JPS6317042B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to cosmetics, and more particularly to cosmetics containing at least one ester compound of a 2-substituted-1-alcohol and a saturated or unsaturated linear fatty acid or a saturated or unsaturated linear dibasic acid. Regarding cosmetics. In general, the properties required for cosmetic raw materials include (1) minimal skin irritation, (2) no coloration or odor, (3) no change over time, and (4) excellent texture or feeling of use. Examples include being present. Conventionally, waxes such as beeswax, carnauba wax, candelilla wax, and montan wax have been generally used as raw materials for cosmetics as they meet these requirements. The present inventors have completed the present invention as a result of intensive research to develop cosmetic raw materials with even more excellent properties in place of these waxes. The present invention is based on the following formula (However, R ₁ and R ₂ are the same or different and represent a saturated or unsaturated alkyl group having 12 to 24 carbon atoms.) The present invention relates to a cosmetic containing at least one ester compound of a saturated linear fatty acid or a saturated or unsaturated linear dibasic acid having 4 to 18 carbon atoms. The 2-substituted-1-alcohol of formula (1) above, which is the raw material for the ester compound used in the present invention, is
Formula R ₁ CH ₂ CH ₂ OH or R ₂ CH ₂ CH ₂ OH (R ₁ and
R ₂ is the same as above) One or a mixture of two or more primary alcohols are converted into 2 by Guerbet reaction.
It is obtained by molecular condensation (the alcohol of formula (1) thus obtained is hereinafter referred to as garbet alcohol in the present invention). A major feature of such garbage alcohol is that it has a lower melting point than a saturated linear primary alcohol having the same number of carbon atoms. The ester compound according to the present invention is synthesized by a known method using the above-mentioned garbage alcohol and a saturated or unsaturated linear fatty acid or a saturated or unsaturated linear dibasic acid. Such ester compounds have a lower melting point than conventional waxes,
It gives a smooth feel to cosmetics containing it, and in particular, in terms of feel or feeling of use, it has excellent spreadability, is thick and non-sticky and has a light feel, and is moisturized and free of roughness. Excellent characteristics are demonstrated. Furthermore, the most distinctive feature of this ester compound was that it has extremely hardness despite its low melting point, and there are almost no other compounds that have such properties.
It can be used as a cosmetic raw material with much superior properties compared to conventional waxes. The garbet alcohol used as a raw material for the synthesis of the ester compound of the present invention is as shown in formula (1).
R ₁ and R ₂ have an alkyl group having 12 to 24 carbon atoms, and if an alkyl group with less than 12 carbon atoms is used, the melting point of the resulting ester compound will be too low, and cosmetics containing this It gives the material a sticky feel, and if an ester compound with more than 24 carbon atoms is used, the melting point of the ester compound becomes high, resulting in poor spreadability and making it impossible to give a moist feel. Representative examples of garbet alcohols used as raw materials for the synthesis of ester compounds according to the present invention are listed in Table 1 below.

【table】

【table】

[Table] In the above table, monoene means one having one double bond, and diene means one having two double bonds. Carboxylic acids, which are other raw materials for the synthesis of the ester compound, include saturated or unsaturated straight chain fatty acids having 8 to 22 carbon atoms (herein, straight chain fatty acids refer to straight chain fatty acids that are unsubstituted or have a hydroxyl substituent). ) and saturated or unsaturated linear dibasic acids having 4 to 20 carbon atoms. Typical examples of the former saturated or unsaturated linear fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, and hydroxystearic acid; Typical examples of dibasic acids include succinic acid, maleic acid, adipic acid, sebacic acid,
Examples include 1,10-decamethylene dicarboxylic acid, 1,14-dodecamethylene dicarboxylic acid, and 1,18-octadecamethylene dicarboxylic acid. In esterification, these dibasic acids are used in the form of an acid or, if necessary, in the form of an anhydride. When the dicarboxylic acids are used, diesters are obtained. The present invention will be explained in more detail below with reference to examples of synthesis of ester compounds.The method of synthesizing the ester compound follows a conventionally known method. Synthesis Example 1 In the formula (1) listed in the representative example above, R ₁ = R ₂ = C ₁₂
100 g of garbet alcohol (hereinafter referred to as garbet alcohol) having an alkyl group of 69 g of stearic acid and 0.3 g of para-toluenesulfonic acid
g is added thereto, and the esterification reaction is carried out at 100 to 120°C under reduced pressure for 3 hours. After the reaction, the resulting soap was neutralized with sodium hydroxide, washed with water, and decolorized with activated clay and activated carbon to obtain a white waxy solid (referred to as ester compound No. 1). Yield is 98%. Synthesis Example 2 0.3 g of p-toluenesulfonic acid was added to 100 g of a mixture of the four types of garbet alcohols listed in the representative example () [hereinafter referred to as garbet alcohol ()] and 57 g of behenic acid, and the mixture was heated at 130 to 140°C under reduced pressure. The esterification reaction is carried out for the next 2 hours. Thereafter, the same operation as in Synthesis Example 1 was performed to obtain a white waxy solid (ester compound No. 2). Yield is 96%. Synthesis Example 3 0.2 g of sulfuric acid is added to 100 g of garbet alcohol () and 8.4 g of succinic anhydride, and an esterification reaction is carried out under reduced pressure at 90 to 100°C for 3 hours. Thereafter, the same operation as in Synthesis Example 1 was performed to obtain a self-colored waxy solid (ester compound No. 3). Yield is 94%. Synthesis Example 4 100 g of garbet alcohol () and 38 g of myristic acid are subjected to an esterification reaction at 150 to 200°C under reduced pressure. Thereafter, the same operation as in Synthesis Example 1 was performed to obtain a white waxy solid (ester compound No. 4).
Yield is 98%. Synthesis Examples 5 to 8 A white wax-like solid or paste-like product was obtained in the same manner as in Synthesis Example 4, except that the fatty acids or dibasic acids shown in Table 2 were used instead of myristic acid. .

[Table] * Synthesis example of light yellow paste-like substance 9 Using 100 g of garbet alcohol (V) and 51 g of palmitic acid, perform an esterification reaction under reduced pressure at 150 to 200°C. Hereinafter, the same operation as in Synthesis Example 1 was performed, and a white solid wax (ester compound No. 9) was obtained.
I got it. Yield is 96%. Synthesis example 10 Garbett alcohol () 100g and 37g of 1,
0.3 g of para-toluenesulfonic acid is added to 14-tetradecamethylene dicarboxylic acid, and an esterification reaction is carried out at 140 to 170°C under reduced pressure for 3 hours. Thereafter, the same operation as in Synthesis Example 1 was performed to obtain a white solid wax (ester compound No. 10). Yield is 97%. Table 3 shows the analysis results of each ester compound obtained in Synthesis Examples 1 to 10 above.

[Table] * Shows hue when melted Solubility tests of the above ester compound and Garbett alcohol () in various existing cosmetic raw materials were conducted according to the test method below, and the results are shown in Table 4.

【table】

[Table] (Solubility test method) 1 part of various ester compounds or garbet alcohol () and 4 parts of various existing cosmetic raw materials were heated and combined, left at room temperature for 12 hours, and then heated for another 24 hours. The condition after being left at ℃ was judged visually according to the following criteria. Binding Criteria A: Solidify at 0°C and create a homogeneous solution at room temperature. B: Becomes a translucent paste at 0°C and forms a homogeneous solution at room temperature. C: Dissolves transparently when heated, but becomes precipitated or opaque at room temperature. D: Dissolves transparently when heated, but solidifies at room temperature. E: Disperses when heated, but solidifies in layers at room temperature. F: Hardly dissolves even when heated. Next, the hydrolysis resistance of the above ester compound was measured according to the following test method, and the results are shown in Table 5. As shown in this table, the ester compound according to the present invention has a branched structure and therefore has excellent hydrolysis resistance. Table 5 Ester compound decomposition rate No. 2 3.4% 3 27.2 4 15.6 6 15.3 7 9.4 9 14.2 IPM 99.4 (Hydrolysis resistance test method) 2 g of sample was refluxed in 1/2 N potassium hydroxide-ethanol solution for 30 minutes. let Next, cosmetics containing the ester compound according to the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these examples in any way. In the following, the blending ratios are expressed in weight % unless otherwise specified. Example 1 Formula of O/W cream (1) Ester compound No. 4 20.0% Setanol 7.0 spermaceti 1.5 Sorbitan monooleate 2.0 Polyoxyethylene cetyl ether 3.5 (2) Glycerin 10.0 Purified water 53.0 (3) Fragrance Appropriate amount Preservative 〃 According to the above recipe, each component in (1) is first heated to 70℃ and stirred and mixed to dissolve, then component (2) is added and mixed, and then component (3) is added. Mix to prepare O/W type cream. Example 2 W/O cream formulation (1) Ester compound No. 5 25.0% Squalane 15.0 Beeswax 10.0 Lanolin 10.0 (2) Ester compound No. 6 5.0 Sorbitan monooleate 2.0 Purified water 33.0 (3) Fragrance Appropriate amount Preservatives 〃 According to the above recipe, first mix each ingredient (1), and add 50
Heat to ~60℃ and stir to dissolve.
Component (2) is added and mixed to this, and then component (3) is added and mixed to prepare a W/O type cream. Example 3 W/O cream formulation (1) Ester compound No. 0.9 20.0% Squalane 18.0 Beeswax 10.0 Lanolin 12.0 (2) Ester compound No. 6 5.0 Sorbitan monooleate 2.0 Purified water 33.0 (3) Fragrance Appropriate amount Preservative Appropriate amount According to the above prescription, W/O
Prepare mold cream. Example 4 Formula of emulsion (1) Ester compound No. 2 15.0% Liquid paraffin 10.0 Lanolin 5.0 Beeswax 10.0 (2) Sorbitan monooleate 4.0 Glycerin monostearate 3.0 Purified water 53.0 (3) Fragrance Appropriate amount Preservative 〃 Above According to the recipe, each component (1) is first dissolved by stirring at 70°C, and then each component (2) and (3) are sequentially added and mixed to prepare an emulsion. Example 5 Formula of hair cream (1) Ester compound No. 5 20.0% 〃No. 6 10.0 Liquid paraffin 45.0 Beeswax 2.0 (2) Sorbitan sesquimonooleate 3.0 Purified water 20.0 (3) Fragrance Appropriate amount Preservative 〃 Above According to the recipe, each component (1) is first dissolved by stirring at 50 to 60°C, and then components (2) and (3) are sequentially added and mixed to prepare a hair cream. Example 6 Lipstick formulation (1) Ester compound No. 7 5.0% No. 8 10.0 Beeswax 15.0 Candelilla wax 10.0 Carnauba wax 2.0 Castor oil 50.0 Sorbitan monooleate 2.0 (2) Lake pigment 2.0 Dye 2.0 Fragrance 2.0 According to the above formulation , First, mix each component (1), 95
The mixture is stirred and mixed at ~100°C, and the component (2) is added and mixed, followed by molding to prepare a lipstick. Example 7 Lipstick formulation (1) Ester compound No. 8 7.0% No. 10 7.0% Beeswax 16.0 Candelilla wax 10.0 Carnauba wax 2.0 Castor oil 50.0 Sorbitan monooleate 2.0 (2) Lake pigment 2.0 Dye 2.0 Fragrance 2.0 According to the above formulation, A lipstick is prepared as in Example 6. Example 8 Eyeshadow formulation Ester compound No. 3 5.0% No. 4 10.0 Vaseline 40.0% Talc 25.0 Titanium oxide 5.0 Cocoa butter 2.0 Beeswax 3.0 Lake pigment Appropriate amount Fragrance 〃 Add and mix each of the above ingredients to create the pigment and base color Thoroughly knead until there are no dark circles, and pass the kneaded mixture through a colloid mill roller to form a product. Example 9 Transparent cosmetic soap formulation Ester compound No. 2 10.0% Beef tallow 14.0 Coconut oil 16.8 Castor oil 6.2% Caustic soda solution (38°Be') 23.5 Ethyl alcohol 8.4 Sucrose 9.8 Purified water 11.5 Composition consisting of the above components The products are melted and mixed and put into a mold. Example 10 Shampoo formulation Lauryl sulfate triethanolamine 25.0% Oleic acid monoethanolamide 4.0 Ester compound No. 1 1.0 Purified water 70.0 Perfume Appropriate amount Colorant 〃 A transparent shampoo is prepared by stirring and mixing the above ingredients uniformly. Comparative Example 1 In the O/W type cream formulation of Example 1,
Solid paraffin 20.0 instead of ester compound No. 4
O/W was carried out in the same manner as in Example 1 except that % was used.
Prepare mold cream. Comparative Example 2 In the formulation of Example 2, 25.0% beeswax was used instead of ester compound No. 5, and 5.0% cetostearyl-2-ethylhexanoate was used instead of ester compound No. 6. A W/O type cream was prepared in the same manner as in Example 2. Comparative Example 3 A milky lotion was prepared in the same manner as in Example 4, except that in the formulation of Example 4, liquid paraffin was used at 25% of the original composition in place of ester compound No. 2. (Practical test) Each of the cosmetics obtained in Examples 1 to 4 and Comparative Examples 1 to 3 above was used as a sample, and 50 women aged 18 to 30 were tested.
Practical tests were conducted on these samples on humans, and the usability was evaluated based on the following criteria.
The results are shown in Table 6. (Evaluation criteria for usability) A: Very moist and long feeling B: Long feeling C: Average

[Table] As is clear from the above results, all cosmetics containing the ester compound according to the present invention provide excellent skin feel. In the above practical tests, the sample cosmetics according to the present invention were also evaluated as being much more spreadable than the comparative examples. Comparative Example 4 Example 6 except that beeswax and lanolin were used in place of ester compounds No. 7 and No. 8 in the formulation of Example 6, and beeswax was added to the original composition to 25%, and lanolin was added to 5%. A lipstick was prepared in the same manner. Comparative Example 5 In the recipe of Example 8, ester compound No. 3
and Vaseline in place of No. 4 with the original composition.
Eye shadow dough was prepared in the same manner as in Example 8 except that 55% was used. (Practical test) The lipsticks and eyeshadow obtained in Examples 6, 7, and 8 and Comparative Examples 4 and 5 were used as samples, and subjects aged 18
When a practical test was conducted on 30 women aged ~30 years, the lipsticks and eye shadows of Examples 6, 7, and 8 according to the present invention were found to be more spreadable than the control products of Comparative Examples 4 and 5, respectively. Most of the evaluations were that it was very easy to apply and had a good feel. Comparative Example 6 In the formulation of Example 10, ester compound No. 1
Example except that 1% cetanol was used instead of
Shampoo was prepared in the same manner as in 10. Using the shampoos obtained in Example 10 and Comparative Example 6, 60 women between the ages of 18 and 25 were asked to evaluate the finish of their hair after washing with these two shampoos using a questionnaire based on the following evaluation items. Ta. Evaluation items: (1) Moisture: (2) Shiny: (3) Light finish The evaluation results are shown in Table 7.

[Table] From the above results, it can be seen that the shampoo containing the ester compound according to the present invention has a fatliquing effect that imparts a light finish without a sticky feeling. Comparative Example 7 100g of 2-hexyldecyl alcohol, 75g of neotridecanoic acid and 0.9g of para-toluenesulfonic acid
was added thereto, and an esterification reaction was carried out at 140 to 160°C under reduced pressure for 4 hours. Thereafter, the same operation as in Synthesis Example 1 was performed to obtain a liquid ester (2-hexyldecyl-neotridecanoate) at room temperature (yield
92%). The analysis results of the obtained ester are as follows. Acid value: 0.18, saponification value: 141, hydroxyl value: 1.1, iodine value: 0.7, hue (AHPA): 100, pale yellow The above esters were mixed into cosmetics in the same manner as in Examples 2 and 4. was prepared and subjected to the same practical tests as in Examples 1 to 4 and Comparative Examples 1 to 3. The results are shown in Table 8.

[Table] As is clear from the results in Tables 6 and 8 above, 46 out of 50 people (92%) evaluated the feel of the W/O cream (Example 2) using the ester of the present invention.
However, only 28 out of 50 people (56%) rated the feel of the W/O cream using the ester of Comparative Example 7 as A. Also, in the case of emulsion, when the ester of the present invention was used (Example 4), 43 people (86%) rated A, whereas when the ester of Comparative Example 7 was used, 24 people gave an A rating.
There were only people (48%). From this, it can be seen that the ester of the present invention has exceptionally superior utility compared to the ester of Comparative Example 7. As described above, the skin cosmetic or hair cosmetic containing at least one ester compound of garbage alcohol and saturated or unsaturated linear fatty acid or saturated or unsaturated linear dibasic acid according to the present invention is It is clearly recognized that the quality and performance, such as touch and feel, are significantly superior to conventional products.

Claims (1)

[Claims] Linear formula (However, R ₁ and R ₂ are the same or different, and the number of carbon atoms is
2-substituted-1-alcohol represented by (representing a saturated or unsaturated alkyl group having 12 to 24 carbon atoms) and a saturated or unsaturated linear fatty acid having 8 to 22 carbon atoms or a saturated or unsaturated fatty acid having 4 to 18 carbon atoms. A cosmetic comprising at least one ester compound with a linear dibasic acid.