JP2000204060A - Esterification product and cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an esterification product having good compatibility with waxes, capable of being perfectly dissolved in caster oil, and having large solubility for medicines, and to provide a cosmetic containing the esterification product as an oily base agent, rich in affinity, adhesivity, wettability and flexibility for skins, not having a color and a smell, and having a proper adhesivity. SOLUTION: This esterification product comprises an esterification product of (1) glycerol with (2) one or more fatty acids selected from 8-28C linear fatty acids, branched fatty acids, unsaturated fatty acids, and hydroxyfatty acids, and (3) a >=2C linear or branched dibasic acid, and is obtained by two step reactions comprising reacting the component (1) with the component (2) and then reacting the reaction product with the component (3). The cosmetic contains the esterification product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an esterification product comprising glycerin, a fatty acid and a dibasic acid, and a cosmetic comprising the product as an oily base.

[0002]

2. Description of the Related Art Oil bases used in cosmetics include:
Low melting waxes and oligoesterified products are exemplified. Representative low melting waxes include lanolin and petrolatum. Lanolin is rich in affinity, adhesion, wettability, etc. to the skin, and has excellent hydrating power and emulsifying power, so it is used in many cosmetics including basic cosmetics and makeup cosmetics. In addition, there are disadvantages as a raw material for cosmetics, such as the amount of the cosmetic is limited because the color tone and aroma of the cosmetic are impaired. In addition, since it is a natural product, its quality is not constant and its price fluctuates greatly. Moreover, it tends to be rancid during long-term storage.
On the other hand, Vaseline is colorless and odorless, chemically inert, and has a strong adhesive property and a characteristic of giving oiliness.
Used in cosmetics such as lipstick and tics. However, since petrolatum is a hydrocarbon, it has drawbacks such as not dissolving in castor oil, which is important as a raw material for cosmetics, and having low solubility in drugs. Since the by-products such as oligoesters, dimers and trimers used in the oil base of cosmetics cannot be controlled, it is difficult to obtain stable properties and, depending on the production conditions, a large amount of free fatty acids may be produced as a by-product. Since the odor becomes strong, these fatty acids must be removed (JP-A-56-45404, JP-A-56-40605, etc.). In addition, generally, oligoesterified products composed of polyhydric alcohols, fatty acids, and dibasic acids and having a high degree of esterification tend to be solid at room temperature, and thus cannot be directly mixed with liquid or low-viscosity components. .

[0003]

An object of the present invention is to provide an esterified product which has good compatibility with waxes, is completely dissolved in castor oil, and has a high dissolving power for drugs, and is useful in cosmetics. The present invention provides a cosmetic composition having excellent affinity, adhesion, wettability, and flexibility to the skin, being colorless and odorless, and having a moderate adhesive strength.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and have found that glycerin,
The present inventors have found that an esterification product obtained by a two-step reaction comprising a fatty acid and a dibasic acid as components has extremely excellent properties as an oily base for cosmetics, and completed the present invention. That is, the present invention provides (1) glycerin and (2)
To 28 linear fatty acids, branched fatty acids, unsaturated fatty acids, or hydroxy fatty acids; and (3) a linear or branched dibasic acid having 2 or more carbon atoms. An esterification product comprising (1) and (2)
And further reacting (3) in two steps. In the esterification reaction, 2 moles of (2) and 1 mole of (3) were added to 1 mole of (1).
Preferably it is molar. Further, it is preferable that the esterification is performed so that the acid value becomes 50 or more. The present invention also relates to a cosmetic containing such an esterification product.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Essential ingredients for obtaining the esterification product of the present invention include glycerin, fatty acids and dibasic acids. It is essential that the fatty acid of the present invention is one or more selected from linear fatty acids having 8 to 28 carbon atoms, branched fatty acids, unsaturated fatty acids and hydroxy fatty acids. Specifically, linear fatty acids such as caprylic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and montanic acid Unsaturated fatty acids such as undecylenic acid, palmito oleic acid and oleic acid; branched fatty acids such as isooctylic acid (2-ethylhexanoic acid), neotridecanoic acid, isomyristic acid, isopalmitic acid and isostearic acid;
Examples thereof include hydroxy fatty acids such as hydroxystearic acid and ricinoleic acid. In the present invention, these may be used alone or in a mixture of any combination. Among these, straight-chain fatty acids are preferred, and specifically, one or more selected from capric acid, myristic acid, palmitic acid, and stearic acid. In the present invention, it is necessary to pay attention to the use of a large amount of a fatty acid having a high degree of unsaturation because the storage stability of the esterified product of the present invention may be reduced. Further, when the fatty acid has less than 8 carbon atoms, the hydrolysis stability is poor and the viscosity cannot be obtained. In addition, carbon number 3
Fatty acids of 0 or more are difficult to obtain as industrial raw materials.
The maximum function as an oily base is exhibited when a fatty acid having 8 to 28 carbon atoms is used.

Next, the dibasic acid is a linear or branched dibasic acid having 2 or more carbon atoms. That is, oxalic acid, malonic acid, succinic acid, malic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid, octadecamethylene dicarboxylic acid, hexaico Samethylene dicarboxylic acid, itaconic acid, maleic acid,
Dibasic acids such as fumaric acid and muconic acid may be used alone or in any mixture. Among these, preferred are adipic acid, sebacic acid and octadecamethylene dicarboxylic acid.

The above-mentioned raw materials can be used in an appropriate combination, and a two-step reaction is indispensable for obtaining the esterification product of the present invention. That is, the two-step reaction is a reaction in which glycerin and a fatty acid are first esterified, and this is further esterified with a dibasic acid. In addition,
When glycerin, fatty acid and dibasic acid are reacted simultaneously, there is no selectivity between glycerin, fatty acid and dibasic acid, and the desired esterification product cannot be obtained. Fatty acids are used in a 200% molar ratio to glycerin,
It is important to use the dibasic acid in a 100% molar ratio to glycerin. Except for this molar ratio, it is not possible to obtain an esterified product as an oily base compounded in the cosmetics characteristic of the present invention.

In the esterification reaction, each of the above-mentioned raw materials is charged into a suitable reaction vessel, and in the presence or absence of an acid, alkali or metal catalyst, preferably in an organic solvent or / and gas inert to the reaction. This is performed at 150 to 200 ° C. for several hours to about 20 hours while removing by-produced water. When a catalyst is used, an acid catalyst or an alkoxide of an alkali metal or an alkaline earth metal is added in an amount of 0.001 to 1.0% based on the weight of the reaction raw materials. The progress of the reaction can be evaluated by measuring the acid value in the reaction system, and the reaction is terminated when the acid value becomes 50 or more, preferably 60 to 80. When the reaction is stopped at less than 50, the structure represented by the general formulas (1) to (4) represented by Chemical Formula 1 becomes less than 80% by weight in the esterification product, which is expected as an oily base. Properties cannot be obtained. After the completion of the reaction, unreacted substances may be contained. These substances are separated and removed by a known method such as washing with water, alkali deacidification, treatment with an adsorbent such as silica gel, and further subjected to decolorization and deodorization treatment for purification.

[0009]

Embedded image(Where R₁, R₂(R₁= R₂, R₁≠ R₂) Is carbon number
8 to 28 linear fatty acids, branched fatty acids, unsaturated fatty acids,
Or a hydrocarbon group derived from a hydroxy fatty acid, X ₁, X
₂(X₁= X₂, X₁≠ X₂) Is a straight chain having 2 or more carbon atoms.
Or a hydrocarbon group derived from a branched dibasic acid. )

[0010] The esterification product of the present invention thus obtained is a mixture in which glycerin, a fatty acid, and a dibasic acid are esterified in a linear or branched form,
It becomes a highly viscous liquid or wax at normal temperature. The esterification product of the present invention mainly has a structure represented by the general formulas (1) to (4) represented by Chemical Formula 1, but other than the above, some polymers, free fatty acids, etc. Also contained.
According to the gas chromatography analysis, those having structures represented by the general formulas (1) to (4) represented by Chemical Formula 1 are contained in the esterification product in an amount of 80% by weight or more. It is considered that this has a feature as an oily base.

The amount of the esterified product of glycerin, a fatty acid, and a dibasic acid as an oily base for cosmetics is determined based on the total amount of the final composition.
The upper limit is not particularly limited as long as it is 0.01% by weight or more.
Further, the type of the cosmetic of the present invention is not particularly limited, but it is particularly desirable to target various known cosmetics used for the skin, such as cold cream, burnishing cream, cleansing cream, Various creams such as emollient cream and sunscreen cream, emulsions, lotions, foundations, facial cleansers, lipsticks, serums, packs and the like can be mentioned. Similarly, there is no limitation on hair care products, but shampoos, rinses, hair styling agents, hair dyes and the like can be particularly preferably exemplified.

The cosmetic of the present invention can be prepared by a conventional method using the above esterified product and other known components. That is, known oil components, aqueous components, surfactants, humectants, thickeners, preservatives, pigments, powders, pH adjusters, antioxidants, ultraviolet absorbers, fragrances, dyes, purified water, etc. May be blended. The esterification product obtained by the reaction of glycerin with a fatty acid and a dibasic acid in the present invention is mainly composed of a two-step reaction that leaves a carboxyl group at the terminal of glycerin, whereby the affinity for the skin, adhesion, It has excellent properties such as excellent wettability, flexibility, colorless and odorless, and appropriate adhesive strength.

[0013]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. Synthesis Example 1 34.2 g of glycerin, 105.7 g of stearic acid, and 84.9 g of myristic acid were added to a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas injection tube, and a water separator.
About 8 at 150-200 ° C using tin chloride as a catalyst.
Allowed to react for hours. When the acid value becomes 1.0 or less,
75.2 g of sebacic acid was added and the reaction was continued. The reaction was performed until the theoretical acid value reached 74.5, and after completion of the reaction, purification was performed by a conventional method. The yield of this esterification product 1 was 245 g, and the acid value was 73.5. Further, the odor, tackiness and solubility of the esterified product 1 were evaluated. Table 1 shows the results.

Synthetic Example 2 In the same manner as in Synthetic Example 1, 35.7 g of glycerin, 77.3 g of stearic acid, 88.6 g of myristic acid and 20.1 g of capric acid were reacted to lower the acid value.
g was added thereto to carry out a reaction until the theoretical acid value was 77.9, and after completion of the reaction, purification was conducted by a conventional method. The yield of this esterification product 2 is 2
34 g, and the acid value was 75.0. The odor, tackiness and solubility of the esterified product 2 were evaluated. Table 1 shows the results.

Synthesis Example 3 In the same manner as in Synthesis Example 1, 32.0 g of glycerin and 197.7 g of stearic acid were reacted to lower the acid value.
The reaction was carried out until 0.39 g was added to the theoretical acid value of 69.4, and after completion of the reaction, purified by a conventional method. The yield of this esterification product was 250 g, and the acid value was 64.0. Further, the odor, tackiness and solubility of the esterified product 3 were evaluated. Table 1 shows the results.

SYNTHESIS EXAMPLE 4 38.9 g of glycerin, 84.1 g of stearic acid, 96.4 g of myristic acid and 21.8 g of capric acid were reacted in the same manner as in Synthesis Example 1 to lower the acid value.
g was added and the reaction was carried out to a theoretical acid value of 84.6. After completion of the reaction, purification was carried out by a conventional method. The yield of this esterification product 4 is 2
48 g, the acid value was 82.8. The esterification product 4 was evaluated for odor, tackiness and solubility. Table 1 shows the results.

Synthesis Example 5 In the same manner as in Synthesis Example 1, 30.3 g of glycerin, 65.4 g of stearic acid, 75.0 g of myristic acid, and 17.0 g of capric acid were reacted to lower the acid value. After adding 4 g, the reaction was carried out to a theoretical acid value of 65.3, and after completion of the reaction, purification was carried out by a conventional method. The yield of this esterification product 5 was 225 g, and the acid value was 61.2. The esterification product 5 was evaluated for odor, tackiness and solubility. Table 1 shows the results.

Synthesis Example 6 In the same manner as in Synthesis Example 1, the same raw materials were simultaneously subjected to an esterification reaction, and purified by a conventional method after the reaction. The yield of this esterification product 6 was 240 g, and the acid value was 88.1. The esterification product 6 was evaluated for odor, tackiness and solubility. Table 1 shows the results.

[0019]

[Table 1] a) Dissolve 10 g of the compound at 70 ° C. and add 5 W of linalool
Add 0.1 ml of a / V% ethanol solution and stir for 1 minute. After allowing to stand at room temperature, 0.1 g was applied to the inner part of the forearm, and the odor at the time of application and the adhesiveness to the skin were evaluated. The evaluation was performed (average value) by ten professional panels based on the following criteria. Evaluation of odor; 3, no raw odor is felt, 2, slight raw odor is felt, 1, raw odor is felt, 0, raw odor is felt. Evaluation of adhesive strength; 4, very strong, 3, good, 2, normal,
1, bad, 0, very bad. b) 2 g of the compound was added to 8 g of castor oil, and the state when the mixture was stirred at 70 ° C. was observed. ；: Transparently dissolved, ×: not dissolved.

Example 1 A cream was prepared according to the formulation and manufacturing method shown in Table 2. A cream (A) containing the esterified product 1, a cream (B) containing the esterified product 6, and a control for comparison were prepared in the same manner, and the sensory evaluation was performed for each cream. Table 3 shows the results. The cream containing the esterification product 1 of the present invention had better elongation to the skin than the cream containing squalane, and a refreshing feeling of use, a moisturizing effect, and a softening effect were recognized. The composition containing the esterification product 6 obtained by the one-step reaction was superior to the control, but the properties of the cream were inferior to those containing the esterification product 1 obtained by the two-step reaction.

[0021]

[Table 2] [Production method] The aqueous phase is mixed and kept at 70 ° C. Next, the oil phase is mixed, heated and dissolved, and kept at 70 ° C. The oil phase is added to the water phase, pre-emulsified, homogenized uniformly with a homomixer, and then emulsified and stirred with cooling to obtain a cream.

[0022]

[Table 3]

Example 2 A lipstick was prepared according to the formulation and manufacturing method shown in Table 4.
A control for comparison was prepared in the same manner, and the sensory evaluation of both lipsticks was performed. Table 5 shows the results. The lipstick containing the esterified product 3 of the present invention had an adhesive force to the lips, and a moisturizing effect and a softening effect were recognized.

[0024]

[Table 4] [Manufacturing method] Part A (oil-based) is heated and dissolved to make it uniform, to which part B (coloring agent) is added, kneaded and uniformly dispersed by a roll mill, and then melted again to obtain part C (antioxidant).・ Fragrance)
Is added, defoamed, poured into a mold, and cooled and solidified to obtain a lipstick.

[0025]

[Table 5]

Example 3 Lip gloss was prepared according to the formulation and the production method shown in Table 6. A control for comparison was prepared in the same manner, and both lip glosses were subjected to sensory evaluation. Table 7 shows the results. The lip gloss blended with the esterification product 5 of the present invention was a paste having a beautiful transparency, and exhibited very good elongation and tackiness. The decorative film had a beautiful luster, was not sticky, was a uniform film, and had a moisturizing effect and a softening effect.

[0027]

[Table 6] [Production method] Titanium dioxide, red No. 204 is added to a part of castor oil and treated with a roller (pigment part). After mixing and heating and dissolving the other components, the pigment portion is added and uniformly dispersed with a homomixer. After dispersion, it is poured into a mold and cooled to obtain a gross slip.

[0028]

[Table 7]

Example 4 A shampoo was prepared according to the formulation and manufacturing method shown in Table 8. A control for comparison was prepared in the same manner, and the sensory evaluation of both shampoos was performed. Table 9 shows the results. The shampoo containing the esterification product 2 of the present invention exhibited a moisturizing effect, a moist feeling, a slipperiness and a softening effect on hair.

[0030]

[Table 8] [Manufacturing method] Purified water is heated, and other components are added thereto, dissolved and stirred well, and then cooled slowly to obtain a shampoo.

[0031]

[Table 9]

Example 5 A rinse was prepared according to the recipe and the production method shown in Table 10. Further, a control for comparison was prepared in the same manner, and the sensory evaluation of both rinses was performed. Table 11 shows the results. In the esterification product 4 of the present invention, it was recognized that the rinse imparted a softening effect and natural gloss to hair.

[0033]

[Table 10] [Production method] Glycerin, a protein derivative and a dye are added to purified water and dissolved by heating, and the temperature is maintained at 70 ° C (aqueous phase). The other components are mixed, heated and melted and kept at 70 ° C. (oil phase). Add the aqueous phase to the oil phase and stir well. Thereafter, the mixture is further stirred while cooling to obtain a rinse.

[0034]

[Table 11]

[0035]

According to the present invention, glycerin and fatty acids,
And a cosmetic comprising an esterified product of a dibasic acid as an oily base. This esterification product has good compatibility with waxes, completely dissolves in castor oil,
This cosmetic, which has a high dissolving power for drugs and contains its esterified product as an oily base, is rich in affinity, adhesion, wettability, flexibility, etc. to the skin, is colorless and odorless, and has a moderate adhesive strength. Have

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 68/08 C07C 68/08 69/34 69/34 69/44 69/44 69/50 69/50 F Terms (reference) 4C083 AA082 AA122 AB232 AB242 AB432 AC012 AC072 AC122 AC182 AC242 AC342 AC392 AC421 AC422 AC542 AC642 AC692 AC782 AC792 AC852 AD152 AD412 AD662 BB45 BB46 BB47 BB48 CC05 CC13 CC38 CC39 EE06 EE07 EE12 BA01 A03 BA03 AB06 BA66 BT12

Claims (4)

[Claims] (1) glycerin, and (2) C8-C.
Ester of one or more fatty acids selected from the group consisting of 28 straight-chain fatty acids, branched fatty acids, unsaturated fatty acids, and hydroxy fatty acids, and (3) a linear or branched dibasic acid having 2 or more carbon atoms An esterification product, wherein (1) and (2) are reacted, and (3) is further reacted in two steps. 2. The esterification product according to claim 1, wherein in the esterification reaction, (2) is 2 mol and (3) is 1 mol per 1 mol of (1). 3. The esterification product according to claim 1, which is esterified so that the acid value becomes 50 or more. 4. A cosmetic comprising the esterified product according to claim 1.