JP2824322B2 - Esterification products and cosmetics containing them - Google Patents

Description

The present invention relates to a novel esterified product of alcohol-modified silicon and carboxyl-modified silicon and a cosmetic composition containing the same.

(B) Conventional technology Silicone oil is excellent in viscosity stability, thermal oxidation stability, lubricity, water repellency, gloss, rust and corrosion resistance, vibration damping oil for instruments, machinery lubricating oil, glass container Widely applied to water repellents, wax additives, defoamers, cosmetic additives, etc.

Normally, dimethylpolysiloxane is generally used for silicone oil. In addition, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dimethylpolysiloxane polyethylene glycol copolymer, dimethylpolysiloxane polypropylene Glycol copolymers and the like are known, but in recent years, organosilicon monomers having two or more different reactive groups in the molecule and derivatives thereof as silane coupling agents, as well as methylstyrene-modified, olefin-modified, Polyether modified,
There are various modified silicone oils such as alcohol-modified, fluorine-modified, hydrophilic special-modified, amino-modified, mercapto-modified, epoxy-modified, carboxyl-modified, and higher fatty acid-modified.
These are commercially available from Shin-Etsu Chemical Co., Ltd., Chisso Corporation, Toray Silicone Co., Ltd.

Such silicone oils are often used as oils for cosmetics, but their main purpose is to make foundations that do not lose their makeup because of their excellent water repellency, non-adhesiveness, and lubricity. To get.
In recent years, use for hair (particularly split hair coat) has been increasing. However, when used as a cosmetic oil, it is required to have the properties of silicone oil, to have high viscosity, not to be sticky, and to be excellent in compatibility with other components.

However, conventionally, in order to increase the viscosity of silicone oil such as dimethylpolysiloxane, it was common to increase the molecular weight, but these high-viscosity silicone oils have very poor compatibility with polar solvents such as ethanol. Further, when used in an emulsifying system, it is difficult to emulsify and has very high water repellency, but has stickiness and greasy luster, and exhibits unfavorable physical properties depending on the purpose of use. Furthermore, highly polar silicone oils such as dimethylpolysiloxane diol have a very high solubility in polar solvents, but have a very poor compatibility with solvents such as petrolatum, lanolin and vegetable oils.

Japanese Patent Publication No. 1-21833 describes an esterification product of dimethylpolysiloxanediol and a dibasic acid, which does not solve the above-mentioned disadvantages.

(C) Problems to be Solved by the Invention It is an object of the present invention to eliminate the above-mentioned disadvantages of silicone oil by means different from the method described in Japanese Patent Publication No. 1-21833, and to use a conventional silicone oil. An object of the present invention is to obtain a novel silicon-based esterification product having excellent properties that cannot be obtained and a cosmetic using the same.

(D) Means for Solving the Problems The present invention relates to an esterification product of alcohol-modified silicon and carboxyl-modified silicon represented by the general formula (I), (II) or (III), and an esterification product of the esterification product. It relates to cosmetics containing one or more types.

(K is an integer of 1 to 10, n and m are 0 or an integer of 1 or more) The above-mentioned alcohol-modified silicon has an ether group at both ends of dimethylpolysiloxane, and has an aliphatic alcoholic hydroxyl group as a functional group. Diol. The above-mentioned carboxyl-modified silicon is a dicarboxylic acid having ether groups at both ends of dimethylpolysiloxane and having a carboxylic acid group as a functional group.

Each silicon having a molecular weight of 300 to 6000 is preferable in terms of physical properties.

When the two are charged in an increased molar ratio of alcohol-modified silicon, an esterification product of the general formula (I) is synthesized. If the charge ratio of the two is set to 1: 1, an esterification product of the general formula (II) is synthesized. When the molar ratio of the carboxyl-modified silicon is further increased, an esterification product of the general formula (III) is synthesized.

Each of them can be used as a single product by synthesizing them by the following synthesis methods, separating and purifying them. Also, a mixture of two or more of the above-mentioned esterification products does not hinder the disadvantages of the conventional silicone oil at all, and these can also be used.

The esterification reaction is carried out in the absence of a catalyst or in the presence of a catalyst at normal pressure or reduced pressure according to a conventional method. After the completion of the esterification, the thus-reacted crude esterified product is decolorized with a decolorizing agent and then deodorized and refined with steam according to a conventional method.

Various cosmetics are prepared by appropriately mixing ordinary components and optional components with the obtained esterification product. That is, it is prepared by a conventional method by replacing all or a part of the conventional oil agent, emollient agent, etc. with the esterification product of the present invention. Although the amount of the esterified product cannot be specified unconditionally, it is generally 0.1 to 30%.
(Weight, the same applies hereinafter). There are no particular restrictions on the type of cosmetics, and there are no particular restrictions on cosmetics for hair, cosmetics for hair washing, lotions, cream emulsions, packs, foundations, powdered white powder, lipsticks, eyebrows, cheek cosmetics, and nail cosmetics. It can be applied to bath cosmetics, cosmetic oils, facial cleansers and soaps.

(E) Examples Example 1 Preparation of Esterified Product Alcohol-modified silicon (average molecular weight about 1000, viscosity 23
400 g of cps / 25 ° C, degree of polymerization n = 10) and carboxyl-modified silicon (average molecular weight about 1000, viscosity 207 cps / 25 ° C, degree of polymerization m
= 10) 200 g was charged into one four-necked flask equipped with a stirrer, thermometer, nitrogen gas injection tube, and water separation tube. Tin chloride was used as a catalyst at 0.3% of the total charge, and xylol was used as a reflux solvent. 5% of the amount was added together and stirred well, and the mixture was reacted at 160-250 ° C. for 8 hours. After completion of the reaction, the catalyst was separated by filtration, then decolorized using activated clay, and then deodorized by blowing steam under reduced pressure to obtain a target product (Sample No. 1). Similarly, the reaction was carried out in a system in which the average molecular weight of the alcohol-modified silicon and the carboxyl-modified silicon was changed, or in a system in which the molar ratio of the alcohol-modified silicon and the carboxyl-modified silicon was changed. I got

Example 2 Properties of Esterification Product Table 2 shows the solubility in various solvents and oils.

Example 3 Stability Test of Esterified Product The primary irritation to the human body was examined by a closed patch test as follows.

That is, excluding the keratin of the epidermis of the upper arm flexion and the sebum on the epidermis, apply the sample to a linch square lint cloth, paste it on the skin surface, cover with oil paper, and fix the four sides to the girder with a paper bandage, Hold on to this with a bandage. This test was performed on 20 healthy subjects, and the results were determined 24 hours, 48 hours, and 1 week later.
No. 1 to 6) show no irritation at all, and are useful as cosmetic oils.

Further, an odor test after application was carried out as follows. That is, about 0.2 g of a sample was applied to the upper arm in a square of 2 inches, and after 10 minutes, 20 minutes, 30 minutes, 1 hour, 4 hours, and 8 hours, the odor was determined by odor. This test was performed on 20 healthy persons, and none of the esterified products (Samples Nos. 1 to 6) felt any odor.

Example 4 Formulation Example (1) Lipstick Candelilla wax 10.0% Carnauba wax 4.0〃 Celesin 4.0〃 Microcrystalline wax 4.0〃 Sample No.4 8.0〃 Liquid paraffin 10.0〃 Tri-2-ethylenehexanoate glyceryl 40.0〃 Diisostearyl malate 20.0〃 Red 202 appropriate amount Red 226 appropriate amount Yellow No. 4 aluminum lake appropriate amount Black iron oxide appropriate amount Fragrance, antioxidant appropriate amount (2) Foundation (cake type) Liquid paraffin 10.0% sorbitan sesquioleate 3.5〃 Sample No.2 2.5〃 Titanium oxide 10.0% Colloidal kaolin 28.0〃 Talc 42.2〃 Bengala 0.6〃 Yellow iron oxide 2.9〃 Black iron oxide 0.3〃 Preservative, perfume (3) Hair liquid Polyoxypropylene butyl ether (40PO) 4.0% Sample No.6 2.0〃 Acrylic Resin alkanolamine liquid 2.0 Polyalkylene glycol derivative 15. 0〃 Ethanol 60.0〃 Fragrance 0.8〃 Dye 0.2〃 Purified water 16.0〃 (4) Cream rinse 1,3-butylene glycol 3.0% Distearyl dimethyl ammonium chloride 3.0〃 Cetanol 2.0% Glycerin monostearate 2.0〃 Liquid paraffin 1.5〃 Sample No. .5 0.5〃 Preservative proper amount Perfume proper amount 100% in purified water (5) Emollient cream sample No.1 2.0% stearic acid 15.0〃 glyceryl monostearate 2.5〃 polyoxypropylene butyl ether (40PO) 4.0〃 propylene glycol 10.0〃 Preservatives Appropriate amount Antioxidant Appropriate amount Fragrance Appropriate amount In purified water 100% in total volume (6) Emollient lotion Microcrystalline wax 2.0% Sample No.3 2.0% Beeswax 2.0〃 Carnauba wax 1.0〃 Liquid paraffin 30.0〃 Sorbitan sesquioleate 4.0〃 Poly Oxyethylene sorbitan Nooleic acid ester (20EO) 1.0〃 Aluminum stearate 0.3〃 Glycerin 10.0〃 Preservative appropriate amount Antioxidant appropriate amount Perfume appropriate amount Purified water 100% in total (f) Effect of the invention The esterified product according to the present invention is pale color and odorless By changing the molecular weight and the charging ratio (molar excess) of the alcohol-modified silicon and the carboxyl-modified silicon, it is possible to freely change lubricity, viscosity, feel, compatibility, and other various physical properties. Also, when compared with silicone oil of the same viscosity even if the viscosity is increased,
It has little greasy luster, no stickiness, and retains the lubricity, water repellency, and luster inherent to silicone oil.

It is a highly stable substance that does not irritate the skin, has excellent affinity and feel to the skin, and has emulsifying, moisturizing, and emollient properties. Excellent cosmetics can be obtained.

Continuation of the front page (56) References JP-A-61-129187 (JP, A) JP-A-2-41323 (JP, A) JP-A-63-150288 (JP, A) JP-A-2-101083 (JP, A) (A) JP-A-3-227993 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/08 A61K 7/00 C08G 63/695 C08G 77/38 CA (STN) WPIDS (STN)

Claims (2)

(57) [Claims] 1. An esterified product of alcohol-modified silicon and carboxyl-modified silicon represented by the general formula (I), (II) or (III). (K is an integer of 1 to 10, n and m are 0 or an integer of 1 or more) 2. A cosmetic comprising one or more of the esterification products according to claim 1.