as a resist material in wavelength-based lithography processes (J. Photopolym. Sci. Techno
l., Vol.12, No.4, 1999). It is also known that a polysiloxane-based polymer has excellent dry etching resistance, and that a resist containing a polyorganosilsesquioxane having a ladder structure has high plasma resistance.

On the other hand, some resist materials using siloxane polymers have already been reported. That is,
JP-A-5-323611 discloses a polymer having an acid-dissociable group in a side chain in which an acid-dissociable group such as a carboxylic acid ester group and a phenol ether group is bonded to a silicon atom via one or more carbon atoms. Japanese Patent Application Laid-Open No. 8-160623 discloses a radiation-sensitive resin composition using siloxane, in which a polymer obtained by protecting a carboxyl group of poly (2-carboxyethylsiloxane) with an acid-dissociable group such as a t-butyl group is used. JP-A-11-60733 discloses a resist resin composition using a polyorganosilsesquioxane having an acid-dissociable ester group. However, resist materials using these conventional acid-dissociable group-containing siloxane-based polymers are not yet at a satisfactory level in terms of basic physical properties of the resist such as transparency to radiation, resolution, and developability. . Further, JP-A-11-302382 discloses a non-aromatic monocyclic or polycyclic hydrocarbon group having a carboxyl group or a bridged cyclic hydrocarbon group in a side chain and the carboxyl group. Discloses a siloxane-based polymer in which at least a part of the polymer is substituted with an acid labile group, and a resist material using the polymer. The resist material is a KrF excimer laser (wavelength: 248 n).
m) or ArF excimer laser (wavelength 193n)
m), the pattern shape is good, and the sensitivity, resolution, dry etching resistance and the like are also excellent. However, Japanese Patent Application Laid-Open No. 11-30238
Even if the siloxane-based polymer of JP-A No. 2 is included, the type of siloxane-based polymer useful as a resin component of the resist material is small, and it effectively responds to short-wavelength radiation, and has a high dry etching resistance, and as a resist, Development of a new siloxane-based polymer that can provide a resist material having excellent basic physical properties has become an important issue from the viewpoint of technology development that can respond to rapid progress in miniaturization of semiconductor devices.

[0004]

The problem to be solved by the present invention is that Kr
Effectively sensitive to far ultraviolet rays such as F excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) or F ₂ excimer laser (wavelength 157 nm), has excellent dry etching resistance, and is transparent to radiation. Another object of the present invention is to provide a novel polysiloxane useful as a resin component of a resist material having excellent basic physical properties as a resist such as sensitivity, resolution and developability.

[0005]

Means for Solving the Problems The present invention has a structural unit (I) and / or a structural unit (II) represented by the following general formula (1) and has a polystyrene equivalent measured by gel permeation chromatography (GPC). It is composed of a polysiloxane having a weight average molecular weight of 500 to 1,000,000 (hereinafter, referred to as "polysiloxane (1)").

[0006]

Embedded image

[In the general formula (1), each R independently represents a hydrogen atom or a methyl group, R 'represents a hydrogen atom, a methyl group or a trifluoromethyl group, and X represents a hydrogen atom or a monovalent group. R '' represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 1 to 2 carbon atoms.
0 represents a monovalent halogenated hydrocarbon group, a halogen atom or a primary, secondary or tertiary amino group;
Wherein each silicon atom is bonded to the 2- or 3-position of the bicyclo [2.2.1] heptane ring at the top. ]

Hereinafter, the present invention will be described in detail. In the structural units (I) and (II) of the polysiloxane (1), R ′ is preferably any of a hydrogen atom, a methyl group and a trifluoromethyl group. Note that R ′ in the structural unit (I) and R ′ in the structural unit (II) may be the same or different from each other.

Next, the structural unit (I) and the structural unit (I
In I), examples of the monovalent acid dissociable group of X (hereinafter referred to as “acid dissociable group (α)”) include a tertiary alkyl group and an acetal group together with an oxygen atom to which X is bonded. A group to be formed (hereinafter, referred to as an “acetal-forming group”);
Examples include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group (excluding a tertiary alkyl group), a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a cyclic acid dissociable group. Can be.

In the acid dissociable group (α), the tertiary alkyl group includes, for example, t-butyl group, 1,1-dimethylpropyl group, 1-methyl-1-ethylpropyl group,
1,1-dimethylbutyl group, 1-methyl-1-ethylbutyl group, 1,1-dimethylpentyl group, 1-methyl-1
-Ethylpentyl group, 1,1-dimethylhexyl group,
Examples thereof include a 1,1-dimethylheptyl group and a 1,1-dimethyloctyl group. Examples of the acetal-forming group include a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, a t-butoxymethyl group,
-Pentyloxymethyl group, n-hexyloxymethyl group, cyclopentyloxymethyl group, cyclohexyloxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-i-propoxyethyl group , 1-n-butoxyethyl group, 1-t-butoxyethyl group, 1-n-pentyloxyethyl group, 1
-N-hexyloxyethyl group, 1-cyclopentyloxyethyl group, 1-cyclohexyloxyethyl group, 1
-Methoxypropyl group, 1-ethoxypropyl group, (cyclohexyl) (methoxy) methyl group, (cyclohexyl)
(Ethoxy) methyl group, (cyclohexyl) (n-propoxy) methyl group, (cyclohexyl) (i-propoxy)
Methyl group, (cyclohexyl) (cyclohexyloxy)
Examples include a methyl group.

The substituted methyl group includes, for example, phenacyl group, p-bromophenacyl group, p-methoxyphenacyl group, p-methylthiophenacyl group, α-
Methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, p
-Bromobenzyl group, p-nitrobenzyl group, p-methoxybenzyl group, p-methylthiobenzyl group, p-ethoxybenzyl group, p-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n -Propoxycarbonylmethyl group, i-
Examples thereof include a propoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, and a t-butoxycarbonylmethyl group. Examples of the 1-substituted ethyl group include 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, n-propoxycarbonylethyl group, 1-i-
Examples thereof include a propoxycarbonylethyl group, a 1-n-butoxycarbonylethyl group, and a 1-t-butoxycarbonylethyl group.

Further, as the 1-branched alkyl group,
For example, i-propyl group, 1-methylpropyl group, 1-
Examples thereof include a methylbutyl group. Examples of the silyl group include, for example, a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, a tri-i-propylsilyl group, Examples thereof include a t-butyldimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. Examples of the germyl group include, for example, a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an i-propyldimethylgermyl group,
Methyl di-i-propylgermyl group, tri-i-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl And a triphenylgermyl group. Further, as the alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group,
Examples thereof include an i-propoxycarbonyl group and a t-butoxycarbonyl group.

The acyl group includes, for example, acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, lauryloyl, myristoyl, palmitoyl, stearoyl, oxalyl. Group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group,
Fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group , P-toluenesulfonyl group, mesyl group and the like. Further, examples of the cyclic acid dissociable group include a 3-oxocyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 3-bromotetrahydropyranyl group, -Methoxytetrahydropyranyl group, 2-oxo-4-methyl-4-tetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group,
Examples thereof include a 3-tetrahydrothiophene-1,1-dioxide group.

X in the structural units (I) and (II) is particularly preferably a hydrogen atom or an acid dissociable group (α).
Preferred are t-butyl, t-butoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, methoxymethyl, ethoxymethyl, 1-methoxyethyl, 1-ethoxyethyl and the like. Note that X in the structural unit (I) and X in the structural unit (II) are
They may be the same or different. The acid dissociable group (α) in the structural units (I) and (II) is a group that dissociates in the presence of an acid to form a hydroxyl group. Further, n in the structural unit (I) and n in the structural unit (II) are each preferably 0 or 1. Note that n in the structural unit (I) and n in the structural unit (II) are
They may be the same or different.

Next, in the structural unit (II), examples of the monovalent hydrocarbon of R ″ having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and an n-propyl group.
-Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n Linear, branched or cyclic alkyl groups such as nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group A phenyl group, an o-tolyl group,
aromatic hydrocarbon groups such as m-tolyl group, p-tolyl group, benzyl group, phenethyl group, α-naphthyl group, β-naphthyl group; norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, adamantyl group And the like. Among these monovalent hydrocarbon groups, a methyl group, an ethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group and the like are preferable.

As the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms for R ″, for example, one or more halogen atoms, preferably one or more halogen atoms, Groups substituted with at least two fluorine atoms, more specifically, trifluoromethyl group, pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n-propyl group, heptafluoro-n-propyl group Group, heptafluoro-i-propyl group, pentafluorophenyl group, pentafluorobenzyl group, pentafluorophenethyl group,
Perfluoronorbornyl group, the following formula (a)

[0017]

Embedded image (In the formula, each Rf independently represents a hydrogen atom or a fluorine atom, and at least one Rf is a fluorine atom, and j is an integer of 0 to 4.)

And the like. Among these monovalent halogenated hydrocarbon groups, trifluoromethyl group, pentafluoroethyl group, 3,3,3
2,2-pentafluoro-n-propyl group, pentafluorophenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group ,
2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-triphenyl Fluorophenyl group, 2,3
6-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group,
A pentafluorobenzyl group, a pentafluorophenethyl group and the like are preferable.

Examples of the halogen atom for R ″ include a fluorine atom, a chlorine atom, and a bromine atom. Among these halogen atoms, a fluorine atom and a chlorine atom are preferred. Examples of the secondary or tertiary amino group for R ″ include a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group,
n-butylamino group, cyclopentylamino group, cyclohexylamino group, phenylamino group, benzylamino group, dimethylamino group, diethylamino group, di-i-propylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, Examples thereof include a dibenzylamino group. As the amino group for R '', an amino group, a dimethylamino group, a diethylamino group,
Dicyclopentylamino, dicyclohexylamino, diphenylamino and the like are preferred.

R '' in the structural unit (II) is particularly preferably a methyl group, an ethyl group, a cyclohexyl group, a pentafluoroethyl group, a fluorine atom, a chlorine atom, a dimethylamino group and the like.

Preferred specific examples of the structural unit (I) include structural units represented by the following formulas (I-1-1) to (I-1-12), and formulas (I-2-1) to (I-2-1). And the structural unit represented by I-2-12).

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

Among these structural units (I), in particular, the formulas (I-1-2), (I-1-3), (I-1-5), and (I-1-
6), Formula (I-1-8), Formula (I-1-9), Formula (I-2-2), Formula (I-2-3), Formula (I-2-5), Formula (I-2-5) I-2-6), the formula (I-2-6)
8) or a structural unit represented by the formula (I-2-9) is preferable.

Next, preferred specific examples of the structural unit (II) are shown below: structural units represented by the following formulas (II-1-1) to (II-1-48); ) To (II-2-48).

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

Among these structural units (II), in particular, the formulas (II-1-14), (II-1-15), (II-1-17) and (II-1-1)
8), Formula (II-1-20), Formula (II-1-21), Formula (II-1-26), Formula (II-1-27), Formula (II-1-29), Formula (II-1-29) II-1-30), Formula (II-1-3
2), Formula (II-1-33), Formula (II-2-14), Formula (II-2-15), Formula (II-2-17), Formula (II-2-18), Formula (II-2-18) II-2-20), Formula (II-2-2
1), Formula (II-2-26), Formula (II-2-27), Formula (II-2-29), Formula (II-2-30), Formula (II-2-32) or Formula (II-2-32) The structural unit represented by II-2-33) is preferred. In the polysiloxane (1), the structural unit (I) and the structural unit (II) are
Alone or two or more can be present.

Examples of the condensation component for providing the structural unit (I) include a silane compound (i) or a silane compound (ii) represented by the following general formula (2).
Examples of the condensation component that provides the structural unit (II) include a silane compound (iii) or a silane compound (iv) represented by the following general formula (3).

[0066]

Embedded image [In the general formula (2), R, R ', X and n have the same meanings as R, R', X and n in the general formula (1), respectively, and Y is a monovalent carbon having 1 to 20 carbon atoms. It represents a hydrogen group, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the following formula (b). ]

[0067]

Embedded image [In the general formula (3), R, R ′, X, n and R ″
Is synonymous with R, R ′, X, n and R ″ in the general formula (2), and Y is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a monovalent hydrocarbon group having 1 to 20 carbon atoms. It represents a halogenated hydrocarbon group or a group represented by the following formula (b). ]

[0068]

Embedded image (Wherein each Y ′ is independently a hydrogen atom, a carbon atom 1)
A monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, and k represents 1 to 1
It is an integer of 0. )

It is to be noted that Y in the silane compounds (i) to (iii) may be the same or different from each other, and R ″ in the silane compound (iii) and the silane compound (iv) may be the same or different from each other. Good.

The silane compounds (i) to (iv) in which X is a hydrogen atom include, for example, a norbornene (that is, bicyclo [2.2.1] hept-2-ene) derivative corresponding to each compound, And a hydrosilane compound corresponding to
According to a conventional hydrosilylation reaction, it can be synthesized by a method in which the reaction is carried out in the presence of a hydrosilylation catalyst, without a solvent or in an appropriate solvent.

The silane compounds (i) to (iv) wherein X is an acid dissociable group (α) can be synthesized by, for example, the following methods. When X is a t-butoxycarbonyl group, a hydroxyl group in the silane compounds (i) to (iv) wherein X is a hydrogen atom is
In the presence of a catalytic amount of 4-dimethylaminopyridine,
a method of esterification with t-butyl dicarbonate; when X is a t-butyl group, a compound obtained by converting a hydroxyl group in a silane compound (i) to (iv) wherein X is a hydrogen atom into a sodium oxide group; A butyl chloride is subjected to a sodium chloride dechlorination reaction by a conventional method, or a compound obtained by converting a hydroxyl group in a silane compound (i) to (iv) into an acid anhydride group and t-butyl alcohol is condensed by a conventional method. When X is a tetrahydropyranyl group, a hydroxyl group in the silane compounds (i) to (iv) wherein X is a hydrogen atom is subjected to an addition reaction with 2,3-dihydro-4H-pyran by a conventional method. When X is an acetal-forming group, the hydroxyl group in the silane compounds (i) to (iv) wherein X is a hydrogen atom is subjected to an addition reaction with a corresponding vinyl ether by a conventional method. How to.

The polysiloxane (1) can be produced by subjecting the silane compounds (i) to (iv) to polycondensation in the presence of an acidic catalyst or a basic catalyst in the absence of a solvent or in a solvent by a conventional method. it can. At the time of the polycondensation, a part or all of the silane compounds (i) to (iv) can be used as partial condensates.

Hereinafter, the polycondensation method for producing the polysiloxane (1) will be described. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, n-propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, and terephthalic acid. Examples include acid, acetic anhydride, maleic anhydride, citric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, aluminum chloride, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, and the like. These acidic catalysts
They can be used alone or in combination of two or more.

Among the basic catalysts, inorganic bases include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate,
Potassium carbonate and the like can be mentioned.

In the basic catalyst, examples of the organic base include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-hexylamine.
Linear, branched or cyclic monoalkylamines such as decylamine and cyclohexylamine; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n -Octylamine, di-n-nonylamine, di-n-decylamine,
Linear, branched or cyclic dialkylamines such as cyclohexylmethylamine and dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, Tri-n-heptylamine,
Tri-n-octylamine, tri-n-nonylamine,
Linear, branched or cyclic trialkylamines such as tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine and tricyclohexylamine;

Aniline, N-methylaniline, N, N-
Aromatic amines such as dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine; ethylenediamine, N, N, N ',
N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4,4 '
-Diaminodiphenylamine, 2,2-bis (4'-aminophenyl) propane, 2- (3'-aminophenyl) -2- (4'-aminophenyl) propane, 2-
(4'-aminophenyl) -2- (3'-hydroxyphenyl) propane, 2- (4'-aminophenyl) -2
-(4′-hydroxyphenyl) propane, 1,4-bis [1 ′-(4 ″ -aminophenyl) -1′-methylethyl] benzene, 1,3-bis [1 ′-(4 ″-) Diamines such as [aminophenyl) -1′-methylethyl] benzene;

Imidazole, benzimidazole, 4-
Imidazoles such as methylimidazole and 4-methyl-2-phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-
Pyridines such as ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline and acridine; piperazine , 1- (2'-hydroxyethyl) piperazine and the like, as well as pyrazine,
Other nitrogen-containing heterocyclic compounds such as pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, etc. Can be mentioned. These basic catalysts can be used alone or in combination of two or more.

Of the above acidic catalysts and basic catalysts, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, maleic anhydride, triethylamine, tri-n-propylamine, tri-n -Butylamine, pyridine and the like are preferred. The used amount of the acidic catalyst or the basic catalyst is usually 0.01 to 10,000 parts by weight based on 100 parts by weight of the total amount of the silane compound.

The solvent used for the polycondensation includes
For example, 2-butanone, 2-pentanone, 3-methyl-
Linear or branched such as 2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone Ketones; cyclopentanone, 3-methylcyclopentanone, cyclohexanone,
Cyclic ketones such as 2-methylcyclohexanone, 2,6-dimethylcyclohexanone and isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate;
Propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-se
propylene glycol monoalkyl ether acetates such as c-butyl ether acetate and propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate;
I-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec- 2-hydroxypropionate
2 such as butyl and t-butyl 2-hydroxypropionate;
-Alkyl hydroxypropionates; methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
Alkyl 3-alkoxypropionates such as methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate;

N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-
Alcohols such as propyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether and diethylene glycol di-n-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; Ethylene glycol monoalkyl ether acetates such as ethylene glycol mono-n-propyl ether acetate; aromatic hydrocarbons such as toluene and xylene;

Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate,
Methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, acetic acid In addition to other esters such as ethyl, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-
Dimethylacetamide, benzylethyl ether, di-
n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate and the like. These solvents can be used alone or in combination of two or more. The amount of the solvent used is usually 2,000 parts by weight or less based on 100 parts by weight of the total amount of the silane compound.

The polycondensation for producing the polysiloxane (1) can be carried out without solvent or with 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, or 4-hexanone.
Methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone, cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-
It is preferably carried out in a solvent such as propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate.

In the polycondensation, water can be added to the reaction system. The amount of water added in this case is usually 10,000, based on 100 parts by weight of the total amount of the silane compound.
0 parts by weight or less. The reaction temperature in the polycondensation is generally -50 to + 300C, preferably 20 to 100C, and the reaction time is generally about 1 minute to 100 hours.

The polysiloxane (1) has the structural unit (I)
And at least one structural unit other than structural unit (II) (hereinafter, referred to as “other structural units”). Examples of the silane compound that provides another structural unit include a silane compound represented by the following general formula (4) (hereinafter, referred to as “silane compound (4)”) and a silane compound represented by the following general formula (5) A silane compound having a monovalent organic group having an oxygen atom such as a compound (hereinafter, referred to as a “silane compound (5)”) or a silane compound represented by the following general formula (6) (hereinafter, a “silane compound ( 6) "), a silane compound represented by the following general formula (7) (hereinafter, referred to as" silane compound (7) "), and a silane compound represented by the following general formula (8) (hereinafter," silane "). Compound (8) ").
And the like. These silane compounds (4)
Each of (8) to (8) can also be used partially or entirely as a partial condensate.

[0085]

Embedded image

[0086] In [Formula (4) and the general formula (5), A represents a monovalent organic group having an oxygen atom, each R ¹
Are independently of each other a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms or a linear chain having 1 to 10 carbon atoms,
A branched or cyclic halogenated alkyl group;
² is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched halogenated alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic group having 6 to 20 carbon atoms. It represents a hydrocarbon group or a monovalent halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms. ]

[0087]

Embedded image

[In the general formulas (6) to (8), each R ¹
Are independently of each other a straight-chain, branched or cyclic alkyl group having 1 to 10 carbon atoms or a linear chain having 1 to 10 carbon atoms,
A branched or cyclic halogenated alkyl group; each R ³ is independently a hydrogen atom, a hydroxyl group, a halogen atom, a linear, branched or cyclic C 1-20 carbon atom which may be substituted; An alkyl group, an optionally substituted linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms, an optionally substituted acetoxy group, or an optionally substituted aromatic group having 6 to 20 carbon atoms Shows a hydrocarbon group. However, each R ³ does not include A in the general formulas (4) and (5). ]

Hereinafter, these silane compounds (4) to (4)
(8) will be described sequentially. In the general formulas (4) and (5), as the monovalent organic group having an oxygen atom of A, for example, a group represented by the following general formula (9) (hereinafter referred to as “hydroxyl-containing organic group (9 ) ")), A group represented by the following general formula (10) (hereinafter referred to as" carboxyl group-containing organic group (10) "), a monovalent organic group having an acid dissociable group, and the like. it can.

[0090]

Embedded image [In the general formulas (9) and (10), P is
Methylene group, difluoromethylene group, linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, 2 carbon atoms
A linear, branched or cyclic fluoroalkylene group having from 20 to 20; a divalent aromatic group having 6 to 20 carbon atoms; or another divalent alicyclic group having 3 to 20 carbon atoms. ]

In the general formulas (9) and (10), examples of the linear, branched or cyclic alkylene group having 2 to 20 carbon atoms of P include ethylene, trimethylene, propylene and tetraalkylene. Examples thereof include a methylene group, a cyclohexylene group, and the like, and examples of the linear, branched, or cyclic fluoroalkylene group having 2 to 20 carbon atoms include a tetrafluoroethylene group, a hexafluorotrimethylene group, and an octafluorotetrane group. Examples of the methylene group include divalent aromatic groups having 6 to 20 carbon atoms, such as phenylene, naphthylene, tetrafluorophenylene, and perfluoronaphthylene. Examples of the other divalent alicyclic group having 3 to 20 carbon atoms include a norbornene skeleton, a tricyclodecane skeleton, And a divalent hydrocarbon group having adamantane skeleton include a halide thereof and the like groups. P in the general formulas (9) and (10)
Preferable examples include a methylene group, a trifluoromethylene group, a divalent hydrocarbon group having a norbornene skeleton and a halide thereof, a divalent hydrocarbon group having an adamantane skeleton and a halide thereof, and the like.

In the general formulas (4) and (5), the monovalent organic group having an acid-dissociable group in A is dissociated by an acid, and is preferably a carboxyl group, a phenolic hydroxyl group or A linear or branched alkyl group having 1 to 20 carbon atoms having an acid dissociable group capable of forming an alcoholic hydroxyl group, and 4 carbon atoms having the acid dissociable group
Stable groups under the reaction conditions for producing polysiloxane (1), such as monovalent alicyclic hydrocarbon groups of from 30 to 30, may be mentioned. As the acid dissociable group in A, for example, a group represented by the following general formula (11) or (12) (hereinafter, these groups are collectively referred to as “acid dissociable group (β)”) and the like. Is preferred.

[0093]

Embedded image

[In the general formulas (11) and (12), Q represents a single bond, a methylene group, a difluoromethylene group, a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms; Represents a linear, branched or cyclic fluoroalkylene group having from 20 to 20 carbon atoms, a divalent aromatic group having 6 to 20 carbon atoms or another divalent alicyclic group having 3 to 20 carbon atoms, and Z represents an acid. Represents a monovalent organic group which dissociates to generate a hydrogen atom. ]

In the general formulas (11) and (12), Q represents a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms. Examples of the fluoroalkylene group, a divalent aromatic group having 6 to 20 carbon atoms and another divalent alicyclic group having 3 to 20 carbon atoms include the general formula (9) and the general formula (1).
And groups corresponding to P in 0). Q in the general formulas (10) and (11) represents an ethylene group, a cyclohexylene group, a phenylene group, a tetrafluorophenylene group, a divalent hydrocarbon group having a norbornene skeleton, a halide thereof, or an adamantane skeleton. Divalent hydrocarbon groups and their halides are preferred.

Examples of the monovalent organic group which is dissociated by the acid of Z to generate a hydrogen atom include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, cyclopentyl group, cyclohexyl group, 4- t-butylcyclohexyl group, cycloheptyl group, straight-chain such as cyclooctyl group,
Branched or cyclic alkyl group; aryloxycarbonyl group such as phenoxycarbonyl group, 4-t-butylphenoxycarbonyl group, 1-naphthyloxycarbonyl group; benzyl group, 4-t-butylbenzyl group, phenethyl group, 4- an aralkyl group such as a t-butylphenethyl group;
t-butoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, i-propoxycarbonyl group, 9
-Fluorenylmethylcarbonyl group, 2,2,2-trichloroethylcarbonyl group, 2- (trimethylsilyl)
Organic carbonyl groups such as an ethylcarbonyl group, an i-butylcarbonyl group, a vinylcarbonyl group, an allylcarbonyl group, a benzylcarbonyl group, a 4-ethoxy-1-naphthylcarbonyl group, and a methyldithiocarbonyl group;

A methoxymethyl group, a methylthiomethyl group,
t-butylthiomethyl group, (phenyldimethylsilyl)
Methoxymethyl group, benzyloxymethyl group, t-butoxymethyl group, siloxymethyl group, 2-methoxyethoxymethyl group, 2,2,2-trichloroethoxymethyl group, bis (2-chloroethoxy) methyl group, 2- ( Trimethylsilyl) ethoxymethyl group, 1-methoxycyclohexyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 1-ethoxyethyl group, 1-methyl -1-methoxyethyl group, 1-methyl-1-benzyloxyethyl group,
1- (2′-chloroethoxy) ethyl group, 1-methyl-
1-benzyloxy-2-fluoroethyl group, 2,2
Organic groups such as 2-trichloroethyl group, 2-trimethylsilylethyl group and 2- (phenylselenyl) ethyl group which form an acetal group by bonding to an oxygen atom in the general formula (11); trimethylsilyl group, triethylsilyl Group,
Tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, t-butyldiphenylsilyl group, tribenzylsilyl group, tri- Examples thereof include organic silyl groups such as a p-xylylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a t-butylmethoxyphenylsilyl group.

Among the monovalent organic groups which dissociate with these acids to generate hydrogen atoms, a t-butyl group, a tetrahydropyranyl group, a 1-ethoxyethyl group, a t-butyldimethylsilyl group and the like are preferable. A in the general formulas (4) and (5) includes a 2-tert-butoxycarbonylethyl group, a 4-tert-butoxycarbonylcyclohexyl group, a 4-tert-butoxycarbonylphenyl group,
-T-butoxycarbonyl-2,3,5,6-tetrafluorophenyl group, 5-t-butoxycarbonylnorbonyl group, 5-t-butoxycarbonyladamantyl group and the like are preferable. Note that A in the general formula (4) and A in the general formula (5) may be the same or different from each other.

Examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and an n-propyl group.
-Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group,
Examples thereof include an n-decyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the linear, branched, or cyclic halogenated alkyl group having 1 to 10 carbon atoms include a fluoromethyl group, a chloromethyl group, and a bromomethyl group. Group, difluoromethyl group, dichloromethyl group, trifluoromethyl group and the like. As R ¹ in the general formulas (4) and (5), a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and the like are preferable. Note that the R ¹ in R ¹ of the general formula in formula (4) (5) may be the same or different from each other.

[0100] In the general formula (5), as the linear or branched alkyl group having a carbon number 1 to 20 R ^2, for example, a methyl group, an ethyl group, n- propyl group, i
-Propyl group, n-butyl group, 2-methylpropyl group,
1-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group,
And a cyclohexyl group, etc., having 1 to 2 carbon atoms.
Examples of the straight-chain or branched halogenated alkyl group of 0 include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, and a heptafluoro-i-propyl group. Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include:
Examples thereof include a phenyl group, an α-naphthyl group, a β-naphthyl group, a benzyl group, a phenethyl group, and the like.
Examples of the 20 monovalent halogenated aromatic hydrocarbon group include, for example, a pentafluorophenyl group, a perfluorobenzyl group, a perfluorophenethyl group, a 2- (pentafluorophenyl) hexafluoro-n-propyl group,
(Pentafluorophenyl) hexafluoro-n-propyl group and the like. As R ² in the general formula (5), a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluorophenethyl group, a 3- (pentafluorophenyl) hexafluoro-n-propyl group and the like are preferable.

Next, in the general formulas (6) to (8), R
¹ of a straight, branched or cyclic alkyl group and a straight, as the halogenated alkyl group branched or cyclic, for example, the general formula (4) and The groups corresponding to R ¹ in the general formula (5) can be exemplified. General formula (6)
As R ¹ in (8), a methyl group, an ethyl group, n
-Propyl, i-propyl, n-butyl and the like are preferred. In addition, R ¹ in the general formula (6) and the general formula (7)
R ^{1 in} formula (8) and R ¹ in formula (8) may be the same or different from each other, and these R ¹ are the same as R ¹ in formula (4) and R ^{1 in} formula (5).
^It may be the same as or different from ¹ .

Examples of the halogen atom for R ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms of R ³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-type alkyl group. -Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n
-Pentyl group, n-hexyl group, n-heptyl group, n-
Octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-i-propyl, hydroxymethyl, 2 -Hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 4-hydroxycyclohexyl group, methoxymethyl group, 2-methoxyethyl group, 3-methoxypropyl group, 4-methoxybutyl group,
4-methoxycyclohexyl group, acetoxymethyl group,
2-acetoxyethyl group, 3-acetoxypropyl group,
4-acetoxybutyl group, 4-acetoxycyclohexyl group, mercaptomethyl group, 2-mercaptoethyl group,
3-mercaptopropyl group, 4-mercaptobutyl group,
4-mercaptocyclohexyl group, cyanomethyl group, 2
-Cyanoethyl group, 3-cyanopropyl group, 4-cyanocyclohexyl group, 3-glycidoxypropyl group, 2-
(3 ′, 4′-epoxy) cyclohexyl group, 2-
(3 ′, 4′-epoxy) cyclohexylethyl group, 3
-Morpholinopropyl group and the like.

Examples of the optionally substituted linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms for R ³ include methoxy, ethoxy, n-propoxy and i-propoxy. Group, n-butoxy group, 2-
Methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclohexyloxy group, fluoromethoxy group, chloromethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 3-chloropropoxy group, 3-bromopropoxy group , 3-glycidoxypropoxy, 4-fluorocyclohexyloxy, 3,4-epoxycyclohexyloxy and the like. Also, R
The ³ an optionally substituted acetoxy group, for example, an acetoxy group, trifluoroacetoxy key group, chloro acetoxy group, and bromoacetoxy group.

Examples of the optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms for R ³ include phenyl, α -naphthyl, benzyl, phenethyl and 2-phenyl.
-Fluorophenyl group, 3-fluorophenyl group, 4-
Fluorophenyl group, pentafluorophenyl group, 4-
Chlorophenyl group, 4-bromophenyl group, perfluorobenzyl group, perfluorophenethyl group, 2- (pentafluorophenyl) hexafluoro-n-propyl group, 3- (pentafluorophenyl) hexafluoro-
n-propyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-acetoxyphenyl, 3-acetoxy Phenyl group, 4-acetoxyphenyl group, 2-trimethylsiloxyphenyl group, 3-trimethylsiloxyphenyl group, 4-trimethylsiloxyphenyl group, 2-
Fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, 2-hydroxybenzyl group, 3-hydroxybenzyl group, 4-hydroxybenzyl group, 2-methoxybenzyl Group, 3-methoxybenzyl group, 4-methoxybenzyl group, 2-acetoxybenzyl group, 3-acetoxybenzyl group, 4-acetoxybenzyl group, 2-trimethylsiloxybenzyl group, 3-trimethylsiloxybenzyl group, 4-trimethylsiloxy A benzyl group and the like can be mentioned.

R ³ in the general formulas (6) to (8) represents a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluorophenethyl group,
(Pentafluorophenyl) hexafluoro-n-propyl group and the like are preferable. Incidentally, R ³ in the general formula (6), R in R ³ and the formula in the formula (7) (8) ³ may be the same or different.

The silane compounds (4) to (8) can be used alone or in admixture of two or more, or two or more of them can be used in combination. The molecular weight and glass transition temperature (Tg) of the resulting polysiloxane (1) can be controlled by selecting
Transparency at a wavelength of 3 nm or less, especially at a wavelength of 157 nm, can be further improved. Further, at the time of polycondensation for producing the polysiloxane (1), hexamethyldisiloxane can be added to control the molecular weight of the obtained polymer and improve the stability of the obtained polymer. The amount of hexamethyldisiloxane added is
Usually, 50 parts with respect to 100 parts by weight of the total amount of the silane compound.
0 parts by weight or less, preferably 50 parts by weight or less. In this case, if the addition amount of hexamethyldisiloxane exceeds 500 parts by weight, the molecular weight of the obtained polymer tends to decrease, and the glass transition temperature (Tg) tends to decrease.

The polysiloxane (1) usually has a partial ladder structure. This ladder structure is basically composed of a silane compound (i) or a silane compound (4) which is trifunctional for a polycondensation reaction,
A silane compound (6) which is functional (provided that R ³ is a hydroxyl group or a halogen atom);
Functional (However, one when R ³ is hydroxyl group or a halogen atom) to tetrafunctional (However, if the two R ³ is a hydroxyl group or a halogen atom) in which the silane compound (7), or a polycondensation reaction Trifunctional (but 2
When R ³ is a hydroxyl group or a halogen atom, it is introduced by the reaction of a silane compound (8) which is tetrafunctional (when 3 R ³ is a hydroxyl group or a halogen atom).

The specific content of each structural unit in the polysiloxane (1) varies depending on the kind and combination thereof, the use of the polysiloxane (1), and the like. The ratio can be appropriately selected by those skilled in the art through tests and the like, but the content of the structural unit (I) is generally 1 to
It is 100 mol%, preferably 2 to 100 mol%, particularly preferably 5 to 100 mol%, and the content of the structural unit (II) is generally 0 to 100 mol%, preferably 1 to 100 mol%, particularly preferably 2 to
100 mol%, and the total content of the structural units (I) and (II) is generally from 1 to 100 mol%, preferably from 2 to 100 mol%, based on all structural units.
Particularly preferably, it is 5 to 100 mol%. The content of other structural units is generally 99% with respect to all structural units.
Mol% or less, preferably 95 mol% or less. Also,
The total content of structural units that are bifunctional with respect to the polycondensation reaction is generally from 0 to 100 mol%, based on all structural units,
It is preferably from 1 to 100 mol%, and the total content of the structural units which are trifunctional with respect to the polycondensation reaction is generally from 1 to 100 mol%, preferably from 2 to 1 with respect to all the structural units.
The total content of structural units that is 00 mol% and is tetrafunctional with respect to the polycondensation reaction is generally
It is at most 98 mol%, preferably at most 95 mol%.

When the polysiloxane (1) is used as an alkali-soluble resin component in a resist material for microfabrication using radiation such as far ultraviolet rays, an electron beam, or an X-ray, a structural unit in which X is a hydrogen atom The content of (I) is usually from 1 to 99 mol%, preferably from 1 to 98 mol%, particularly preferably from 5 to 95 mol%, based on all structural units, and the structure in which X is a hydrogen atom. The content of the unit (II) is usually 100 mol% or less, preferably 1 to 98 mol%, particularly preferably 5 to 9 mol%, based on all structural units.
5 mol%, and the total content of the structural unit (I) and the structural unit (II) is usually
It is 1 to 100 mol%, preferably 2 to 100 mol%, particularly preferably 5 to 100 mol%. In this case, the content of other structural units is usually
99 mol% or less, preferably 95 mol% or less, the structural unit (I), the structural unit (II), another structural unit having a hydroxyl group-containing organic group (9), and a carboxyl group-containing organic group (10). The total content of other structural units having
Usually, it is 1 to 100 mol%, preferably 2 to 100 mol%, particularly preferably 5 to 100 mol%. In this case, the total content of the structural units that are bifunctional with respect to the polycondensation reaction is usually 99 mol% or less, preferably 90 mol% or less, particularly preferably 80 mol% or less, based on all the structural units. The total content of the structural units that are trifunctional with respect to the polycondensation reaction is usually 1 to
100 mol%, preferably 5 to 100 mol%, and the total content of the structural units that are tetrafunctional with respect to the polycondensation reaction is usually 98 mol% or less, preferably 95 mol% or less, based on all structural units. It is.

The polysiloxane (1) is used, for example, as a resin component having an acid-dissociable group and becoming alkali-soluble when the acid-dissociable group is dissociated in the same resist material for fine processing as described above. In this case, the content of the structural unit (I) in which X is an acid dissociable group (α) is usually 1 to 100 mol%, preferably 2 to 1 mol%, based on all structural units.
00 mol%, particularly preferably 5 to 100 mol%,
The content of the structural unit (II) in which X is an acid-dissociable group (α) is usually from 0 to 100 mol%, based on all structural units.
Preferably 1 to 100 mol%, particularly preferably 2 to 10
0 mol%, and the total content of the structural unit (I) and the structural unit (II) is usually
It is 1 to 100 mol%, preferably 2 to 100 mol%, particularly preferably 5 to 100 mol%. In this case, the content of other structural units is usually
The total content of the structural unit (I), the structural unit (II) and the other structural unit having an acid dissociable group (β) is 99 mol% or less, preferably 95 mol% or less. To 1 to 100 mol%, preferably 2 to 100 mol%
It is 100 mol%, particularly preferably 5 to 100 mol%. In this case, the total content of the structural units that are bifunctional with respect to the polycondensation reaction is usually 1 to the total structural units.
The total content of the structural units that are trifunctional with respect to the polycondensation reaction is usually 1 to 100 mol%, preferably 5 to 100 mol%, preferably 99 mol% or less. Mol%, and the total content of the structural units that are tetrafunctional with respect to the polycondensation reaction is usually 98 mol% or less, preferably 95 mol% or less, based on all the structural units.

The polysiloxane (1) has a weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC).
Is from 500 to 1,000,000, preferably from 500 to 1,000,000
500,000, particularly preferably 800 to 100,00
0. In this case, if Mw is less than 500, the glass transition temperature (Tg) of the obtained polymer tends to decrease, while if it exceeds 1,000,000, the solubility of the obtained polymer in a solvent tends to decrease. is there. The glass transition temperature (Tg) of the polysiloxane (1) is generally -50 to + 500C, preferably 0 to 300C. In this case, if the glass transition temperature (Tg) is lower than −50 ° C., it tends to be difficult to form a pattern when used as a resist material. Tends to decrease.

Uses of the polysiloxane (1) X has a structural unit (I) in which a hydrogen atom is present and / or a structural unit (II) in which X is a hydrogen atom.
Is a hydroxyl group-containing organic group (9) or a carboxyl group-containing organic group (10), and other structural units derived from the silane compound (4) and / or A is a hydroxyl group-containing organic group (9)
Alternatively, the polysiloxane (1) further having another structural unit derived from the silane compound (5), which is a carboxyl group-containing organic group (10), is usually alkali-soluble, and particularly includes far ultraviolet rays, an electron beam, X It is useful as an alkali-soluble resin component in a resist material for fine processing using radiation such as radiation (hereinafter, referred to as “resist material (a)”). This resist material (a) has excellent dry etching resistance and also has excellent basic physical properties as a resist such as transparency to radiation, sensitivity, resolution, and developability.

Further, it has a structural unit (I) in which X is an acid-dissociable group (α) and / or a structural unit (II) in which X is an acid-dissociable group (α). Silane compound (4), which is a monovalent organic group having a dissociable group (β)
A silane compound (5) in which the other structural unit derived from and / or A is a monovalent organic group having an acid dissociable group (β)
The polysiloxane (1) further having another structural unit derived from is usually alkali-soluble when these acid-dissociable groups are dissociated. Processing resist materials (hereinafter referred to as
It is called "resist material (b)." It is useful as the acid-dissociable group-containing resin component in (1). This resist material (b) has excellent dry etching resistance and also has excellent basic physical properties as a resist such as transparency to radiation, sensitivity, resolution, and developability.

The resist material (a) further contains, in addition to the alkali-soluble polysiloxane (1), usually a radiation-sensitive acid generator that generates an acid upon exposure, an alkali solubility controller, and the like. The resist material (b) further contains, in addition to the polysiloxane (1) having an acid-dissociable group, a radiation-sensitive acid generator that usually generates an acid upon exposure. Examples of the radiation-sensitive acid generator include an onium salt, a halogen-containing compound, a diazoketone compound, a sulfone compound, and a sulfonic acid compound. Examples of the alkali solubility controlling agent include, for example, compounds in which a substituent capable of dissociating in the presence of an acid is introduced into an acidic functional group such as a phenolic hydroxyl group and a carboxyl group. Further, the resist material (a) and the resist material (b) include an acid diffusion controller,
Surfactants, sensitizers, antihalation agents, adhesion aids,
A storage stabilizer, an antifoaming agent, and the like can be added.

[0115]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples.

EXAMPLES Synthesis Example 1 38.8 g of triethoxysilane and 5- [2-hydroxy-2,2-di (trifluoromethyl) ethyl were placed in a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer. ]
After adding 43.2 g of bicyclo [2.2.1] hept-2-ene and stirring at room temperature, 0.1 ml of a 0.2 mol solution of chloroplatinic acid in i-propyl alcohol was added to start the reaction. The mixture was heated and refluxed at 100 ° C. for 30 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the crude product was
Purified by distillation under reduced pressure at Hg and 105 ° C. to give Compound 5
9.8 g were obtained. About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), ¹⁹ F-NMR spectrum (chemical Shift “σF”), infrared absorption spectrum (I
R) and mass spectrum (FABMS) were measured, and the measured values were as follows, and the above formula (i) (where R = hydrogen atom, R ′ = trifluoromethyl group, X = hydrogen atom, Y
= Ethyl group, n = 0). σH: 3.8 ppm (ethoxy group), 1, 2 ppm
(Ethoxy group). σC: 123 ppm (trifluoromethyl group), 59
ppm (ethoxy group), 18 ppm (methyl group). σSi: -48 ppm. ? F: -76 to -79 ppm. IR: 3400 cm ^-1 (hydroxyl group), 2878 cm ^-1
(Ethoxy group), 1215 cm ^-1 (CF bond), 10
82 cm ^-1 (siloxane group). FABMS: m / z = 439 (M ++ 1)

Synthesis Example 2 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 3.0 g of the silane compound obtained in Synthesis Example 1 and 10 ml of tetrahydrofuran were added. When the temperature of the reaction solution reaches 5 ° C. or lower, 16.7 mg of 4-dimethylaminopyridine is added, and then 1.64 g of di-t-butyl dicarbonate is added.
Was dissolved in 5 ml of tetrahydrofuran and added dropwise over 15 minutes. One hour after the completion of the dropwise addition, the reaction solution was returned to room temperature, and further stirred for 5 hours. Thereafter, 50 ml of n-hexane was added to the reaction solution, and the mixture was transferred to a separating funnel. The organic layer was washed three times with ice water. Thereafter, the organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel chromatography to obtain 3.5 g of a compound from the n-hexane fraction. For this compound, ¹ H-NM
R spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), ¹⁹ F-NMR spectrum (chemical shift “σF”), red External absorption spectrum (I
R) and mass spectrum (FABMS) were measured, and the measured values were as follows, and the above formula (i) (where R = hydrogen atom, R ′ = trifluoromethyl group, X = t-butoxycarbonyl group) , Y = ethyl group, n = 0). σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group). σC: 149 ppm (carbonate group), 123 pp
m (trifluoromethyl group), 85 ppm (t-butoxy group), 59 ppm (ethoxy group), 28 ppm (t-
Butyl group), 18 ppm (methyl group). σSi: -48 ppm. ? F: -72.7 to -73.3 ppm. IR: 2879 cm ^-1 (ethoxy group), 1774 cm
^-1 (carbonate group), 1221 cm ^-1 (CF bond), 1082 cm ^-1 (siloxane group). FABMS: m / z = 537 (M ++ 1)

Synthesis Example 3 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 18.1 g of triethoxysilane and 8- [2-hydroxy-2,2-di (trifluoromethyl) ethyl] were added.
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
After adding 25.0 g of 3-ene and stirring at room temperature, 0.2 mol of chloroplatinic acid in 0.2 mol of i-propyl alcohol was added.
The reaction was started by adding 2 ml, and the mixture was heated and refluxed at 150 ° C. for 70 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered by suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel column chromatography to obtain 19.4 g of a compound from the n-hexane fraction. When this compound was measured for ¹ H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (IR), the measured values were as follows, and the above formula (i) (where R = hydrogen atom) , R ′ = trifluoromethyl group, X = hydrogen atom, Y = ethyl group, n = 1). σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group). IR: 3400 cm ^-1 (hydroxyl group), 1220 cm
^-1 (CF bond), 1098 cm ^-1 (siloxane group).

Synthesis Example 4 To a three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 3 g of the compound obtained in Synthesis Example 3 and 10 ml of tetrahydrofuran were added, and the mixture was stirred in a nitrogen stream under ice cooling. When the temperature of the reaction solution reaches 5 ° C. or less,
4.5 mg of 4-dimethylaminopyridine was added, and then a solution of 1.43 g of di-tert-butyl dicarbonate in 5 ml of tetrahydrofuran was added dropwise over 15 minutes. After stirring for 1 hour, the reaction solution was returned to room temperature, and further stirred at room temperature for 5 hours. Thereafter, 50 ml of n-hexane was added to the reaction solution, transferred to a separating funnel, and the organic layer was washed three times with ice water. Thereafter, the organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel column chromatography to obtain 3.2 g of a compound. For this compound,
^{When the 1} H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (IR) were measured, the measured values were as follows, and the above formula (i) (where R = hydrogen atom,
It was identified as a silane compound represented by R ′ = trifluoromethyl group, X = t-butoxycarbonyl group, Y = ethyl group, n = 1). σH: 3.8 ppm (ethoxy group), 1.5 ppm
(T-butoxycarbonyl group), 1.2 ppm (ethoxy group). IR: 1771 cm ^-1 (carbonate group), 1218
cm ^-1 (C-F bond), 1098cm ^-1 (siloxane group).

Synthesis Example 5 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 12.0 g of methylhydrocyclosiloxane and 5
After adding 54.8 g of-[2-hydroxy-2,2-di (trifluoromethyl) ethyl] bicyclo [2.2.1] hept-2-ene and stirring at room temperature, 0.1 ml of chloroplatinic acid was added. The reaction was started by adding 5.0 ml of a 2 mol i-propyl alcohol solution, and the mixture was heated and refluxed at 150 ° C. for 100 hours. Thereafter, the reaction solution was returned to room temperature, and n-
After dilution with hexane, the mixture was subjected to suction filtration on Celite, and the solvent was distilled off under reduced pressure to obtain 66.0 g of a compound. When this compound was measured for ¹ H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (IR), the measured values were as follows, and the above formula (iv) (where R = hydrogen atom) , R '= trifluoromethyl group, X =
A silane compound represented by a hydrogen atom, R ″ = methyl group, n = 0). ΣH: 0.2 ppm (SiCH ₃ group) IR: 3400 cm ⁻¹ (hydroxyl group), 2847 cm
^-1 (methoxy group), 1218 cm ^-1 (CF bond), 1
098 cm ^-1 (siloxane group).

Synthesis Example 6 To a three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 5 g of the compound obtained in Synthesis Example 5 and 15 ml of tetrahydrofuran were added, and the mixture was stirred in a nitrogen stream under ice cooling. When the temperature of the reaction solution reaches 5 ° C. or less,
36.6 mg of 4-dimethylaminopyridine was added, and then a solution of 3.6 g of di-tert-butyl dicarbonate in 5 ml of tetrahydrofuran was added dropwise over 15 minutes. After stirring for 1 hour, the reaction vessel was returned to room temperature, and further stirred at room temperature for 5 hours. Thereafter, 70 ml of n-hexane was added to the reaction solution, transferred to a separating funnel, and the organic layer was washed three times with ice water. Thereafter, the organic layer was poured into a beaker, dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain 5.5 g of a compound. The ¹ H-NMR spectrum (chemical shift “σH”) of this compound was measured.
It was identified as a silane compound represented by the formula (iv) (where R = hydrogen atom, R ′ = trifluoromethyl group, X = t-butoxycarbonyl group, R ″ = methyl group, n = 0). σH: 1.5 ppm (t-butoxycarbonyl group),
0.2 ppm (SiCH ₃ groups).

Synthesis Example 7 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 13.8 g of diethoxymethylsilane and 5- [2
-Hydroxy-2,2-di (trifluoromethyl) ethyl] bicyclo [2.2.1] Hept-2-ene (40 g) was added, and the mixture was stirred at room temperature.
The reaction was started by adding 0.2 ml of a propyl alcohol solution. Thereafter, the mixture was heated under reflux at 100 ° C. for 48 hours, returned to room temperature, diluted with n-hexane, the reaction solution was subjected to suction filtration on Celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Then, the crude product was
Purification by vacuum distillation at mmHg and 98 ° C. gave 41 g of compound. For this compound, ¹ H-
When the NMR spectrum (chemical shift “σH”) and the infrared absorption spectrum (IR) were measured, the measured values were as follows, and the above formula (iii) (where R = hydrogen atom, R ′ =
Trifluoromethyl group, X = hydrogen atom, Y = ethyl group,
R "= methyl group, n = 0). ΣH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group), 0.2 ppm (SiCH ₃ group). IR: 3400 cm ^-1 (hydroxyl group), 1218 cm
^-1 (CF bond), 1098 cm ^-1 (siloxane group).

Example 1 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 2.5 g of the compound obtained in Synthesis Example 1 was added.
2.5 g of 2-pentanone and 0.42 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups). IR: 3400 cm ^-1 (hydroxyl group), 1221 cm
^-1 (CF bond), 1130 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). Mw: 3,300.

Example 2 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 1.5 g of the compound obtained in Synthesis Example 2 and 4-methyl-
1.5 g of 2-pentanone and 0.20 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 5 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
5 ppm (t-butoxycarbonyl group). IR: 1774 cm ^-1 (carbonate group), 1217
cm ^-1 (C-F bond), 1132cm ^-1 (siloxane group), 1082cm ^-1 (siloxane group). Mw: 7,500.

Example 3 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 1.98 g of the compound obtained in Synthesis Example 1 and 1.62 of 2-t-butoxycarbonylethyltriethoxysilane were prepared.
g, 2.41 g of methyltriethoxysilane, 6.0 g of 4-methyl-2-pentanone and 1.65 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
5 ppm (t-butoxycarbonyl group), 0.2 ppm
(SiCH ₃ group). IR: 3400 cm ^-1 (hydroxyl group), 1703 cm
^-1 (carbonyl group), 1213 cm ^-1 (CF bond),
1130 cm ^-1 (siloxane group), 1080 cm ^-1 (siloxane group). Mw: 2,500.

Example 4 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 4.0 g of the compound obtained in Synthesis Example 3 was added.
4.0 g of 2-pentanone and 0.58 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups). IR: 3400 cm ^-1 (hydroxyl group), 1220 cm
^-1 (CF bond), 1130 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). Mw: 2,200.

Example 5 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 5.0 g of the compound obtained in Synthesis Example 4 was added.
5.0 g of 2-pentanone and 0.61 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
5 ppm (t-butoxycarbonyl group). IR: 1775 cm ^-1 (carbonate group), 1220
cm ^-1 (C-F bond), 1130 cm ^-1 (siloxane group), 1080 cm ^-1 (siloxane group). Mw: 2,400.

Example 6 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 2.22 g of the compound obtained in Synthesis Example 5, 2.78 g of methyltriethoxysilane, and 4-methyl-2-methyl-2-ethoxysilane were obtained. 5.0 g of pentanone and 1.41 g of a 1.75% by weight aqueous oxalic acid solution
Was added and reacted at 80 ° C. for 6 hours with stirring. After that, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral.
The organic layer was distilled off under reduced pressure to obtain a resin. About this resin, ¹ H-NMR spectrum (chemical shift “σH”),
When the infrared absorption spectrum (IR) and Mw were measured, they were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
2 ppm (SiCH ₃ groups). IR: 3400 cm ^-1 (hydroxyl group), 1221 cm
^-1 (CF bond), 1311 cm ^-1 (siloxane group),
1078 cm ^-1 (siloxane group). Mw: 3,300.

Example 7 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 2.48 g of the compound obtained in Synthesis Example 6, 2.52 g of methyltriethoxysilane, and 4-methyl-2- 5.0 g of pentanone and 1.28 g of a 1.75% by weight aqueous oxalic acid solution
Was added and reacted at 80 ° C. for 6 hours with stirring. Thereafter, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the water was repeatedly washed with ion-exchanged water until the reaction solution became neutral.
The organic layer was distilled off under reduced pressure to obtain a resin. About this resin, ¹ H-NMR spectrum (chemical shift “σH”),
When the infrared absorption spectrum (IR) and Mw were measured, they were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
5 ppm (t-butoxycarbonyl group), 0.2 ppm
(SiCH ₃ group). IR: 1775 cm ^-1 (carbonate group), 1221
cm ^-1 (C-F bond), 1131cm ^-1 (siloxane group), 1078cm ^-1 (siloxane group). Mw: 3,500.

Example 8 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 4.0 g of the compound obtained in Synthesis Example 7, 4-methyl-
15 g of 2-pentanone and 0.72 g of 1.75 wt% oxalic acid aqueous solution were added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. After that, the reaction vessel was cooled with ice to stop the reaction,
The reaction solution was transferred to a separatory funnel, the aqueous layer was discarded, and water washing was repeated with ion-exchanged water until the reaction solution became neutral. Then, the organic layer was distilled off under reduced pressure to obtain a resin. For this resin, the ¹ H-NMR spectrum (chemical shift “σ
H "), infrared absorption spectrum (IR) and Mw were as follows. σH: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups);
2 ppm (SiCH ₃ groups). IR: 3400 cm ^-1 (hydroxyl group), 1220 cm
^-1 (CF bond), 1130 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). Mw: 2,200.

Comparative Example 1 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 20 g of 2-t-butoxycarbonylethyltriethoxysilane, 60 g of 4-methyl-2-pentanone and 1.75% by weight were added. 4.09 g of oxalic acid aqueous solution was added, and the mixture was reacted at 80 ° C. for 6 hours with stirring. After that, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and water washing was repeated with ion-exchanged water until the reaction solution became neutral. The layer was distilled off under reduced pressure to obtain a resin. ¹ H-NMR spectrum (chemical shift “σH”), infrared absorption spectrum (IR) and Mw of this resin were measured, and the results were as follows. σH: 1.5 ppm (t-butoxycarbonyl group). IR: 3400 cm ^-1 (hydroxyl group), 1703 cm
^-1 (carbonyl group), 1130 cm ^-1 (siloxane group), 1080 cm ^-1 (siloxane group). Mw: 2,700.

Evaluation Example 1 (Evaluation of Radiation Transmittance) A film thickness of 1,0 formed from each resin produced in Example 1, Example 2, Example 3, Example 4, Example 8, and Comparative Example 1.
For the 00 ° coating, the wavelengths were 157 nm and 193
The radiation transmittance in nm was measured. Table 1 shows the measurement results.

[0132]

[Table 1]

As is clear from Table 1, the polysiloxane (1) of the present invention has a polysiloxane structure as its basic skeleton, and thus has a radiation transmittance at a wavelength of 193 nm equivalent to that of the resin of Comparative Example 1. The above high values are shown. On the other hand, at a wavelength of 157 nm, while the radiation transmittance of the resin of Comparative Example 1 is 30%, the resins of Examples 1, 2, 3, 4, and 8 are: All have higher radiation transmittance than the resin of Comparative Example 1. Although the radiation transmittance at a wavelength of 157 nm is generally considered to decrease due to the relative increase in the proportion of the hydrocarbon structure in the polysiloxane, the polysiloxane (1) of the present invention has a relatively low proportion of the hydrocarbon structure. Despite the large number, even if the partial structure in the resin changes, the radiation transmittance at a wavelength of 157 nm is at a high level.

Evaluation Example 2 (Evaluation of resist performance) 2-resins of each resin obtained in Examples 1, 4 and 8 were evaluated.
The heptanone solution was applied on a silicon wafer by a spin coater, and heated on a hot plate maintained at 130 ° C. for 90 seconds to form a film having a thickness of 1,000 °. Thereafter, when each coating was immersed in ion-exchanged water for 60 seconds, the thickness of the coating hardly changed. On the other hand, when each coating was immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds, the coating was completely dissolved and removed from the wafer. From these results, the polysiloxane (1) of the present invention shows the property of being insoluble or hardly soluble in ion-exchanged water,
It has high solubility in ordinary alkaline developers and has sufficient utility as a resin component in chemically amplified resists.

Further, 100 parts by weight of each resin obtained in Examples 2 and 3, 1 part by weight of triphenylsulfonium trifluoromethanesulfonate (radiation-sensitive acid generator), and tri-n-octylamine (acid diffusion control) Agent) 0.
02 parts by weight and 900 parts by weight of 2-heptanone (solvent) were uniformly mixed to prepare a composition solution. Next, each composition solution was applied on a silicon wafer by spin coating, and was applied on a hot plate maintained at 130 ° C. for 9 hours.
A heat treatment was performed for 0 second to form a resist film having a thickness of 100 nm. Then, for each resist film, Ar
Exposure was performed by changing the exposure amount using an F excimer laser (wavelength: 193 nm), and heat treatment was performed on a hot plate maintained at 110 ° C. for 90 seconds, followed by development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Then, a resist pattern was formed. As a result of observing each of the obtained resist patterns with a scanning electron microscope, the resin of Example 2 was resolved to 0.30 μm, and the resin of Example 3 was resolved to 0.15 μm. Was.

[0136]

The polysiloxane (1) of the present invention is particularly useful as an alkali-soluble resin component or an acid-dissociable group-containing resin component in a resist material for fine processing using radiation such as far ultraviolet rays, electron beams, and X-rays. It is useful to use these resist materials with a KrF excimer laser (wavelength 2).
48 nm), ArF excimer laser (wavelength 193n)
m) or F ₂ excimer laser (wavelength 157 nm)
It is effectively sensitive to radiation such as far ultraviolet rays represented by, and has excellent dry etching resistance, and also has excellent basic physical properties as a resist, such as transparency, sensitivity, resolution, and developability to radiation. Further, the polysiloxane (1) is useful alone or in combination with a general polysiloxane resin, for example, as a molded product, a film, a laminate material, a paint component and the like.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tsutomu Shimokawa 2--11-2 Tsukiji, Chuo-ku, Tokyo FSR term in JSR Co., Ltd. (reference) 2H025 AA01 AA02 AA04 AA09 AB16 AC04 AC05 AC06 AC08 AD03 BE00 BE10 BG00 CC20 FA03 FA12 FA17 4J035 BA04 BA14 CA01N CA022 CA152 CA192 LA05 LB16

Claims (1)

[Claims] 1. A structural unit (I) represented by the following general formula (1)
And / or having a structural unit (II) and a weight average molecular weight in terms of polystyrene of 500 to 1,000,000 as measured by gel permeation chromatography (GPC).
00 polysiloxane. Embedded image [In the general formula (1), each R independently represents a hydrogen atom or a methyl group, R ′ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and X represents a hydrogen atom or a monovalent acid dissociation. R '' is a hydrogen atom, having 1 to 1 carbon atoms.
20 represents a monovalent hydrocarbon group, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or a primary, secondary or tertiary amino group, and n is an integer of 0 to 3. ,
Each silicon atom in the formula is a bicyclo [2.2.
1] attached to the 2- or 3-position of the heptane ring. ]