JP2002308990A - Polysiloxane, method for producing the same, and radiation-sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polysiloxane which can give a radiation-sensitive resin composition having a high transparency to light of a wavelength of 193 nm or shorter and being highly sensitive, and excellent in dry etching resistance, developability, adhesion to a substrate, or the like, to provide a method for producing the same, and to obtain a radiation-sensitive resin composition containing the polysiloxane. SOLUTION: The polysiloxane is an alkali-insoluble or difficulty alkali-soluble acid-dissociable-group-containing polysiloxane which becomes alkali-soluble when the acid-dissociable groups are dissociated and has an Mw/Mn ratio of at most 2.5. The polysiloxane is produced by a method having a step of polycondensing a starting silane compound in the presence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polysiloxane, a polysiloxane having a specific polycondensation step, and a fine processing using the polysiloxane containing radiation such as far ultraviolet rays, electron beams and X-rays. It relates to a suitable radiation-sensitive resin composition.

[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 such as an F excimer laser (wavelength 193 nm), electron beams, X-rays, and the like are used. By the way, in the conventional resist composition, novolak resin, poly (vinylphenol), and the like have been used as resin components.
Since there is strong absorption at a wavelength of 3 nm, the lithography process using an ArF excimer laser has high sensitivity,
High accuracy corresponding to high resolution and high aspect ratio cannot be obtained. Therefore, a resist resin material that is transparent to a wavelength of 193 nm or less, particularly 157 nm, and has a dry etching resistance equal to or higher than that of an aromatic ring is required. One of them is a siloxane-based polymer. MIT RRKunz et al.
The results show that the polymer has excellent transparency at a wavelength of 193 nm or less, particularly at 157 nm.
It is reported to be suitable as a resist material in lithography processes using wavelengths below 93 nm (J. P.
hotopolym. Sci. Technol., 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 polyorganopolysilsesquioxane 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. A radiation-sensitive resin composition using a siloxane is disclosed. However, in this polysiloxane, the resolution cannot be increased unless the acid dissociable carboxylic acid ester groups in the side chains are efficiently dissociated, and when many acid dissociable groups are dissociated, the curing shrinkage stress of the resist film increases. In addition, there is a problem that the resist film is likely to be cracked or peeled off. Also, JP-A-8-1606
No. 23 discloses a positive resist using a polymer obtained by protecting a carboxyl group of poly (2-carboxyethylsiloxane) with an acid-dissociable group such as a t-butyl group. However, in this resist, since the protection ratio of the carboxyl group is low, a large amount of the carboxylic acid component is present in the unexposed portion, and it is difficult to develop the resist with a normal alkali developing solution.

Further, JP-A-11-60733 discloses a resist resin composition using a polyorganosilsesquioxane having an acid-labile ester group. However, this polyorganosilsesquioxane,
It is produced by subjecting a condensation product such as vinyl trialkoxysilane or γ-methacryloxypropyl trialkoxysilane to an addition reaction of an acid dissociable group-containing (meth) acrylic monomer, and (meth) is added to the polymer side chain.
Because the unsaturated group derived from the acrylic monomer remains,
There is a problem in terms of transparency at a wavelength of 193 nm or less. The publication also describes a resist resin composition using a polymer obtained by esterifying polyhydroxycarbonylethylsilsesquioxane with t-butyl alcohol. However, this polymer also has a low protection ratio of carboxyl groups, and resist There is a problem similar to that of JP-A-8-160623.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to
Polysiloxane which provides a radiation-sensitive resin composition having high transparency at a wavelength of 3 nm or less, high sensitivity, and excellent in dry etching resistance, developability, adhesion to a substrate, and the like, and a method for producing the polysiloxane And a radiation-sensitive resin composition containing the polysiloxane.

[0006]

The present invention firstly provides an alkali-insoluble or sparingly alkali-soluble acid-dissociable group-containing polysiloxane which becomes alkali-soluble when its acid-dissociable group is dissociated, The polysiloxane is characterized in that the ratio between the weight average molecular weight in terms of polystyrene and the number average molecular weight by gel permeation chromatography (GPC) is 2.5 or less.

The present invention secondly provides a compound represented by the following general formula (1) or a linear or cyclic oligomer obtained by partially condensing the compound; a compound represented by the following general formula (2): A step of polycondensing at least one component of the group consisting of a linear or cyclic oligomer in which the compound is partially condensed in the presence of an acidic catalyst, characterized in that it is an alkali-insoluble or alkali-soluble acid. Method for producing dissociable group-containing polysiloxane

[0008]

Embedded image

[In the general formulas (1) and (2), A ¹ and A ² each independently represent a monovalent organic group having an acid dissociable group which is dissociated by an acid, and R ¹ and R ²
Each independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms or a halogenated saturated hydrocarbon group having 1 to 10 carbon atoms, and R ³ represents a linear, branched or A cyclic alkyl group, a linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms;
And a monovalent aromatic hydrocarbon group or a monovalent halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms. ].

The present invention provides, thirdly, (a) an alkali-insoluble or alkali-soluble acid-dissociable group-containing polysiloxane which becomes alkali-soluble when its acid-dissociable group is dissociated, and which comprises gel permeation. A polysiloxane and a (b) radiation-sensitive acid generator, wherein the ratio of the weight average molecular weight to the number average molecular weight in terms of polystyrene measured by chromatography (GPC) is 2.5 or less. It consists of a radiation resin composition.

Hereinafter, the present invention will be described in detail. Polysiloxane (a) and method for producing the same The polysiloxane of the present invention is an alkali-insoluble or slightly alkali-soluble acid-dissociable group-containing polysiloxane which becomes alkali-soluble when its acid-dissociable group is dissociated. Permeation chromatography (GPC)
Weight average molecular weight (hereinafter referred to as “M
w ". ) And a number average molecular weight (hereinafter, referred to as “Mn”) (Mw / Mn) of 2.5 or less, preferably 2 or less, more preferably 1.8 or less (hereinafter “polysiloxane”). (A) ”).

The polysiloxane (a) is a compound represented by the above general formula (1) (hereinafter referred to as "silane compound (1)") or a linear or cyclic compound obtained by partially condensing the silane compound (1). At least one of the group consisting of an oligomer, a compound represented by the general formula (2) (hereinafter referred to as “silane compound (2)”), and a linear or cyclic oligomer in which the silane compound (2) is partially condensed; It is preferred to produce the seed components by a method having a step of polycondensing in the presence of an acidic catalyst.

The “linear or cyclic oligomer in which the silane compound (1) is partially condensed” referred to in the present invention is formed by condensation between two R ¹ O—Si groups in the silane compound (1).
In the case of a linear oligomer, it usually forms a dimer to 10-mer, preferably a dimer to a pentamer, and in the case of a cyclic oligomer,
Usually, it means an oligomer in which a 3- to 10-mer, preferably a 3- to 5-mer is formed, and the "linear or cyclic oligomer in which the silane compound (2) is partially condensed" refers to an oligomer in the silane compound (2). Between the two R ² O-Si groups of
In the case of a linear oligomer, it usually forms a dimer to 10-mer, preferably a dimer to a pentamer, and in the case of a cyclic oligomer,
Usually, it means an oligomer which has formed a 3- to 10-mer, preferably a 3- to 5-mer.

In the general formulas (1) and (2),
The monovalent organic group having an acid dissociable group dissociated by an acid of A ¹ and A ² is preferably one or more acid dissociation that dissociates with an acid to generate a carboxyl group, a phenolic hydroxyl group or an alcoholic hydroxyl group. Polysiloxane (a) such as a linear or branched hydrocarbon group having 1 to 20 carbon atoms having a functional group and a monovalent cyclic hydrocarbon group having 4 to 30 carbon atoms having an acid dissociable group; And a group which is stable under the reaction conditions for producing.

The acid dissociable group is preferably a group represented by the following general formula (3).

Embedded image [In the general formula (3), P is a single bond, a methylene group, a difluoromethylene group, a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, a linear or branched alkylene group having 2 to 20 carbon atoms. Or a cyclic fluoroalkylene group, a divalent aromatic group having 6 to 20 carbon atoms, or a divalent aromatic group having 3 to 20 carbon atoms.
And Q represents -COO- or -O-.
And R ⁴ represents a monovalent organic group which is dissociated by an acid to generate a hydrogen atom. ]

In the general formula (3), P has 2 to 2 carbon atoms.
Examples of the linear, branched, or cyclic alkylene group of 0 include an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
Examples of the linear, branched, or cyclic fluoroalkylene group of to 20 include a tetrafluoroethylene group,
Hexafluoropropylene group, hexafluorotrimethylene group, octafluorotetramethylene group and the like can be mentioned, and as the divalent aromatic group having 6 to 20 carbon atoms,
For example, a phenylene group, a naphthylene group, a perfluorophenylene group, a perfluoronaphthylene group, and the like can be given. Examples of the other divalent alicyclic group having 3 to 20 carbon atoms include a norbornane skeleton and tricyclodecane. Examples include divalent hydrocarbon groups having a skeleton or an adamantane skeleton, and halides of these groups. P in the general formula (3) represents a single bond, a methylene group, a difluoromethylene group, a divalent hydrocarbon group having a tricyclodecane skeleton or a halide thereof, a divalent hydrocarbon group having an adamantane skeleton or a halogen thereof. Or a divalent hydrocarbon group having a norbornane skeleton or a halide thereof, more specifically, a group represented by the following general formula (4)

[0017]

Embedded image [In the general formula (4), each R ⁵ independently represents a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom, a methyl group or a trifluoromethyl group, and n is 0 or 1. However, a bond crossing the bicyclo [2.2.1] heptane ring is bonded to the 2- or 3-position of the highest bicyclo [2.2.1] heptane ring. And the like.

Examples of the monovalent organic group which is dissociated by the acid of R ⁴ to generate a hydrogen atom include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group. Butyl group, sec-butyl group, t-butyl group,
n-pentyl group, n-hexyl group, n-heptyl group, n
Linear, branched or cyclic alkyl groups such as -octyl group, n-decyl group, cyclopentyl group, cyclohexyl group, 4-t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group; phenoxycarbonyl group, 4
Aryloxycarbonyl groups such as -t-butylphenyl group and 1-naphthyl group; aralkyl groups such as benzyl group, 4-t-butylbenzyl group, phenethyl group and 4-t-butylphenethyl group; t-butoxycarbonyl group; A methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, a 9-fluorenylmethylcarbonyl group,
2,2,2-trichloroethylcarbonyl group, 2- (trimethylsilyl) ethylcarbonyl group, i-butylcarbonyl group, vinylcarbonyl group, allylcarbonyl group,
Carbonyl groups such as a benzylcarbonyl group, a 4-ethoxy-1-naphthylcarbonyl group, and a methyldithiocarbonyl group;

A methoxymethyl group, a methylthiomethyl group,
An ethoxymethyl group, an ethylthiomethyl group, a t-butoxymethyl group, a t-butylthiomethyl group, a (phenyldimethylsilyl) methoxymethyl group, a 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-methoxyethyl group, 1-methoxyethyl group Ethoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1-methyl-1-methoxyethyl group, 1-methyl-1-benzyloxyethyl group, 1- (2-chloroethoxy) ethyl group, 1
A -methyl-1-benzyloxy-2-fluoroethyl group,
2,2,2-trichloroethyl group, 2-trimethylsilylethyl group, 2- (phenylselenyl) ethyl group and the like,
An organic group which forms an acetal structure by bonding to an oxygen atom in the general formula (3); trimethylsilyl group, triethylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl Group, dimethylethylsilyl group, t-butyldimethylsilyl group,
Examples thereof include an alkylsilyl group such as a t-butyldiphenylsilyl group, a tribenzylsilyl group, a tri-p-xylylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a t-butylmethoxyphenylsilyl group.

Among the monovalent organic groups which are dissociated by these acids to generate hydrogen atoms, t-butyl, tetrahydropyranyl, tetrahydrofuranyl, methoxymethyl, ethoxymethyl, 1-methoxyethyl, A 1-ethoxyethyl group, a t-butyldimethylsilyl group and the like are preferable.

In the general formulas (1) and (2), the saturated hydrocarbon group having 1 to 10 carbon atoms and the halogenated saturated hydrocarbon group having 1 to 10 carbon atoms for R ¹ and R ² include: For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group,
n-hexyl group, n-heptyl group, n-octyl group, n
A linear, branched or cyclic alkyl group such as a nonyl group, an n-decyl group, a cyclopentyl group, a cyclohexyl group; a trifluoromethyl group, a pentafluoroethyl group,
Heptafluoro-n-propyl group, heptafluoro-i
Linear, branched or cyclic halogenated alkyl groups such as -propyl group and perfluorocyclohexyl group. As R ¹ and R ² in the general formulas (1) and (2), a methyl group, an ethyl group and the like are preferable, respectively.

In the general formula (2), examples of the 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 and an i- Propyl group, n-butyl group, i-butyl group, s
ec-butyl group, t-butyl group, n-pentyl group, n-
A hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, a cyclopentyl group, a cyclohexyl group and the like can be mentioned. Examples of the halogenated alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoro-i-propyl group, a perfluorocyclohexyl group, and the like. Examples of the 20 monovalent aromatic hydrocarbon group include a phenyl group, an α-naphthyl group, a β-naphthyl group, a benzyl group, a phenethyl group and the like, and a monovalent halogen having 6 to 20 carbon atoms. Examples of the hydrogenated aromatic hydrocarbon group include, for example, a perfluorophenyl group, a perfluorobenzyl group, a perfluorophenethyl group, and a 2- (perf (Fluorophenyl) hexafluoro-n-propyl group, 3- (perfluorophenyl) hexafluoro-n-propyl group and the like.
As R ³ in the general formula (2), a methyl group, an ethyl group, a trifluoromethyl group, a pentafluoroethyl group,
Perfluorophenethyl, 3- (perfluorophenyl) hexafluoro-n-propyl and the like are preferred.

In the present invention, the silane compound (1) and the silane compound (2) can be used alone or as a mixture of two or more. In the present invention,
Silane compound (1) and / or silane compound (2)
Alternatively, one or more other silane compounds can be used in combination with the partial condensate of these silane compounds. As the other silane compound, for example, the following general formula (5)
(Hereinafter referred to as “silane compound (5)”), a silane compound represented by the following general formula (6) (hereinafter referred to as “silane compound (6)”),
Examples thereof include a silane compound represented by the following general formula (7) (hereinafter, referred to as “silane compound (7)”) and a partial condensate of these silane compounds. The "partial condensate" as used herein means that each silane compound is usually 2 to 1
A linear oligomer forming a 0-mer, preferably a 2- to 5-mer, or usually a 3- to 10-mer, preferably a 3- to 5-mer.
Means a cyclic oligomer having formed a pentamer.

[0024]

Embedded image

[In the general formulas (5) to (7), X ¹ ,
X ² and X ³ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an optionally substituted carbon number 1 to 30 linear, branched or cyclic alkoxyl groups, optionally substituted acetoxy groups,
Substituted good 6 to 15 carbon atoms which may have an aryl group, a monovalent other organic group having an aralkyl group or an oxygen atom substituted carbon atoms and optionally 7 to 20, each R ^7,
R ⁸ , R ⁹ , R ¹⁰ and each R ¹¹ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Represents a halogenated alkyl group. Where X ¹ , X ² and X
³ does not include A ¹ in the general formula (1) and A ² in the general formula (2). ]

In the general formulas (5) to (7), X ¹ , X
Examples of the halogen atom of ² and X ³ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Examples of the optionally substituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms of X ¹ , X ² and X ³ include, for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
Butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, hydroxy Methyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 4-hydroxycyclohexyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 4 -Carboxycyclohexyl 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, Kaputomechiru group, 2-mercaptoethyl group, 3-mercaptopropyl group, 4-mercapto-butyl group, 4-mercapto-cyclohexyl group, cyanomethyl group, 2-cyanoethyl, 3-cyanopropyl group,
4-cyanobutyl group, 4-cyanocyclohexyl group, 3
-Glycidoxypropyl group, 2- (3,4-epoxy)
Examples thereof include a cyclohexyl group, a 2- (3,4-epoxy) cyclohexylethyl group, and a 3-morpholinopropyl group.

Examples of the optionally substituted linear, branched or cyclic alkoxyl group having 1 to 30 carbon atoms of X ¹ , X ² and X ³ include, for example, methoxy, ethoxy and n- Propoxy group, i-propoxy group, n-
Butoxy group, i-butoxy group, sec-butoxy group, t
-Butoxy, cyclohexyloxy, fluoromethoxy, chloromethoxy, 2-chloroethoxy, 2
-Bromoethoxy, 3-chloropropoxy, 3-bromopropoxy, 3-glycidoxypropoxy, 4
-Fluorocyclohexyloxy group, 3,4-epoxycyclohexyloxy group, and the like. Examples of the optionally substituted acetoxy group of X ¹ , X ² and X ³ include, for example, an acetoxy group, a trifluoroacetoxy group, a chloroacetoxy group, a bromoacetoxy group and the like.

Examples of the optionally substituted aryl group having 6 to 15 carbon atoms of X ¹ , X ² and X ³ include, for example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group , Α-naphthyl group, β-naphthyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,6-difluorophenyl group, 3,5-
Difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,
3,4,5,6-pentafluorophenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2,6
-Bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 3,4,5-
Tris (trifluoromethyl) phenyl group, 2,3
4,5,6-pentakis (trifluoromethyl) phenyl group, 4-chlorophenyl group, 4-bromophenyl group,
2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4- Examples include a methoxyphenyl group, a 2-acetoxyphenyl group, a 3-acetoxyphenyl group, a 4-acetoxyphenyl group, a 2-trimethylsiloxyphenyl group, a 3-trimethylsiloxyphenyl group, and a 4-trimethylsiloxyphenyl group.

Examples of the optionally substituted aralkyl group having 7 to 20 carbon atoms of X ¹ , X ² and X ³ include, for example, a benzyl group, a phenethyl group, a 2-fluorobenzyl group and a 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,
Examples thereof include a 4-acetoxybenzyl group, a 2-trimethylsiloxybenzyl group, a 3-trimethylsiloxybenzyl group, and a 4-trimethylsiloxybenzyl group.

Examples of the other monovalent organic group having an oxygen atom represented by X ¹ , X ² and X ³ include a group represented by the following general formula (8) and a group represented by the following general formula (9). And the like.

[0031]

Embedded image [In the general formulas (8) and (9), Y is a methylene group, a difluoromethylene group, a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms,
0 linear, branched or cyclic fluoroalkylene group, 6-20 carbon atoms, divalent aromatic group, or 3 carbon atoms
20 represents another divalent alicyclic group of 20. ]

In the general formulas (8) and (9), Y is 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. A fluoroalkylene group having 2 to 6 carbon atoms
Examples of the valent aromatic group and the other divalent alicyclic group having 3 to 20 carbon atoms include corresponding groups exemplified for P in the general formula (3). In the general formulas (8) and (9), Y represents a difluoromethylene group, a divalent hydrocarbon group having an adamantane skeleton or a halide thereof, or a divalent hydrocarbon group having a norbornene skeleton or a halide thereof. And more preferably a group represented by the general formula (4).

In the general formulas (5) to (7), R
⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms and 1 carbon atoms.
Examples of the linear, branched or cyclic halogenated alkyl group of 10 to 10 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group and a sec-butyl group. Group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group,
Examples include cyclohexyl, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, and trifluoromethyl.

In the present invention, the silane compound (5)
(7) At least one member of the group of the partial condensates thereof
A polysiloxane (a) obtained by co-condensing a seed, preferably a silane compound (5) or a partial condensate thereof, with a silane compound (1) and / or a silane compound (2) or a partial condensate thereof. Control molecular weight and glass transition temperature (Tg)
Hereinafter, in particular, the transparency at a wavelength of 157 nm can be further improved. The total amount of the silane compound (5), the silane compound (6), the silane compound (7) or the partial condensate thereof is usually 99 mol% or less, preferably 5 to 95 mol%, based on all silane compounds. And more preferably 10 to 90 mol%. In this case, if the total amount exceeds 99 mol%, the resolution as a resist tends to decrease.

The method for producing a polysiloxane according to the present invention is characterized in that it comprises a step of polycondensing the silane compound in the presence of an acidic catalyst. By using the acidic catalyst in this manner, the polycondensation reaction accompanied by the hydrolysis reaction occurs uniformly and promptly, and the Si-
Since the hydrolyzable groups such as OR ¹ group and Si-OR ² group are not hydrolyzed and remain in the polymer,
Absorption of radiation by the hydrolyzable group is extremely reduced. Therefore, regarding the radiation transmittance at a wavelength of 193 nm or less, it is more advantageous to perform polycondensation under acidic conditions than to perform polycondensation under basic conditions. Moreover, by performing a polycondensation reaction under acidic conditions, a polysiloxane (a) having a narrow molecular weight distribution can be obtained, and a radiation-sensitive resin composition obtained using such a polysiloxane (a) is: When exposed to radiation of a short wavelength below the far ultraviolet region, the negative is less likely to occur, the adhesion of the resist pattern to the substrate is improved, and also when developing with a general developer after exposure, As a result of dissolving the resist film more uniformly, there is an advantage that a finer and better-shaped resist pattern is formed. This feature is particularly noticeable when exposure is performed at a wavelength of 193 nm or less.

Among the acidic catalysts, inorganic acids include
Examples thereof include hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, titanium tetrachloride, zinc chloride, and aluminum chloride. Examples of the organic acids include formic acid, acetic acid, and n-
Propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, acetic anhydride, maleic anhydride, citric acid, benzenesulfonic acid, p-toluenesulfone Acids, methanesulfonic acid and the like can be mentioned. Among these acidic catalysts, hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid,
Maleic acid, fumaric acid, acetic anhydride, maleic anhydride and the like are preferred. The acidic catalysts can be used alone or in combination of two or more. The amount of the acidic catalyst used is usually 0.0% based on 100 parts by weight of the total amount of the silane compound.
It is 1 to 10,000 parts by weight, preferably 0.1 to 100 parts by weight.

In the present invention, it is preferable that the silane compound is polycondensed in the presence of an acidic catalyst, and then the reaction is further advanced by adding a basic catalyst. By performing such a reaction, even when a silane compound having an acid dissociable group that is unstable under acidic conditions is used,
A cross-linking reaction can be caused, a polysiloxane (a) having a high molecular weight and a high glass transition temperature (Tg) and exhibiting good properties can be obtained. Further, by controlling the reaction conditions under basic conditions, the degree of crosslinking can be controlled to adjust the solubility of the obtained polysiloxane in a developer.

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

As the organic bases, for example, n-
Linear, branched or cyclic monoalkylamines such as hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; di-n-butylamine, di-n-pentyl Amines, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, linear or branched such as dicyclohexylamine Cyclic dialkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine,
Straight-chain such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, and tricyclohexylamine;
Branched or cyclic trialkylamines;

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-aminophenyl) -1-methylethyl
] Aromatic diamines such as 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, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine,
1,4-dimethylpiperazine, 1,4-diazabicyclo
[2.2.2] Other nitrogen-containing heterocyclic compounds such as octane can be exemplified.

Of these basic catalysts, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and the like are preferred. The basic catalysts can be used alone or in combination of two or more. The amount of the basic catalyst to be used is generally 0.01 to 10,000 parts by weight, preferably 0.1 to 1,000 parts by weight, based on 100 parts by weight of the total amount of the silane compound.

The polycondensation reaction under the acidic condition and the basic condition is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. There is.

The polycondensation reaction can be carried out without a solvent or in a solvent. Examples of the solvent include 2-butanone, 2-pentanone, and 3-methyl-2.
Linear or branched ketones such as butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone And cyclopentanone,
3-methylcyclopentanone, cyclohexanone, 2-
Cyclic ketones such as 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-sec-
Propylene glycol monoalkyl ether acetates such as butyl ether acetate and propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, 2-
Alkyl 2-hydroxypropionates such as i-propyl hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate Class: methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-
Alkyl 3-alkoxypropionates such as methyl 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; -Hydroxy-3
-Methyl methylbutyrate, 3-methoxybutyl acetate,
3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-
3-methoxybutyl butyrate, ethyl acetate, n-acetic acid n-
Other esters such as propyl, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate and ethyl pyruvate, N-methylpyrrolidone, N, N
-Dimethylformamide, N, N-dimethylacetamide, benzyl ethyl 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,
Examples include ethylene carbonate and propylene carbonate. 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 reaction is carried out without solvent or
-Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone,
-Methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone, 2-octanone, cyclopentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, Performed in a solvent such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-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. Is preferred.

In the above polycondensation reaction, water can be added to the reaction system. The amount of water added in this case is usually based on 100 parts by weight of the total amount of the silane compound.
It is not more than 10,000 parts by weight. Further, at the time of the polycondensation reaction, hexamethyldisiloxane may be added to control the molecular weight of the obtained polysiloxane (a) and to improve the stability. The addition amount of hexamethyldisiloxane is usually 500 parts by weight or less, preferably 5 parts by weight, based on 100 parts by weight of the total amount of the silane compound.
0 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 reaction temperature in the polycondensation,
Usually, it is -50 to 300C, preferably 20 to 100C, and the reaction time is usually about 1 minute to 100 hours.

In the polysiloxane (a), a structural unit derived from the silane compound (1) (hereinafter referred to as “structural unit (1)”) and a structural unit derived from the silane compound (2) (hereinafter referred to as “structural unit”) (2) ") to the total of the structural units (1), (2) and structural units derived from other silane compounds (hereinafter referred to as" other structural units "). On the other hand, it is usually 1 to 99 mol%, preferably 1 to 95 mol%, more preferably 5 to 95 mol%.
It is 80 mol%, particularly preferably 10 to 60 mol%.
In this case, if the total content is less than 1 mol%, the resolution of the resist tends to decrease, while the content of the resist tends to decrease.
If it exceeds mol%, the adhesiveness to a substrate when formed into a resist coating tends to decrease. Further, the content of the structural unit (1) is preferably 1 to 95 mol% with respect to the total of the structural unit (1), the structural unit (2) and other structural units.
More preferably, it is 5 to 80 mol%, particularly preferably 10 to 80 mol%.
６０60 mol%. In this case, if the content of the structural unit (1) is less than 1 mol%, the resolution of the resist may be reduced, while if it exceeds 95 mol%, the transparency of the obtained polymer to radiation decreases. Tend.

The content of the structural unit (2) is preferably at most 95 mol%, more preferably at least 80 mol%, based on the total of the structural units (1), (2) and other structural units. Or less, particularly preferably 30 mol% or less. In this case, if the content of the structural unit (2) exceeds 95 mol%, the glass transition temperature (Tg) of the obtained polymer
And the transparency to radiation tends to decrease. Also,
The content of the structural unit derived from the silane compound (5) (hereinafter, referred to as “structural unit (5)”) is determined based on the structural unit (1),
Preferably 5 to 95 mol%, more preferably 20 to 95 mol%, based on the total of the structural unit (2) and other structural units.
Mol%, particularly preferably 40 to 90 mol%. In this case, if the content of the structural unit (5) is less than 5 mol%, the transparency of the obtained polymer to radiation may decrease. There is a risk. The polysiloxane (a) preferably has a partially ladder structure.
This ladder structure is basically introduced by a condensation reaction of a silane compound (1) or a silane compound (5) which is trifunctional with respect to the condensation reaction.

The weight average molecular weight in terms of polystyrene (hereinafter, referred to as “Mw”) of polysiloxane (a) measured by gel permeation chromatography (GPC).
Is usually 500 to 100,000, preferably 500
To 50,000, particularly preferably 1,000 to 10,000.
00. In this case, if the Mw of the polysiloxane (a) is less than 500, the glass transition temperature (Tg) of the obtained polymer tends to decrease, while if it exceeds 100,000, the solubility of the obtained polymer in a solvent is reduced. Tends to decrease. In addition, Mw / M of polysiloxane (a)
n is 2.5 or less, preferably 2 or less, and more preferably 1.8 or less. The glass transition temperature (Tg) of the polysiloxane (a) is usually from 0 to 500C, preferably from 50 to 250C. In this case, if the glass transition temperature (Tg) of the polysiloxane (a) is less than 0 ° C., it may be difficult to form a pattern when it is used as a resist. Solubility tends to decrease.

Radiation-Sensitive Resin Composition The radiation-sensitive resin composition of the present invention comprises the above polysiloxane (a) and (b) a radiation-sensitive acid generator. In the radiation-sensitive resin composition of the present invention, the polysiloxane (a) can be used alone or in combination of two or more.

(B) Radiation-Sensitive Acid Generator The radiation-sensitive acid generator (hereinafter referred to as “acid generator (b)”) in the radiation-sensitive resin composition of the present invention generates an acid upon exposure. Component, and by the action of its acid,
The acid dissociable group present in the polysiloxane (a) is dissociated, and as a result, the exposed portion of the resist film becomes soluble in an alkali developing solution, and has a function of forming a positive resist pattern. Examples of such an acid generator (b) include an onium salt, a halogen-containing compound, a diazoketone compound, a sulfone compound, and a sulfonic acid compound. Examples of these acid generators (b) include the following.

Onium salt: Examples of the onium salt include an iodonium salt, a sulfonium salt (including a tetrahydrothiophenium salt), a phosphonium salt, a diazonium salt, and a pyridinium salt. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium heptadecafluoro-n-octanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyl Iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-
t-butylphenyl) iodonium nonafluoro-n-
Butanesulfonate, bis (4-t-butylphenyl)
Iodonium heptadecafluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-
(Butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium naphthalene sulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium heptadecafluoro-n-octane Sulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium 10-camphorsulfonate,

4-hydroxyphenyl phenyl methylsulfonium p-toluenesulfonate, cyclohexyl 2-oxocyclohexyl methylsulfonium trifluoromethanesulfonate, cyclohexyl
2-oxocyclohexyl methylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl.
-Oxocyclohexylmethylsulfonium heptadecafluoro-n-octanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium nonafluoro-n-butanesulfonate, dicyclohexyl-2-oxocyclohexadecathonium Fluoro-n-octanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium nonafluoro-
n-butanesulfonate, 2-oxocyclohexyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxyphenylbenzylmethylsulfonium p-toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium nonafluoro -N-butanesulfonate, 1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 1-naphthyldiethylsulfoniumheptadecafluoro -N-octanesulfonate,

4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-
1-naphthyldimethylsulfonium nonafluoro-n-
Butanesulfonate, 4-cyano-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-cyano-1
-Naphthyl diethylsulfonium nonafluoro-n-butanesulfonate, 4-cyano-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-nitro-1-naphthyldimethylsulfoniumtrifluoromethanesulfonate, 4-nitro-1-
Naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldimethylsulfoniumheptadecafluoro-n-octanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethyl Sulfonium nonafluoro-n-butanesulfonate, 4-nitro-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate,

4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-
1-naphthyldimethylsulfonium nonafluoro-n-
Butanesulfonate, 4-methyl-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-methyl-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl-1
-Naphthyl diethylsulfonium nonafluoro-n-butanesulfonate, 4-methyl-1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyl Dimethylsulfonium nonafluoro-
n-butanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium heptadecafluoro-n-octanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4
-Hydroxy-1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 4-hydroxy-
1-naphthyldiethylsulfonium heptadecafluoro-n-octanesulfonate,

4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4
-Methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4- (1-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4- (2-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-methoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t-butoxycarbonyloxy-
1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium Trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (1-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium Nonafluoro-n-butanesulfonate and the like can be mentioned.

Halogen-containing compound: Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include phenylbis (trichloromethyl) -s-triazine and 4-methoxyphenylbis (trichloromethyl)-
(Trichloromethyl) -s- such as s-triazine and 1-naphthylbis (trichloromethyl) -s-triazine
Examples thereof include a triazine derivative and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane. Diazoketone compound: Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound. Specific examples of preferred diazoketones include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphtho of 2,3,4,4'-tetrahydroxybenzophenone. Quinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-
5-sulfonic acid ester; 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane or 1,2-naphthoquinonediazide-5-sulfonic acid ester; Can be.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like. Sulfonic acid compound: Examples of the sulfonic acid compound include alkylsulfonic acid esters, alkylsulfonic acid imides, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-
9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.
1] hept-5-ene-2,3-dicarbodiimide, N
-Hydroxysuccinimide trifluoromethanesulfonate, 1,8-naphthalenedicarboximide trifluoromethanesulfonate, and the like.

Among these acid generators (b), diphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n -Butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyl Dimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-
Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1-
(1-naphthyl acetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, And 8-naphthalenedicarboximide trifluoromethanesulfonate are preferred.

In the present invention, the acid generators (b) can be used alone or in combination of two or more. The amount of the acid generator (b) used is from 10% of polysiloxane (b) from the viewpoint of securing the sensitivity and developability as a resist.
The amount is usually 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight with respect to 0 parts by weight. In this case, if the amount of the acid generator (b) used is less than 0.1 part by weight, the sensitivity and developability as a resist tend to decrease, while 10
When the amount is more than parts by weight, the transparency to radiation decreases,
There is a tendency that it is difficult to obtain a rectangular resist pattern as a resist.

Various Additives The radiation-sensitive resin composition of the present invention controls the diffusion phenomenon of the acid generated from the acid generator (b) in the resist film by exposure, and suppresses undesired chemical reactions in the unexposed area. It is preferable to add an acid diffusion controlling agent having an action of acting. By blending such an acid diffusion controller, the storage stability of the obtained composition is further improved, the resolution as a resist is further improved, and the delay time (PED) from exposure to development processing is reduced. The line width change of the resist pattern due to fluctuations can be suppressed,
A composition with excellent process stability is obtained. As the acid diffusion controller, a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern forming step is preferable. Such nitrogen-containing organic compounds include:
For example, the following general formula (10)

[0063]

Embedded image [In the general formula (10), each R ¹² independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. ]

(Hereinafter, referred to as "nitrogen-containing compound (i)"), a compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (ii)"),
Examples thereof include polymers having three or more nitrogen atoms (hereinafter, referred to as “nitrogen-containing compound (iii)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

As the nitrogen-containing compound (i), for example, n
Linear, branched or cyclic monoalkylamines such as hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and cyclohexylamine; di-n-butylamine, di-n- Linear or branched such as pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Or cyclic dialkylamines; triethylamine,
Tri-n-propylamine, tri-n-butylamine,
Tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexyl Linear, such as amines,
Branched or cyclic trialkylamines; aniline, N-methylaniline, N, N-dimethylaniline,
2-methylaniline, 3-methylaniline, 4-methylaniline, 2,6-di-t-butylaniline, 2,6-
Di-t-butyl-N-methylaniline, 2,6-di-t
And aromatic amines such as -butyl-N, N-dimethylaniline, 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine.

Examples of the nitrogen-containing compound (ii) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 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-aminophenyl) -1-methylethyl] benzene and the like. Examples of the nitrogen-containing compound (iii) include polyethyleneimine, polyallylamine, and 2-dimethylaminoethylacrylamide polymers.

Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-
Adamantylamine, N, N-di-tert-butoxycarbonyl-1-adamantylamine, N, N-di-tert-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4 ′ -Diaminodiphenylmethane, N, N'-di-tert-butoxycarbonylhexamethylenediamine, N, N, N'N'-tetra-tert-butoxycarbonylhexamethylenediamine,
N, N'-di-tert-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-tert-butoxycarbonyl-1,8-diaminooctane, N, N'-di-tert-butoxycarbonyl- 1,9-diaminononane, N, N'-
Di-tert-butoxycarbonyl-1,10-diaminodecane, N, N′-di-tert-butoxycarbonyl-1,12
-Diaminododecane, N, N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt
-Butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, N
N-t-butoxycarbonyl group-containing amino compounds such as -t-butoxycarbonyl-2-phenylbenzimidazole, formamide, N-methylformamide,
N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like can be mentioned.

Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-
Examples thereof include dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n-butylthiourea. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine and 2-ethylpyridine , 4-ethylpyridine, 2-phenylpyridine, 4-
Pyridines such as phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline and acridine; piperazine, 1- (2-hydroxyethyl) piperazine Other than piperazines such as pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like. Can be mentioned.

Among these nitrogen-containing organic compounds, a nitrogen-containing compound (i) and a nitrogen-containing heterocyclic compound are preferable, and among the nitrogen-containing compounds (i), tri (cyclo) alkylamines are particularly preferable. Among the nitrogen heterocyclic compounds,
Pyridines and piperazines are particularly preferred. The acid diffusion controllers can be used alone or in combination of two or more. The amount of the acid diffusion controller is usually 15 parts by weight or less based on 100 parts by weight of the polysiloxane (a).
It is preferably at most 10 parts by weight, more preferably at most 5 parts by weight. In this case, if the amount of the acid diffusion controller exceeds 15 parts by weight, the sensitivity as a resist and the developability of an exposed portion tend to decrease. If the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity as a resist may be reduced depending on the process conditions.

Further, the radiation-sensitive resin composition of the present invention may contain a surfactant having an effect of improving coatability, developability and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene In addition to nonionic surfactants such as glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow No. No. 75, the same No. 95
(Manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, E-top
F303, EF352 (Tochem Products Co., Ltd.)
), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florado FC430, F
C431 (manufactured by Sumitomo 3M Limited), Asahi Guard A
G710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, S
C-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) and the like. These surfactants can be used alone or in combination of two or more. The amount of the surfactant is as follows: polysiloxane (a) and acid generator (b)
Is usually 2 parts by weight or less based on 100 parts by weight in total. In addition, examples of the additives other than the above include an antihalation agent, an adhesion aid, a storage stabilizer, and an antifoaming agent.

Preparation of Composition Solution The radiation-sensitive resin composition of the present invention is usually used such that the total solid content is usually 1 to 25% by weight, preferably 2 to 10% by weight. After dissolving in a solvent, the composition is prepared as a composition solution by filtering through, for example, a filter having a pore size of about 0.2 μm. As the solvent used for preparing the composition solution, for example, 2-
Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone,
Linear or branched ketones such as -methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; cyclopentanone, 3-methylcyclopentanone, cyclohexanone, -Methylcyclohexanone, 2,6-dimethylcyclohexanone,
Cyclic ketones such as 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-sec-butyl ether acetate, propylene glycol mono-t-
Propylene glycol monoalkyl ether acetates such as 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-butyl 2-hydroxypropionate, 2
Alkyl 2-hydroxypropionates such as t-butyl-hydroxypropionate; 3-alkoxypropion such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate In addition to alkyl acid salts,

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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-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, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, N-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, -N-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid,
Examples thereof include 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, and propylene carbonate.

These solvents can be used alone or as a mixture of two or more. Among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates , Alkyl 2-hydroxypropionates and alkyl 3-alkoxypropionates are preferred.

[0074] The following method of forming a resist pattern, a method for forming a resist pattern using the radiation-sensitive resin composition of the present invention. In the radiation-sensitive resin composition of the present invention, an acid is generated from the acid generator (b) upon exposure, and an acid-dissociable group in the polysiloxane (a) is dissociated by the action of the acid, for example, carboxylic acid As a result, the solubility of the exposed portion of the resist in an alkali developing solution is increased, and the exposed portion is dissolved and removed by the alkali developing solution to obtain a positive resist pattern. When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution, by a suitable application means such as spin coating, casting coating, roll coating, for example, silicon wafer, coated with aluminum A resist film is formed by applying the resist film on a substrate such as a wafer which has been subjected to a heat treatment beforehand, and then the resist film is exposed to form a predetermined resist pattern. The radiation used at this time is F ₂ excimer laser (wavelength 157 nm), ArF
An excimer laser (wavelength 193 nm) or a KrF excimer laser (wavelength 248 nm) is preferable. In the present invention, heat treatment is preferably performed after exposure.
By this heat treatment, the dissociation reaction of the acid dissociable group in the polysiloxane (a) proceeds smoothly. The temperature of the heat treatment is
Depending on the composition of the resist composition, it is usually 3
It is 0-200 ° C, preferably 50-170 ° C.

In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example,
As disclosed in Japanese Patent No. 12452 or the like, an organic or inorganic antireflection film can be formed on a substrate to be used, and the influence of basic impurities and the like contained in an environmental atmosphere can be reduced. To prevent this, see, for example, JP-A-5-18
As disclosed in Japanese Patent No. 8598 and the like, a protective film can be provided on a resist film, or these techniques can be used in combination. Next, a predetermined resist pattern is formed by developing the exposed resist film. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine,
Methyl diethylamine, ethyl dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4. An alkaline aqueous solution in which at least one kind of alkaline compound such as 3.0] -5-nonene is dissolved. The concentration of the alkaline aqueous solution is usually
10% by weight or less. In this case, if the concentration of the alkaline aqueous solution exceeds 10% by weight, unexposed portions may be dissolved in the developer, which is not preferable.

Further, for example, an organic solvent can be added to the developer comprising the alkaline aqueous solution. Examples of the organic solvent include acetone, 2-butanone,
4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-
Ketones such as dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i
Alcohols such as -propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; ethyl acetate And esters such as n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone, and dimethylformamide. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably 100% by volume or less based on the alkaline aqueous solution.
In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability may be reduced and the undeveloped portion of the exposed portion may be increased. In addition, an appropriate amount of a surfactant or the like can be added to a developer composed of an alkaline aqueous solution. In addition,
After developing with a developing solution composed of an alkaline aqueous solution, it is generally washed with water and dried.

[0077]

Embodiments of the present invention will now be described more specifically with reference to the following examples. However, the present invention is not limited to these embodiments. Each measurement and evaluation in Examples and Comparative Examples was performed in the following manner. Mw and Mn: GPC column (G20 manufactured by Tosoh Corporation)
00HXL two, G3000HXL one, G4000HXL one
This was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C. Radiation transmittance: Each polysiloxane was dissolved in 2-heptanone to prepare a polymer solution having a solid concentration of 5% by weight. Thereafter, each polymer solution was applied on a magnesium fluoride substrate by spin coating, and heated on a hot plate maintained at 140 ° C. for 90 seconds to form a film having a thickness of 100 nm. Then, for this coating, wavelength 15
From the absorbances at 7 nm and 193 nm, the radiation transmittance was calculated and used as a measure of transparency in the deep ultraviolet region.

Synthesis Example 1 (Synthesis of Silane Compound (1)) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 5.01 g of trimethoxysilane, 5-t-butoxycarbonylbicyclo [2. 2.1] 4.99 g of hept-2-ene was added and stirred at room temperature, and then 1.0 ml of a 0.1 mol i-propyl alcohol solution of chloroplatinic acid was added to start the reaction. Then at 140 ° C 4
After heating under reflux for 8 hours, the temperature was 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. Thereafter, the crude product was purified by distillation under reduced pressure at 0.2 mmHg and 105 ° C. to obtain 48 g of a reaction product. When a nuclear magnetic resonance spectrum (chemical shift σ) and an infrared absorption spectrum (IR) of this reaction product were measured, the measured values were as follows, and the product was identified as a compound represented by the following formula (11). Was. Compound (1)
1). σ: 3.6 ppm (methoxy group), 1.4 ppm (t
-Butyl group). IR: 2847 cm ^-1 (methoxy group), 1730 cm ^-1
(Ester group), 1153 cm ^-1 (siloxane group), 1
095 cm ^-1 (siloxane group).

[0079]

Embedded image [In the formula (11), the silicon atom is bicyclo [2.
2.1] It is bonded to the 2- or 3-position of the heptane ring. ]

Synthesis Example 2 (Synthesis of silane compound (1)) In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 76.0 g of triethoxysilane, 8-t-butoxycarbonyltetracyclo [4 .4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene (100 g), and the mixture was stirred at room temperature. Then, 5.0 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction. The mixture was heated and refluxed at 150 ° C. for 75 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 53 g of a reaction product as an n-hexane fraction. When a nuclear magnetic resonance spectrum (chemical shift σ) and an infrared absorption spectrum (IR) of this reaction product were measured, the measured values were as follows, and the product was identified as a compound represented by the following formula (12). Was. This compound is referred to as compound (12). σ: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group), 1.4 ppm (t-butyl group). IR: 2885 cm ^-1 (ethoxy group), 1726 cm ^-1
(Ester group), 1153 cm ^-1 (siloxane group), 1
080 cm ^-1 (siloxane group).

[0081]

Embedded image [In the formula (12), the silicon atom is tetracyclo [
4.4.0.1 ^2,5 . [ ^7,10 ] dodecane ring at the 3- or 4-position. ]

Synthesis Example 3 (Synthesis of silane compound (5)) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 38.8 g of triethoxysilane and 5- [2-hydroxy-2,2 were added. -Di (trifluoromethyl)] bicyclo [
2.2.1] hept-2-ene 43.2g was added, After stirring at room temperature, was added a 0.2 molar i- propyl alcohol solution 0.1 ml of chloroplatinic acid (H ₂ PtCl ₆₎ The reaction was started, and 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 by suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was
Purification was performed by distillation under reduced pressure at mHg and 105 ° C. to obtain 59.8 g of a reaction product. When a nuclear magnetic resonance spectrum (chemical shift σ) and an infrared absorption spectrum (IR) of this reaction product were measured, the measured values were as follows, and the product was identified as a compound represented by the following formula (13). Was. This compound is referred to as compound (13). σ: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group). IR: 3400 cm ^-1 (hydroxyl group), 2878 cm ^-1 (methoxy group), 1215 cm ^-1 (CF bond), 1082
cm ^-1 (siloxane group).

[0083]

Embedded image [In the formula (13), the silicon atom is bicyclo [2.
2.1] bonded to the 2- or 3-position of the heptane ring. ]

Synthesis Example 4 (Synthesis of Silane Compound (1)) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 3.0 g of compound (13) and 10 g of tetrahydrofuran were placed.
Then, the mixture was stirred in a nitrogen stream under ice-cooling. When the temperature of the reaction solution reached 5 ° C. or lower, 16.7 mg of 4-dimethylaminopyridine was added, and then di-t-butyl dicarbonate 1 was added. .64 g in tetrahydrofuran 5
The solution dissolved in milliliter was added dropwise over 15 minutes. After stirring for 1 hour after the completion of the dropwise addition, the reaction solution was returned to room temperature and further stirred for 5 hours. Thereafter, n-
Hexane (50 ml) was added, the mixture was transferred to a separating funnel, and the organic layer was washed three times with ice water. Thereafter, the organic layer was transferred to 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 reaction product from the n-hexane fraction. When a nuclear magnetic resonance spectrum (chemical shift σ) and an infrared absorption spectrum (IR) of this reaction product were measured, the measured values were as follows, and the product was identified as a compound represented by the following formula (14). Was. This compound is referred to as compound (14). σ: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group), 1.5 ppm (t-butyl group). IR: 3400 cm ^-1 (hydroxyl group), 2879 cm ^-1 (methoxy group), 1774 cm ^-1 (carbonate group), 12
21 cm ^-1 (CF bond), 1082 cm ^-1 (siloxane group).

[0085]

Embedded image [In the formula (14), the silicon atom is bicyclo [2.
2.1] bonded to the 2- or 3-position of the heptane ring. ]

Synthesis Example 5 (Synthesis of silane compound (5)) 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 were added. -Di (trifluoromethyl)] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene 2
After adding 5.0 g and stirring at room temperature, 0.2 ml of a 0.2 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction.
The mixture was heated and refluxed at 70 ° 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 a reaction product from the n-hexane fraction.
4 g were obtained. For the reaction product, a nuclear magnetic resonance spectrum (chemical shift σ) and an infrared absorption spectrum (I
When R) was measured, the measured values were as follows, and the compound was identified as a compound represented by the following formula (15). This compound is referred to as compound (15). σ: 3.8 ppm (ethoxy group), 1.2 ppm (ethoxy group). IR: 3400 cm ^-1 (hydroxyl group), 1220 cm ^-1 (C
—F bond), 1098 cm ⁻¹ (siloxane group).

[0087]

Embedded image [In the formula (15), the silicon atom is tetracyclo [
4.4.0.1 ^2,5 . [ ^7,10 ] dodecane ring at the 3- or 4-position. ]

Example 1 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 4.99 g of compound (11), 5.01 g of methyltrimethoxysilane, 0.43 methyldisiloxane
g, 30 g of 4-methyl-2-pentanone, 2.91 g of a 2.37% by weight aqueous oxalic acid solution and, with stirring, 8 g of oxalic acid.
The reaction was performed at 0 ° C. for 4 hours. Thereafter, the reaction vessel was cooled with ice to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added to wash with water, and the water washing was repeated until the reaction solution became neutral. . Thereafter, the organic layer was distilled off under reduced pressure to obtain 5.9 g of a polymer. The nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw, and Mw / Mn of this polymer were measured. The results were as follows. σ: 1.4 ppm (t-butyl group), 0.2 p
pm (SiCH ₃ groups). IR: 1730 cm ^-1 (ester group), 1150
cm ^-1 (siloxane group). Mw: 1,700 Mw / Mn: 1.4 This polymer is referred to as polysiloxane (a-1).

Example 2 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 4.99 g of compound (11), 5.01 g of methyltrimethoxysilane, 0.43 methyldisiloxane
g, 30 g of 4-methyl-2-pentanone, 2.91 g of a 2.37% by weight aqueous oxalic acid solution and, with stirring, 8 g of oxalic acid.
The reaction was performed at 0 ° C. for 4 hours. Thereafter, the reaction solution was ice-cooled to stop the reaction, and then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was added to wash the reaction solution. The water washing was repeated until the reaction solution became neutral. . Thereafter, the organic layer was distilled off under reduced pressure to obtain 6.7 g of a polymer having an Mw of 1,700.
Then, the polymer was treated with 4-methyl-2-pentanone 3
After dissolving in 0 g, 5.7 g of distilled water and 8.0 g of triethylamine were added, and the mixture was heated at 40 ° C. in a nitrogen stream. After a lapse of 2 hours, the reaction solution was stirred while being cooled with ice. Then, an aqueous solution in which 3.5 g of oxalic acid was dissolved in 150 g of distilled water was added, and stirring was continued. Then, transfer the reaction solution to a separating funnel,
Discard the aqueous layer, add ion-exchanged water and wash with water,
Washing with water was repeated until the reaction solution became neutral. afterwards,
The organic layer was distilled off under reduced pressure to obtain 5.9 g of a polymer. For this polymer, the nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw and Mw /
Mn was measured and was as follows. σ: 1.4 ppm (t-butyl group), 0.2 p
pm (SiCH ₃ groups). IR: 1730 cm ^-1 (ester group), 1150
cm ^-1 (siloxane group). Mw: 2,700 Mw / Mn: 1.5 This polymer is referred to as polysiloxane (a-2).

Example 3 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 3.84 g of compound (12) and 7.9 of compound (13) were placed.
3 g, 3.22 g of methyltriethoxysilane, 10.5 g of 4-methyl-2-pentanone, 3.32 g of a 1.75% by weight aqueous oxalic acid solution, and stirred at 80 ° C. for 6 hours.
Allowed to react for hours. After that, the reaction solution was cooled on ice to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added to wash the solution, and the water washing was repeated until the reaction solution became neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 8.2 g of a polymer. About this polymer,
The nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw, and Mw / Mn were measured and were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.4 ppm (t-butyl group), 0.2 ppm (SiC
H ₃ group). IR: 1700 cm ^-1 (ester group), 1213
cm ^-1 (C-F bond), 1151cm ^-1 (siloxane group). Mw: 2,100. Mw / Mn: 1.6 This polymer is referred to as polysiloxane (a-3).

Example 4 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 3.84 g of compound (12) and 7.9 of compound (13) were placed.
3 g, 3.22 g of methyltriethoxysilane, 15.0 g of 4-methyl-2-pentanone, 3.32 g of a 1.75% by weight aqueous oxalic acid solution, and the mixture was stirred at 80 ° C. for 2 hours.
Allowed to react for hours. Thereafter, the reaction solution was ice-cooled to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was added to wash the reaction solution, and the water washing was repeated until the reaction solution became neutral. . Thereafter, the organic layer was distilled off under reduced pressure to obtain 10 g of a polymer having Mw of 1,600. Then
This polymer was dissolved in 23 g of 4-methyl-2-pentanone, 4.9 g of distilled water and 6.9 g of triethylamine were added, and the mixture was heated at 40 ° C. in a nitrogen stream. After a lapse of 2 hours, the reaction solution was stirred while being cooled with ice. Then, an aqueous solution in which 5.7 g of oxalic acid was dissolved in 200 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 10.1 g of a polymer. For this polymer, a nuclear magnetic resonance spectrum (chemical shift σ),
When the infrared absorption spectrum (IR), Mw and Mw / Mn were measured, they were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.4 ppm (t-butyl group), 0.2 ppm (SiC
H ₃ group). IR: 1700 cm ^-1 (ester group), 1213
cm ^-1 (C-F bond), 1151cm ^-1 (siloxane group). Mw: 2,600. Mw / Mn: 1.3 This polymer is referred to as polysiloxane (a-4).

Example 5 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a cold flow cooler and a thermometer, 3.83 g of compound (13) and 1.1 of compound (14) were added.
7 g, 4-methyl-2-pentanone 2.50 g, 1.7
0.80 g of a 5 wt% oxalic acid aqueous solution was added, and the mixture was reacted at 40 ° C. for 10 hours with stirring. Thereafter, the reaction solution was ice-cooled to stop the reaction, and then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was added to wash the reaction solution. The water washing was repeated until the reaction solution became neutral. . Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.65 g of a semi-solid polymer. The nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw, and Mw / Mn of this polymer were measured. The results were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxy group). IR: 1775 cm ^-1 (ester group), 1219
cm ^-1 (C-F bond), 1131cm ^-1 (siloxane group). Mw: 1,700. Mw / Mn: 1.1 In this case, a peak at 1.5 ppm indicating the presence of a t-butoxy group was confirmed in the chemical shift σ, but ethoxy originated from SiOC ₂ H ₅ groups remaining in the polymer. No peak around 3.8 ppm indicating the presence of the group was observed. A peak at 1775 cm ^-1 indicating the presence of a carbonate ester was also observed in the infrared absorption spectrum. In this reaction, only the SiOC ₂ H ₅ group was selectively hydrolyzed and t
It was confirmed that the butoxy group elimination reaction hardly occurred. Further, in the gel permeation chromatography (GPC) analysis, no peak indicating the presence of the unreacted monomer was observed. This polymer is referred to as polysiloxane (a-5).

Example 6 (Synthesis of polysiloxane (a)) Polysiloxane (e5) obtained in the same manner as in Example 5
3.7 g was dissolved in 10.8 g of 4-methyl-2-pentanone, and 1.18 g of distilled water and 1.18 g of triethylamine were dissolved.
After adding 65 g, the mixture was heated to 40 ° C. in a nitrogen stream and reacted for 5 hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 1.38 g of oxalic acid was dissolved in 50 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.6 g of a polymer.
I got For this polymer, nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw
When Mw / Mn was measured, it was as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxy group). IR: 1775 cm ^-1 (ester group), 1220
cm ^-1 (C-F bond), 1133cm ^-1 (siloxane group). Mw: 2,400. Mw / Mn: 1.1 This polymer is referred to as polysiloxane (a-6).

Example 7 (Synthesis of polysiloxane (a)) Polysiloxane (a-5) obtained in the same manner as in Example 5
3.7 g was dissolved in 10.8 g of 4-methyl-2-pentanone, and 1.18 g of distilled water and 1.18 g of triethylamine were dissolved.
After adding 65 g, the mixture was heated to 60 ° C. in a nitrogen stream and reacted for 5 hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 1.38 g of oxalic acid was dissolved in 50 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.6 g of a polymer.
I got For this polymer, nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw and M
When w / Mn was measured, it was as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxy group). IR: 1775 cm ^-1 (ester group), 1221
cm ^-1 (C-F bond), 1133cm ^-1 (siloxane group). Mw: 2,700. Mw / Mn: 1.1 This polymer is referred to as polysiloxane (a-7).

Example 8 (Synthesis of polysiloxane (a)) Polysiloxane (a-5) obtained in the same manner as in Example 5
3.7 g was dissolved in 10.8 g of 4-methyl-2-pentanone, and 1.18 g of distilled water and 1.18 g of triethylamine were dissolved.
After adding 65 g, the mixture was heated to 80 ° C. in a nitrogen stream and reacted for 5 hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 1.38 g of oxalic acid was dissolved in 50 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.5 g of a polymer.
I got For this polymer, nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw
When Mw / Mn was measured, it was as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxy group). IR: 1775 cm ^-1 (ester group), 1220
cm ^-1 (C-F bond), 1129cm ^-1 (siloxane group). Mw: 3,500. Mw / Mn: 1.2 This polymer is referred to as polysiloxane (a-8).

Example 9 (Synthesis of polysiloxane (a)) 1.90 g of compound (12) and 6.8 of compound (13) were placed in a three-necked flask equipped with a stirrer, a cold condenser and a thermometer.
9 g, 1.21 g of the compound (14), 10.0 g of 4-methyl-2-pentanone, 1.65 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 40 ° C. for 10 hours with stirring. After that, the reaction solution is cooled with ice to stop the reaction, then transferred to a separating funnel, the aqueous layer is discarded, and ion-exchanged water is further added and washed, and the water washing is repeated until the reaction solution becomes neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 7.5 g of a viscous oily polymer. This polymer has a Mw
Was 1,500 and Mw / Mn was 1.1. Then
22.5 g of this polymer was 4-methyl-2-pentanone
, And 2.43 g of distilled water and 3.40 g of triethylamine were further added thereto.
Allowed to react for hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 2.83 g of oxalic acid was dissolved in 70 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 7.38 g of a solid polymer. The nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw and Mn of this polymer were measured, and the results were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxycarbonyl group), 1.4 p
pm (t-butoxy group). IR: 1775 cm ^-1 (carbonate group), 17
26cm ^-1 (ester group), 1221cm ^-1 (C-F bond), 1133cm ^-1 (siloxane group). Mw: 2,300. Mw / Mn: 1.1. This polymer is referred to as polysiloxane (a-9).

Example 10 (Synthesis of polysiloxane (a)) 1.86 g of compound (12) and 5.7 of compound (13) were placed in a three-necked flask equipped with a stirrer, a cold condenser and a thermometer.
7 g, 2.36 g of the compound (14), 10.0 g of 4-methyl-2-pentanone, 1.61 g of a 1.75% by weight aqueous oxalic acid solution were added, and the mixture was reacted at 40 ° C. for 10 hours with stirring. After that, the reaction solution was cooled on ice to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added to wash the solution, and the water washing was repeated until the reaction solution became neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 7.5 g of a viscous oily polymer. This polymer is
w was 1,500 and Mw / Mn was 1.1. The polymer was then treated with 4-methyl-2-pentanone.
The resultant was dissolved in 7 g, further added with 2.37 g of distilled water and 3.33 g of triethylamine, heated to 60 ° C. in a nitrogen stream, and reacted for 5 hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 2.77 g of oxalic acid was dissolved in 70 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 7.34 g of a solid polymer. The nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw, and Mw / Mn of this polymer were measured. The results were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxycarbonyl group), 1.4 p
pm (t-butoxy group). IR: 1775 cm ^-1 (carbonate group), 17
26cm ^-1 (ester group), 1220cm ^-1 (C-F bond), 1131cm ^-1 (siloxane group). Mw: 2,300. Mw / Mn: 1.1. This polymer is referred to as polysiloxane (a-10).

Example 11 (Synthesis of polysiloxane (a)) 1.28 g of compound (12) and 3.3 of compound (13) were placed in a three-necked flask equipped with a stirrer, a cold flow cooler and a thermometer.
0 g, 2.43 g of compound (14), 7.0 g of 4-methyl-2-pentanone, 1.75% by weight aqueous oxalic acid solution.
10 g was added and reacted at 40 ° C. for 10 hours with stirring. After that, the reaction solution was cooled on ice to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added to wash the solution, and the water washing was repeated until the reaction solution became neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 5.2 g of a viscous oily polymer. This polymer is
w was 1,400 and Mw / Mn was 1.1. The polymer was then treated with 4-methyl-2-pentanone.
0 g, further added 1.63 g of distilled water and 2.28 g of triethylamine, heated at 60 ° C. in a nitrogen stream, and reacted for 5 hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 1.90 g of oxalic acid was dissolved in 5 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 5.03 g of a solid polymer. The nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw, and Mw / Mn of this polymer were measured. The results were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxycarbonyl group), 1.4 p
pm (t-butoxy group). IR: 1776 cm ^-1 (carbonate group), 17
26cm ^-1 (ester group), 1221cm ^-1 (C-F bond), 1132cm ^-1 (siloxane group). Mw: 2,300. Mw / Mn: 1.1. This polymer is referred to as polysiloxane (a-11).

Example 12 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a cold flow cooler, and a thermometer, 2.79 g of compound (13) and 1.1 g of compound (14) were added.
4 g, 1.07 g of compound (15), 5.0 g of 4-methyl-2-pentanone, 1.75% by weight aqueous solution of oxalic acid.
78 g was added and reacted at 40 ° C. for 10 hours with stirring. After that, the reaction vessel was cooled with ice to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed, and the water washing was repeated until the reaction solution became neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.6 g of a viscous oily polymer. This polymer has a Mw
Was 1,600 and Mw / Mn was 1.1. Then
This polymer was weighed with 11.4 g of 4-methyl-2-pentanone.
, And 1.15 g of distilled water and 1.61 g of triethylamine were further added.
Allowed to react for hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 1.34 g of oxalic acid was dissolved in 50 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.23 g of a solid polymer. The nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw, and Mw / Mn of this polymer were measured. The results were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxycarbonyl group). IR: 1775 cm ^-1 (carbonate group), 12
21 cm ^-1 (CF bond), 1130 cm ^-1 (siloxane group). Mw: 2,500. Mw / Mn: 1.1. This polymer is referred to as polysiloxane (a-12).

Example 13 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a cold flow cooler and a thermometer, 3.19 g of compound (13) and 2.3 of compound (14) were placed.
5 g, compound (15) 1.47 g, 4-methyl-2-pentanone 7.0 g, 1.75% by weight oxalic acid aqueous solution 1.
After adding 07 g, the mixture was reacted at 40 ° C. for 10 hours while stirring. After that, the reaction vessel was cooled with ice to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed, and the water washing was repeated until the reaction solution became neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 5.3 g of a viscous oily polymer. This polymer has a Mw
Was 1,500 and Mw / Mn was 1.1. Then
This polymer was weighed with 16.1 g of 4-methyl-2-pentanone.
, And 1.57 g of distilled water and 2.20 g of triethylamine were further added thereto.
Allowed to react for hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 1.83 g of oxalic acid was dissolved in 50 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 5.24 g of a solid polymer. The nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw, and Mw / Mn of this polymer were measured. The results were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxycarbonyl group). IR: 1774 cm ^-1 (carbonate group), 12
20 cm ^-1 (CF bond), 1132 cm ^-1 (siloxane group). Mw: 2,500. Mw / Mn: 1.1. This polymer is referred to as polysiloxane (a-13).

Example 14 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a cold flow condenser and a thermometer, 0.45 g of compound (12) and 2.3 of compound (13) were placed.
3 g, compound (14) 1.15 g, compound (15) 1.
07 g, 5.0 g of 4-methyl-2-pentanone, 1.7
Add 0.78 g of a 5% oxalic acid aqueous solution and, with stirring,
The reaction was performed at 40 ° C. for 10 hours. After that, the reaction vessel was cooled with ice to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed, and the water washing was repeated until the reaction solution became neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.7 g of a viscous oily polymer.
This polymer has Mw of 1,600 and Mw / Mn of 1.
It was one. The polymer was then converted to 4-methyl-2-
Dissolved in 11.5 g of pentanone, and
g and 1.61 g of triethylamine, and the mixture was heated to 60 ° C. in a nitrogen stream and reacted for 5 hours. Thereafter, the reaction solution was stirred while being cooled with ice, and then an aqueous solution in which 1.34 g of oxalic acid was dissolved in 50 g of distilled water was added, and stirring was continued. Then, transfer the reaction solution to a separatory funnel, discard the aqueous layer,
Further, ion-exchanged water was added and the mixture was washed with water, and the washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.57 g of a solid polymer. For this polymer, a nuclear magnetic resonance spectrum (chemical shift σ),
When the infrared absorption spectrum (IR), Mw and Mw / Mn were measured, they were as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxycarbonyl group), 1.4 p
pm (t-butoxy group). IR: 1776 cm ^-1 (carbonate group), 17
25 cm ^-1 (ester group), 1220cm ^-1 (C-F bond), 1130 cm ^-1 (siloxane group). Mw: 2,500. Mw / Mn: 1.1. This polymer is referred to as polysiloxane (a-14).

Example 15 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a cold flow condenser and a thermometer, 0.92 g of compound (12) and 2.3 of compound (13) were placed.
9 g, compound (14) 0.59 g, compound (15) 1.
10 g, 5.0 g of 4-methyl-2-pentanone, 1.7
0.80 g of a 5% oxalic acid aqueous solution is added, and while stirring,
The reaction was performed at 40 ° C. for 10 hours. Then, the reaction vessel is cooled with ice to stop the reaction, then transferred to a separating funnel, the aqueous layer is discarded, and ion-exchanged water is further added to wash the water, and the water washing is repeated until the reaction liquid becomes neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.7 g of a viscous oily polymer. This polymer has Mw of 1,500 and Mw / Mn of 1.1.
Met. Next, this polymer was dissolved in 11.4 g of 4-methyl-2-pentanone, and further dissolved in 1.18 of distilled water.
g and 1.65 g of triethylamine, and the mixture was heated to 60 ° C. in a nitrogen stream and reacted for 5 hours. afterwards,
After the reaction solution was stirred while being cooled with ice, oxalic acid 1.37 was added.
g was dissolved in 50 g of distilled water, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was added for washing with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.57 g of a solid polymer. For this polymer, the nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw and Mw /
Mn was measured and was as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxycarbonyl group), 1.4 p
pm (t-butoxy group). IR: 1775 cm ^-1 (carbonate group), 17
26cm ^-1 (ester group), 1221cm ^-1 (C-F bond), 1132cm ^-1 (siloxane group). Mw: 2,400. Mw / Mn: 1.1. This polymer is designated as polysiloxane (a-15).

Example 16 (Synthesis of polysiloxane (a)) In a three-necked flask equipped with a stirrer, a cold flow condenser and a thermometer, 0.91 g of compound (12) and 1.8 of compound (13) were added.
7 g, compound (14) 1.15 g, compound (15) 1.
08 g, 4-methyl-2-pentanone 5.0 g, 1.7
Add 0.78 g of a 5% oxalic acid aqueous solution and, with stirring,
The reaction was performed at 40 ° C. for 10 hours. After that, the reaction vessel was cooled with ice to stop the reaction, then transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was further added and washed, and the water washing was repeated until the reaction solution became neutral. Was. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.6 g of a viscous oily polymer.
This polymer has Mw of 1,500 and Mw / Mn of 1.
It was one. The polymer was then converted to 4-methyl-2-
Dissolved in 11.4 g of pentanone and further distilled water 1.15 g
g and 1.62 g of triethylamine, and the mixture was heated to 60 ° C. in a nitrogen stream and reacted for 5 hours. afterwards,
After stirring the reaction solution while cooling it with ice, oxalic acid 1.35 was added.
g was dissolved in 50 g of distilled water, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain 3.30 g of a solid polymer. For this polymer, the nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw and Mw /
Mn was measured and was as follows. σ: 2.3 ppm (CH ₂ C (CF ₃ ) ₂ groups),
1.5 ppm (t-butoxycarbonyl group), 1.4 p
pm (t-butoxy group). IR: 1774 cm ^-1 (carbonate group), 17
26cm ^-1 (ester group), 1226cm ^-1 (C-F bond), 1130 cm ^-1 (siloxane group). Mw: 2,400. Mw / Mn: 1.1. This polymer is referred to as polysiloxane (a-16).

Comparative Example 1 (Synthesis of Polysiloxane) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 4.99 g of compound (11), 5.01 g of methyltrimethoxysilane, and hexamethyldisiloxane 0.43
g, 4-methyl-2-pentanone 30 g, distilled water 5.9
7 g and 8.37 g of triethylamine were added and reacted at 80 ° C. for 8 hours with stirring. Thereafter, the reaction solution was ice-cooled to stop the reaction, and a solution obtained by dissolving 7.31 g of oxalic acid in 250 ml of ion-exchanged water was added thereto, followed by stirring. Then, transfer the reaction solution to a separating funnel,
The aqueous layer was discarded, and 100 ml of ion-exchanged water was added and washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain a polymer. For this polymer, nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR), Mw
When Mw / Mn was measured, it was as follows. σ: 3.6 ppm (methoxy group), 1.4 pp
m (t-butyl group), 0.2 ppm (SiCH ₃ group). IR: 1730 cm ^-1 (ester group), 1149
cm ^-1 (siloxane group). Mw: 4,900 Mw / Mn: 2.0. In this case, the peak at 3.6 ppm in the chemical shift σ is
This is due to methoxy groups derived from SiOCH ₃ groups remaining in the polymer. In contrast, in Examples 1 to 8, almost no peak due to the methoxy group was observed in the chemical shift σ. This polymer is referred to as comparative polysiloxane (1).

Comparative Example 2 (Synthesis of Polysiloxane) 3.84 g of compound (12) and 7.9 of compound (13) were placed in a three-necked flask equipped with a stirrer, a cold flow cooler and a thermometer.
3 g, 3.22 g of methyltriethoxysilane, 15.0 g of 4-methyl-2-pentanone, 4.9 g of distilled water, and 6.9 g of triethylamine, and added at 80 ° C. in a nitrogen stream.
The mixture was heated to reflux for 0 hour. Thereafter, the reaction solution was cooled with ice to stop the reaction, and then an aqueous solution in which 5.7 g of oxalic acid was dissolved in 200 g of distilled water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, ion-exchanged water was added, and the mixture was washed with water. The washing with water was repeated until the reaction solution became neutral. Thereafter, the organic layer was distilled off under reduced pressure to obtain a polymer. When the nuclear magnetic resonance spectrum (chemical shift σ) and the infrared absorption spectrum (IR) of this polymer were measured, the values were the same as those of Examples 3 and 4, but SiOC ₂ remaining in the polymer was measured. The peak of the ethoxy group derived from the H ₅ group was slightly observed at 3.8 ppm. This polymer has a Mw of 3,90.
0, and Mw / Mn was 1.6. This polymer is referred to as Comparative Polysiloxane (2).

Evaluation Example 1 (Evaluation of Resolution and Pattern Shape by KrF Excimer Laser Exposure) Polysiloxane (a-1), polysiloxane (a-2)
Or 100 parts by weight of each of the comparative polysiloxane (1),
1 part by weight of triphenylsulfonium nonafluoro-n-butanesulfonate, 0.1 part by weight of tri-n-octylamine.
02 parts by weight and 900 parts by weight of 2-heptanone were uniformly mixed to prepare a radiation-sensitive resin composition. Then
Each composition was applied on a silicon wafer by spin coating, and 90 ° C. on a hot plate kept at 130 ° C.
A heat treatment was performed for seconds to form a resist film having a thickness of 100 nm. After that, KrF
Exposure was performed by changing the exposure amount using an excimer laser (wavelength: 248 nm).
After heat treatment for 90 seconds, development was carried out with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Then, as a result of observing the exposed portion with a scanning electron microscope, the limit resolution was 0.30 μm when the comparative polysiloxane (1) was used, whereas the limit resolution was 0.30 μm.
When 1) was used, it was 0.24 μm, and when polysiloxane (a-2) was used, it was 0.22 μm. Regarding the pattern shape, when using polysiloxane (a-1) and polysiloxane (a-2), a better rectangular shape was obtained than when using comparative polysiloxane (1). Had.

Evaluation Example 2 (Evaluation of Radiation Transmittance) Polysiloxane (a-1), polysiloxane (a-6)
-(A-16) or each 2-heptanone solution of the comparative polysiloxane (1) was applied on a silicon wafer by a spin coater, and then heated on a hot plate maintained at 110 ° C. for 90 seconds to obtain a film. 1,000mm thick
Was formed. Then, for each coating, a wavelength of 15
The radiation transmittance at 7 nm and a wavelength of 193 nm was measured. Table 1 shows the measurement results.

[0108]

[Table 1]

As is clear from Table 1, the radiation transmittance of the comparative polysiloxane (1) polycondensed under basic conditions and the polysiloxane (a) polycondensed under acidic conditions was 193 nm. Is substantially the same, but the wavelength 157
It was confirmed that the polysiloxane (a) was considerably high in nm. This fact indicates that polysiloxane (a) polycondensed under acidic conditions is promising as a material for microfabrication with shorter wavelength radiation.

Evaluation Example 3 (Evaluation of Tg) Polysiloxane (a-3) to Polysiloxane (a-8)
Table 2 shows the results of measuring the glass transition temperature (Tg) of the comparative polysiloxane (2).

[0111]

[Table 2]

As is evident from Table 2, the Tg of the polysiloxane (a) polycondensed under acidic conditions was lower than that of the comparative polysiloxane (2) polycondensed under basic conditions.
Was confirmed to be high. Also, compared to polysiloxane (a-3) synthesized only by polycondensation under acidic conditions,
It was clarified that Tg was higher in the polysiloxane (a-4) in which polycondensation was performed under basic conditions following polycondensation under acidic conditions. This fact suggests that in synthesizing polysiloxane (a), a polymer that has increased the degree of polymerization by performing polycondensation under basic conditions followed by polycondensation under basic conditions to increase the degree of cross-linking is better. This indicates that the Tg is increased, and that the Tg of the polysiloxane (a) can be controlled by selecting the polymerization conditions. Increasing the Tg of the resin component used in the radiation-sensitive resin composition is one of the important factors in forming a finer resist pattern by a lithography process. In that sense, the T of the polysiloxane (a) is increased.
The fact that g can be controlled supports the usefulness of the present invention.

Evaluation Example 4 (Evaluation of Resolution by ArF Excimer Laser Exposure) Polysiloxane (a-3), polysiloxane (a
4) 100 parts by weight of each of polysiloxane (a-6) to polysiloxane (a-10), polysiloxane (a-12) to polysiloxane (a-16) or comparative polysiloxane (2), triphenyls 1 part by weight of ruphonium nonafluoro-n-butanesulfonate, 0.02 part by weight of tri-n-octylamine and 2-heptanone 900
The parts by weight were uniformly mixed to prepare a radiation-sensitive resin composition. Next, each composition was applied on a silicon wafer by spin coating, and then heat-treated on a hot plate maintained at 140 ° C. for 90 seconds to obtain a film thickness of 100 n.
m of the resist film was formed. Then, an ArF excimer laser (wavelength 193 nm) is applied to each resist coating.
And then heat-treated on a hot plate maintained at 110 ° C. for 90 seconds, and then the resist film using polysiloxane (a-6) and polysiloxane (a-7) was removed. 3.38% by weight of an aqueous solution of tetramethylammonium hydroxide, and polysiloxane (a-6) and polysiloxane (a-7)
Was developed with a 1.19% by weight aqueous solution of tetramethylammonium hydroxide. Next, the exposed portion was observed with a scanning electron microscope,
The critical resolution of each resist was measured. Table 3 shows the measurement results.
Shown in

[0114]

[Table 3]

Evaluation Example 5 (Evaluation of Dry Etching Resistance) The resist film using polysiloxane (a-1) and polysiloxane (a-2) formed in evaluation example 1 is used for a general KrF resist. An etching test was performed in comparison with the polystyrene coating. Table 4 shows the measurement results of the etching conditions and the etching rates.

[0116]

[Table 4]

As is clear from Table 4, the dry etching of the resist film using polysiloxane (a-1) and polysiloxane (a-2) was 30 times or more that of the polystyrene film under the organic film etching condition. It was confirmed that the film exhibited resistance to dry etching under SiO ₂ etching conditions, and had almost the same dry etching resistance as a polystyrene film.

Evaluation Example 6 (Evaluation of developability) Polysiloxane (a-5) to polysiloxane (a-8)
Each 2-heptanone solution was applied on a silicon wafer by a spin coater, and then heated on a hot plate maintained at 110 ° C. for 90 seconds to form a film having a thickness of 1000 ° C.
Was formed. Thereafter, when each resist film was immersed in ion-exchanged water for 60 seconds, the film thickness of the film hardly changed. Further, each resist film was immersed in a 2.38% by weight or 1.19% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 20 seconds, respectively, and the amount of film reduction of the resist film was measured. Table 5 shows the measurement results.

[0119]

[Table 5]

As is clear from Table 5, even when polysilanes having the same composition are polycondensed, the solubility of each polysiloxane in an alkali developing solution is clearly different depending on the polymerization conditions. That is, polysiloxane (a-5) to polysiloxane (a-8) have an alkali-functional acidic functional group in the side chain, but polysiloxane (a-5) polycondensed only under acidic conditions. ) Has a very low degree of crosslinking and therefore has a very high solubility in an alkaline developing solution.
8) has low solubility. These results indicate that, according to the method for producing a polysiloxane of the present invention, the degree of crosslinking of the polymer can be adjusted, and the solubility in an alkali developing solution can be easily controlled.

Evaluation Example 7 (Evaluation by F ₂ Excimer Laser Exposure) Polysiloxane (a-1) to polysiloxane (a
4) 100 parts by weight of each of polysiloxane (a-7), polysiloxane (a-10), polysiloxane (a-13) or comparative polysiloxane (1), triphenylsulfonium nonafluoro-n-butane Sulfonate 1
Parts by weight, 0.02 parts by weight of tri-n-octylamine and 900 parts by weight of 2-heptanone were uniformly mixed to prepare a radiation-sensitive resin composition. Then, after applying each composition by spin coating on a silicon wafer,
Heat treatment was performed on a hot plate maintained at 140 ° C. for 90 seconds to form a resist film having a thickness of 100 nm. Thereafter, each resist film was exposed to light with a different exposure amount using an F2 excimer laser (wavelength: 157 nm), and was heated on a hot plate kept at 110 ° C. for 90 seconds, and then 2.38% by weight. Development was performed with an aqueous solution of tetramethylammonium hydroxide. Then
The exposed portion was observed with a scanning electron microscope, and the critical resolution of each resist was measured. Table 6 shows the measurement results.

[0122]

[Table 6]

When the exposed portion was observed with a scanning electron microscope, when the comparative polysiloxane (1) was used, the adhesiveness of the resist pattern to the substrate was low, a part of the resist pattern was negative, and further development occurred. Occasionally, phenomena such as difficulty in uniformly applying the developer on the surface of the resist film were observed.
On the other hand, when the polysiloxane (a) of the present invention was used, defects related to the resist performance such as a decrease in adhesion to a substrate, negative conversion, and uneven development were not observed.

[0124]

According to the present invention, the polysiloxane (a) has 19
It has a high radiation transmittance at a wavelength of 3 nm or less, has high sensitivity when used as a resist, and has excellent dry etching resistance, developability, adhesion to a substrate, and the like. Further, in the present invention, by producing a polysiloxane by a method having a step of polycondensing polysiloxane in the presence of an acidic catalyst, a condensation reaction involving a hydrolysis reaction occurs uniformly and promptly, and the hydrolysis in the raw material silane compound is performed. The functional group is not hydrolyzed and does not remain in the polymer, and the absorption of radiation by the hydrolyzable group is extremely reduced. Therefore, the polysiloxane has a high radiation transmittance at a wavelength of 193 nm or less, and the polysiloxane has a high transmittance. It has high sensitivity and excellent dry etching resistance, developability, and adhesion to a substrate. Furthermore, by conducting polycondensation under basic conditions following polycondensation under acidic conditions during the production of polysiloxane, the degree of polymerization increases and the degree of crosslinking increases, resulting in a glass transition temperature (Tg). Get higher. Therefore, by using a polysiloxane that has been subjected to polycondensation under basic conditions following polycondensation under acidic conditions, a finer resist pattern can be formed very advantageously by a lithography process. By selecting the polymerization conditions, the glass transition temperature (Tg) of the polysiloxane can be controlled. In addition, the radiation-sensitive resin composition of the present invention obtained by using the polysiloxane (a), when exposed to radiation having a short wavelength of not more than the far ultraviolet region, is less likely to be negative, and the resist pattern on the substrate In the case where the adhesion is improved and the resist film is developed with a common developer after exposure, the resist film is more uniformly dissolved, resulting in an advantage that a finer and better-shaped resist pattern is formed. However, this feature is especially
m when exposed at a wavelength of less than m. Moreover, the radiation-sensitive resin composition has a high radiation transmittance at a wavelength of 193 nm or less, has high sensitivity, and has excellent dry etching resistance. Therefore, the radiation-sensitive resin composition is useful in a wide range of technical fields related to semiconductor elements, and can be used extremely suitably for manufacturing semiconductor elements in which miniaturization is expected to progress more and more in the future.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) H01L 21/027 H01L 21/30 502R (72) Inventor Satoru Nishiyama 2-1-24-1 Tsukiji, Chuo-ku, Tokyo Within JSR Co., Ltd. (72) Inventor Tsutomu Shimokawa 2-11-24 Tsukiji, Chuo-ku, Tokyo FSR in JSR Co., Ltd. (reference) 2H025 AA01 AA02 AA03 AA06 AA09 AA14 AB16 AC08 AD03 BE00 BE10 BG00 BJ10 CB33 CB41 CB56 4J002 CP051 EN136 EV236 EV296 EW176 FD206 GP03 4J035 AB01 BA02 BA04 BA12 BA14 CA01N CA06N CA061 CA07N CA071 CA10N CA101 CA16N EB01 EB03 EB04 EB10 LA03 LB16

Claims (3)

[Claims] 1. An alkali-insoluble or sparingly-soluble acid-dissociable group-containing polysiloxane, which becomes alkali-soluble when the acid-dissociable group is dissociated, wherein the polysiloxane-equivalent weight average is determined by gel permeation chromatography (GPC). The ratio of molecular weight to number average molecular weight is 2.5
A polysiloxane characterized by the following. 2. A compound represented by the following general formula (1) or a linear or cyclic oligomer partially condensed with the compound, and a compound represented by the following general formula (2) or partially condensed with the compound An alkali-insoluble or alkali-soluble acid-dissociable group-containing polysiloxane, comprising a step of polycondensing at least one component of the group consisting of linear or cyclic oligomers in the presence of an acidic catalyst. Manufacturing method. Embedded image [In the general formulas (1) and (2), A ¹ and A ² each independently represent a monovalent organic group having an acid-dissociable group which is dissociated by an acid, and R ¹ and R ² are each other And independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms or a halogenated saturated hydrocarbon group having 1 to 10 carbon atoms, and R ³ represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. A linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a monovalent halogenated aromatic group having 6 to 20 carbon atoms Shows a hydrocarbon group. ] 3. A radiation-sensitive resin composition comprising the alkali-insoluble or slightly alkali-soluble polysiloxane containing an acid-dissociable group according to claim 1 and (b) a radiation-sensitive acid generator. object.