JP2003089699A - Silane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silane compound which has an excellent oil-solidifying ability and has a low melting point and whose production method is easy, to provide a method for producing the same, to obtain a solidifying agent comprising the same, and a composition containing the same. SOLUTION: The silane compound (I): R2 SiX2 (two R are each independently an alkyl most frequently having 22 to 100 carbon atoms; two X are each independently a 1 to 10C alkyl, H, OH or a 1 to 10C alkoxy), the method for producing the same, the oil-solidifying agent comprising the silane compound (I), and the composition comprising the silane compound (I) and an oil are respectively provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silane compound having two long-chain alkyl groups useful as a raw material for cosmetics, a method for producing the same, a solidifying agent comprising the same, and a composition containing the same.

[0002]

BACKGROUND OF THE INVENTION Hydrocarbon compounds that are solid at normal temperatures, such as paraffin,
Acid, ester, alcohol, natural wax, resin, etc.,
By heating and mixing liquid oil and cooling, oily solids such as cosmetics such as lipsticks and foundations and stationery such as crayons are produced.

However, since the solidifying performance of the oil agent is insufficient with paraffin and the like, JP-A-2001-39986 discloses the use of disiloxane as a solidifying agent for the oil agent. However, since the manufacturing method of disiloxane is complicated, there is a demand for a solidifying agent for an oil agent which can be manufactured more easily and has a lower melting point.

An object of the present invention is to provide a silane compound having an excellent solidifying ability of an oil agent, an easy production method and a lower melting point, a production method thereof, a solidification agent comprising the same and a composition containing the same. It is to be.

[0005]

The present invention has the general formula (I)
A silane compound represented by (hereinafter referred to as silane compound (I)), its production method, a solidifying agent for an oil agent comprising the silane compound (I), and a composition containing the silane compound (I) and an oil agent.

R ₂ SiX ₂ (I) [wherein R: two R's each independently have a mode of carbon number
22 to 100 alkyl groups are shown. X: Two X's each independently represent a hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. ]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION [Silane Compound (I)] In the silane compound (I), the carbon numbers of two R's may be independent of each other. The mode value is an alkyl group of 22 to 100, preferably 26 to 100, more preferably 32 to 70.

In the present invention, the mode of the number of carbon atoms means the number of carbon atoms of the alkyl group having the largest content, and the shape retention when the silane compound (I) is used as a solidifying agent for the oil agent is The mode of carbon number is an important factor. That is, when the mode of carbon number is 22 or more, it does not become oily and does not melt at a temperature near room temperature, so it can be suitably used as a solidifying agent such as an oil agent, and is 100 or less. , The melting point does not become too high, and the compounding into the product becomes good.

The mode of the carbon number of R of the silane compound (I) can be measured by the following method.

When the melting point (for example, temperature rising rate: 1 ° C./min) measured by a melting point measuring device (for example, manufactured by YANACO) coincides with the melting point of the similarly measured n-alkane standard product within the range described below, It is obtained as the carbon number of the n-alkane standard product. That is, the melting temperature of the silane compound (I) of the present invention is A ° C., the melting temperature is B ° C., and n−
When the melting start temperature of the alkane standard product is E ° C. and the melting end temperature is F ° C., when the conditions represented by the following formulas are satisfied, the mode of the carbon number of R of the silane compound (I) is ,
It shall be the same as the carbon number of the standard n-alkane. From the viewpoint of the ability of the silane compound (I) as a solidifying agent, the difference (BA) between the temperature at the end of melting and the temperature at the beginning of melting is preferably 6 ° C or less, and particularly preferably 4 ° C or less.

[0011]

[Equation 1]

In the silane compound (I), the two X's may be the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. The hydrocarbon group is preferably an alkyl group, particularly a methyl group, and the alkoxy group is particularly preferably a methoxy group or an ethoxy group.

[Production Method] The silane compound (I) of the present invention
As a method for producing, a general synthetic method of an organically modified silane compound in which a long-chain 1-olefin (for example, Mitsubishi Chemical's dialene series) is added to a silane compound having a hydrogen-silicon bond in the presence of a platinum catalyst or the like. Can be used.

In this production method, however, the raw material silane compound used is a gas, which is not easy to handle, and the chain length distribution of olefins tends to be broad, so that the obtained silane compound is sufficient to solidify the oil agent. It has no performance.

A preferred method for producing the silane compound (I) is
For example, with respect to 1 equivalent of a silane compound having 2 or more, preferably 2 or 3, more preferably 2 leaving groups,
A polyethylene having a mode of carbon number obtained by polymerizing ethylene using an initiator containing alkyl lithium is reacted with 22 to 100 polyethylene, preferably 1.5 to 2.5 equivalents, more preferably 2 equivalents. Is the way.

In this production method, the step of obtaining polyethylene can be carried out, for example, by the method described in JP 03032420, page 3, column 5, line 31 to column 6, line 19.

Specifically, for example, by introducing ethylene into a solution containing alkyllithium and a tertiary diamine,
Living polymerization of ethylene is performed. The introduction pressure of ethylene is not particularly limited, but 0.098 to 9.8 MPa is suitable. The polymerization temperature is not particularly limited, but is 0 ° C to 100 ° C.
Is suitable, and preferably 20 ° C to 80 ° C. The polymerization time varies depending on the polymerization temperature, the concentration of the tertiary diamine, the ethylene introduction pressure, etc., but is generally about 0.1 to 24 hours. However, it is preferable to be as short as possible to remove the heat of polymerization in order to prevent deactivation of the living end. By changing these polymerization conditions, especially by adjusting the ratio of alkyllithium and ethylene, the mode of the carbon number of the resulting polyethylene having a living end can be accurately controlled. The carbon number of the polyethylene having a living end is preferably 22 to 10 as the mode.
It is 0, more preferably 26 to 100, particularly preferably 32 to 70.

The mode of the carbon number of the living-terminated polyethylene obtained here is determined by liquid chromatography capable of measuring high temperature, particularly gel permeation chromatography (for example, GPC150C manufactured by Waters), gas chromatography, ultra It can be measured by comparison with the peak of a standard product (normal alkane sold as a reagent from Aldrich, etc.) measured by critical fluid chromatography or the like. It can also be measured simply by comparing the melting point with a standard product.

Then, the thus obtained polyethylene having a living end is reacted with a silane compound having two or more leaving groups in the above proportion. Here, the leaving group may, for example, be a hydrogen atom, a hydroxyl group, an alkoxy group or a halogen atom. The silane compound having a leaving group preferably has 1 or 2 methyl groups and a chlorine atom, since the reaction proceeds under mild conditions and the by-products can be easily removed after the reaction. A silane compound having preferably 2 or 3, and more preferably 2 leaving groups selected from the group consisting of a bromine atom, a methoxy group and an ethoxy group is suitable.

The reaction conditions of the reaction between the silane compound having two or more leaving groups and the polyethylene having a living end are not particularly limited, and appropriate conditions may be adopted depending on the reactivity of the silane compound. However, the reaction temperature is −
The reaction time is preferably 78 to 200 ° C. and the reaction time is preferably 1 minute to 100 hours. When a silane compound having a chlorine atom, a bromine atom, a methoxy group or an ethoxy group as a leaving group is used, it varies depending on the amount added, the ratio, and the number of leaving groups, but after the completion of living polymerization of ethylene, -78 to It is preferable that the silane compound is added dropwise to the solution cooled to 70 ° C., and when the total amount has been added, the temperature is gradually raised and the reaction is performed at 80 to 100 ° C. for 1 to 24 hours.

From the reaction-finished product thus obtained,
If necessary, by-products are removed to obtain the silane compound (I). Specific examples include a method of removing salts and the like by washing with water, a method of adsorbing and removing salts and the like with an adsorbent, and the like. Most preferably, the reaction mixture in which the silane compound (I) is uniformly dissolved is dropped into a solvent in which the silane compound (I) is insoluble and impurities are dissolved, for example, methanol, and the precipitated portion is recovered to obtain a silane compound (I) having a high purity. .

[Solidifying Agent for Oil Agent] The silane compound (I) is useful as a solidifying agent for an oil agent. The oil agent solidified by the silane compound (I) is not particularly limited, and may be any non-aqueous liquid that maintains fluidity at room temperature (25 ° C.) and can dissolve or disperse the silane compound (I). .

For example, (a) hydrocarbons such as toluene, xylene, liquid paraffin, squalane, and petroleum ether; (b) alcohols such as ethanol, glycerin and cresol; (c) anisole, dioxane, 1,2-
Ethers or ketones such as dimethoxyethane, acetone, methyl ethyl ketone, cyclohexanone, (di) ethyl acetate, isopropyl palmitate, γ-butyrolactone, propylene glycol methyl ether acetate,
Lactic acid esters, esters of ethylene carbonate, etc., (e) Chloroform, trichloroethane, carbon disulfide, halogen-containing / sulfur / nitrogen solvents such as dimethyl sulfoxide, acetonitrile, pyridine, nitrobenzene, etc. (f) Palm oil, oils such as olive oil And derivatives thereof, (e) silicones and the like. You may mix and use 2 or more types of these oil agents.

[Composition] The mixing ratio of the silane compound (I) and the oil agent in the composition of the present invention is preferably 0.1 to 100 parts by weight of the silane compound (I) per 100 parts by weight of the oil agent. 0.5 to 30 parts by weight is more preferable, and 1 to 20 parts by weight is particularly preferable. Here, the silane compound (I) may be used alone or in combination of two or more kinds.

The composition of the present invention is obtained by appropriately heating the silane compound (I) and mixing the silane compound (I) with an oil agent in a fluid state.

The composition of the present invention can be suitably used for cosmetics such as lipsticks and foundations, and oily solids such as stationery such as crayons.

[0027]

EXAMPLES Example 1 (Synthesis of a silane compound in which R = 46 in the formula (I) is an alkyl group having a mode number of carbon atoms of 46 and X = CH ₃ ) Cyclohexane was placed in a 1 L glass pressure-resistant reaction vessel substituted with nitrogen. 400mL, dipiperidinoethane 4mL, 15% n-butyllithium hexane solution (1.6mol / L) 12.50mL (0.02mol)
While maintaining the temperature of the reaction system at 43 to 56 ° C and the ethylene gas introduction pressure at 0.098 to 0.37 MPa.
Polymerization was carried out by introducing 0.9 L (converted to standard state). Then,
Dichlorodimethylsilane (1.29 mL, 0.01 mol) was added dropwise to the polymerization mixture, and the mixture was reacted at 90 ° C for 2 hours. The reaction mixture was poured into 2 L of cold methanol, and the precipitate was collected by filtration to obtain a white powder. The yield was 14g.

As a result of ¹ H-NMR analysis of this compound in deuterated chloroform, a methyl group bonded to a silicon atom at 0.0 ppm, a methyl group at the end of an alkyl group at 0.4 ppm, and a silicon atom at 0.8 ppm. A methylene group attached, 1.
A methylene group signal of an alkyl group was observed at 2 ppm.
The ¹ H-NMR spectrum is shown in FIG.

When the melting point was measured by a trace melting point measuring device, it was found to be 87 to 90 ° C., and tetratetracontane (carbon number 4
4, melting point 87-88 ℃, pentacontane (carbon number 50, melting point 9
It was confirmed that the mode of carbon number was 46 from the value measured by the same measuring device (2-96 ° C) (Aldrich reagent).

Example 2 (Synthesis of a silane compound in which R = the number of carbon atoms in the formula (I) is 34 and X = CH ₃ ) In the same reaction vessel as in Example 1, n- 450 mL heptane,
N, N, N ', N'-Tetramethylethylenediamine 2mL, 15%
n-Butyllithium hexane solution (1.6mol / L) 60mL (0.0
(96 mol) was charged, and while maintaining the temperature of the reaction system at 28 to 82 ° C and the ethylene gas introduction pressure at 0.098 to 0.39 MPa, 39 L of ethylene gas (converted to the standard state) was introduced to carry out polymerization. Then, 6.3 mL (0.048 mol) of diethoxydimethylsilane was added dropwise to the polymerization mixture, and the mixture was reacted at 90 ° C for 2 hours. To the reaction mixture, 29 g of Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) and 4.5 g of activated carbon were added and stirred to carry out dealkalization and decolorization. The mixed liquid was filtered at 95 ° C., and the solvent of the filtrate was distilled off under reduced pressure to obtain a white solid. The yield was 45g.

As a result of ¹ H-NMR analysis of this compound in deuterated chloroform, a methyl group bonded to a silicon atom at 0.0 ppm, a terminal methyl group of an alkyl group at 0.4 ppm, and a silicon atom at 0.8 ppm. A methylene group attached, 1.
A methylene group signal of an alkyl group was observed at 2 ppm.
The ¹ H-NMR spectrum is shown in FIG.

When the melting point was measured with a trace melting point measuring device, it was 71 to 75 ° C., and tetratriacontane (carbon number 3
(4, Aldrich reagent) was in agreement with the value measured by the same measuring device.

Example 3 (Synthesis of Silane Compound where R = Alkyl Group with Carbon Number of 34 in Formula (I), X = CH ₃ and OCH ₂ CH ₃ ) The same reaction vessel as in Example 1 , N-heptane 150 mL,
N, N, N ', N'-Tetramethylethylenediamine 1.5mL, 15
% n-Butyllithium hexane solution (1.6mol / L) 50mL (0.
(08 mol) was charged, and while maintaining the temperature of the reaction system at 24 to 80 ° C. and the ethylene gas introduction pressure at 0.059 to 0.34 MPa, ethylene gas was introduced at 32 L (standard state conversion) to carry out polymerization. Then, 7.1 mL (0.04 mol) of triethoxymethylsilane was dropped into the polymerization mixture, and the mixture was reacted at 90 ° C. for 2 hours. 12.5 g of KYOWARD 700 was added to the reaction mixture and stirred to carry out dealkalization. Isopropyl alcohol was added to the mixed solution to make the filtrate transparent and then filtered at 70 ° C., and the solvent of the filtrate was distilled off under reduced pressure to obtain a white solid. The yield was 36g.

As a result of ¹ H-NMR analysis of this compound in deuterated chloroform, a methyl group bonded to a silicon atom at 0.0 ppm, a methyl group at the end of an alkyl group at 0.4 ppm, and a silicon atom at 0.8 ppm. A methylene group attached, 1.
A signal in which a methylene group of an alkyl group and a methyl group of an ethoxy group overlapped at 2 ppm, and a methylene group signal of an ethoxy group was observed at 3.6 ppm. This ¹ H-NMR spectrum is shown in FIG.

When the melting point was measured with a trace melting point measuring device, it was found to be 71 to 75 ° C., and tetratriacontane (carbon number 3
(4, Aldrich reagent) was in agreement with the value measured by the same measuring device.

Test Example Silane compounds synthesized in Examples 1 to 3, disiloxane (Example 3 in JP 2001-39986 A), and other commercial products shown in Table 1 were used as ester oils (neopentyl glycol dicaprate). A composition was prepared by using it as a solidifying agent, and its shape retention property was evaluated by the following method. The results are shown in Table 1.
Shown in.

<Evaluation Method of Shape Retention> A solidifying agent (1.05 g, 15% by weight) and an oil agent (5.95 g, in a glass dish having a diameter of 3 cm)
(85% by weight) was melted by heating and allowed to cool overnight at room temperature (22 ° C.) to prepare a sample. Using a handy compression tester (KES-G5 manufactured by Kato Tech Co., Ltd.), a cylinder with a diameter of 3 mm is 0.01 cm /
The change in stress when pressed about 2 mm at a speed of sec was measured three times, the average of the maximum values of stress was obtained, and the shape retention was evaluated according to the following criteria.

◎: The maximum value of stress is 500 gf or more ○: The maximum value of stress is 300 gf or more and less than 500 gf △: Maximum stress is less than 300 gf X: Does not solidify the oil

[0039]

[Table 1]

* 1 Disiloxane: JP 2001-399A
No. 86 gazette Example 3 disiloxane * 2 Polywax 850: High melting point polyethylene wax (Toyo Petrolite) * 3 HNP-9: High melting point paraffin (Nippon Seiwa Co., Ltd.) * 4 TSL8185: Octadecyltrimethoxysilane (GE) (Toshiba Silicone)

[0041]

[Effects of the Invention] The perfumes and medicinal agents used in cosmetics are
Since it is affected by the temperature, it is desired to mix it without raising the temperature as much as possible. The silane compound (I) of the present invention has a lower melting point and higher shape retention property than other solidifying agents, and thus is particularly useful as a solidifying agent for solid oily cosmetics and the like.

Further, since the silane compound (I) of the present invention does not require a coupling step, it can be produced at a lower cost as compared with disiloxane and has a high industrial utility value.

[Brief description of drawings]

FIG. 1 ¹ H—N of silane compound obtained in Example 1
It is an MR spectrum.

FIG. 2 ¹ H—N of silane compound obtained in Example 2
It is an MR spectrum.

FIG. 3 ¹ H—N of silane compound obtained in Example 3
It is an MR spectrum.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // A61K 7/00 A61K 7/00 EF term (reference) 4C083 AC911 BB11 CC01 FF01 4H049 VN01 VP01 VQ02 VR24 VS12 VU25 VW02 VW32 4J002 AE051 BB202 4J100 AA02 DA01 HA55 HA61 HC78 HC79 JA15

Claims (5)

[Claims] 1. A silane compound represented by the general formula (I). R ₂ SiX ₂ (I) [In the formula, R: two R's each independently have a mode of carbon number;
22 to 100 alkyl groups are shown. X: Two X's each independently represent a hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms. ] 2. The silane compound according to claim 1, wherein the mode of the carbon number of R is 32 to 70. 3. The mode of the carbon number obtained by polymerizing ethylene using a silane compound having two or more leaving groups and an initiator containing alkyllithium is 22 to 100.
The method for producing a silane compound according to claim 1 or 2, wherein the polyethylene is reacted with the polyethylene. 4. An oil agent solidifying agent comprising the silane compound according to claim 1. 5. A composition containing the silane compound according to claim 1 or 2 and an oil agent.