JPH0121833B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Industrial Application Field The present invention relates to a novel esterification product of a dimethylpolysiloxane-modified diol and a dibasic acid, and a cosmetic containing the same. (b) Conventional technology Silicone oil has excellent durability, weather resistance, water repellency, rust prevention/corrosion prevention, and lubricity, and is used as a wax additive, surfactant for car washes, water repellent for mortar, etc., and rust prevention. It is used in a wide range of applications, including additives, cosmetic additives, paintable mold release agents, and defoaming of engine oil. Normally, silicone oil is commonly dimethylpolysiloxane, but other silicone oils include methylphenylpolysiloxane, methylhydrodienepolysiloxane,
Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dimethylpolysiloxane polyethylene glycol copolymer, dimethylpolysiloxane polypropylene glycol copolymer, etc. are commercially available, but in recent years they have been used as silane coupling agents with two or more different molecules in the molecule. Organosilicon monomers having reactive groups and derivatives thereof, as well as various modified silicone oils such as amino-modified, polyether-modified, olefin-modified, epoxy-modified, fluorine-modified, alcohol-modified and fatty acid-modified silicone oils are commercially available. These silicone oils are often used as oils for cosmetics, but their main purpose is to use them as foundations, etc., which are lightweight, give a refreshing feel, and have water repellent properties that prevent makeup from coming off easily. It's about getting. However, when used as a cosmetic oil, it is required to have the characteristics of silicone oil, have high viscosity and be non-sticky, and have excellent compatibility with other ingredients. However, conventionally, to increase the viscosity of silicone oil, it was common to increase the molecular weight, but these highly viscous silicone oils have very poor compatibility with oils and solvents, and are difficult to use in emulsion systems. When used, it was difficult to emulsify, and although it had very high water repellency, it was very sticky and had an oily sheen, showing physical properties that were undesirable depending on the purpose of use. (c) Problems to be Solved by the Invention The object of the present invention is to eliminate the above-mentioned drawbacks of silicone oil and to provide a new silicone-based esterified product that has excellent properties that cannot be obtained with conventional silicone oils. The purpose is to obtain used cosmetics. (d) Means for solving the problems The present invention is directed to a compound having a molecular weight of 300 and expressed by the general formula ().
The present invention relates to an esterification product of a dimethylpolysiloxane-modified diol having a molecular weight of 2,000 or less and a dibasic acid, and a cosmetic containing the same. R is - (CH ₂ ) _l - or

[Formula] (k is an integer of 1 to 10 l is 0 or an integer of 1 to 18 m and n are integers of 0 or 1 or more) Dibasic acids include saturated, unsaturated, hydroxy,
Any dibasic acid such as aromatic acid can be used, but considering the compatibility with oils, solvents, oxidation stability, safety, etc., oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid, Aliphatic saturated dibasic acids having 20 or less carbon atoms, such as suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, eicosadicarboxylic acid, and hydroxy dibasic acids. Malic acid and tartaric acid are preferred. The dimethylpolysiloxane-modified diol and dibasic acid shown above may be used singly or in combination.
Can be used in combination of more than one species. The esterification reaction is carried out without a catalyst or in the presence of a catalyst under normal pressure or reduced pressure according to a conventional method. Since a product with a low acid value is usually preferred, the dimethylpolysiloxane-modified diol is reacted in molar excess, and the esterification is carried out until there is almost no decrease in the acid value.After the esterification is completed, decolorization with a decolorizing agent is performed according to a conventional method. Deodorizing and purifying using water vapor. Various cosmetics are prepared by appropriately blending commonly used ingredients and optionally produced ingredients with the obtained esterified product. That is, it is prepared by a conventional method by replacing all or part of conventional oil agents, emollients, etc. with the esterified product of the present invention. The proportion of the esterified product cannot be absolutely specified, but it is generally 0.1 to 30% by weight. There are no particular restrictions on the type of cosmetics, including creams such as cold cream and vanishing cream, emulsion, lotion, face pack, shampoo, conditioner, hair treatment, hair liquid, pomade, lipstick, blusher, powder cake, eye shadow, etc. It can be applied to Example 1 Preparation of esterification product A dimethylpolysiloxane modified diol having the structural formula of Table 1 (average molecular weight approximately 700, viscosity
40CPS/25℃, degree of polymerization n = approx. 5) 400g and 80g of succinic anhydride in a stirrer, thermometer, nitrogen gas blowing tube,
Into a four-necked flask equipped with a water separator, 0.3% of the total amount of tin chloride was added as a catalyst, and 5% of Shiquirol (based on the total amount of the amount) was added as a refluxing solvent, stirred well, and the mixture was heated to 160 The reaction was carried out at ~250°C for 8 hours. After the reaction is complete, the catalyst is filtered off, decolorized using activated clay, and deodorized by blowing steam under reduced pressure to produce the desired product (sample no.
1) was obtained. In the same way, the average molecular weight of each is approximately 1500.
The esterification products shown in Table 1 were obtained using dimethylpolysiloxane-modified diols having a degree of polymerization (n=about 17), about 300 (n=about 4), and 2000 (n=about 25).

[Table] Example 2 Properties of esterified product Table 2 shows the solubility in various solvents and oils.

[Table] Example 3 Stability test of esterified product The primary irritation to the human body was examined by an occlusion patch test as follows. That is, remove the dead skin and sebum on the epidermis of the anterior or flexor side of the upper arm, apply the sample to a 1-inch square lint cloth, apply this to the skin surface, cover with oiled paper, and cover all sides with a paper bandage. Then, secure the top with a bandage. This test was conducted on 20 healthy people, and judgments were made after 24 hours, 48 hours, and one week, and the results showed that the esterification products (sample Nos. 1 to 8) were not irritating at all. It is useful as a cosmetic oil. Further, an odor test after application was conducted as follows.
That is, approximately 0.2 g of the sample was applied to a 2-inch square area on the anterior apex, and after 10 minutes, 20 minutes, 30 minutes, 1 hour, 4
The odor was determined by the sense of smell after 8 hours and after 8 hours. This test was conducted on 20 healthy people, and no odor was detected in any of the esterified products (Samples No. 1 to 8). Example 4 Formulation example (1) Emollient cream Stearic acid 14.0% (Weight. The same applies below) Sample No. 1 2.0〃 Glycerin monostearate 2.5〃 Polyoxyethylene sorbitan monostearate (20E・O) 1.5〃 Propylene glycol 10.0 〃 Preservatives, antioxidants, fragrances 100% total amount with appropriate amount of purified water (2) Emollient lotion microcrystalline wax 1.0% Sample No. 3 2.0〃 Beeswax 2.0〃 Liquid paraffin 30.0〃 Sorbitan sesquioleate 4.0〃 Poly Oxyethylene sorbitan monooleate (20E・O) 1.0〃 Aluminum stearate 0.2〃 Glycerin 8.0〃 Preservative, antioxidant, fragrance 100% with appropriate amount of purified water (3) Foundation (oil-based ointment type) Liquid Paraffin 24.0% Isopropyl palmitate 15.0 Lanolin alcohol 2.0 Sample No. 5 5.0 Microcrystalline wax 5.0 Candelilla wax 1.0 Ozokerite 8.0 Titanium oxide 15.0 Kaolin 15.0 Talc 6.0 Colored face 4.0〃 Preservatives, antioxidants , fragrance appropriate amount (4) Foundation (cake type) Liquid paraffin 10.0% Sorbitan sesquioleate 3.5〃 Sample No. 2 3.0〃 Titanium oxide 10.0〃 Colloidal kaolin 25.0〃 Talc 45.1〃 Red iron oxide 0.8〃 Yellow iron oxide 2.5〃 Black oxide鉄 0.1〃 防腐剤、香料 適量(5) 口紅キヤンデリラロウ 10.0％ カルナウバロウ 4.0〃 セレシン 3.0〃 マイクロクリスタリンワツクス 3.0〃 試料No.８ 10.0〃 流動パラフイン 10.0〃 トリ―２エチレンヘキサン酸グリセリン 40.0〃 リンゴ酸ジイソStearyl 20.0〃 Red No. 202 Appropriate amount Red No. 226 Appropriate amount Yellow No. 4 Aluminum Lake Appropriate amount Black iron oxide Appropriate amount Fragrance, antioxidant Appropriate amount (6) Hair liquid polyoxypropylene butyl ether (40P・
O) 4.0% Polyalkylene glycol derivative 13.0〃 Acrylic resin alkanolamine liquid 1.0〃 Sample No. 1 2.0〃 Ethanol 64.0〃 Fragrance, pigment 1.0〃 Purified water 15.0〃 (7) Cream rinse 1.3 Butylene glycol 3.0% Distearyl dimethyl ammonium chloride 3.0〃 Setanol 1.5〃 Self-emulsifying glyceryl monostearate 2.0〃 Squalane 1.0〃 Sample No. 5 0.2〃 Preservatives, fragrances Appropriate amount of purified water Total amount 100% Example 5 Evaluation of cosmetics Which of the various cosmetics shown in the formulation examples It was found to be excellent as a cosmetic as it had a good texture, no sticky feeling, had good emulsifying properties, and did not easily cause makeup to come off. The sensual superiority of the foundation and lipstick shown in formulation examples (3) and (5), commercial product A (creamy foundation), and commercial product B (lipstick) was obtained by having 30 women use the product continuously for two weeks. The results (recovery rate 90%) are shown in Table 3.

[Table] From Table 3, it can be seen that the foundation and lipstick according to the present invention had excellent sensory evaluations. (e) Effect of the invention The esterification product according to the invention is light-colored and odorless, and the type, charge amount (molar excess), and degree of esterification (degree of polymerization) of the dimethylpolysiloxane-modified diol and dibasic acid can be changed. This makes it possible to freely change lubricity, viscosity, feel, compatibility, and other various physical properties. In addition, even when the viscosity is increased, there is very little sticky feeling, and when compared with silicone oil of the same viscosity, there is less oily shine.
It is non-sticky and retains the smoothness, water repellency, gloss, etc. characteristic of silicone oil. It is a highly stable substance that does not irritate the skin, has excellent affinity and texture to the skin, and has emulsifying, moisturizing, and emollient properties. A variety of excellent cosmetics can be obtained.

Claims (1)

[Claims] 1. Molecular weight of 300 or more, represented by the general formula ()
Esterification product of dimethylpolysiloxane-modified diol of 2000 or less and dibasic acid. R is -(CH ₂ ) _l - or [Formula] (k is an integer of 1 to 10, l is 0 or an integer of 1 to 18, m and n are integers of 0 or 1 or more) 2 represented by the general formula (), Molecular weight 300 or more
A cosmetic made by blending a dimethylpolysiloxane-modified diol with a molecular weight of 2000 or less and an esterification product with a dibasic acid. R is -(CH ₂ ) _l - or [Formula] (k is an integer from 1 to 10 l is 0 or an integer from 1 to 18 m and n are integers of 0 or 1 or more)