JPH07286044A - Silicone compound, its production, and cosmetic - Google Patents

Abstract

PURPOSE:To obtain a silicone compd. which has an excellent capability of emulsifying an oil such as a silicone oil, an ester oil, a hydrocarbon oil, or their mixture, emits neither the hydrocarbon odor nor the olefin odor due to a long-chain alkyl group, and can easily be produced in one step. CONSTITUTION:A silicone compd. is represented by the formula: R<1>aR<2>bSiO(4-a-b)/2 [wherein R<1> is 1-10C alkyl, aryl, aralkyl, or fluorinated alkyl; R<2> is -CmH2mO(C2H4O)-c(C3H6O)dR<3> (wherein R<3> is a 14C or higher monovalent hydrocarbon group; c and d are each an integer of 2-200 provided c+d is an integer of 3-200; and m is an integer of 0-5); 1<=a<=2.5; and 0.001<=b<=1.5].

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has a novel emulsifying ability for various oil agents such as silicone oil and mixed oil agents, has no peculiar odor, is easy to produce, and is suitable as a raw material for cosmetics. The present invention relates to a silicone compound, a method for producing the same, and a cosmetic containing the same.

[0002]

2. Description of the Related Art In recent years,
In the water-in-oil emulsion composition, there is little stickiness as a refreshing agent, and a silicone oil is used as an oil agent to obtain a product having good water repellency, but a water-in-oil emulsion containing this silicone oil is It is difficult to obtain an emulsion with good stability by using an emulsifier such as a polyoxyalkylene fatty acid ester type which has been conventionally used.

Therefore, a method of using a polyoxyalkylene-modified organopolysiloxane having good compatibility with silicone oil as a surfactant in the above water-in-oil emulsion is disclosed in JP-A-61-293903 and 61-63. -29390
No. 4, No. 62-187406, No. 62-215510.
No. 62-216635 and the like.
Furthermore, these polyoxyalkylene-modified organopolysiloxanes have a problem that when used in cosmetics, an irritating odor is generated due to aging during preparation of an emulsion,
As a countermeasure for this, JP-A-2-302438 proposes a method for producing a purified polyoxyalkylene-modified organopolysiloxane that does not generate an offensive odor.

When an emulsion for cosmetic use is obtained, not only silicone oil but also ester oil or hydrocarbon oil is often used together as an oil agent. The above polyoxyalkylene-modified organopolysiloxane is Such a mixed oil system is inferior in emulsifying power and has a drawback that it is difficult to obtain a stable water-in-oil emulsion.

As a method for solving this problem, a method of using an organopolysiloxane having both a long chain alkyl group represented by the following formula and a polyoxyalkylene group as an emulsifier is disclosed in JP-A-61-90732. Proposed.

[0006]

[Chemical 1]

However, this organopolysiloxane compound has a terminal 2 group on the organohydrogenpolysiloxane.
It is produced by addition-polymerizing a long-chain alkylene compound having a heavy bond and an allylated polyether. When the long-chain alkylene compound having a terminal double bond and the allylated polyether are simultaneously reacted with each other. ,
Since the addition reaction rates of the two are different, the modification ratio does not reach the set value, and as a result, the two layers are separated. Therefore, the organopolysiloxane compound is prepared by reacting, for example, an organohydrogenpolysiloxane with a long-chain alkylene compound having a terminal double bond, and then with an allylated polyether.
The manufacturing process was troublesome because it required a stepwise manufacturing process.
Moreover, the above-mentioned organopolysiloxane compound is not suitable for cosmetics because hydrocarbon odor and olefin odor due to the long-chain alkyl group remain in the final product.

On the other hand, by using an allylated product of a higher alcohol in place of the long chain alkylene compound having a terminal double bond, the reaction rate with the allylated polyether is made equal, and the co-modified organopolysiloxane is A method of manufacturing in stages is disclosed in Japanese Patent Application Laid-Open No. 4-36324. However, even with this method, the off-flavor due to the higher alcohol remains, so that the above organopolysiloxane is not suitable for cosmetics. Further, when the refining method proposed in the above-mentioned JP-A-2-302438 is applied to the organopolysiloxane compound obtained by this method, the generation of offensive odor due to aging is suppressed, but it remains in the silicone compound itself. Since it does not remove the offensive odor derived from higher alcohols, it cannot be said to be sufficient for use in cosmetics.

Therefore, it has been desired to develop an emulsifying agent having an excellent emulsifying property and suitable for use in cosmetics.

The present invention has been made in order to meet the above-mentioned demand, and has excellent emulsifying performance for each oil agent such as silicone oil used in cosmetics and a mixed oil agent thereof, and has no specific odor. Moreover, it is an object of the present invention to provide a silicone compound that can be produced by simple steps, a method for producing the same, and a cosmetic containing the same.

[0011]

Means for Solving the Problems The present inventor has conducted extensive studies in order to achieve the above object, and as a result, the organohydrogenpolysiloxane represented by the following general formula (2) and the following general formula (3) are used. It was found that the novel silicone compound represented by the following general formula (1) obtained by addition reaction with the represented polyoxyalkylene compound has excellent properties as an emulsifier.

R ¹ _a H _b SiO _{(4-ab) / 2} (3) C _m H _2m-1 —O— (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d —R ³ (4) R ¹ _a R ² _b SiO _{(4-ab) / 2} (1) [wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a fluorine-substituted alkyl group, R ²
Following general formula _{(2) -C m H 2m -O-} (C 2 H 4 O) c (C 3 H 6 O) d -R 3 (2) an organic group represented by (R ³ is 14 or more carbon atoms Is a monovalent hydrocarbon group, c and d are each an integer of 2 to 200, c + d is 3 to 200, and m is an integer of 0 to 5), and a and b are each 1 ≦ a ≦ 2.5, 0.
001 ≦ b ≦ 1.5. ]

That is, the present inventor has the above formula (4) having an aliphatic unsaturated group at the terminal and an organic group having a polyoxyalkylene unit and a long-chain alkyl unit in the same molecule.
The silicone compound of the formula (1) can be easily produced in one step by addition-reacting the polyoxyalkylene compound of the formula (3) with the organohydrogenpolysiloxane of the formula (3). The silicone compound has excellent emulsification performance for oil agents widely used in cosmetics such as silicone oils, ester oils, hydrocarbon oils and mixed oil agents thereof, and has hydrocarbon odor and olefin derived from long chain alkyl groups. The present invention has been completed by finding that there is no peculiar odor such as odor and therefore it can be suitably used as a raw material for cosmetics.

Therefore, the present invention provides a silicone compound represented by the general formula (1), an organohydrogenpolysiloxane represented by the general formula (3), and a polyoxyalkylene compound represented by the general formula (4). The present invention provides a method for producing a silicone compound of the above formula (1) in which an addition reaction is carried out, and a cosmetic containing the silicone compound.

The present invention will be described in more detail below. The silicone compound of the present invention is represented by the following general formula (1).

R ¹ _a R ² _b SiO _{(4-ab) / 2} (1) [wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a fluorine-substituted alkyl group, R ²
Following general formula _{(2) -C m H 2m -O-} (C 2 H 4 O) c (C 3 H 6 O) d -R 3 (2) an organic group represented by (R ³ is 14 or more carbon atoms Is a monovalent hydrocarbon group, c and d are each an integer of 2 to 200, c + d is 3 to 200, and m is an integer of 0 to 5), and a and b are each 1 ≦ a ≦ 2.5, 0.
001 ≦ b ≦ 1.5. ]

Here, R ¹ in the above formula (1) has 1 carbon atom.
-10 is an alkyl group, an aryl group, an aralkyl group or a fluorine-substituted alkyl group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Alkyl groups such as decyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group and phenethyl group, trifluoropropyl group, heptadecafluorodecyl group, etc. Examples thereof include a fluorine-substituted alkyl group, and especially R
It is desirable that 50% or more of all ¹ is a methyl group.

R ² is an organic group represented by the following general formula (2).

[0019] _{-C m H 2m -O- (C 2} H 4 O) c (C 3 H 6 O) d -R 3 (2)

Here, R ³ in the above formula (2) has 1 carbon atom.
When it is a monovalent hydrocarbon group of 4 or more, preferably 16 to 30, and the carbon number of R ³ is less than 14, a peculiar odor due to the long-chain alkyl group is generated. Examples of R ³ include linear saturated hydrocarbon groups such as myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosanyl group, behenyl group, pentacosanyl group, octacosanyl group and triacontanyl group, Branched saturated hydrocarbon groups such as isostearyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decylpentadecyl group, 2-decyltetradecyl group, unsaturated hydrocarbon groups such as oleyl group, octylphenyl Group, aromatic ring-containing hydrocarbon group such as nonylphenyl group, alicyclic hydrocarbon group such as cholesteryl group, and the like, particularly myristyl group, cetyl group, stearyl group, behenyl group, isostearyl group, oleyl group. Groups are preferred.

Further, a is 1 to 2.5, preferably 1.2.
It is ~ 2.3, and when a is smaller than 1, the dispersibility of the silicone oil is poor, and it is difficult to obtain a stable water-in-oil emulsion using a silicone oil as a base oil, and when it is larger than 2.5, the hydrophilicity is poor. Therefore, it is difficult to obtain a stable water-in-oil emulsion. b is 0.001 to 1.5, preferably 0.05 to 1,
When b is less than 0.001, it becomes difficult to obtain a stable water-in-oil emulsion because the hydrophilicity is poor, and when it is more than 1.5, the dispersibility of the silicone oil is poor and the stability of the silicone oil as a base oil is stable. It is difficult to obtain a water-in-oil emulsion.

C and d are each 2 to 200, preferably 5 to 100, and c + d is 3 to 200, and in order to impart sufficient hydrophilicity to obtain a water-in-oil emulsion, c is required.
It is desirable that / d ≧ 1. m is 0-5,
When m is 0, the hydrolysis resistance may be inferior, so 3 to
It is preferably 5.

The polyoxyalkylene moiety of the above formula (2) may be either a block polymer or a random polymer of ethylene oxide units and propylene oxide units.

The weight average molecular weight of the silicone compound of the above formula (1) is not particularly limited, but is 500 to 100,00.
0, especially 1,000 to 10,000 is preferable.

The silicone compound of the above formula (1) of the present invention is obtained by using an organohydrogenpolysiloxane represented by the following general formula (3) and a polyoxyalkylene compound represented by the following general formula (4) as a platinum catalyst or rhodium. It can be synthesized by an addition reaction in the presence of a catalyst. ^{_{R 1 a H b SiO (4}} -ab) / 2 (3) C m H 2m-1 -O- (C 2 H 4 O) c (C 3 H 6 O) d -R 3 (4) ( where, In the formula, R ¹ , R ³ , c, d, m, a, and b are the same as above.)

Here, the organohydrogenpolysiloxane of the above formula (3) may be linear, branched or cyclic, but it is preferably linear to facilitate the addition reaction. preferable.

The mixing ratio of the organohydrogenpolysiloxane of the above formula (3) and the polyoxyalkylene compound of the above formula (4) is 0.5 to 2.0, preferably a molar ratio of SiH groups to terminal unsaturation. Is 0.8 to 1.2.

The above addition reaction is preferably carried out in the presence of a platinum catalyst or a rhodium catalyst. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid-vinylsiloxane complex, etc. are preferably used. To be done. The amount of the catalyst used may be a catalytic amount, but in particular, the amount of platinum or rhodium is 50 ppm or less, preferably 20 ppm.
It is the following.

The above-mentioned addition reaction may be carried out in an organic solvent if necessary, and examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, and aromatic compounds such as benzene, toluene and xylene. Group hydrocarbons, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and the like can be given, but especially for use as cosmetics. Ethanol and 2-propanol are preferred.

The addition reaction conditions are not particularly limited, but it is preferable to carry out the reaction under reflux for 1 to 10 hours.

The silicone compound thus obtained may be purified by applying the purification method described in JP-A-2-302438, and the odorlessness can be further improved by this purification.

The silicone compound of the present invention can be used for various purposes by utilizing its emulsifying ability, but it is particularly suitable as a raw material for cosmetics and is compounded in various creams, foundations, lipsticks, emulsions, shampoos, rinses and the like. can do. In this case, the blending amount of the silicone compound of the above formula (1) is preferably 0.1 to 10 parts by weight based on the whole cosmetic product.

When the silicone compound of the above formula (1) is used as a raw material for cosmetics, the other compounding ingredients are not particularly limited, and ingredients depending on the dosage form can be added. For example, moisturizing agents, waxes, Powders, pigments, activators, fragrances, antioxidants and the like can be mentioned.

[0034]

INDUSTRIAL APPLICABILITY The silicone compound of the present invention has excellent emulsifying ability for oil agents such as silicone oils, ester oils, hydrocarbon oils, and mixed oil agents thereof, and is a hydrocarbon derived from a long-chain alkyl group. It has no specific odor such as odor and olefin odor and is useful as a raw material for cosmetics. Further, according to the production method of the present invention, the silicone compound can be easily produced in one step.

[0035]

EXAMPLES The present invention will be specifically described below with reference to Examples, Experimental Examples, Comparative Examples and Formulation Examples, but the present invention is not limited to the following Examples. All parts in each example are parts by weight. Further, in the following formula, Me is a methyl group.

Example 1 228 parts of organohydrogenpolysiloxane represented by the following average composition formula (5), 173 parts of polyoxyalkylene represented by the following average composition formula (6) and 270 parts of ethanol were mixed in a reactor. 2% by weight of chloroplatinic acid in ethanol solution 0.2
Parts were added, and the mixture was reacted for 6 hours under reflux of the solvent.

[0037]

[Chemical 2]

The reaction product was heated under reduced pressure to distill off the solvent and then filtered to obtain a target product represented by the following average composition formula (7). This product was a pale yellow transparent liquid and had a viscosity of 151 cs (25 ° C.). In addition, there was no odor due to stearyl alcohol, and it was odorless.

[0039]

[Chemical 3]

Example 2 A reactor was mixed with 235 parts of organohydrogenpolysiloxane represented by the following average composition formula (8), 176 parts of polyoxyalkylene represented by the following average composition formula (9), and 270 parts of ethanol. 2% by weight of chloroplatinic acid in ethanol solution 0.2
Parts were added, and the mixture was reacted for 6 hours under reflux of the solvent.

[0041]

[Chemical 4]

The reaction product was heated under reduced pressure to remove the solvent and then filtered to obtain the target product represented by the following average composition formula (10). The product is a pale yellow transparent liquid,
The viscosity was 212 cs (25 ° C.). Further, there was no odor due to oleyl alcohol, and it was odorless.

[0043]

[Chemical 5]

Example 3 The following average composition formula (1
120 parts of the organohydrogenpolysiloxane represented by 1), 693 parts of polyoxyalkylene represented by the following average composition formula (12) and 550 parts of ethanol are mixed, and 0.3% of an ethanol solution containing 2% by weight of chloroplatinic acid is added thereto.
Parts were added, and the mixture was reacted for 6 hours under reflux of the solvent.

[0045]

[Chemical 6]

The reaction product was heated under reduced pressure to distill off the solvent and then filtered to obtain a target product represented by the following average composition formula (13). The product is a pale yellow transparent liquid,
The viscosity was 2500 cs (25 ° C). Further, there was no odor due to behenyl alcohol, and it was odorless.

[0047]

[Chemical 7]

[Experimental Example 1] Using the silicone compounds obtained in Examples 1 to 3 as an emulsifier, an emulsification test was conducted. As the test method, 3 parts of an emulsifier and 47 parts of squalane or glyceryl trioctanoate were mixed, and 50 parts of purified water was gradually added over 3 minutes while stirring with a homomixer (7500 rpm). After the addition was completed, the mixture was further stirred for 2 minutes. The state after 1 minute and 1 hour after emulsification was visually observed.

For comparison, the same test as above was conducted using a polyether-modified silicone of the following formula (14) as an emulsifier. The above results are shown in Tables 1 and 2.

[0050]

[Chemical 8]

[0051]

[Table 1]

[0052]

[Table 2]

[Experimental Example 2] Using the silicone compounds obtained in Examples 1 to 3 as an emulsifier, dimethyl silicone (20 cs) was used as an oil agent for 3 parts of each emulsifier.
An emulsification test was conducted in the same manner as in Experimental Example 1 using a mixed solution of 17 parts, 15 parts of squalane and 15 parts of glyceryl trioctanoate, and adding 50 parts of water thereto. The results are shown in Table 3.

[0054]

[Table 3]

From the results of the above Experimental Examples 1 and 2, the silicone compounds of the present invention (Examples 1 to 3) have excellent emulsification performance for each oil agent and mixed oil agent used for cosmetics. Was confirmed.

[Experimental Example 3] Silicone compounds represented by the following general formula (15) (m, n, a and x are shown in Table 4, respectively)
The value shown in FIG. ) Was synthesized, and the emulsifying property with respect to squalane or glyceryl trioctanoate was performed in the same manner as in Experimental Example 1. In addition, the odor of each silicone compound itself was sensory evaluated. The results are shown in Tables 4-6.

[0057]

[Chemical 9]

From the results shown in Tables 4 and 5, it was found that the long-chain alkyl group (R) having 14 or more carbon atoms had excellent emulsification performance. Regarding the odor of the emulsifier itself, as shown in Table 6, it was found that when the long-chain alkyl group has 14 or more carbon atoms, the specific odor disappears and the organoleptic properties are excellent.

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

[Formulation Example 1] Hand cream (oil phase component) Dimethylpolysiloxane (6cs) 15.0 parts by weight Liquid paraffin 5.0 Silicone compound of Example 1 5.0 (water phase component) Purified water 66.0 L-Glutamate sodium 4.0 1,3-butylene glycol 5.0 The oil phase component was heated to 70 ° C., the aqueous phase component preheated to 70 ° C. was added thereto, and the mixture was emulsified to obtain a hand cream.

[Formulation Example 2] Hair cream (oil phase component) Dimethylpolysiloxane (20cs) 15.0 parts by weight Squalane 4.0 Trimethylsiloxysilicate 1.0 Glyceryldiolate 2.0 Silicone compound of Example 2 4. 0 (Aqueous phase component) Purified water 68.0 Glycine 3.0 Propylene glycol 3.0 The oil phase component is heated to 70 ° C, and the aqueous phase component preheated to 70 ° C is added to this to emulsify the hair cream. Got

Claims (3)

[Claims] 1. A silicone compound represented by the following general formula (1). R ¹ _a R ² _b SiO _{(4-ab) / 2} (1) [wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a fluorine-substituted alkyl group, R ²
Following general formula _{(2) -C m H 2m -O-} (C 2 H 4 O) c (C 3 H 6 O) d -R 3 (2) an organic group represented by (R ³ is 14 or more carbon atoms Is a monovalent hydrocarbon group, c and d are each an integer of 2 to 200, c + d is 3 to 200, and m is an integer of 0 to 5), and a and b are each 1 ≦ a ≦ 2.5, 0.
001 ≦ b ≦ 1.5. ] 2. The method for producing a silicone compound according to claim 1, wherein the organohydrogenpolysiloxane represented by the following general formula (3) and the polyoxyalkylene compound represented by the following general formula (4) are subjected to an addition reaction. _{^{R 1 a H b SiO (4}} -ab) / 2 (3) C m H 2m-1 -O- (C 2 H 4 O) c (C 3 H 6 O) d -R 3 (4) was prepared in which In the formula, R ¹ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a fluorine-substituted alkyl group, R ³
Is a monovalent hydrocarbon group having 14 or more carbon atoms, c and d are each an integer of 2 to 200, c + d is 3 to 200, and m is an integer of 0 to 5. Further, a and b are 1 ≦ a ≦ 2.5 and 0.001 ≦ b ≦ 1.5, respectively. ] 3. A cosmetic comprising the silicone compound according to claim 1.