JPH0324093A - Trialkylsilylmethyl group-containing silane compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R<1> and R<2> are alkyl; R<3> is >=2C (substituted) monohydrocarbon or trialkylsilylmethyl (R<1>)3SiCH<2>]. EXAMPLE:Trimethylsilylmethyl(n-propyl)dimethoxysilane shown by formula II. USE:A synthetic raw material for upper layer resist useful for two-layer resist method, having high resistance to oxygen plasma. Also useful as a promotor to be used with Ziegler-Natta catalyst. PREPARATION:A Grignard reagent (e.g. trimethylsilylmethylmagnesium chloride) shown by formula III is reacted with a trialkoxysilane compound (e.g. npropyltrimethoxysilane) shown by formula IV usually in an aprotic solvent such as toluene preferably under reflux. The amount of the Grignard reagent used is preferably 1-1.2 equivalent based on the compound shown by formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel trialkylsilylmethyl group-containing silane compound.

[Prior Art] In recent years, various microfabrication techniques have been developed as the density of ultra-LSIs increases. For example, there is a two-layer resist method as a method for accurately forming fine patterns on steps caused by multilayer wiring. This two-layer resist method is a method in which different resists are used for each of the upper layer and the lower layer. In this two-layer resist method, the resist applied as an upper layer not only has high sensitivity and high resolution, but also is required to have excellent resistance to oxygen plasma in plasma etching. Various polysiloxane resists have been developed as resists that meet this requirement, which react with oxygen plasma to form silicon oxide, have relatively high resistance to oxygen plasma, and are easy to assemble.

(Problems to be Solved by the Invention) However, a polysiloxane resist with sufficient oxygen plasma resistance has not yet been developed.

[Means to solve the problem]

In order to develop a resist with high resistance to oxygen plasma, the present inventors conducted intensive research and as a result, developed a novel trialkylsilylmethyl group-containing silane compound useful as a raw material for synthesizing the resist.

That is, the present invention has the following formula: General formula (■): R3 ■ (R'): +SiCtizSi(OR'')z
(1) [In the formula, 3 Rl and 2 Rt may be the same or different and are an alkyl group,
R3 is a substituted or unsubstituted monovalent hydrocarbon group having 2 or more carbon atoms, or formula (■): ? R'): +SiCl■1 (II
) (wherein, the three Rl's may be the same or different and are as described above) A novel trialkylsilylmethyl group-containing silane compound represented by This is what we provide.

In the above formula (1) representing the trialkylsilylmethyl group-containing silane compound of the present invention, three Rl and two RZ may be the same or different and are an alkyl group, such as a methyl group, an ethyl group, Representative examples include alkyl groups having 1 to 4 carbon atoms such as n-probyl group, i-probyl group, and n-butyl group. R'' is a substituted or unsubstituted monovalent hydrocarbon group having 2 or more carbon atoms, or the above formula (II)
It is a trialkylsilylmethyl group represented by Examples of substituted or unsubstituted monovalent hydrocarbon groups having 2 or more carbon atoms include alkyl groups such as ethyl, n-propyl, and i-propyl; aryl groups such as phenyl and tolyl; cyclohexyl; A typical example is a cycloalkyl group such as a group. Furthermore, representative examples of the trialkylsilylmethyl group represented by formula (II) include a trimethylsilylmethyl group and a triethylsilylmethyl group.

Typical examples of the trialkylsilylmethyl group-containing silane compounds represented by general 2N) of the present invention include trimethylsilylmethyl (n-propyl) dimethoxysilane, trimethylsilylmethyl (cyclohexyl) dimethoxysilane, and triethylsilylmethyl (ethyl) dimethoxysilane. Examples include ethoxysilane and bis(trimethylsilylmethyl)dimethoxysilane.

The silane compound of the present invention can be produced using, for example, the formula (■): (R')zsicH2Mgcj!
(m) (where R' is the same as above) and a Grignard reagent represented by the formula (■): R'Si
(OR”) x (IV
) (wherein R2 and R3 are the same as above).

Representative examples of the Grignard reagent represented by formula (I[I) used in this production method include trimethylsilylmethylmagnesium chloride, triethylsilylmethylmagnesium chloride, i-probyldimethylsilylmethylmagnesium chloride, and the like. This Grignard reagent can be obtained according to a conventional method, and is appropriately selected depending on the substituent R' of the silane compound represented by formula (1).

Further, representative examples of the trialkoxysilane compound represented by formula (IV) include n-propyl 4J methoxysilane, cyclohexyltrimethoxysilane, ethyltriethoxysilane, trimethylsilylmethyltrimethoxysilane, and the like. The trialkoxysilane compound represented by formula (IV) is appropriately selected depending on the desired substituents R' and R2 of the silane compound represented by formula (I).

In this production method, the amount of the Grignard reagent represented by II (III) used is usually about 1 to 1.2 equivalents relative to the trialkoxysilane compound represented by the formula (IV).

Examples of the reaction solvent used include aprotic solvents such as toluene, xylene, and hexane.

The reaction is usually preferably carried out under reflux of the solvent.

Further, the silane compound of the present invention includes a Grignard reagent represented by the above formula (III) and a formula (V): R'SiX. J(
V) (wherein, R3 is the same as above, and X is a halogen atom) to react with a trihalosilane compound represented by the formula: It can also be produced by obtaining a dihalosilane compound represented by the formula (same as above) and subjecting this dihalosilane compound to an esterification reaction with an alcohol represented by the formula: R2011 (where R2 is the same as above).

Representative examples of the trihalosilane compound represented by the formula (V) include n-propyltrichlorosilane, cyclohexyltrichlorosilane, ethyltrichlorosilane, trimethylsilylmethyltrichlorosilane, and the like.

Grignard reagent represented by this formula (It) and 2 (V)
When the dihalosilane compound produced by the reaction with the trihalosilane compound represented by the above is subjected to an esterification reaction with an alcohol, triethylamine, N,N-dimethylamine, etc. It is preferable to use 2 to 3 equivalents of the base based on the dihalosilane compound.

The reaction solvent, reaction temperature, etc. are the same as in the above method.

Examples of the alcohol compound used for esterification include methanol, ethanol, i-probanol, and the like.

The amount of alcohol used is about 2 to 3 equivalents relative to the dihalosilane compound obtained by the reaction of the Grignard reagent represented by formula (III) and the trihalosilane compound represented by formula (V).

The reaction mixture obtained by the above two methods can be filtered to remove precipitated salts, and then purified by distillation to obtain the silane compound of the present invention.

The organoborisiloxane obtained by polymerizing the trialkylsilylmethyl group-containing silane compound of the present invention alone or together with other dialkoxysilane compounds has excellent high oxygen plasma resistance, and can be used, for example, as an upper layer resist used in a two-layer resist method. It is useful as a raw material for gathering precepts.

In addition, since the silane compound of the present invention has a bulky substituent, trialkylcy,lylmethyl group, in the molecule,
It is also useful as a cocatalyst in conjunction with Ziegler-Nata catalysts to enhance the stereoregularity of polymers obtained by polymerization of propylene.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 In a glass reactor with internal volume if equipped with a reflux condenser, thermometer, stirrer and addition funnel, 164.3 g of n-propyltrimethoxysilane and 300 d of T H
I prepared it. Next, 122.7 g of trimethyl (chloromethyl) silane and 24.3 g of magnesium were dissolved in THF30.
The Grignard reagent obtained by the reaction in 0.05 mL was added dropwise under reflux, and the mixture was allowed to stand for 24 hours. The resulting reaction mixture was filtered to remove precipitated salts, and then distilled to obtain a fraction with a boiling point of 81-83°C/3 mm llg.

When the mass spectrum, 'H-NMR spectrum and IR spectrum of the obtained fraction were measured, the results shown below were obtained.

Mass spectrum electron impact method: m/z (spectral intensity ratio) 205 (1
00), 189(4), 177(91), 163(3
4), 147(57), 133(36), 117(
35), 91 (22), 73 (57), 59 (6
7) Chemical ionization method: Reaction gas: i-butane m/z: 220 H-NMR spectrum δ: 0.01 ppm (s, (CH3) ssi
)0.22ppm(s, -SiCH.Si-)3.
43ppm (s, 10CI,) 0.55ppm (m, SiCHzCHzCH:+)
1.34 pplll (m, SiCHzCHzCH:
+)0.92ppm(t, SiCHzCHzCH3
) rR spectrum: Absorption peaks were observed at the following wave numbers.

2940cm-', 2820cm-', 1450C11
-', 1410C1!1-'1250cm-', 11
90cm-', 1090cm-', 1050cm-'
830 cm- From the above measurement data, the following formula: (CH'3) :+SiCHzSi (OCH3) z
It was found that trimethylsilylmethyl(n-propyl)dimethoxysilane, expressed as I CHzCHzCHz, was obtained.

(Yield: 73%) Example 2 The reaction was carried out in the same manner as in Example 1 except that 204.3 g of cyclohexyltrimethoxysilane was used instead of n-propyltrimethoxysilane, and the boiling point was 89-91.
A fraction with °C/2 mmHg was obtained.

When the mass spectrum, IH-NMR spectrum and IR spectrum of the obtained fraction were measured, the results shown below were obtained.

Mass spectrum electron impact method: m/z (spectral intensity ratio) 245 (29
), 207(2), 177(100), 163(1
3), 147(38), 133(10), 117(
19), 9F (7), 73 (10) Chemical ionization method: Reactant gas: i-butane m/z: 260'H-NMR spectrum δ: 0.05 ppm (s, (CH3)3Si-)-
0.22ppm(s, -SiCHzSi)3.4
9 ppm (s, OCHz) IR spectrum: Absorption peaks were observed at the following wave numbers.

2900c+r', 2820cm-', 1450cm-
', 1350c+k-'1245cm-', 1190c
m-', 1085cm-', 1045cm-'880
cm-', 830 cm-' From the measurement data above, trimethylsilylmethyl (cyclohexyl) represented by the following formula:
It was found that dimethoxysilane was obtained. (yield:
62%) Example 3 221.7 g of trinotylsilylmethyltrichlorosilane and T f{ F
300 ml was charged. Next, 122.7 g of trimethyl(chloromethyl)silane and 24.3 g of magnesium
The Grignard reagent obtained by reacting in 300 ml of g@T H F was added dropwise under reflux, and then aged for 10 hours. The resulting reaction mixture was filtered to remove precipitated salts, and then distilled to boiling point: 75-76°C/2tm I
A fraction of tg was obtained.

This fraction was transferred to a 1 liter glass reactor equipped with a stirrer, reflux condenser, thermometer and dropping funnel with 161.9 g of triethylamine and 500 ydl of hexane.
I prepared it with Next, 54.5 g of methanol was added dropwise from the dropping funnel at room temperature, and the mixture was allowed to sit for 1 hour. After filtering the resulting reaction mixture to remove precipitated salts,
Distillation yielded a fraction with a boiling point of 63-64°C/1 mm, 11 g.

When the mass spectrum, 'H-NMR spectrum and IR spectrum of the obtained fraction were measured, the results shown below were obtained.

Mass spectrum electron impact method 2 m/z (spectral intensity ratio) 249 (1
00), 233(2), 177(26), 161(8
), 147(11), 129(15), 117(1
2), 89 (21), 73 (29), 59 (2
5) Chemical ionization method: Reactive gas: i-butane m/z:
264 IH-NMR spectrum δ: 0.05ppm(s, (CH3):+St-
)0.16ppm(s, -SiCHzSi-)3.
Absorption peaks were observed at wave numbers below 45 ppm (s, -OCR.) in the TR spectrum.

2940cm-', 2820CIl-'% 1350c
m-', 1250cm-'1185cm-', 1090
From the measurement data of C'', 1055 cm-', 830 CTI+-', the obtained compound is bis(trimethylsilylmethyl)dimethoxy represented by the following formula: ((C!h)3SiCJ)zsi(OClh)z It turned out that silane was obtained. (Yield=76%) [Effects of the Invention] The novel trialkylsilylmethyl group-containing silane compound of the present invention is useful as a raw material for organoborisiloxane resists having high oxygen plasma resistance. Furthermore, since it contains a trialkylsilylmethyl group, which is a very bulky substituent, in its molecule, it is useful as a cocatalyst for the Ziegler-Nanta catalyst in the stereoregular polymerization of propylene.

Claims (1)

[Claims] General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, three R^1 and two R^2 may be the same or different, is an alkyl group, and R^3 is a substituted or unsubstituted monovalent hydrocarbon group having 2 or more carbon atoms, or formula (II): (R^1)_3SiCH_2-(II) (where, three R^1 may be the same or different and is as described above) A trialkylsilylmethyl group-containing silane compound represented by the following.