JP2665799B2 - Ester-modified silicone derivative and cosmetic containing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel ester-modified silicone derivative and a cosmetic containing the same.

[Conventional technology and its problems]

Silicon oil has been widely used as a cosmetic oil agent because it has excellent properties of lubricity, water repellency, gloss imparting property, stability, and safety.

However, among silicone oils, high-molecular-weight dimethylpolysiloxane is most commonly used as an oil for cosmetics, but has poor solubility in polar oils and water, and in systems containing hydrocarbon oils. There was a disadvantage that it was difficult to emulsify. In addition, cosmetics containing these have a peculiar tingling sensation and are not sufficiently satisfactory in terms of feel.

Therefore, it has been desired to solve the above-mentioned drawbacks and to develop a silicone derivative having an excellent usability that is not available in conventional silicone oils.

[Means for solving the problem]

Under such circumstances, the present inventors have conducted intensive studies, and as a result, the ester-modified silicone derivative represented by the following general formula (I) has good compatibility with hydrocarbon oils, polar oils, water and the like. Maintaining a stable system containing
Furthermore, they found that cosmetics containing the same did not have the tingling sensation peculiar to silicone oil and had an excellent feeling of use, and completed the present invention.

That is, the present invention provides the following general formula (I) (Wherein, R represents a saturated or unsaturated linear, branched or alicyclic hydrocarbon group or an aromatic hydrocarbon group;
Represents an integer of 1 to 3, and n represents an integer of 0 to 90.) and a cosmetic containing the same.

In the ester-modified silicone derivative of the present invention, in the general formula (I), the group RCO ₂ — has, for example, 2 to 30 carbon atoms.
Examples of the carboxylic acid residue include, for example, acetic acid, butyric acid, capric acid, lauric acid, myristic acid,
Palmitic acid, stearic acid, behenic acid, melicic acid,
Palmitooleic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, erucic acid, 2-ethylhexanoic acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid, 5,7,7-trimethyl-2- (1, 3,3-Trimethylbutyl) octanoic acid, methyl branched isostearic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, abietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, cholic acid, deoxycholic acid, glycyrrhizic acid, benzoic acid And carboxylic acid residues such as acids and naphthoic acids. The molecular weight of the dimethylpolysiloxane part is preferably 100 or more and 7,000 or less.

The ester-modified silicone derivative (I) of the present invention can be produced, for example, by any of the following methods.

Method A: Ester-modified silicone derivative (I) is obtained by hydrosilylation of α-hydrogenpolysiloxane (II) and allyl ether (III) in the presence of a catalytic amount of a chloroplatinic acid catalyst at room temperature or under heating. .

(Wherein R, a, and n have the above-mentioned meanings) Allyl ether (III), which is one of the raw materials, is reacted with a reactive derivative (IV) such as a carboxylic acid or a carboxylic acid chloride by known methods, for example. Alcohol (V)
Can be easily manufactured.

(In the formula, R and a have the same meanings as described above.) Further, α-hydrogenpolysiloxane (II) is
For example, it can be synthesized by the method described in U.S. Pat. No. 3,481,965 to Serin et al.

Method B: Carboxylic acid (IV) is allowed to act on alcohol-modified dimethylpolysiloxane (VI) in the presence of an acid catalyst such as tin chloride or toluene sulfonic acid, or carboxylic acid chloride (IV) in the presence of a base such as pyridine. By acting VII), an ester-modified silicone derivative (I) is obtained.

(R, a, and n have the same meanings as described above.) Raw material alcohol-modified dimethylpolysiloxane (VI)
Is the corresponding α-hydrogenpolysiloxane (II)
And allyloxy alcohol (V) by hydrosilylation.

The cosmetic of the present invention contains the ester-modified silicone derivative (I), and the amount of the ester-modified silicone derivative is not particularly limited.
%), Preferably 1 to 50%. The cosmetic of the present invention is not particularly limited in its dosage form, type and the like, and can be produced according to a usual method, for example, an oily cosmetic, an emulsified cosmetic, an aqueous cosmetic, a lipstick, a foundation, a skin cleanser, It is applied as a hair tonic, hair styling agent, hair restorer, hair restorer and the like.

〔The invention's effect〕

The ester-modified silicone derivative (I) of the present invention has good compatibility with silicone oils, hydrocarbon oils, polar oils, water and the like, and can keep a system containing these stable. Useful as a broad cosmetic oil. Further, the ester-modified silicone derivative (I) of the present invention is (1) liquid at ordinary temperature, (2) low-viscosity, non-sticky, (3) chemically stable, (4) extremely low skin irritation, etc. It is also useful as a cosmetic oil agent used directly on the skin.

Further, the ester-modified silicone derivative (I) of the present invention
The cosmetics containing the compound greatly reduce the tingling sensation peculiar to silicone oil and have an excellent feeling of use.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 3- (2-tetrahydroabietoyloxyethoxy) propyl-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,1
5,17,17,17-nonadecamethylnonasiloxane [in the general formula (I), a = 1, n = 8] Synthesis of (Ia): (i) Synthesis of 2-allyloxyethyl tetrahydroabietic acid (Va): 200 ml equipped with a stirrer, thermometer and reflux condenser A flask was charged with 15.93 (156 mmol) of 2-allyloxyethanol, 15.42 g (195 mmol) of pyridine, and 42.24 g (130 mmol) of tetrahydroabietoyl chloride, and charged under a stream of nitrogen under a nitrogen stream.
The mixture was heated and stirred at 8 ° C for 8 hours. After completion of the reaction, the produced pyridine hydrochloride was removed by washing with water, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel flash chromatography to give the title compound (V-a) 42.0.
g was obtained as a colorless viscous oil (83% yield). ¹ H-NMR (δ, C ₆ D ₆ ): 0.42-1.97 (m, 33H), 3.25-3.35 (m, 2H), 3.69-3.78 (m, 2H), 4.02-4.24 (m, 2H), 4.95 -5.23 (m, 2H), 5.77-5.96 (m, 1H) (ii) Synthesis of compound (Ia): In a 200 ml flask equipped with a stirrer and a thermometer, (i)
36.0 g (92 mmol) of the compound (Va) obtained in 1, 1,1,3,3,5,
5,7,7,9,9,11,11,13,13,15,15,17,17,17-nonadecamethylnonasiloxane [compound of the general formula (II) where n = 8] (II- a) 47.3 g (71 mmol), potassium acetate 0.18 g
(1.84 mmol), 9.5 mg (0.018 mmol) of chloroplatinic acid, and 72 g of isopropyl alcohol, and stirred at 40 ° C. for 18 hours. After completion of the reaction, isopropyl alcohol was distilled off under reduced pressure, and the residue was purified by silica gel flash chromatography to obtain 68.8 g of the title compound (Ia) as a colorless low-viscosity oil (yield: 92%).

IR (neat): 2964,2868,2384,1730,1454,1414,1388,126
^{2,1092,1024,840,802,700cm -1 1 H-NMR (δ} , C 6 D 6): 0.0-0.3 (m, 57H, 0.5−0.8 (m, 2H, 0.8-2.0 (m, 35H, alkyl abietic acid moiety and _{3.2-3.3 (m, 2H, -CH 2} -O-C H 2), 3.38 (t, J = 4.9Hz,
_{2H, -C H 2 OCH 2 -} ), 4.0-4.3 (m, 2H, ¹³ C-NMR (C ₆ D ₆ , δ): 0.33-1.91 (m, 14.7-56.8 (m, alkyl abietate moiety and 63.8,69.0,74.0 (more -O- C H ₂ -), 178.2 ²⁹ Si-NMR (C ₆ D ₆ , δ): −21.54, −21.51, −21.39, −21.37, −20.94 (or more 7.68,8.29 (or more Example 2 The viscosity and solubility in a solvent were examined for the ester-modified silicone derivative (Ia) produced in Example 1 and a silicone oil KF-96-100cs manufactured by Shin-Etsu Chemical Co., Ltd. as a comparative product. The results are shown in Table 1.

Example 3 Ester-modified silicone derivative (Ib) [in the general formula (I), a = 1, (average value) = 66 compound]: Alcohol-modified dimethylpolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd .; in a 100 ml flask equipped with a stirrer, a thermometer, and a reflux condenser; , A = 1, (average value) = 66 compound] (VI-b) 25.1 g (5 mmol), tetrahydroabietoyl chloride 2.44 g (7.5 mmol), pyridine 1.2 g (15 mmol), and toluene 25 g, The mixture was heated and stirred at 100 ° C. for 14 hours under a nitrogen stream. After completion of the reaction, the produced pyridine hydrochloride was removed by washing with water, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel flash chromatography to give the title compound (I-
b) 17.54 g were obtained as a colorless low-viscosity oil.

IR (neat): 2968,1732,1582,1450,1416,1264,1102,103
_{^{0,864,804,686,662cm -1 1 H NMR (C 6}} D 6, δ): 0.1-0.4 (m, about 399H, 0.4−0.7 (m, 2H, 0.7-2.0 (m, 35H, alkyl abietic acid moiety and 3.2-3.3 (m, 4H, -C H 2 -O-C H 2 -), 4.0-4.3 (m, 2H, ¹³ C NMR (C ₆ D ₆ , δ): 0.34-1.94 (m, 12.3-56.8 (m, alkyl abietic acid moiety and 63.7,69.0,74.0 _{(above, -O- C H 2 -),} 178.0 Example 4 Moisturizing cream: <Composition> 1) Compound (Ia) 10.0 (%) 2) Fixed paraffin 2.0 3) Cetyl 2-ethylhexanoate 5.0 4) Lanolin 5.0 5) Beeswax 2.0 6) Stearyl alcohol 4.0 7) Self-emulsifying glycerol monostearate 1.5
8) Polyoxyethylene sorbitan monooleate (2
0.EO) 1.0 9) Proper amount of ethyl paraben 10) Proper amount of methyl paraben 11) Proper amount of flavor 12) Purified water Balance meter 100.0 <Production method> 1) to 8) were heated and dissolved and kept at 70 ° C. 9) -1
0) and 12) were similarly heated and mixed at 70 ° C., and the above-mentioned mixture of 1) to 8) was added thereto and emulsified by an emulsifier. The obtained emulsion was cooled to 40 ° C. while stirring, and 11) was added thereto and mixed uniformly. It was cooled to a final temperature of 30 ° C. by a heat exchanger to prepare a moisturizing cream.

This moisturizing cream had a moist feeling, less stickiness, and was excellent in moisturizing properties and feeling of use.

Example 5 Emulsion: <Composition> 1) Compound (Ia) 1.0 (%) 2) Cetanol 0.5 3) Vaseline 1.0 4) Squalane 4.0 5) Liquid paraffin 5.0 6) Stearic acid 2.0 7) Polyoxyethylene oleyl ether ( 20.EO)
2.0 8) Triethanolamine 1.0 9) Ethylparaben qs 10) Fragrance qs 11) Purified water Balance meter 100.0 <Production method> 1) to 7) were heated and dissolved at 70 ° C and mixed uniformly. 8)
9) and 11) were also uniformly mixed by heating to 70 ° C., and the above mixture of 1) to 7) was gradually added thereto with stirring to emulsify. The obtained emulsion was cooled to 30 ° C in a heat exchanger,
0) was added and mixed uniformly to prepare an emulsion.

This emulsion was moist and familiar to the skin, and was excellent in use.

Example 6 Lipstick: <Composition> 1) Compound (Ia) 30.0 (%) 2) Carnalba wax 2.0 3) Celesin 4.0 4) Candelilla wax 5.0 5) Microcrystalline Wax 2.0 6) Beeswax 3.0 7) Lanolin 3.0 8) Castor oil 20.0 9) Hexadecyl alcohol 20.0 10) Glycerol monostearate 2.0 11) Titanium oxide 2.0 12) Pigment (Red 202) 2.0 13) Pigment (Red 204) 1.0 14) Pigment (Yellow 4 A1) Lake) 3.0 15) Antioxidant appropriate amount 16) Flavor appropriate amount meter 100.0 <Production method> 1) to 7), 9) and 10) are heated and melted, and 11) to
The components dispersed in 16) and 8) were added, and the mixture was stirred to make the mixture uniform. This was poured into a mold and cooled to produce a lipstick.

This lipstick gave a moist feeling, was less sticky, and was excellent in usability.

Example 7 Creamy moisturizing foundation: <Composition> 1) Compound (Ib) 10.0 (%) 2) Liquid paraffin 8.0 3) Squalane 8.0 4) Neopentyl glycol dioctanoate 3.0 5) Sorbitan sesquiisostearate 7.0 6) Aluminum Distearate 0.2 7) Magnesium sulfate 0.7 8) Methyl paraben 0.1 9) Titanium oxide 8.0 10) Krk 5.0 11) Sericite 2.0 12) Bengala 0.4 13) Yellow iron oxide 0.7 14) Black iron oxide 0.1 15) Fragrance Appropriate amount 16) Purification Water balance meter 100.0 <Manufacturing method> 1) to 6) are heated to 70 ° C and uniformly mixed.
9) to 14) were dispersed. 7) to 8) and 16), which were uniformly mixed at 70 ° C, were gradually added with stirring to emulsify, then cooled while stirring, 15) was added at 40 ° C, and further cooled to room temperature with stirring. did.

This creamy foundation gave a moist feeling, was less sticky, and was excellent in moisturizing properties and feeling in use.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08G 77/46 NUL C08G 77/46 NUL

Claims (2)

(57) [Claims] 1. The following general formula (I) (Wherein, RCO ₂ — represents a tetrahydroabietic acid residue, a represents an integer of 1 to 3, and n represents an integer of 0 to 90). 2. A cosmetic comprising the ester-modified silicone derivative according to claim 1.