JP3046341B2 - Esterification products and cosmetics containing them - Google Patents

Description

The present invention relates to an oligomer product of alcohol-modified silicon and a dibasic acid, an esterification product of alcohol, and a cosmetic prepared by blending the product.

(B) Conventional technology Silicon oil is excellent in viscosity stability, thermal oxidation stability, lubricity, water repellency, gloss, rust and corrosion resistance, etc., anti-vibration oil for instruments, machinery lubricating oil, glass It is widely applied to water repellents for containers, wax additives, defoamers, cosmetic additives and the like.

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, as a silane coupling agent, organosilicon monomers having two or more different reactive groups in a molecule and derivatives thereof, further, 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, and these are Shin-Etsu Chemical Co., Ltd., Chisso Corporation,
Commercially available from Toray Silicone Co., Ltd.

Such silicone oils are often used as cosmetic oils, but their main purpose is to provide foundation with good water repellency, non-adhesiveness, lubricity, etc., so that makeup is not easily dislodged, and lipstick with good spread. Is 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 a very high water repellency but has a sticky and greasy luster, and exhibits undesirable 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 an alcohol with a dicarboxylic acid represented by the general formula (I) or (II) obtained by oligomerizing alcohol-modified silicon with a dibasic acid, and The present invention relates to a cosmetic containing an esterification product.

R ₁ and R ₂ are residues of an alcohol, and R ₁ R ₂ or R ₁ ≠
R _2.

R ₃ is — (CH ₂ ) _m — or Or (K is an integer of 1 to 10, n is an integer of 0 or 1 or more, and m is an integer of 1 to 18.) The above-mentioned alcohol-modified silicon is a dimethylpolysiloxane having an ether group at both terminals and a fatty acid alcohol. It is a diol having a hydroxyl group as a functional group. By reacting 2 moles of dibasic acid with 1 mole of this alcohol-modified silicon, an oligomer of alcohol-modified silicon and dibasic acid is generated. Here, as the dibasic acid, any dibasic acid such as saturated, unsaturated, hydroxy, and aromatic can be used.However, oils, compatibility with solvents, oxidative stability, safety, etc., oxalic acid, Malonic acid, succinic acid,
Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandionic acid, tridecandionic acid, tetradecandionic acid, pentadecandionic acid, hexadecandionic acid, carbon such as eicosandioic acid Preferred are aliphatic saturated dibasic acids having a number of 20 or less, and malic acid and tartaric acid, which are hydroxy dibasic acids.

When the charge ratio of the alcohol is 2 mol or more with respect to 1 mol of the oligomerized dicarboxylic acid, the esterification product of the general formula (I) is synthesized. At this time, two or more alcohols may be mixed. If the charging ratio of the two is set to 1: 1, an esterification product represented by the general formula (II) is synthesized. Here, as the alcohol, an alcohol such as a saturated or unsaturated, linear or branched type, aromatic or sterol type is used. Think, heptanol, octanol,
Nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, isoheptanol, isooctanol, isononanol, isodecanol, isoundound Nol, isododecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isoheptadecanol, isooctadecanol, isononadecanol, isoeicosanol, isodocosanol, etc. Cholesterol, phytosterol and the like are preferable as the alcohol having 2 to 22 carbon atoms or having a sterol skeleton.

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. First, an esterification reaction between alcohol-modified silicon and a dibasic acid, that is, an oligomerization proceeds. Here, when the oxidation is no longer reduced, the reaction is temporarily stopped, an alcohol corresponding to the acid value at that time is newly added, and the esterification reaction is advanced again. At this time, the molar ratio of the alcohol added is appropriately adjusted. Further, when synthesizing an esterified product having a low degree of oligomerization (K) of the alcohol-modified silicon and the dichloride acid, the alcohol-modified silicon and the above alcohol can be charged and reacted simultaneously with the dibasic acid. However, at this time, the degree of oligomerization (K) of the alcohol-modified silicon and the dibasic acid is usually 3 or less. 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. The composition of the esterification product cannot be specified unconditionally, but is generally 0.1 to 30% by weight.
It is. There are no particular restrictions on the types of cosmetics, and cosmetics for hair, cosmetics for hair washing, lotions, cream emulsions, packs, foundations, powdered white powder, lipsticks, eyebrows, cheek cosmetics, nail cosmetics, Bath cosmetics, cosmetic oils,
It can be applied to facial cleansers and soaps.

(E) Examples Example 1 Preparation of Esterified Product Alcohol-modified silicon (average molecular weight about 1000, viscosity 23
cps / 25 ° C, degree of polymerization n = 10) 310 g and adipic acid 100 g were charged into a four-necked flask equipped with a stirrer, thermometer, nitrogen gas injection tube, and water separation tube, and all tin chloride was charged as a catalyst. 0.3% of the total amount, 5% of the total amount of xylol as refluxing solvent were added together, stirred well, and the mixture was heated to 160-250 ° C.
For 6 hours. After the reaction, measure the acid value (AV =
92) 190 g of stearyl alcohol was added in an amount corresponding to this value. Here, the temperature of the system was returned to 160 to 250 ° C., and the mixture was further reacted with good stirring for 10 hours. After the completion of the reaction, the catalyst was filtered off, and then decolorized using activated clay.
Deodorization was performed by blowing steam under reduced pressure to obtain the desired product (Sample No. 1). In the same manner, the reaction was carried out in a system in which the composition of the dibasic acid and the alcohol was changed, or in a system in which the degree of oligomerization of the alcohol-modified silicon and the dibasic acid was changed, to obtain the esterified product shown in Table 1. Obtained.

Example 3 Stability Test of Esterified Product The primary irritancy to the human body was examined by an occlusive patch test as follows.

That is, remove the keratin of the upper arm flexion side skin and 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. All of the esterification products (Sample Nos. 1 to 6) were completely irritating. Not recognized, useful as cosmetic oil.

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, odor was determined by smell. This test was carried out on 20 healthy persons, and the esterification product (Sample No. 1 ~
No odor was felt in any of 6).

Example 4 Formulation Examples (1) Lipstick Candelilla wax 8.0% Carnauba wax 5.0〃 Celesin 5.0〃 Microcrystalline wax 5.0〃 Sample No.1 7.0〃 Liquid paraffin 10.0〃 Tri-2-ethylhexanoate glyceryl 40.0〃 Diisostearyl malate 20.0〃 Red 202 appropriate amount Red 226 appropriate amount Yellow 4 aluminum lake appropriate amount Black iron oxide appropriate amount Flavor, antioxidant appropriate amount (2) Foundation (cake type) Liquid paraffin 8.0% sorbitan sesquioleate 3.0〃 Sample No.2 6.02 Titanium oxide 10.0% Colloidal kaolin 27.0〃 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.4 1.0〃 Acrylic Resin alkanolamine liquid 2.0〃 Polyalkylene glycol derivative 13.0〃 Ethanol 62.0〃 Fragrance 0.8〃 Dye 0.2〃 Purified water 17.0〃 (4) Cream rinse 1,3-butylene glycol 3.0% Distearyl dimethyl ammonium chloride 3.0〃 Cetanol 2.0% Glyceryl monostearate 2.0〃 Liquid paraffin 0.8〃 Sample No.5 1.2〃 Preservatives Appropriate amount Perfume Appropriate amount 100% in purified water (5) Emollient cream Sample No.3 3.0% Stearic acid 15.0〃 Glyceryl monostearate 1.5〃 Polyoxypropylene butyl ether (40PO) 5.0〃 Propylene glycol 10.0〃 Preservative Appropriate amount Antioxidant Appropriate amount Perfume Appropriate amount In purified water 100% in total (6) Emollient lotion ceresin 1.0% Sample No.6 1.5% Beeswax 2.0〃 Carnauba wax 2.0〃 Liquid paraffin 30.0〃 Sorbitan sesquioleate 4.0〃 Polyoxyethylene sorbitan mono Oleic acid ester 20 EO) esterification product of the effect the present invention the total amount 100% (f) invention in 2.0〃 aluminum stearate 0.3〃 glycerin 10.0〃 Preservative qs antioxidant qs Perfume qs Purified water light color, odorless,
Lubricating by changing the composition and degree of oligomerization of a dibasic acid that forms an oligomer with alcohol-modified silicon, or by adjusting the composition and charge ratio of a fatty acid that reacts with the oligomer of alcohol-modified silicon and an oligomer of dibasic acid It is possible to freely change properties, viscosity, feel, compatibility with various oils and solvents including wax, and other various physical properties. Also, when compared with silicone oil of the same viscosity, there is less stickiness even when the viscosity is increased, there is less greasy luster, there is no stickiness, and the lubricity, water repellency, gloss, etc. peculiar to silicone oil are retained as it is I have.

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

Claims (2)

(57) [Claims] 1. An esterified product of an alcohol and a dicarboxylic acid represented by the general formula (I) or (II) obtained by oligomerizing alcohol-modified silicon with a dibasic acid. R ₁ and R ₂ are residues of an alcohol, and R ₁ R ₂ or R ₁ ≠
R _2. R ₃ is — (CH ₂ ) _m — or Or (K is an integer of 1 to 10, n is an integer of 0 or 1 or more, m is an integer of 1 to 18) 2. A cosmetic comprising one or more of the esterification products according to claim 1.