JPS6033821B2 - Esterification products and cosmetics containing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel waxy esterification products and cosmetic compositions containing them.

Hitherto, various waxes have been used as oily bases for hair or skin oils.

In addition to high-melting-point products such as carnauba wax and candelilla wax, there are relatively low-melting-point products such as beeswax and lanolin, which are derived from animals and plants. In addition to being flexible and flexible, it also has physical properties such as excellent water-holding and emulsifying properties, and also has properties required as a base for Japanese materials, such as affinity for the skin and non-irritation. are doing. However, since it is a natural product, the price fluctuates widely.
Furthermore, there are problems with quality stability such as uniformity of composition, color, and odor, and the condition is not always satisfactory. In addition, petroleum jelly, which is a petroleum-based hydrocarbon, compensates for the instability of Tosonzo because it is a natural product and has water-retaining properties, but it has poor viscosity, poor skin feel, and poor breathability. Therefore, it cannot be said that it satisfies various properties as a base for cosmetics.

The present inventors have discovered that a certain esterification reaction product has excellent viscosity, water-holding properties, and self-emulsifying properties, has good compatibility with perfume ingredients, and has a greasy feel on the skin. The present invention has been achieved based on the discovery that a wax-like material can be obtained which retains flexibility without imparting any properties of wax, and which satisfies quality stability.

One of the present inventions is based on the following general formula (HO)nR-○-R(OH)n (wherein R is a residue obtained by removing the hydroxyl group from a polyhydric alcohol having 2 to 4 hydroxyl groups, and n is A condensate of a polyhydric alcohol having 2 to 4 hydroxyl groups, each of which is 1, 2 or 3, and 50 mol% or more of 12-hydroxystearic acid and a linear chain with a balance of 14 carbon atoms. It relates to an esterification reaction product with a fatty acid mixture consisting of higher fatty acids, which has a number of hydroxyl groups in one molecule of the product that is less than half of the total hydroxyl groups in the polyhydric alcohol condensate.

Another aspect of the present invention relates to cosmetics containing one or more of the above esterification reaction products.

Polyhydric alcohol represented by the above general formula (2 to 4 hydroxyl groups)
Examples of the condensation products of dipropylene glycol (having a dimethyl chloride) include dipropylene glycol, diglycerin, diventaerythritol, ditrimethylolpropane, and the like.

These are known compounds and can be produced by conventionally known methods. C, linear higher fatty acids of 4 or more have the general formula R, COO
(R is an alkyl group having 13 or more carbon atoms), and examples include myristic acid, palmitic acid, stearic acid, and behenic acid.

The wax-like substance according to the present invention is a colorless semi-transparent to white semi-solid wax, more specifically a paste-like or cream-like substance, including the type of raw fatty acid, the number of ester bonds, and the number of residual hydroxyl groups in the esterified product. One of the features of the present invention is that various properties such as melting point, viscosity, and water-holding ability can be adjusted by changing the .

In particular, in the present invention, it is necessary that one molecule of the esterification product has a number of free hydroxyl groups equal to or less than half of the total number of hydroxyl groups in the starting polyhydric alcohol condensate. If more than half of the total hydroxyl groups of the starting polyhydric alcohol condensate remain in the molecules of the esterification product, the melting point, viscosity, water-holding property, etc. will be significantly inferior, and the object of the present invention will be impaired. A wax-like substance with the properties described above cannot be obtained. In the present invention, the number of residual hydroxyl groups of the starting polyhydric alcohol condensate in the esterification reaction product is 0.
Particularly preferred.

For example, in the ester reaction of a starting polyhydric alcohol condensate and 12-hydroxystearic acid (hereinafter simply referred to as 12-OHSt), when more than half of the free OH of the starting polyhydric alcohol condensate remains, the product The physical properties of are shown in the table below. Table 1 As is clear from comparing the results in Table 1 with Table 2 described below, products with more than half of the OH remaining in the starting polyhydric alcohol condensate have poor melting point, viscosity, water retention, etc. The desired properties cannot be obtained.

In the present invention, if the content of straight mirror higher fatty acids in the fatty acid mixture exceeds 50 mol %, the water-retentivity and viscosity of the esterified product will be significantly inferior.

The esterification reaction is carried out using conventional methods, with or without the use of a catalyst. The amount of reaction between the polyhydric alcohol condensate and the fatty acid mixture is determined so that the number of OHs remaining in one molecule of the product is less than half of the total number of OHs in the starting polyhydric alcohol condensate. That is, according to calculations, for example, the reaction amount of the fatty acid mixture is in the range of 0.5 to 2 moles per mole of dipropylene glycol. Similarly, diglycerin 1
The reaction amounts of the fatty acid mixture are 1 to 4 mol, 1 to 4 mol, and 1.5 to 6 mol per mol of ditrimethylolpropane and 1 mol of dibentaerythritol, respectively. After completion of the esterification reaction, the reaction mixture is subjected to alkaline deoxidation, decolorization with a decolorizing agent, and deodorization and purification by steam distillation according to conventional methods, if necessary.

The resulting products are light-colored, odorless, semisolid, and waxy. Table 2 shows the physical properties of the esterified products of the present invention, as compared to petrolatum, bleached castor oil, lanolin, and
It is also shown together with the esterification reaction product using a side chain higher fatty acid described in JP-A No. 52-48613.

Table 2 Note: Numbers in brackets indicate calculated values.

Sample modification 1, modification 2, and modification 3 are the same as Example 1 described later.
, 2 and 3, and the products of other sample pigs were synthesized according to Examples.

*1: Ox2 measured in accordance with the method of JIS K2560 using a cone (made of synthetic resin) specified in JIS K2809 (grease and grease. Latam consistency tester): Distilled on sample 10 days. The mixture was thoroughly stirred while adding water, and then immersed in an excess amount of distilled water and left for 3 days. The excess distilled water was then dried and the weight increase was expressed (2
5℃).

From the above results, the waxy esterified product of the present invention exhibits a melting point comparable to that of human sebum, has an appropriate degree of steel, has high water-holding power with self-emulsifying properties, and is excellent as a wax for cosmetics. It is recognized that it possesses physical properties. Next, Table 3 shows the solubility in these various oils or solvents.

Solubility is measured by mixing equal amounts of sample and oil or solvent at 70%
After melting the base at ~85°C, it was left to cool indoors and examined at 25°C. The samples listed in Table 2 were used. From the above results in Table 3, it is recognized that the waxy substance according to the present invention has excellent compatibility with various oils or solvents for scented products compared to petrolatum, lanolin, etc.

Next, sample M in Table 2. For samples 1 to 4, 5 parts by weight of olive oil was added to 5 parts by weight of sample 5 to prepare a creamy substance, and the feel of this cream when applied to the hands was tested.

This test was conducted using a panel of 50 people to compare the feel of an ointment made of 5 parts by weight of petrolatum and olive oil applied to their hands. 4th table: Units are shown by number of members.

From the above results, it is clear that the wax-like substance according to the present invention has significantly better texture than petrolatum.

In addition, primary irritation to the human body was investigated using an occlusion patch test as follows.

That is, remove the dead skin and sebum on the epidermis of the front corner 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 remove the sample using a paper tube. Fasten the four sides to the cross-legs, and press the top with a woven belt. This test was conducted on 20 healthy people, and judgments were made after 2 hours, 4 hours, and 1 week. ) were found to be useful as bases for iqhoko materials, with no irritation observed at all. The amount of the esterified product of the present invention incorporated into cosmetics and ointments is generally 20-7% by weight of blood.

Example 1 (Synthesis example of sample M.1 in Table 2) 2 equipped with a rope companion, a thermometer, a nitrogen gas blowing pipe, and a water separator with a reflux condenser.
12-hydroxystearic acid (
(purity 90% or more) 3 mol, stearic acid 3 mol, dibentaerythritol 1 mol, xylol (5% based on the total amount charged) and para-toluenesulfonic acid (0.3% based on the total amount charged) was added, and the reaction was carried out at 180 to 260°C until a calculated amount of by-product water accumulated in the porcelain.

After the reaction was completed, the reaction mixture was deoxidized and decolorized (using activated clay and activated carbon decolorizers) and deodorized by blowing steam under reduced pressure to obtain a white, odorless esterified product. Acid value 0. The hydroxyl value entered was 84, the saponification value was 178, and the yield was 84%. Example 2 (Synthesis example of sample M.1 in Table 2). In the same manner as in Example 1, 4.5 mol of 12-hydroxystearic acid, 1.5 mol of stearic acid, 1 mol of dibentaerythritol, xylol and stannous chloride were used to react, and the mixture was purified and esterified. A reaction product was obtained.

Acid value 0.2, hydroxyl value 122, saponite value 165, yield 82%
Met. Example 3 (Synthesis example of sample M.3 in Table 2) In the same manner as in Example 1, 5 mol of 12-hydroxystearic acid, 1 mol of stearic acid, 1 mol of dibentaerythritol
mol, xylol and stannous chloride,
The esterification reaction product was obtained by purification.

Acid value 0.1, hydroxyl value 130, potassium value 161, yield 75
%Met. Example 4 (Lipstick) Candelilla wax, beeswax, ceresin, and the esterification reaction product of Example 2 were added to isostearic acid and liquid paraffin, and then 15 parts of isostearic acid and a pigment well dispersed in silicone oil were added. Add 80~
After heating to 85°C and adding fragrance, pour into a mold, cool to 10°C, and remove from the mold.

Example 5 (hair cream) Oil and fat raw materials, emulsifiers, and preservatives were heated and dissolved to a temperature of 80 to 8,500, and a propylene glycol/distilled water mixture heated to the same temperature was gradually added to the solution while stirring. Cool to 6 psi, add flavorings, cool further to 3 psi, and then pack into containers.

Example 6 (Hydrophilic cartilage) Oil and fat raw materials were heated and dissolved to 70 to 8 psi, and an aqueous solution was gradually added to sodium lauryl sulfate heated to the same temperature while stirring, and the mixture was cooled until the concentration reached 30 q. to obtain an emulsion ointment.

Claims (1)

[Claims] 1 The following general formula (HO)_nR-O-R(OH)_n (wherein R is a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 2 to 4 hydroxyl groups, and n is 1, 2 or 3), a condensate of polyhydric alcohol having 2 to 4 hydroxyl groups, 50 mol% or more of 12-hydroxystearic acid, and a straight chain higher carbon number of 14 or more An esterification reaction product with a fatty acid mixture consisting of fatty acids, the esterification reaction product having a number of hydroxyl groups in one molecule of the product that is less than half of the total hydroxyl groups in the polyhydric alcohol condensate. 2. The esterification reaction product according to claim 1, wherein the number of residual hydroxyl groups of the starting polyhydric alcohol condensate in the esterification reaction product is zero. 3 The following general formula (HO)_nR-O-R(OH)_n (In the formula, R is a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 2 to 4 hydroxyl groups, and n is 1, 2, or 3), a condensate of a polyhydric alcohol having 2 to 4 hydroxyl groups, and a fatty acid mixture consisting of 50 mol% or more of 12-hydroxystearic acid and a linear higher fatty acid having a balance of 14 or more carbon atoms. is an esterification reaction product containing one or more esterification reaction products having a number of hydroxyl groups in one molecule of the product that is not more than half of the total hydroxyl groups of the polyhydric alcohol condensate. Cosmetics.