JPS6246553B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an esterified product with excellent emulsifying properties, water-retaining properties, etc., and cosmetics and external preparations containing the same. Today, various types of esters are used as raw materials for cosmetics, including naturally occurring oils and fats, side-chain fatty acids obtained through various synthetic reactions, and alcohol derivatives. In general, the following are necessary conditions for oily raw materials for cosmetics. In other words, it not only has stable supply, compositional variations, color and odor stability, but also clear safety against skin irritation and toxicity, does not impede skin ventilation or moisture permeation, has good wettability, It is desirable to maintain the skin's original functions such as flexibility and elasticity, and it should also have physical properties such as affinity with other base materials, excellent emulsifying or dispersing ability, and good oxidation stability. It is. Various studies have been carried out in the past to provide oil-based raw materials that satisfy these conditions. For example, cholesterol stearate esters and oleic acid esters are used in stick-like products such as lipsticks and eye shadows, as well as creams and ointments. It is known that it can be done. These esters have excellent emulsifying properties, water-holding properties, etc. to some extent, but in order to improve the performance of cosmetics, external preparations, etc., it is desirable to have properties even higher than these. As a result of intensive research, the present inventors have found that an esterification product of lactic acid or an oligoesterified carboxylic acid of lactic acid and a sterol has emulsifying properties, water-holding properties, and moisture retention properties that are several steps higher than that of conventional sterol esters. I discovered that it is a thing. The present invention was completed based on such knowledge, and one of them is an esterification product of lactic acid or an intermolecular oligoesterified carboxylic acid of lactic acid represented by the following general formula and a sterol. (In the formula, n is an integer of 0 or 1 or more.) The other one is a cosmetic composition and an external preparation containing one or more of the above esterified products. The upper limit of n in the above general formula is not particularly limited, but is approximately 5, and may be higher if the reaction conditions are made more severe. The lactic acid used in the present invention is an organic acid having three carbon atoms and one hydroxyl group in the molecule. Sterols that can be used include cholesterin, which is widely distributed in animal cells, phytosterin, which is distributed in plants such as soybean oil, methylsterine, which has a methyl group in the sterin bone core, and hydrogenated products of these. . The present invention involves esterifying lactic acid or an oligoesterified carboxylic acid of lactic acid as described above with a sterol, which can be produced by the following method. That is, lactic acid and the oligoesterified carboxylic acid of lactic acid are subjected to an esterification reaction in accordance with a conventional method in the absence of a catalyst or in the presence of a catalyst (for example, tin chloride, etc.) at normal pressure or reduced pressure to obtain desired properties. After the product is obtained, an esterification reaction is performed by adding a predetermined amount of sterol. The oligoesterified carboxylic acid of lactic acid is obtained by performing an intermolecular esterification reaction of lactic acid without a catalyst or in the presence of a catalyst (for example, tin chloride, etc.) under normal pressure or reduced pressure according to a conventional method. It is then prepared. The esterification reaction between a sterol and lactic acid or an oligoesterified carboxylic acid of lactic acid can be carried out almost quantitatively without a catalyst or in the presence of a catalyst. The end points of both the reaction with the oligoesterified carboxylic acid and the esterification reaction with the sterol can be determined by the acid value. Alternatively, instead of producing the oligoesterified carboxylic acid of lactic acid in advance, a certain amount of excess lactic acid and sterol are simultaneously charged and reacted, and the esterification reaction of the oligoesterified carboxylic acid of lactic acid and the esterification reaction with the sterol are carried out. It can also be carried out in the same reaction vessel. In this case, a mixture of an ester of lactic acid and a sterol and an ester of an oligoesterified carboxylic acid of lactic acid and a sterol is obtained, and such a mixture can also achieve the object of the present invention. After removing the catalyst from the obtained crude sterol ester in a conventional manner, it is decolorized using a decolorizing agent, and then deodorized and purified by steam distillation or the like. Various cosmetics and external preparations can be prepared by appropriately blending commonly used ingredients and optional ingredients with the thus obtained product. Although the blending ratio cannot be absolutely defined, it is generally 0.05 to 50% by weight. The sterol esterification products of the present invention are light colored;
It is odorless, does not irritate the skin, exhibits excellent affinity and texture to the skin, and has much higher emulsifying, water-retaining and moisturizing properties than conventional sterol esters, making it suitable for cosmetics and other applications. It has properties suitable as an oil for external use. Some examples of cosmetics that can be applied are shown in the examples below, but they are not particularly limited.
For example, when added to creams such as cold creams and vanishing creams, milky lotions, lotions, and face packs, it can increase emulsion stability and improve emollient properties and texture, and can also be added to hair products such as shampoos, hair rinses, hair treatments, etc. It can be expected to have a fatliquing effect and a protective effect on the skin, and can impart strength and flexibility to the skin. Furthermore, it is also possible to use the surfactant in place of a part or all of the conventionally used surfactant, and the problem of skin irritation caused by surfactants can also be improved. Furthermore, due to its emulsifying power and safety, it can also be used as a general surfactant in external medicines, such as ointments, emulsions, and food emulsifiers. Examples of esterification products according to the invention are given below. Example 1 Preparation of sterol ester Synthesis example 1 130 g of lactic acid (90 g
% aqueous solution (1.3 mol) and 463 g of cholesterin (1.2 mol), 0.2 of the total amount charged as a catalyst.
% tin chloride and 5% of the total charge as refluxing solvent
of toluene and stir well to form a mixture.
The reaction was carried out at 140-220°C for about 8 hours. After the reaction is complete,
After separating the catalyst and decolorizing using activated clay,
455g of target cholesteryl lactate was deodorized by steam injection under reduced pressure at ℃~220℃.
I got it. (Experiment No. 1) The sterol esters of Experiment Nos. 2, 3, and 4 were obtained by the same reaction. Synthesis Example 2 Charge 300g of lactic acid into a 500ml flask, add 0.2% of tin chloride to the charge, and react at 120 to 200°C in the same manner as in Synthesis Example 1 until the acid value of the reactant is 200.
The reaction was carried out for about 5 hours until 240 g of the desired oligoesterified carboxylic acid of lactic acid was obtained. 224g of this oligoesterified carboxylic acid of lactic acid
Then, 309 g of cholesterin was charged into one flask, and the reaction was carried out in the same manner as in Synthesis Example 1 to obtain 440 g of the desired esterification product of oligoesterified carboxylic acid of lactic acid and cholesterin. (Experiment No. 5) Synthesis Example 3 Lactic acid 200g (2 moles) and phytosterin 410
(1 mol) was charged into one flask, 0.2% of tin chloride was added to the charged amount, and the reaction was carried out at 140 to 220°C for about 11 hours in the same manner as in Synthesis Example 1 to obtain the desired oligoesterified carboxylic acid of lactic acid. 490 g of an esterification product of and phytosterin was obtained. (Experiment No.
6) Synthesis Example 4 300g (3 moles) of lactic acid and isocholesterin
337g (1 mol) was charged into one flask, 0.2% of tin chloride was added to the charge, and the reaction was carried out in the same manner as in Synthesis Example 1 at 140 to 220°C for about 15 hours to obtain the desired oligoesterified carboxylic acid of lactic acid. 480 g of the esterification product with isocholesterin was obtained. (Experiment No. 7) Example 2 Properties of sterol esters When the acid value, saponification value, hydroxyl value, and melting point of each sterol ester were measured, the results shown in Table 1 were obtained. Table 2 shows the results of measuring the water-retentivity of the sample when a certain amount of the sample was added to vaseline and liquid paraffin. For comparison, ordinary sterol esters, petrolatum, and liquid paraffin were also measured and listed in the same table.

【table】

[Table] As shown in Table-2, the esters of the present invention (No. 1 to
It can be seen that No. 9) has a superior water-holding power compared to the comparative example, and therefore also has a strong emulsifying power. Furthermore, the ester 10 of the present invention was added under conditions of relative humidity of 80% and 25°C.
% was applied on a 12 x 7 cm glass plate to an average thickness of 5 μm, and the amount of water absorbed was measured after standing for 200 hours. The results are shown in Table-3. For comparison, measurements were also made on petrolatum, lanolin, and petrolatum to which 10% of normal fatty acid and sterol esters were added.

【table】

[Table] From Table 3, the sterol ester of the present invention is
The value is more than three times that of the comparative example, and it is recognized that the moisturizing effect is strong. In addition, in order to examine the safety of the above-mentioned samples of the present invention (No. 1 to No. 9) on the skin, primary irritation was tested on 20 healthy subjects using an occlusion patch test method.
That is, the presence or absence of irritation was measured after being left as is for 24 hours, 48 hours, and 72 hours. As a result, none of them were irritating. As mentioned above, the esterified product according to the present invention has various properties, and can be said to be extremely useful as a raw material for cosmetics and a raw material for external preparations. Example 3 Preparation of cosmetics, etc. Next, various cosmetics and external preparations were prepared by mixing commonly used ingredients with the sterol esterified product. Using samples No. 1 to 9 as esterification products,
Cosmetics of Formulation Examples 1 to 5 and external preparations of Formulation Examples 6 were manufactured by appropriately blending other ingredients, and all had good properties. Formulation example 1 (A) Liquid paraffin 35% by weight White petrolatum 5 Beeswax 5 Sample No. 1 10 (B) Preservative appropriate amount Water balance (C) Flavor appropriate amount Dissolve (A) at 80℃ Then, (B) heated to 80°C was gradually added to this while stirring, and then cooled to 55°C. To this, (C) was added and cooled to 35°C to obtain cold cream. Formulation example 2 (A) Liquid paraffin 50.0% by weight White petrolatum 10.0 Sample No. 6 5.0 Polyoxyethylene (4) glyceryl ether distearate 1.5 Polyoxyethylene (10) oleyl ether 2.0 (B) Polyethylene glycol 1000 0.5 〃 Propylene glycol 0.5 〃 Water Remaining part After heating (A) to 75℃ and dissolving it uniformly, gradually add (B) heated to 70℃, stirring well for 30 minutes.
A cleansing cream was obtained by cooling to ℃. Formulation example 3 (A) Isostearyl alcohol 1.5% by weight Sample No. 8 0.5 〃 Stearyldimethylbenzylammonium chloride 2.0 〃 Glyceryl monostearate 5.0 〃 (B) Propylene glycol 4.0 〃 Water Balance (A) heated to 70℃ After dissolving it uniformly, heat it to 75℃.
Gradually add the homogeneously dissolved aqueous phase by heating to
Stir gently to avoid air bubbles. Thereafter, it was cooled to 30°C to obtain a milky hair rinse. Formulation example 4 (A) Candelilla wax 5.0% by weight Beeswax 10.0 〃 Carnauba wax 5.0 〃 Sample No. 3 10.0 〃 Malic acid diisostearate 25.0 〃 Castor oil 25.0 〃 Hardened oil 15.0 〃 (B) Titanium oxide 3.0 〃 Red pigment 0.5 〃 (C) Flavor 1.5 〃 After heating (A) to 80℃ and dissolving it uniformly, cool it and knead it uniformly with a roll mill. To this, (B) was uniformly dissolved and added, and (C) was further added and after defoaming, the mixture was poured into a mold and rapidly cooled to obtain a lipstick. Formulation example 5 Vinyl acetate resin emulsion 10% by weight Polyvinyl alcohol 10 Sample No. 2 4 Sorbitol 5 Titanium oxide 7 Kaolin 7 Ethyl alcohol 5 Water 52 Preservatives, fragrance Appropriate amounts Add each raw material to purified water in sequence The mixture was added with stirring, polyvinyl alcohol moistened with some ethyl alcohol, and then dissolved by heating. Flavors and preservatives were mixed while cooling to obtain a pack. Formulation example 6 (A) Liquid paraffin 20.0% by weight White petrolatum 10.0 Cetyl alcohol 20.0 Sample No. 1 4.0 Polyoxyethylene (15) stearyl ether 4.0 (B) Sodium lauryl sulfate 1.0 Water Balance (A) 70 After heating to 0.degree. C. to uniformly dissolve, (B) was added at the same temperature, emulsified, and cooled to obtain an ointment base.

Claims (1)

[Scope of Claims] 1. An esterification product of lactic acid or an intermolecular oligoesterified carboxylic acid of lactic acid represented by the following general formula and a sterol. (In the formula, n is an integer of 0 or 1 or more) 2 Contains one or more esterification products of lactic acid or an intermolecular oligoesterified carboxylic acid of lactic acid represented by the following general formula and a sterol. Cosmetics and external preparations. (In the formula, n is an integer of 0 or 1 or more)