JPS6026087B2 - 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 cream, emulsion, lotion, and oil skin cosmetics and hair cosmetics such as hair conditioners, shampoos, and conditioners.

Conventionally, the conditions that many cosmetics should meet are '1'.
Highly safe without irritating the skin, etc.

■High emulsion stability and stability over time. '3' Good affinity for skin, etc. ■It must be easy to use.
'5} Good appearance such as texture and glossiness are mentioned. 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, in addition to water, Imonoseki is composed of components such as oil bases (oils and fats, waxes, higher alcohols, hydrocarbons, ester oil, etc.), wetting agents, surfactants, ethanol, fragrances, etc. Among them, surfactants have a great influence on the factors mentioned above, such as emulsion stability, stability over time, resistance to skin irritation, physiological safety, affinity for the skin, feeling of use, appearance, etc. Great care must be taken when using it. It is especially widely used as a nonionic surfactant and solubilizer. Among them, those that are relatively good in terms of skin irritation, toxicity, emulsifying power, etc. are currently being used as raw materials for Isukan products, but there is still no material that can satisfy all of the above conditions. I don't get it. For example, polyoxyethylene higher alcohol ethers such as polyoxyethylene oleyl ether and polyoxyethylene cetyl ether are highly irritating to the skin and have poor emulsion stability.

In addition, glyceryl stearyl ether, glyceryl cetyl ether, glyceryl lauryl ether (monoether, ether), etc. have poor emulsifying properties, resulting in poor texture, gloss, and stability over time of the resulting cream. In addition, polyol higher fatty acid esters such as glycerin higher fatty acid ester, solpitan higher fatty acid ester, and polyethylene glycol higher fatty acid ester have poor emulsification stability, tend to cause gel-a phenomenon, and are poor in stability over time. Furthermore, higher fatty acid amides such as jetanolamine do not have sufficient emulsifying power and some skin irritation, although slight, has been observed, and therefore their use has been limited. The present inventors took advantage of this current situation and conducted intensive research. As a result, the compound represented by the general formula below has no irritation to the skin, is physiologically stable, and has a
We have discovered that when incorporated into salmon ingredients, not only the stability is significantly increased, but also the usability and appearance are extremely excellent, eliminating all the drawbacks of conventional nonionic surfactants. Completed the invention.

The purpose of the present invention is to provide 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 long-term stability, and have a good appearance. The purpose of the present invention is to provide hair care products such as skin cosmetics, hair styling products, hair conditioners, shampoos, and conditioners.

That is, the present invention relates to y-(N-methylN-trimethylolmethyl)aminopropylene glycol o-2-octyldodecyl ether, y-(N-methyl-N-1,1-dimethylolethyl)aminop. A convex salmon characterized by containing at least one compound selected from the group consisting of pyrene glycol Q1n-9-octadecenyl ether (hereinafter referred to as the compound of the present invention for convenience) It is a fee. Embodiments of the present invention will be explained in detail below.

At least one of the compounds of the present invention is mixed with the base of the Japanese salmon material by a known method to be incorporated into the cosmetic composition.

The amount used (content) is usually 0.1 to 3% by weight (preferably 1 to 2% by weight) based on the weight of the cosmetic.
is within the range of For example, in the case of skin care cosmetics, it is usually 1
~1% by weight is blended, and in the case of hair cosmetics, it is 5~1% by weight.
It is often used within a range of 2% by weight.

The compound used in the present invention can be obtained by heating the glycidyl ether of the higher alcohol and the N-methyl-alkanolamine in an amount of 1.2 to 3 times the mole thereof to cause an addition reaction. obtained in high yield.

An example of its synthesis is shown below.

Synthesis Example 1 Synthesis of y-(N-methyl N-trimethylolmethyl)aminopropylene glycol, Q-2-octidodecyl ether, a 2000 [
1.2 mol of N-methyl-trimethylolaminomethane and 1.0 mol of glycidyl 2-octyl dodecyl ether were placed in a flask and reacted at 120°C for 4 hours.

After the reaction, 1,000 ml of petroleum ether was added to the contents, and the mixture was thoroughly stirred and then allowed to stand at room temperature for 2 hours. The precipitated unreacted N-methyl-trimethylaminomethane is removed by decantation, and the supernatant liquid is concentrated. Next, the residue was distilled under high vacuum (0.05Ton) to remove fractions up to 160 qo to obtain the target compound.

Yield 91%, pale yellow, paste. It was confirmed by various analyzes (IR, NM town, MS, etc.) that this product was the above-mentioned target compound.

Synthesis example 2: y-(N-methyl-N-1,1-dimethylolethyl)
Synthesis of aminopropylene glycol Q-n-9-octadecenether In a reactor similar to Synthesis Example 1, 7.2 mol of N-methyl-2-amino-2-methyl-1,3-prohanediol and glycidyl oleyl ether were added. Add 1.0 mol and heat at 120℃ for 3. After the reaction was completed, the same post-treatment as in Synthesis Example 1 was carried out.
The target compound was obtained after 16 days.

Yield 93%. Light yellow vest. The product thus obtained was also analyzed in the same manner as in Synthesis Example 1, and was confirmed to be the target compound.

The compounds of the present invention are less irritating to the skin. A. Animal Hide Deer Irritation Test - Test Method According to Draize's method, a batch piece coated with 0.5 kg of the test sample is applied to the skin of white domestic 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.

The determination is also made after 7 hours, and the average value of the score 1 after 2 hours and after 7 hours is calculated, and the stimulation score is set as 1. Judgment: '11 No erythema or skin-forming erythema -0 Very slight erythema 11 Confirmed erythema
-2 Moderate to severe erythema
-3 Severe erythema and mild skin formation -4t2)
Formation of edema No edema -0 Very slight edema 11 Slight edema
-2 Moderate edema -3 Severe edema
14 Evaluation: Based on the calculated score, the degree of stimulation is evaluated as follows.

0-2 Slight irritation or almost no irritation 2 or more and 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) B Human skin irritation test test method: Using the closed rust patch test method, a flannel cloth (1. & 4 sides) coated with the test sample on the upper or anteromedial part is applied to the skin, and then Cover with a bandage.

After 24 hours, the flannel cloth and sample are removed, and the degree of reaction is determined 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 positive, and evaluation was performed based on the positive rate.

However, the subjects were 50 randomly selected males and 50 females. Preparation of test sample: Olive oil containing 1% by weight of each of the test substances shown in Table 1 was prepared and used as a test sample.

1st Omote Kanji: The above location. 9~No. Compound 14 is a conventional nonionic surfactant.

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

Further, as a result of an oral toxicity test using mice, it was confirmed that all the compounds in Table 1 had an LD rule of 20 min/kg or more. The shown 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 oily bases (e.g., liquid paraffin, fats, oils, ester oils, waxes, higher alcohols, etc.). It is completely dissolved or miscible in water, 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 mixture to emulsify it. In the case of type cosmetics, by a method such as adding water to an alcoholic solution of the compound and an oily base while stirring,
In the case of cosmetics such as shampoo, the cosmetics of the present invention can be easily prepared by applying known techniques such as heating the compound and other raw materials to uniformly disperse them. is manufactured. Examples will be described below. Parts shown in the examples mean parts by weight, and % means % by weight. Example 1 (oily skin cream) y-(N-methyl-N-1,1-dimethylolethyl)
Mix 3 parts of aminopropylene glycol Q1n-9-octadecenyl ether, 2.0 parts of ceresin, 4 parts of petrolatum, 1.5 parts of Millo, 1 part of tuna wax, and 14 parts of liquid paraffin to make 7.0 parts. The mixture was heated for 5 minutes to dissolve it uniformly.

Next, 7 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 stir, to obtain an oil-based skin cream (nutritional cream). The cream obtained here has an extremely good texture and a gloss level of 82 (J
According to IS28741-1962 Flow Rate Measurement Method 2), the stability over time at 4500 was also stable for more than 6 months. Example 2 (Nutritional Oil) (Base 1) Lanolin 5 parts Olive oil 12 parts Octidodecyl myristate 5 parts Liquid paraffin
4.5 parts oily vitamins
1.5 parts diisopropylazibate
15 parts (base 2) y-(N-methyl-N
2 parts y-(N-methyl-N-1,1-dimethylolethyl)aminopropylene glycol Q-n-9-octadecenyl ether 1 .5 parts water lacquer vitamins 1 part propylene glycol 2.5 parts fragrance
Add an appropriate amount of the ingredients of Base 2 at 50°C to 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 main pot is a water-soluble substance and 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 had a rich penetrating effect and was extremely stable even after 6 months at 45°C without separating hydrophilic vitamins or propylene glycol.

Example 3 (Oily hair cream) (Oil phase) y-(N-methylN-trimethylolmethyl)aminopropylene glycol Q 1 part 2-octyldodecyl ether y-(N-methyl-N-1,1-dimethylolethyl) Aminopropylene glycol Q-n-9 octadecenyl ether 3 parts liquid paraffin 15 parts beeswax 2.5 parts solid paraffin 2.5 parts spermaceti
3.5% fragrance
Appropriate amount (aqueous phase) glycerin
3 parts thickener 1.5 parts pure
65 parts of water The oil phase and water phase having the above composition were heated separately to 7,000 ℃,
Dissolve uniformly.

Next, the aqueous phase was gradually added into the oil phase while stirring vigorously, and after the 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 4 (Daily emulsion stability of oil-based cream) In the above-mentioned Example 1, y-(N-methyl-N-1,
1 dimethylolethyl) aminopropylene glycol Q
In place of 1n19-octadecenyl-7yl, it is a compound of the present invention.

y-(N-methyl-N-trimethylolmethyl)aminopropylene glycol Q-2-octidodecyl Able (M.4) and known y-(N-methyl-N-2-hydroxyethyl)aminopropylene glycol Q-decyl A cream was prepared using each of ether (M.6), polyoxyethylene stearyl ether (3, ED) (M.7), and stearic acid jetanolamide (M.8) and placed in a thermostatic chamber kept at 45°C. The emulsion stability was examined over time. The results are shown in Table 2. As is clear from the results in Table 2 and above, the cosmetics of the present invention (1 to 5
) was significantly superior to conventional products in terms of emulsion stability over time, and also had good appearance, gloss, and feel.

Example 12 (Pigment dispersibility in liquid makeup material) As a surfactant (emulsifying dispersant), y-(N-
Methyl-N-1,1-dimethylolethyl)aminopropylene glycol Q-n-9-octadecenyl ether (M.2), y-(N-methyl-N-trimethylolmethyl)amino/propylene glycol 2-octyldodecyl ether (M.3) and commercially available sorbitan monostearate (M.5), y-(N-methyl-N-2-hydroxyethyl)aminopropylene glycol Q-ocdadecyl ether (M.5). 6), each liquid makeup composition was prepared as described below, and its dispersibility with respect to titanium oxide was examined.

(Oil phase) Surfactant 3 parts liquid paraffin 35 parts cetanol
5 parts castor oil
5 parts isopropyl halumitate 2 parts fragrance
Appropriate amount (aqueous phase) titanium oxide
2 parts pure water
5th side The above oil phase component is heated to 8000℃,
Dissolve uniformly while concentrating vigorously.

Similarly, the aqueous phase components are uniformly dispersed. Next, the aqueous phase is added to the oil phase while stirring at the same temperature, and after uniformly dispersing it, it is cooled to room temperature while stirring to form a liquid make-up agent (M.1 to Lung). 6) was obtained. Next, for each sample 10 [
Place each sample in a 20' centrifuge tube and heat centrifuge (45℃1).
50 ratio pm. After carrying out 1.0 μm of the upper layer liquid, accurately weigh out approximately 1.0 μm of the upper layer liquid and place it in the crucible. By heating the crucible on a burner until it reaches a constant weight (about 1 hour) to completely incinerate the contents, and quantifying the titanium oxide in the ignition residue (Cosmetic Raw Materials Standard Commentary, 1st Edition, oxidation The dispersion forces (by titanium volumetric method) were compared. The results are shown in Table 5. In addition, in the table, the converted value is shown when the value in the case of sorbitan monostearate (sample M5) is set as 100. As shown in Table 3, 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 13 (Modifying power of oil-based foundation cream) As a surfactant, y-(N-methyl-N-1,1-dimethylolethyl)aminopropylene glycol Q-n-9-octadecenyl ether (No. 3), commercially available sorbitan sesquibehenate (No. 5), oleic acid diisopropanolamide (No. 6), y-(N-methyl-N-2-hydroxyethyl) aminopropylene glycol Q doco A foundation cream having the following composition was prepared according to Example 3 using Silether (M.7).

(Oil phase) Surfactant 5 parts Vaseline
2.5 parts carnauba wax 1.5 parts lanolin
1.5 parts liquid paraffin
15 parts fragrance
Appropriate amount (aqueous phase) 1,3-butanediol
Tripartite titanium oxide
Part 2 Kaolin 1.
5th part Hengara 0.02
0.02 parts yellow iron oxide 65 parts pure water.

method) Using a cribtometer equipped with a thin steel plate with a thickness of 0.5, the Ando force measurement method (JISK5101-19M
).

The results are shown in Table 6. The values shown in the table are converted values based on the value obtained when sorbitan sesquibehenate is used (sample M.5) as 100. Table 4

Claims (1)

[Claims] 1 γ-(N-methyl N-trimethylolmethyl)aminopropylene glycol α-2-octyldodecyl ether γ-(N-methyl-N-1,1-dimethylolethyl)aminopropylene glycol α-n-9-octa A cosmetic comprising at least one compound selected from the group consisting of decenyl ether.