JPS6026084B2 - cosmetics - Google Patents

Description

[Detailed Description of the Invention] The present invention is non-irritating to the skin, has high safety and affinity, has excellent stability over time, emulsion stability, feeling of use, etc., and has a good appearance (texture, gloss). The present invention relates to hair cosmetics such as cream, emulsion, lotion, and oil skin cosmetics and hair conditioners, hair conditioners, shampoos, and conditioners.

Conventionally, many cosmetics must meet the following requirements: m) be highly safe without irritating the skin, etc. ■High emulsion stability and stability over time. t3' Good affinity for skin, etc. {4' Excellent usability. '6'
It has a good appearance, etc. However, these conditions can only be met by using appropriate cosmetic raw materials, and the selection of raw materials is the most important issue. In general, IQ materials are composed of components other than water, such as oil bases (oils, waxes, higher alcohols, hydrocarbons, ester oil, etc.), wetting agents, surfactants, ethanol, fragrances, etc. Among them, surfactants have a large influence on the factors mentioned above, such as emulsion stability, stability over time, skin irritation, physiological safety, affinity for the skin, feel of use, appearance, etc., so their use is prohibited. Great care must be taken when doing so. In particular, nonionic surfactants are widely used as emulsifiers and solubilizers.
Among them, some that are relatively good in terms of skin irritation, plexus properties, emulsifying power, etc. are currently used as cosmetic raw materials, but it has not yet been possible to find a product that satisfies all of the above conditions. . For example, polyoxyethylene higher alkyl ethers have poor emulsifying power and therefore must be used in considerably large amounts in order to obtain stable emulsions. Further, higher fatty acid esters such as glycerin, sorbitan, and polyethylene glycol tend to cause gelation and have defects due to poor stability over time. Furthermore, among higher fatty acid esters and amides such as jetanolamine, the former does not have sufficient emulsifying power, and the latter has been found to cause some skin irritation, although it is slight, and therefore its use is limited. was. In view of the current situation, the present inventors conducted intensive research and found that the compound represented by the general formula below has almost no irritation to the skin, is physiologically safe, and is found in IQ Soryo. The present invention has been completed based on the discovery that the inclusion of surfactants not only significantly increases the safety but also eliminates all the drawbacks of nonionic surfactants.

The object of the present invention is to produce cream-like, emulsion-like, lotion-like, and oil-like products that are non-irritating to the skin, have physiological safety, high affinity, excellent emulsion stability, and bonito-day stability, and have a good appearance. The purpose of the present invention is to provide skin cosmetics, and hair care products such as hair styling products, hair conditioners, shampoos, and conditioners.

That is, the present invention provides y-(N-2-hydroxyethyl)aminopropylene glycol-myristate, y-(N-2-hydroxyethyl)aminopropylene glycol
-1,1-dimethylolethyl)aminopropylene glycol Q-2-heptyl undecanoate, y-(N-trimethylolmethyl)aminopropylene glycol-oleate, y-(N-2,3,4,5,6 -bentahydroxyhexyl)aminopropylene glycol Q-oleate, y-(N-1,1-dimethylolethyl)
Aminopropylene glycol Q-oleate, y-(N
-2,3-dihydroxypropyl)aminopropylene glycol Q-oleate, N-2-hydroxy-3-(
Contains at least one compound selected from the group consisting of cis-9-octadecenoyloxy)propylglucosamine, y-(N-trimethylolmethyl)aminopropylene glycol Q-2-octyldodecanoate It is a cosmetic product characterized by: Hereinafter, embodiments of the present invention will be explained in detail. At least one of the compounds of the present invention is mixed with the base of the cosmetic by a known method to be incorporated into the cosmetic.

Its usage amount (content) is usually 0.1 to 30% by weight (preferably 1 to 20% by weight) based on the weight of the cosmetic.
is within the range of The compound used in the present invention is in the form of a paste or liquid, and is very easily obtained by the reaction of a higher fatty acid ester of glycidol with an alkanolamine, and is therefore extremely advantageous from an industrial perspective.

An example of its synthesis is shown below. Synthesis Example 1Y-(N-2-Hydroxyethyl)aminopropylene glycol is synthesized by Myristate.Into a flask with an internal volume of 2,000 mm and equipped with a flask, 1 y-(N-2-hydroxyethyl)aminopropylene glycol (2.2 mol) is placed. It overflows to 60 qo.

Next, while bowing violently, glycidyl myristate 284
Aqueous solution (1.0 mol) was added dropwise over a period of about 1 hour, and the reaction was then further carried out at 6 psi for 3 hours. After the reaction, add 800 ml of petroleum ether to the cold contents, stir thoroughly, and let stand at room temperature for about 3 hours. The precipitated excess monoethanolamine is removed by decantation, and the supernatant is concentrated. The residue was distilled under reduced pressure (0.05 ton) and fractions up to 160°C were removed to obtain the target compound (pale yellow paste) 324 ml. The yield was %, and it was confirmed that this product was the target compound based on its melon, NM crotch, and MS spectrum. Synthesis Example 2 y-(N-1,1-dimethylolethyl)aminopropylene glycol.

Synthesis of 2-heptyl undecanoate 340 glycidyl-2-heptyl undecanoate (1.0 mol) and 2-amino-2-methyl 1 were placed in a reactor similar to Synthesis Example 1.
．． 210 moles (2.0 mol) of 3-propanediol was added, and the reaction was carried out at 110° C. for 3 hours while shaking the door vigorously.

After completion, 800% fake petroleum ether was added to the contents, and after sufficient lighting, the same post-treatment as in Synthesis Example 1 was carried out, and 414%
Obtained the said objective in the evening. Yield: 93%, pale yellow, paste-like. The product obtained here was also confirmed to be the target compound based on its IR, NMR, MS spectra, etc. Synthesis Example 3 Synthesis of y-(N-trimethylolmethyl)aminopropylene glycol Q-oleate 1.0 mol of glycidyl oleate and 1.9 mol of trimethylol aminomethane were placed in the same reactor as in the synthesis example, and the mixture was heated with a hawk vigorously. While worshiping, 12
The reaction was carried out at 0°C for 4 hours.

After completion, post-processing is performed according to Synthesis Example 2. The target compound was obtained. Yield 95%, pale yellow, paste to liquid. The product obtained here was also confirmed to be the desired product based on its IR, NMR, MS spectra, etc. Synthesis Example 4 Synthesis of y-(N-2,3,4,5,6-bentahydrohexyl)aminopropylene glycol Q-oleate In a reactor similar to Synthesis Example 1, glycidyl oleate (1.0
mol) and glycamine (1.2 mol) were added, and the reaction was carried out at 130q○ for 4 hours while stirring vigorously.

After completion, vacuum distillation similar to Synthesis Example 1 was performed to obtain the target product. Yield 91%, pale yellow, paste. The product obtained here was also confirmed to be the target compound based on its IR, NM yield, MS spectrum, etc. Synthesis example 5y-(N-1,1
-dimethylolethyl)aminopropylene glycol Q
- Synthesis of oleate Glycidyl oleate (1.0 mol) and 2-amino-2-methyl-1,3-propanediol (1.8 mol) were placed in a reactor similar to Synthesis Example 1,
The reaction was carried out at 110° C. for 3 hours while being concentrated vigorously.

After completion, vacuum distillation similar to Synthesis Example 1 was performed to obtain the target product. Yield 93%, pale yellow, paste. The product obtained here was also confirmed to be the desired product based on its melon, NM old, MS spectra, etc. Synthesis Example 6 Synthesis of y-(N-2,3-dihydroxypropyl)aminopropylene glycol Q-oleate In a reactor similar to Synthesis Example 1, glycidyl oleate (1.0 mol) and glycerolamine (1.8 mol) were added. ) and the reaction was carried out at 70°C for 3 hours while stirring vigorously.

After completion, vacuum distillation similar to Synthesis Example 1 was performed to obtain the target product. Yield: 94%, pale yellow, viscous liquid. The product obtained here was also confirmed to be the desired product based on its IR, NMR, MS spectra, etc. Synthesis example 7N-2-hydroxy-3
Synthesis of -(cis-9-octadecenoyloxy)propylglucosamine Into the same reactor as in Synthesis Example 1, glycidyl oleate (1.0 mol) and glucomine (1.3 mol) were placed and stirred vigorously. The reaction was carried out at 130q0 for 4 hours.

After the completion of the reaction, vacuum steaming was carried out in the same manner as in Synthesis Example 1 to obtain the desired product. Yield 90%, pale yellow, paste. The product obtained here was also confirmed to be the target compound by its IR, NM spectrum, MS spectrum, etc. Synthesis example 8y-(N-trimethy.

Synthesis of aminopropylene glycol q-2-octyldodecanoate Glycidyl 2-octyldodecanoate (1.0 mol) and trimethylol aminomethane (1.0 mol) were placed in a reactor similar to Synthesis Example 1. The reaction was carried out at 12,000 for 4 hours while vigorously worshiping the power.

After completion, vacuum distillation similar to Synthesis Example 1 was performed to obtain the target product. Yield 91%, pale yellow, paste. What I got here,
It was confirmed that it was the target compound based on its m, NM calm, MS spectrum, etc. The compounds of the invention are non-irritating to the skin.

oAnimal skin and human skin irritation test oTest method According to Draize's method, a batch piece coated with 0.5 kg of the nuclear test sample is applied to the skin of white rabbits (3 rabbits were used) whose back hair has been shaved. .

Cover the rabbit with a rubber garment and secure it in the animal holder to prevent it from moving. After 24 hours, remove the batch pieces and record the degree of reaction according to the criteria below.

Judgment is also carried out after 72 hours, and the average value of the scores 1 after 2 hours and 7 hours is calculated and used as the stimulation score 1. Judgment: '11 No erythema and skin formation - 0 Very slight erythema - 1 One visible erythema - 2 Moderate to severe erythema - 3 Severe erythema and light skin formation - 4 ■ Edema formation No edema 10 Very slight edema - 1 Slight edema - 2 Moderate edema - 3 Severe edema - 4 Evaluation: Based on the calculated score-value, the degree of irritation is evaluated as follows.

0-2 - Slight irritation or almost no irritation 2 or more - 5 or less - Moderate irritation 5 or more - Strong irritation Next, a primary skin irritation test was conducted on the human body and it was found to be non-irritating. .

(Table 1) Test method: Using the closed patch test method, a flannel cloth (1. & 4 sides) coated with the test sample is applied to the upper or front inner side, and then covered with a bandage.

After 2 hours, the flannel cloth and sample are removed, and the degree of reaction is judged according to the criteria below, and also after 4 hours.

Judgment: No change at all... - Faint erythema... Obvious erythema... In addition to the erythema, edema, vesicles, etc. are observed...
10 evaluation: (10) and (10) were considered intestinal, and evaluation was performed based on the intestinal rate.

However, the subjects were 50 randomly selected males and 50 females. 1st surface sea: The above wind. 15~M. Compound 19 is a conventional nonionic surfactant.

As is clear from the above, the compounds used in the present invention cause much less irritation to the skin than conventional nonionic surfactants.

Further, as a result of an oral toxicity test using mice, all the compounds in Table 1 were found to have an LD5o209/k9 or higher. The compounds according to the present invention are not only hypoallergenic and non-toxic as mentioned above, but also all of them are based on ordinary oil bases (
For example, it is completely dissolved or miscible in liquid paraffin, fats and oils, ester oil, wax, higher alcohols, etc.), and is also well dispersed or dissolved in water.

Therefore, in the case of emulsion-type cosmetics, the compound and the oil base are mixed by heating, and then water is added to the base and mixed to emulsify. In the case of a type of Izaihoko, water is added to an alcoholic solution of the compound and an oily base while stirring, or in the case of cosmetics such as shampoo, the compound and other The cosmetic of the present invention can be easily produced by applying known techniques such as heating and uniformly dispersing the raw materials. Examples will be described below. Parts shown in the examples mean parts by weight, and % means % by weight. Example 1 (oily nutritional cream) 3 parts of 2-(N-1,1-dimethylolethyl)aminopropyresoglycol Q-oleate, 2 parts of solid paraffin
4 parts Vaseline, 1 part beeswax, 18 parts liquid paraffin
The mixture was heated at 75° C. for 5 minutes to uniformly dissolve the mixture.

Next, 72 parts of purified water heated to 75° C. was added thereto while stirring, and after the addition, the mixture was cooled to room temperature while continuing to cool the mixture to obtain an oil-based nutritional cream. The cream obtained here has an extremely good skin texture and an excellent gloss of 86 (according to JIS Z8741-1962 Clamsawa Degree Measurement Method 2), and
The daily stability at 45:00 was also stable for more than 6 months. Example 2 (oily hair cream) (Oil phase) y-(N-trimethylolmethyl)aminopropylene glycol Q-2-octyldodecanoate 3 parts N-2-hydroxy-3-(cis-9-octadecenoxy) ) Propylglucosamine 1 part Vaseline 4 parts Beeswax 2 parts Liquid paraffin 15 parts Solid paraffin 2 parts Fragrance
Appropriate amount (aqueous phase) glycerin
4 parts thickener 1 part pure water
65 parts The oil phase and aqueous phase having the above composition were heated separately to 70°C to uniformly dissolve them.

Next, the aqueous phase was gradually added into the oil phase while stirring vigorously, and after addition, the mixture was cooled to room temperature while continuing to stir, to obtain an oil-based hair cream. When the cream thus obtained was applied to the hair, it did not give any unpleasant or strange feeling such as stickiness, and its setting power lasted for 3 to 4 days. Example 3 (Natural emulsion stability of oil-based cream) In the above-mentioned Example 1, y-(N-1,1-dimethylolethyl)aminop.

In place of pyrene glycol Q-oleate, other compounds of the present invention, y-(N-2-hydroxyethyl)aminopropylene glycol Q-myristate '1', and commercially available polyoxyethylene (polar.0.) stearyl ether Creams were prepared using 61, sorbitan monostearate '7' and glumitic acid diethanolamide, respectively, and were left in a greenhouse maintained at 4y0 to examine emulsion stability over time. . The results are shown in Table 2. Table 2 (Separation after emulsification) As is clear from the above data, the cosmetics of the present invention (1 to 1)
5) was significantly superior to conventional products in terms of emulsion stability over time, and also had good appearance, gloss, and feel.

Example 4 (Pigment dispersibility in liquid makeup) y-(N-trimethylolmethyl)aminopropylene glycol Q- of the present invention as a surfactant (emulsifying dispersant)
Using 2-octyldodecanoate (Shame.3) and commercially available sorpitan sesquistearate (Lung.5), N-(3-octadecyloxy-2-hydroxypropyl)-diethanolamine (M.6) Each liquid makeup composition was prepared as described below, and its dispersibility with respect to titanium oxide was examined.

Each of the above surfactants 3.0%, isopropyl myristate 1.5%, cetanol 2.0%, olive oil 2.5%
, liquid paraffin solution 2 containing 1.5% Oka type paraffin
Add 0.0 ml of [ to each 50 ml test tube, then add 0.2 t of titanium oxide (average grain size 3 ml) to each and shake for 5 q, then add 10 ml of pure water. In addition, the mixture was shaken 100 times at 5-0 degrees and left to stand at the same temperature for 1 hour to obtain each liquid makeup composition. Next, 1.0% of the upper layer liquid is collected and poured onto a quantitative paper. The furnace paper is placed in a crucible and incinerated on a burner until a constant weight is reached (about 1 hour), and the weight of titanium oxide is determined. The dispersibility was compared by examining the amount of titanium oxide present on the Gisatsuro paper in this way. 3rd result
Shown in the table. In addition, in the table, the ball total value is shown when the value in the case of sorbitan sesquistearate (sample port .5) is set as 100. Table 3 Sample ship. Dispersing power 3 141 5 100 6 103 In this manner, it can be seen that the surfactant of the present invention is significantly superior in pigment dispersibility compared to existing related compounds.

Also, almost similar results were obtained in tests using other pigments such as kaolin, talc, ultramarine blue, and carbon black. Example 5 (Shiampu) Potassium laurate...25 parts Sodium lauryl sulfate...1.5 parts y-(N-
2-hydroxyethyl)aminopropylene glycol Q
-Myristate...3 parts y1 (N12,3-dihydro.

xypropyl) aminopropylene glycol Q-oleate...4 parts pure water...64 parts fragrance
Materials: Appropriate amounts of each component of the above composition were heated to 50° C. to uniformly dissolve, and further cooled to room temperature under a vacuum to obtain a shampoo.

The shampoo obtained here had excellent detergency and foaming power, and also gave good shine and suppleness to the hair without giving a squeaky feeling after washing. Example 6 (Liquid hair styling agent) y-(N-2,3,4,5,6-bentahydroxyhexyl)aminopropylene glycol Q-oleate...2 parts Polyoxyethylene polyoxypropylene copolymer...14.5 parts ethanol (95%) …6 Foundation pure water
…Two-legged fragrance
Light ink Each component of the above composition was mixed and dissolved well at room temperature to obtain a liquid hair styling agent.

This product had less stickiness and good setting power. Example 7 (Oil-based foundation cream) (Oil phase) y-(N-1,1-dimethylolethyl)aminopropylene glycol Q- 2-heptylundecanoate...3 parts y-(N-trimethylolmethyl)amino Propylene glycol Q-oleate...2 parts Solid paraffin...2 parts Vaseline...3 parts lanolin
...1 part liquid paraffin ...16 parts fragrance ...appropriate amount (aqueous phase)
Glycerin: Tripartite titanium oxide
…1.5 parts kaolin
…1.5 parts pengara
...0.00 group part yellow iron oxide
...0.02 part water
...67 parts of the above-composed oil phase components were uniformly dispersed at 80:00.

On the other hand, the aqueous phase components are similarly dispersed uniformly at 80%. Next, the aqueous phase was added to the oil phase while emulsifying it, and the mixture was gradually cooled to room temperature to obtain a foundation cream. This foundation was also found to be extremely stable even after 6 months when stored at 45'0, and it was also confirmed that it was a very rich foundation that surpassed the IQ name collapse. Example 8 (Skin lotion) (Base 1) Glycerin...2 parts Propylene glycol...1 part Solpitol...2 parts Pure water
…76 parts dye
...Appropriate amount (base 2) eta/al (95%) ...13 parts ethyl sebacate ...2 parts y-2-hydroxy-3-(cis-9-ocdadece/iloxy)propylglucosamine ...1 part fragrance ...Appropriate amounts of Base 1 and Base 2 having the above composition were thoroughly mixed at room temperature to obtain a skin lotion.

It has been found that the lotions obtained here exhibit a pronounced moisturizing effect on dry skin, and the compounds of the invention also have an effect as humectants. Example 9 (Nutritional oil) (Base 1) Lanolin...5 parts Olive oil...15 parts Vaseline
...7.5 parts liquid paraffin
...44 parts oleaginous vitamins
...3-part isopropyl myristate
...15 parts (base 2) y-(N-2,3-dihydroxypropyl)aminopropylene glycol Q-oleate ...5 parts propylene glycol ...3 parts water-soluble vitamins ...2 parts fragrance
...Add an appropriate amount of the ingredients in Base 2 with 5 pi○ to thoroughly dissolve.

Also, the components of Base 1 are dissolved at room temperature. Next, Base 1 was gradually added to Base 2 at a temperature of 30°C or less, and thoroughly mixed to obtain a nutritive oil. As described above, by using the surfactant of the present invention, the surfactant is essentially a water-dropping substance and is a component that hardly dissolves in oils. It has been found that it is an extremely useful surfactant that can also solubilize water-soluble vitamins and propylene glycol in oils. In addition, the nutritive oil obtained here was highly penetrating and remained extremely stable even after 6 months at 45°C without separating water-soluble vitamins and propylene glycol.

Claims (1)

[Claims] 1 γ-(N-2-hydroxyethyl)aminopropylene glycol α-myristate, γ-(N-1,1-dimethylolethyl)aminopropylene glycol α-2
-heptyl undecanoate, γ-(N-trimethylolmethyl)aminopropylene glycol α-oleate, γ-(N-2,3,4,5,6-pentahydroxyhexyl)aminopropylene glycol α-oleate,
γ-(N-1,1-dimethylolethyl)aminopropylene glycol α-oleate, γ-(N-2,3-dihydroxypropyl)aminopropylene glycol α-
Oleate, N-2-hydroxy-3-(cis-9-octadecenoyloxy)propylglucosamine, γ-(N
A cosmetic comprising at least one compound selected from the group consisting of -trimethylolmethyl)aminopropylene glycol α-2-octyldodecanoate.