JP2002105086A - Silicon-containing alicyclic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new silicon-containing alicyclic compound useful as a raw material, etc., for a polysiloxane-based resin used for a chemical amplifying type resist excellent in dry etching resistance, transparency, resolution, developability, etc., for radiations. SOLUTION: This silicon-organic alicyclic compound has a structure in which t-butoxycarbonyl group and a (substituted) silyl group are bound to bicyclo[2.2.1]heptane ring or a ring in which the 2-4 bicyclo[2.2.1]heptane rings are condensed and is represented by 2-trimethoxysilyl-5-t- butoxycarbonylbicyclo[2.2.1]heptane, 2-methyldiethoxysilyl-5-t- butoxycarbonylbicyclo[2.2.1]heptane, 3-trimethoxysilyl-8-t- butoxycarbonyltetracyclo[4.4.0.12,517,10]dodecane or a cyclic polysiloxane derivative thereof, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon-containing alicyclic compound and, more particularly, to a raw material of a polysiloxane resin used for a chemically amplified resist suitable for fine processing using various radiations. It relates to useful novel silicon-containing alicyclic compounds.

[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 finer wiring patterns, there is a method of shortening the wavelength of exposure light used in a lithography process.
m) and 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 93 nm, high accuracy corresponding to high sensitivity, high resolution, and high aspect ratio cannot be obtained in a lithography process using an ArF excimer laser. Therefore, 193 nm or less, for example, 157 nm
There is a demand for a resist resin material which is transparent to the above wavelength and has a dry etching resistance equal to or higher than that of an aromatic ring. One such example is a siloxane-based polymer. MIT RRKunz et al. Have shown that polysiloxane-based polymers have excellent transparency at wavelengths of 193 nm or less.
Reported as suitable for resist materials in lithography processes using the following wavelengths (J. Photopoly
m. Sci. Technol., Vol.12, No.4, 1999). In addition, polysiloxane polymers have excellent dry etching resistance,
Among them, it is known that a resist containing a polyorganopolysilsesquioxane having a ladder structure has high plasma resistance.

On the other hand, some resist compositions using siloxane polymers have already been reported. That is, JP-A-5-323611 discloses that an acid-dissociable group such as a carboxylic acid ester group or a phenol ether group is bonded to a silicon atom via one or more carbon atoms, and the side chain has an acid-dissociable group. Japanese Patent Application Laid-Open No. 8-160623 discloses that a carboxyl group of poly (2-carboxyethylsiloxane) is protected by an acid-dissociable group such as a t-butyl group. Positive resists using polymers are further disclosed in
No. 0733 discloses a resist resin composition using a polyorganosilsesquioxane having an acid dissociable ester group. However, a conventional resist composition using an acid-dissociable group-containing siloxane-based polymer is still unsatisfactory in terms of basic physical properties as a resist such as transparency to radiation, resolution, and developability.
Therefore, there has been a strong demand for the development of a new resin which provides a resist composition having excellent basic physical properties as a resist while having excellent dry etching resistance of a siloxane-based polymer, and a raw material compound for providing the resin.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is, in particular, as a raw material for a polysiloxane resin used in a chemically amplified resist excellent in dry etching resistance, transparency to radiation, resolution, developability and the like. It is an object of the present invention to provide a novel silicon-containing alicyclic compound which is suitable and is useful as a raw material for polysiloxane-based resins and various silane-containing alicyclic compounds in other technical fields.

[0005]

The present invention comprises, first, a silicon-containing alicyclic compound represented by the following general formula (I) (hereinafter, referred to as "compound (I)").

[0006]

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[In the general formula (I), each R independently represents a hydrogen atom or a methyl group, and each R ¹ independently represents a hydrogen atom; a monovalent having 1 to 20 carbon atoms. A hydrocarbon group; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms;
A halogen atom; or a primary, secondary or tertiary amino group, wherein each R ² is independently of each other a monovalent hydrocarbon group having 1 to 20 carbon atoms; A halogenated hydrocarbon group; or the following formula (i)

[0008]

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Wherein each X is independently a hydrogen atom; a monovalent hydrocarbon group having 1 to 20 carbon atoms;
0 monovalent halogenated hydrocarbon group; or 1 to 2 carbon atoms
0 represents a linear, branched or cyclic alkoxyl group, and a is an integer of 1 to 10. )

Wherein m is 0 or 1, two R ² may be mutually bonded to form a ring together with two oxygen atoms and a silicon atom, and m is 0 ~ 3
And n is an integer of 0 to 3, and represented by the general formula (I)
Is the bicyclo [2.
2.1] is attached to the 2- or 3-position of the heptane ring. ]

[0011] The present invention relates to a silicon-containing alicyclic compound represented by the following general formula (II) (hereinafter referred to as "compound (I
I) ". ), Consisting of

[0012]

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[In the general formula (II), each R independently represents a hydrogen atom or a methyl group; each Y independently represents a hydrogen atom; a monovalent carbon atom having 1 to 20 carbon atoms. A hydrogen group; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom; a primary, secondary or tertiary amino group; or -OR ² , wherein R ² is 1 to 20 carbon atoms. Divalent hydrocarbon group; monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or the following formula (i)

[0014]

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Wherein each X is independently a hydrogen atom; a monovalent hydrocarbon group having 1 to 20 carbon atoms;
0 monovalent halogenated hydrocarbon group; or 1 to 2 carbon atoms
0 represents a linear, branched or cyclic alkoxyl group, and a is an integer of 1 to 10. )

The group represented by ｝ Indicates that p is 3 to
And n is an integer of 0 to 3, and each silicon atom represented by the general formula (II) is a 2-position or 3-position of the bicyclo [2.2.1] heptane ring at the highest position. Bound to the position. ]

Hereinafter, the present invention will be described in detail. Compound (I) In the general formula (I), R¹And R^Two1 to 2 carbon atoms
Examples of the monovalent hydrocarbon group of 0 include a methyl group and an
Tyl group, n-propyl group, i-propyl group, n-butyl
Group, 2-methylpropyl group, 1-methylpropyl group, t
-Butyl group, n-pentyl group, neopentyl group, n-
Xyl group, n-heptyl group, n-octyl group, 2-ethyl
Ruhexyl group, n-nonyl group, n-decyl group, n-dode
A sil group, an n-tetradecyl group, an n-hexadecyl group, n
-Octadecyl group, cyclobutyl group, cyclopentyl
Group, cyclohexyl group, etc., linear, branched or cyclic
Alkyl group; phenyl group, o-tolyl group, m-tolyl
Group, p-tolyl group, benzyl group, phenethyl group, 1-na
Aromatic hydrocarbon groups such as a futyl group and a 2-naphthyl group; nor
Bornyl group, tricyclodecanyl group, tetracyclodeca
And a bridged hydrocarbon group such as an enyl group and an adamantyl group.
Can be Of these monovalent hydrocarbon groups, R
¹As a methyl group, an ethyl group, a cyclopentyl group,
Cyclohexyl group, norbornyl group, tetracyclodeca
And the like.^TwoAs a methyl group, d
Til, n-propyl, i-propyl and the like are preferred.
No.

The monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms for R ¹ and R ² includes, for example,
A group in which a divalent hydrocarbon group is substituted with one or more or one or more halogen atoms, preferably one or more fluorine atoms,
More specifically, a trifluoromethyl group, a pentafluoroethyl group, 3,3,3,2,2-pentafluoro-n
-Propyl group, perfluoro-n-propyl group, perfluoro-i-propyl group, pentafluorophenyl group,
Pentafluorobenzyl group, pentafluorophenethyl group, perfluoronorbornyl group, the following formula (ii)

[0019]

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

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

Further, examples of the halogen atom for R ¹ include a fluorine atom, a chlorine atom, and a bromine atom. Of these halogen atoms, a chlorine atom is preferred. Examples of the secondary or tertiary amino group for R ¹ include a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, a cyclopentylamino group, and a cyclohexylamino. Group, phenylamino group, benzylamino group, dimethylamino group, diethylamino group, di-i-propylamino group, dicyclopentylamino group, dicyclohexylamino group, diphenylamino group, dibenzylamino group and the like. As the amino group for R ¹ , an amino group, a dimethylamino group, a diethylamino group, a dicyclopentylamino group, a dicyclohexylamino group, a diphenylamino group and the like are preferable.

In the formula (i) representing R ² , X is a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent hydrocarbon group having 1 to 2 carbon atoms.
Examples of the monovalent halogenated hydrocarbon group of 0 include the same monovalent hydrocarbon groups and the same groups as the monovalent halogenated hydrocarbon groups exemplified above for R ¹ and R ^2. . Among these groups, the monovalent hydrocarbon group is preferably a methyl group, an ethyl group, a phenyl group, etc., and the monovalent halogenated hydrocarbon group is preferably a trifluoromethyl group, a pentafluoroethyl group, a pentafluoro group. A phenyl group is preferred.

Examples of the linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms for X include, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy group, sec-butoxy group, t-butoxy group, cyclopentyloxy group,
Examples include a cyclohexyloxy group. Among these alkoxyl groups, a methoxy group, an ethoxy group and the like are preferable. X in the formula (i) is particularly preferably a methyl group, a phenyl group, a methoxy group or the like. Further, a in formula (i) is particularly preferably 1 to 5.

R ¹ in the general formula (I) is particularly preferably a methyl group, an ethyl group, a cyclohexyl group, a phenyl group, a pentafluorophenyl group, a chlorine atom, a dimethylamino group and the like. Further, R ² in the general formula (I)
As particularly, a methyl group, an ethyl group, a t-butyl group,
Trimethylsilyl groups and the like are preferred. In addition, the general formula (I)
Is preferably both a hydrogen atom and a methyl group. Further, m and n in the general formula (I) are each preferably 0 or 1.

Preferred specific examples of compound (I) include:
Formulas (I-1-1) to (I-1-36) (where Me represents a methyl group; the same applies hereinafter), formulas (I-2-1) to (I-2-44), (I-3-1) to (I-3-4) or formulas (I-4-1) to (I-4-
4) and the like.

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0051]

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Among these compounds (I), the compounds represented by the formulas (I-1-2), (I-1-3), (I-1-5) and (I-1-
6), formula (I-1-8), formula (I-1-9), formula (I-1-10), formula (I-1-11) or formula (I-1-12) Are preferred.

Compound (I) can be synthesized from, for example, norbornene represented by the general formula (III) (ie, bicyclo [2.
2.1] Hept-2-ene) derivative and the corresponding hydrosilane compound are subjected to a conventional hydrosilylation reaction,
It can be synthesized by reacting in the presence of a hydrosilylation catalyst without solvent or in an appropriate solvent.

[0056]

Embedded image ^{(Wherein, R, R 1, R 2} , m and n have the same meanings as ^{R, R 1, R 2,} m and n, respectively, in the general formula (I).)

Examples of the hydrosilylation catalyst include a transition metal catalyst and a radical reaction initiator. Among the hydrosilylation catalysts, examples of the transition metal catalyst include H ₂ PtCl ₆ , K ₂ PtCl ₆ , Na ₂ PtCl ₆ ,
(NH ₄ ) ₂ PtCl ₆ , K ₂ PtCl ₄ , Na ₂ PtCl ₄ , (NH ₄ ) ₂ PtCl ₄ , Pt
Cl ₂ , H ₂ PtBr ₆ , K ₂ PtBr ₆ , Na ₂ PtBr ₆ , PtBr ₄ , K ₂ PtBr
_{4, PtBr 2, K 2 PtI} 6, Na 2 PtI 6, PtI 4, PtI 2, PtCl 2 (C 6
_{H 5 CN), PtCl 2 (} CH 3 CN) 2, PtCl 2 [P (C 6 H 5) 3] 2, cis-PtCl
₂ (styrene) ₂ , cis-PtCl ₂ (p-chlorostyrene) ₂ , KPtC
l ₃ (styrene) ₂ , (n-Bu) ₄ NPtCl ₃ (styrene) ₂ (however, nB
u shows an n-butyl group. The same applies hereinafter. ) And the following formula (iii)
A compound represented by

[0058]

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Trans-PtCl ₂ (NH ₃ ) ₂ , cis-PtCl ₂ [P (C
_{2 H 5) 3) 2,} cis-PtCl 2 [P (n-Bu) 3] 2, [(n-Bu) 4 N] 2 PtCl 6,
[P (C ₆ H ₅ ) ₄ ] ₂ PtCl ₄ , (n-Bu) ₄ NPtI ₃ (CO), [(n-Bu) ₄ N] ₂ -ci
s-PtCl ₂ (SnCl ₃ ) ₂ , [(CH ₃ ) ₄ N] ₃ Pt (SnCl ₃ ) ₅ , [bis (triphenylphosphine) iminium] Pt (SnCl ₃ ) ₃ [As (C ₂ H
₅ ) ₃ ] ₂ , (C ₂ H ₅ ) ₄ NPt (SnCl ₃ ) ₃ (1,5-cyclooctadiene), platinum-activated carbon, platinum catalyst such as platinum black; PdCl
₂ [P (C ₆ H ₅ ) ₃ ] ₂ , palladium catalyst such as PdCl ₂ (1,5-cyclooctadiene), palladium-activated carbon, palladium black; HRh [P (C ₆ H ₅ ) ₃ ] ₄ , rhodium A rhodium catalyst such as activated carbon; an iridium catalyst such as IrCl ₃ ; a ruthenium catalyst such as RuCl ₃ ; a cobalt catalyst such as Co ₂ (CO) ₈ ; NiCl ₂ , NiBr ₂ , Ni
Nickel catalysts such as (CN) ₂ ; CuCl ₂ , CuBr ₂ , CuCl, CuB
r, copper catalysts such as CuCN, and the like.

Among these transition metal catalysts, H ₂ PtCl ₆ ,
_{K 2 PtCl 6, Na 2 PtCl} 6, K 2 PtCl 4, Na 2 PtCl 4, PtCl 2, H 2
_{PtBr 6, K 2 PtBr 6,} Na 2 PtBr 6, K 2 PtBr 4, platinum - platinum catalysts such as activated carbon are preferred. The transition metal catalysts can be used alone or in combination of two or more. Further, the transition metal catalyst may be added after being dissolved in an organic solvent such as i-propyl alcohol. The amount of the transition metal catalyst used is usually 0.00001 to 1,000 parts by weight based on 100 parts by weight of the hydrosilane compound.

Further, as the radical reaction initiator,
For example, benzoyl parkide, lauroyl parkide, diisopropyl peroxydicarbonate, t-
Butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobis (2,
4-dimethylvaleronitrile), azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like. These radical reaction initiators can be used alone or in combination of two or more. The amount of the radical reaction initiator to be used is generally 0.01 to 1,000 parts by weight based on 100 parts by weight of the hydrosilane compound.

Examples of the solvent used in the hydrosilylation reaction include aromatic hydrocarbons such as benzene, toluene and xylene; n-hexane, n-heptane and n-hexane.
Aliphatic hydrocarbons such as octane; ethers such as benzyl ethyl ether, di-n-hexyl ether and tetrahydrofuran; dichloromethane, chloroform, 1,
Halogenated hydrocarbons such as 2-dichloroethane; 2-butanone, 2-pentanone, 3-methyl-2-butanone,
Linear or branched ketones such as 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; Cyclic ketones such as pentanone, 3-methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, 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 Propylene glycol monoalkyl ether acetates such as coal mono-sec-butyl ether acetate and propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, I-propyl hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate,
Alkyl 2-hydroxypropionates such as sec-butyl 2-hydroxypropionate and t-butyl 2-hydroxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Alkyl 3-alkoxypropionates such as ethyl ethoxypropionate;

N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, 1-octanol, 1-nonanol, benzyl 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-
alcohols such as n-propyl ether; dialkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate; 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, Other esters such as n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N- Dimethylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Examples thereof include caproic acid, caprylic acid, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and acetonitrile. 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 hydrosilane compound.

This hydrosilylation reaction is preferably carried out without a solvent or in a solvent such as toluene, xylene, n-hexane, tetrahydrofuran or dichloromethane. Furthermore, this hydrosilylation reaction is preferably performed in a stream of nitrogen or argon under anhydrous conditions.
The temperature of this hydrosilylation reaction is usually -50 to +3
00 ° C., preferably 0-200 ° C., and the reaction time is:
Usually, it is about 5 minutes to 1,000 hours. It is generally considered that the general hydrosilylation reaction is desirably performed under normal pressure or higher pressure. However, in the case of the hydrosilylation reaction for synthesizing the compound (I), the reaction is performed under a pressure lower than normal pressure. The reaction is also possible and has the advantage that no special reaction vessel is required.

In such a hydrosilylation reaction, the compound (I) in which the silicon atom represented by the general formula (I) is bonded to the 2-position of the bicyclo [2.2.1] heptane ring at the highest position is usually used. ) And compound (I) bonded to the 3-position
Are generated at the same time. This mixture can be used as it is, for example, as a raw material for producing a polysiloxane-based resin having a t-butoxycarbonyl group in a side chain.If necessary, for example, distillation, recrystallization, liquid chromatography, Both compounds (I) can be separated by a method such as gas chromatography.

Uses of Compound (I) Compound (I) is prepared by combining a halogen atom as R ¹ with a group OR ²
Is 2 or 3, the acid dissociable t-butoxycarbonyl group via a hydrolysis reaction of a Si-halogen atom bond and / or a Si—OR ² bond and a polycondensation reaction of a silanol group. Is very useful as a raw material for producing a polysiloxane resin having a side chain. When producing this polysiloxane resin, R
Used to convert the silanol group in advance hydrolyzing at least a portion of the halogen atom or a group OR ² in total number of 2 or 3, Compound (I) with a halogen atom and the group OR ² as ¹ Alternatively, the compound (II) described later can be copolycondensed. Further, if necessary, the compound (I) in which the total number of the halogen atom as R ¹ and the group OR ² is 1 and / or the halogen atom or the group OR ² in the compound (I) is hydrolyzed in advance. The compound converted to a silanol group can be co-condensed to adjust the molecular weight or molecular structure of the polysiloxane resin. Further, as the case may be, another silane compound having two or more functionalities with respect to the condensation reaction, another silane compound or compound (II) with a monofunctionality with respect to the condensation reaction
Other cyclic polysiloxanes can also be co-condensed or co-polycondensed.

The polysiloxane-based resin thus obtained has an increased affinity for an alkaline aqueous solution because its t-butoxycarbonyl group dissociates in the presence of an acid to form a carboxyl group. For example, radiation-sensitive acid generators that generate acids upon irradiation with various radiations such as far ultraviolet rays, ultraviolet rays, charged particle beams, and X-rays (eg, onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds) etc)
By mixing with, a chemically amplified resist excellent in dry etching resistance, transparency to radiation, resolution, developability, and the like can be extremely suitably used. Compound (I) may be a raw material of a general polysiloxane resin or the same norbornane (that is, bicyclo [2.2.
1] Heptane) It is useful as a raw material for other silicon-containing alicyclic compounds having a ring structure.

Compound (II) In the general formula (II), Y is a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom and a secondary or Examples of the tertiary amino group include a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms as exemplified for R ¹ in the general formula (I). A group similar to a halogen atom and a secondary or tertiary amino group. Of these groups, the monovalent hydrocarbon group is preferably a methyl group, an ethyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, an adamantyl group, or the like, and is preferably a monovalent halogenated hydrocarbon group. Are preferably a trifluoromethyl group, a pentafluoroethyl group, a pentafluorophenyl group and the like, a halogen atom is preferably a chlorine atom, and an amino group is preferably a dimethylamino group.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms for R ² in Y include, for example, R 2 in the above general formula (I). Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and the same groups as the monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms exemplified for ² can be given. Among these groups, a monovalent hydrocarbon group is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group or the like, and as a monovalent halogenated hydrocarbon group, a trifluoromethyl group, A pentafluoroethyl group is preferred.

In the formula (i) representing R ² , X is a monovalent hydrocarbon group having 1 to 20 carbon atoms and a monovalent hydrocarbon group having 1 to 2 carbon atoms.
Examples of the monovalent halogenated hydrocarbon group of 0 include, for example, the monovalent hydrocarbon groups and the same groups as the monovalent halogenated hydrocarbon groups exemplified for R ² in the formula (I). be able to. Of these groups,
As the monovalent hydrocarbon group, a methyl group, an ethyl group, a phenyl group and the like are preferable, and as the monovalent halogenated hydrocarbon group, a trifluoromethyl group and a pentafluoroethyl group are preferable.

The straight-chain, branched or cyclic alkoxyl group having 1 to 20 carbon atoms for X includes, for example, the same groups as those exemplified for the alkoxyl group for X in the aforementioned general formula (I). Can be mentioned. Among these alkoxyl groups, a methoxy group, an ethoxy group and the like are preferable. X in the formula (i) is particularly preferably a methyl group, a phenyl group, a methoxy group or the like. Further, a in formula (i) is particularly preferably 1 to 4.

As Y in the general formula (II),
Methyl, phenyl, trifluoromethyl, pentafluorophenyl, chlorine, dimethylamino, methoxy, ethoxy and the like are preferred. The general formula (I
As R in I), both a hydrogen atom and a methyl group are preferred. In addition, p in the general formula (II) is particularly preferably 3 to 5, and n in the general formula (II) is preferable.
Is particularly preferably 0 or 1.

Preferred specific examples of compound (II) include:
Examples include compounds represented by the following formula (II-1-1), formula (II-1-2), formula (II-2-1) or formula (II-2-2).

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Synthesis of Compound (II) Compound (II) can be prepared, for example, by reacting norbornene (ie, bicyclo [2.2.1] hept-2- represented by general formula (III) as shown in the following formula.
A method of subjecting an ene) derivative and a corresponding hydrosilane compound to a hydrosilylation reaction in the same manner as in the method for synthesizing compound (I)

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The compound (I) in which the total number of the halogen atom as R ¹ and the group OR ² is 2 or 3, and / or at least a part of the halogen atom or the group OR ² of the compound (I) is hydrolyzed A compound into which a silanol group has been introduced by decomposition can be synthesized by a conventional method, for example, by condensing in a suitable solvent in the presence of an alkaline catalyst or an acidic catalyst. In the condensation reaction in the above method,
When two or more compounds (II) having different p's indicating the degree of condensation are produced simultaneously, or when compounds other than compound (II) (that is, compounds in which p is less than 3 or more than 10) are by-produced. is there. In the former case, the separation into individual compounds and the composition adjustment of a mixture of two or more compounds (II) can be appropriately performed according to the use of the compound (II). In the latter case, the separation of the compound (II) from the other compounds and the adjustment of the content of the compounds other than the compound (II) can be appropriately performed depending on the use of the compound (II).

Use of Compound (II) Compound (II) is used for producing a polysiloxane resin having an acid-dissociable t-butoxycarbonyl group in a side chain by a ring-opening polyaddition reaction of the cyclic polysiloxane bond. It is extremely useful as a raw material for. In producing the polysiloxane resin, a halogen atom as R ¹ and a group O
Compound (I) having a total number of 2 or 3 with R ² , and / or a compound in which at least a part of a halogen atom or a group OR ^{2 in} the compound (I) has been converted to a silanol group by hydrolysis in advance. Copolycondensation can also be performed.
If necessary, a halogen atom as R ¹ and a group O
Compound (I) in which the total number of R ² is 1 and / or a compound obtained by previously hydrolyzing a halogen atom or a group OR ² in the compound (I) and converting it to a silanol group are converted to a polysiloxane resin. Co-condensation can be performed to adjust the molecular weight or molecular structure. Furthermore, depending on the case, another cyclic polysiloxane, another silane compound having two or more functional groups for the condensation reaction, or another monofunctional silane compound for the condensation reaction can be co-condensed or co-polycondensed.

The polysiloxane resin thus obtained has an increased affinity for an alkaline aqueous solution because its t-butoxycarbonyl group dissociates in the presence of an acid to form a carboxyl group. For example, radiation-sensitive acid generators that generate acids upon irradiation with various radiations such as far ultraviolet rays, ultraviolet rays, charged particle beams, and X-rays (eg, onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds) etc)
By mixing with, a chemically amplified resist excellent in dry etching resistance, transparency to radiation, resolution, developability, and the like can be extremely suitably used. Compound (II) is also useful as a raw material for general polysiloxane-based resins and as a raw material for other silicon-containing alicyclic compounds having the same norbornane-based ring structure.

[0081]

Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention is not limited to these embodiments.

EXAMPLE 1 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 48.5 g of trimethoxysilane and 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-. En 7
After adding 7.1 g and stirring at room temperature, 1.0 ml of a 0.1 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction.
The mixture was heated at reflux at 48 ° C. for 48 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product.
Thereafter, the crude product was purified by distillation under reduced pressure at 0.2 mmHg and 105 ° C. to obtain 48 g of a compound.

For this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), infrared absorption spectrum (I
R) and mass spectrum (FABMS) were measured. The measured values were as follows, and the compound was identified as compound (I) represented by the above formula (I-1-3). The compound (I)
Was a substantially equal mixture of a compound in which a trimethoxysilyl group was bonded to the 2-position and a compound in which the trimethoxysilyl group was bonded to the 3-position of the bicyclo [2.2.1] heptane ring. σH: 3.6 ppm (methoxy group), 1.4 ppm
(T-butyl group). σC: 175 ppm (carbonyl group), 80 ppm
(T-butoxy group), 51 ppm (methoxy group), 28
ppm (t-butyl group). σSi: -45 ppm. IR: 2847 cm ^-1 (methoxy group), 1730 cm
^-1 (ester group), 1153 cm ^-1 (siloxane group),
1095 cm ^-1 (siloxane group). FABMS: m / z = 317 (M ⁺⁺ 1).

Example 2 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 46.5 g of triethoxysilane and 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene. 4
2.0g was added, After stirring at room temperature, was added a 0.2 molar i- propyl alcohol solution 1.0 ml of chloroplatinic acid (H ₂ PtCl _6), to initiate the reaction, 140
The mixture was heated at reflux at 24 ° C. for 24 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product.
Thereafter, the crude product was purified by distillation under reduced pressure at 0.4 mmHg and 155 ° C. to obtain 54 g of a compound.

About this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), infrared absorption spectrum (I
R) and mass spectrum (FABMS) were measured. The measured values were as follows, and the compound was identified as compound (I) represented by the above formula (I-1-6). The compound (I)
Was a mixture of approximately equal amounts of a compound having a triethoxysilyl group bonded to the 2-position of the bicyclo [2.2.1] heptane ring and a compound having a triethoxysilyl group bonded to the 3-position. σH: 3.8 ppm (ethoxy group), 1.4 ppm
(T-butyl group). σC: 175 ppm (carbonyl group), 80 ppm
(T-butoxy group), 59 ppm (ethoxy group), 28
ppm (t-butyl group), 19 ppm (methyl group). σSi: -48 ppm. IR: 2879 cm ^-1 (ethoxy group), 1726 cm
^-1 (ester group), 1155 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). FABMS: m / z = 359 (M ⁺⁺ 1).

Example 3 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 49.0 g of trimethoxysilane and 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5. . 1
^7,10 ] dodeca-3-ene (73.0 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, and the mixture was reacted. And heated to reflux at 150 ° C. for 100 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel column chromatography to obtain 30 g of a compound as an n-hexane fraction.

For this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), infrared absorption spectrum (I
R) and mass spectrum (FABMS) were measured. The measured values were as follows, and the compound was identified as compound (I) represented by the above formula (I-2-3). The compound (I)
Has a trimethoxysilyl group of tetracyclo [4.4.
0.1 ^2,5 . [ ^7,10 ] dodecane ring was a mixture of approximately equal amounts of the compound bonded to the 3-position and the compound bonded to the 4-position. σH: 3.6 ppm (methoxy group), 1.4 ppm
(T-butyl group). σC: 175 ppm (carbonyl group), 80 ppm
(T-butoxy group), 51 ppm (methoxy group), 28
ppm (t-butyl group). σSi: -45 ppm. IR: 2839 cm ^-1 (methoxy group), 1726 cm
^-1 (ester group), 1153 cm ^-1 (siloxane group),
1090 cm ^-1 (siloxane group). FABMS: m / z = 383 (M ⁺⁺ 1).

Example 4 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 76.0 g of triethoxysilane and 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 with 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 compound as an n-hexane fraction.

For this compound, ¹ H-NMR spectrum (chemical shift “σH”), ¹³ C-NMR spectrum (chemical shift “σC”), ²⁹ Si-NMR spectrum (chemical shift “σSi”), infrared absorption spectrum (I
R) and mass spectrum (FABMS) were measured. The measured values were as follows and were identified as compound (I) represented by formula (I-2-6). The compound (I)
Has a triethoxysilyl group of tetracyclo [4.4.
0.1 ^2,5 . [ ^7,10 ] dodecane ring was a mixture of approximately equal amounts of the compound bonded to the 3-position and the compound bonded to the 4-position. σH: 3.8 ppm (ethoxy group), 1.2 ppm
(Ethoxy group), 1.4 ppm (t-butyl group). σC: 175 ppm (carbonyl group), 80 ppm
(T-butoxy group), 59 ppm (ethoxy group), 28
ppm (t-butyl group), 19 ppm (methyl group). σSi: -48 ppm. IR: 2885 cm ^-1 (ethoxy group), 1726 cm
^-1 (ester group), 1153 cm ^-1 (siloxane group),
1080 cm ^-1 (siloxane group). FABMS: m / z = 425 (M ⁺⁺ 1).

Example 5 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 28.6 g of trimethylsilane and 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene-5 were added.
After adding 0.0 g and stirring at room temperature, 1.0 ml of a 0.1 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction.
The mixture was heated at reflux at 48 ° C. for 48 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product.
Thereafter, the crude product was purified by distillation under reduced pressure at 0.2 mmHg and 105 ° C., and R ^{1 of the} general formula (I) was a methyl group,
Compound (I) wherein R is a hydrogen atom, m is 3 and n is 0
2 g were obtained.

Example 6 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 52.3 g of trichlorosilane and 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene-5.
After adding 0.0 g and stirring at room temperature, 1.0 ml of a 0.1 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction.
The mixture was heated at reflux at 48 ° C. for 48 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product.
Thereafter, the crude product was purified by distillation under reduced pressure at 0.2 mmHg and 98 ° C. to obtain 62 g of the compound (I) represented by the formula (I-1-12).

Example 7 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 51.8 g of methyldiethoxysilane and 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-. After adding 50.0 g of ene and stirring at room temperature, 1.0 ml of a 0.1 mol i-propyl alcohol solution of chloroplatinic acid (H ₂ PtCl ₆ ) was added to start the reaction.
The mixture was heated at reflux at 48 ° C. for 48 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product.
Thereafter, the crude product was purified by distillation under reduced pressure at 0.2 mmHg and 112 ° C. to obtain 60 g of the compound (I) represented by the formula (I-1-5).

Example 8 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 17.1 g of trimethylsilane, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
After adding 40.0 g of dodeca-3-ene and stirring at room temperature, 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 100 hours. afterwards,
After returning the reaction solution to room temperature and diluting with n-hexane,
Suction filtration on celite, further distilling off the solvent under reduced pressure,
A crude product was obtained. Thereafter, the crude product is subjected to silica gel column chromatography to obtain an n-hexane fraction, wherein R ^{1 in the} general formula (I) is a methyl group, R is a hydrogen atom, m
Was obtained and 23 g of compound (I) having n of 1 was obtained.

Example 9 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 31.3 g of trichlorosilane, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
After adding 40.0 g of dodeca-3-ene and stirring at room temperature, 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 100 hours. afterwards,
After returning the reaction solution to room temperature and diluting with n-hexane,
Suction filtration on celite, further distilling off the solvent under reduced pressure,
A crude product was obtained. Thereafter, the crude product was subjected to silica gel column chromatography to obtain 37 g of the compound (I) represented by the above formula (I-2-12) as an n-hexane fraction.
Obtained.

Example 10 A three-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 30.9 g of methyldiethoxysilane and 8-t-butoxycarbonyltetracyclo [4.4.0.12 ^{. 5} ． 1
^7,10 ] dodeca-3-ene (40.0 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, and the mixture was reacted. And heated to reflux at 150 ° C. for 100 hours. Thereafter, the reaction solution was returned to room temperature, diluted with n-hexane, filtered with suction on celite, and the solvent was distilled off under reduced pressure to obtain a crude product. Thereafter, the crude product was subjected to silica gel column chromatography to obtain the compound (I) represented by the above formula (I-2-5) as an n-hexane fraction by 2
4 g were obtained.

Example 11 A three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with methylhydrocyclosiloxane (S per molecule).
i number 3 to 5) 12.0 g, 8-t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.
^12.5 . [ ^7,10 ] dodeca-3-ene (52.0 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 was added to start the reaction. And heated to reflux for 100 hours. Thereafter, the reaction solution is returned to room temperature, diluted with n-hexane, suction-filtered on celite, and the solvent is distilled off under reduced pressure to obtain the compound (II) represented by the formula (II-2-1). 59g
Obtained. For this compound, ¹ H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (I
When R) was measured, it was as follows. σH: 1.4 ppm (t-butyl group), 0.2 ppm
(SiCH ₃ group). IR: 1730 cm ^-1 (ester group), 1150 cm ^-1
(Siloxane group).

Example 12 In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 3.0 g of the compound obtained in Example 10 (the compound represented by the formula (I-2-5)) was added. , 4-methyl-2-pentanone 9
g of 1.75 wt% oxalic acid aqueous solution, and the mixture was reacted at 40 ° C. for 2 hours with stirring. After that, the reaction vessel was cooled with ice to stop the reaction, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and ion-exchanged water was added to wash the reaction solution. Repeated. Thereafter, the organic layer was distilled off under reduced pressure to obtain 1.90 g of the compound (II) represented by the formula (II-2-1). The ¹ H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (IR) of this compound were measured and found to be consistent with the values of the compound obtained in Example 11.

Application Example 1 (Production of copolymerized polysiloxane) Compound (I) 12 represented by the above formula (I-1-2) was placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer. .4
7 g, 12.53 g of methyltrimethoxysilane, 1.07 g of hexamethyldisiloxane (molecular weight regulator), 4-
75 g of methyl-2-pentanone, 14.92 g of distilled water,
Add 20.93 g of triethylamine and, with stirring,
The reaction was performed at 75 ° C. for 8 hours. Then, cool the reaction vessel with ice,
A solution in which 18.2 g of oxalic acid was dissolved in 500 ml of ion-exchanged water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and 100 ml of ion-exchanged water was added and washed with water. Then, the organic layer was distilled off under reduced pressure to obtain a resin. This resin, ¹ H
-The NMR spectrum (chemical shift "? H"), the infrared absorption spectrum (IR) and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) were as follows. σH: 1.4 ppm (t-butyl group), 0.2 ppm
(SiCH ₃ group). IR: 1730 cm ^-1 (ester group), 1149 cm ^-1
(Siloxane group). Mw: 6,400.

Comparative Application Example 1 (Production of Copolymerized Polysiloxane) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 9.7 g of 2-t-butoxycarbonylethyltrimethoxysilane, methyltrimethoxy 5.3 g of silane, 1.3 g of hexamethyldisiloxane (molecular weight regulator), 4
-Methyl-2-pentanone 75 g, distilled water 4.2 g, triethylamine 4.2 g were added, and the mixture was stirred at 62 ° C.
For 3 hours. Thereafter, the reaction vessel was cooled with ice and oxalic acid 1
A solution of 1.1 g in 200 ml of ion-exchanged water was added, and stirring was continued. Thereafter, the reaction solution was transferred to a separating funnel, the aqueous layer was discarded, and the ion-exchanged water 1
After adding 00 ml and washing with water, the organic layer was distilled off under reduced pressure to obtain a resin.

The resin was analyzed by ¹ H-NMR spectrum (chemical shift “σH”) and infrared absorption spectrum (I
R) and gel permeation chromatography (G
PC) weight average molecular weight in terms of polystyrene (Mw)
Was as follows. σH: 2.4 to 2.0 ppm (α-methylene group);
3 to 0.9 ppm (β-methylene group), 1.4 ppm
(T-butyl group), 0.2 ppm (SiCH ₃ group). IR: 1730 cm ^-1 (ester group), 1149 cm ^-1
(Siloxane group). Mw: 44,700.

Evaluation Example 1 (Glass Transition Temperature) The glass transition temperature of each of the copolymerized polysiloxanes obtained in Application Example 1 and Comparative Application Example 1 was measured. On the other hand, the copolymerized polysiloxane of Application Example 1 has a temperature of 97 ° C., and the copolymerized polysiloxane using the compound (I) is:
It had a sufficiently high glass transition temperature as a resist component.

Evaluation Example 2 (Radiation Transmittance) The transmittance (film thickness: 0.1 μm) formed from each of the copolymerized polysiloxanes obtained in Application Example 1 and Comparative Application Example 1 was measured for the radiation having a wavelength of 157 nm. However, it was 31% in the copolymerized polysiloxane of Application Example 1 and 32% in the copolymerized polysiloxane of Comparative Application Example 1.
It is generally believed that the transmittance at a wavelength of 157 nm decreases as the proportion of the hydrocarbon structure in the polysiloxane relatively increases, but the compound (I) of the present invention
Although the copolymerized polysiloxane using is relatively large in the ratio of the hydrocarbon structure, the transmittance at a wavelength of 157 nm is almost equal to that of the copolymerized polysiloxane of Comparative Application Example 1, and It became clear that almost no decrease in transmittance was observed.

Evaluation Example 3 (Formation of Resist Pattern) The copolymerized polysiloxane obtained in Application Example 1 was used in combination with a radiation-sensitive acid generator (triphenylsulfonium trifluoromethanesulfonate) and a basic additive (tri-N-octylamine). together), a solution prepared by dissolving in 2-heptanone, coating the solution onto a substrate, relative to the dry coating film, through a photomask, it was irradiated by F ₂ laser, the line width 0.5μm Was formed in a good shape.

[0103]

The compound (I) of the present invention has an acid dissociable t-butoxycarbonyl group in the side chain when the total number of the halogen atom as R ¹ and the group OR ² is 2 or 3. It is extremely useful as a raw material for producing a polysiloxane resin, and this polysiloxane resin is extremely suitable as a resin component of a chemically amplified resist excellent in dry etching resistance, transparency to radiation, resolution, developability, etc. Can be used for Compound (I)
Is useful as a raw material for producing a general polysiloxane-based resin, a raw material for other silicon-containing alicyclic compounds having a similar norbornane-based ring structure, and the like. Further, the compound (II) of the present invention is extremely useful as a raw material for producing a polysiloxane-based resin having an acid-dissociable t-butoxycarbonyl group in a side chain. It can be very suitably used as a resin component of a chemically amplified resist excellent in resistance, transparency to radiation, resolution, developability and the like. Further, the compound (II) is useful as a raw material for producing a general polysiloxane-based resin, a raw material for another silicon-containing alicyclic compound having a similar norbornane-based ring structure, and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H049 VN01 VP01 VP03 VP04 VP05 VQ29 VQ87 VR21 VR22 VR33 VR42 VR43 VU20 VW02 4J035 BA01 BA11 CA01N CA06N CA061 CA10N CA101 CA15N CA151 CA19N CA191 HA01 HB02 LA03 LB20

Claims (2)

[Claims] 1. A silicon-containing alicyclic compound represented by the following general formula (I). Embedded image [In the general formula (I), each R independently represents a hydrogen atom or a methyl group, and each R ¹ independently represents
A hydrogen atom; a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; a halogen atom; or a primary, secondary or tertiary amino group;
Each R ² is independently of each other a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or the following formula (i): (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. ), When m is 0 or 1, two R ² may be mutually bonded to form a ring with two oxygen atoms and a silicon atom, and m is 0 to 3 And n is an integer of 0 to 3, and the silicon atom represented by the general formula (I) is
[2.2.1] It is bonded to the 2- or 3-position of the heptane ring. ] 2. A silicon-containing alicyclic compound represented by the following general formula (II). Embedded image [In the general formula (II), each R independently represents a hydrogen atom or a methyl group; each Y independently represents a hydrogen atom; a monovalent hydrocarbon group having 1 to 20 carbon atoms; Carbon number 1
To 20 monovalent halogenated hydrocarbon groups; halogen atoms;
A primary, secondary or tertiary amino group; or -OR
^{2 wherein} R ² is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
A monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or the following formula (i): (Wherein each X is independently a hydrogen atom;
20 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; or a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms.
It is an integer of 0. ). Indicates｝ and p
Is an integer of 3 to 10, n is an integer of 0 to 3, and each silicon atom represented by the general formula (II) is a 2-position of the bicyclo [2.2.1] heptane ring at the highest position. Or it is bonded to the 3-position. ]