JPS6026367B2 - cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an emulsified material containing Q-mo/(methyl-branched alkyl)glyceryl ether and a water-insoluble inorganic or organic powder that spreads easily when used.

Additionally, Q-monoalkylglyceryl ethers such as chimyl alcohol, batyl alcohol, and serakyl alcohol present in fish lipids have excellent performance as emulsifiers, especially W/O type emulsion stabilizers. Are known.

However, these have drawbacks such as being solids with high melting points, being too lipophilic, and being chemically unstable. In our research on emulsion stabilizers, the present inventors previously discovered the following general formula (1), (where m is an integer of 2 to 14, n is an integer of 3 to 11, and m and n Q-mono(methyl branched alkyl) glyceryl ether represented by (the sum of 9 to 21) is liquid at room temperature, chemically stable, has excellent emulsion stability, and has no skin irritation. He discovered that it was an excellent emulsifier for cosmetics and applied for a patent (Samurai Gan No. 54-1131, No. 54-114).
No. 792).

However, the emulsified salmon material obtained by blending this Q-mono (methyl branched alkyl) glyceryl ether,
It has the disadvantage that it is hard and does not spread sufficiently on the skin.
It turns out that this is not always satisfactory.

Therefore, as a result of further research, the inventor found that this Q-
The present invention has been completed based on the discovery that the above-mentioned drawbacks can be improved and an emulsified cosmetic with good spreadability can be obtained by blending mono(methyl branched alkyl)glyceryl ether with a water-insoluble inorganic or organic powder.

That is, the present invention provides a Q-mono (
The present invention provides an emulsified cosmetic containing methyl-branched alkyl)glycerylphenol, a water-insoluble inorganic or organic powder, and a cosmetic oil base.

The Q-mono(methyl branched alkyl)glyceryl ether (1) of the present invention is a new compound, for example,
-1131 issue, that is, R-X to the alkali metal alcoholate of isopropylidene glycerol
(X is a halogen atom, R has the meaning described above) is reacted by a conventional method to form 2,310-isopropylidene-1-○-methyl branched alkyl glyceryl ether, which is then hydrated. Easily produced by decomposition.

The method of using Q-mono(methyl branched alkyl) glyceryl ether as an emulsifier is not particularly limited, but the following three methods can be used.
It is preferable to blend the components as a W/O type emulsifier.

In this specification, % means weight % unless otherwise specified. ■ Q-mono (methyl branched alkyl) glyceryl ether 43-90% ■ Polyvalent metal salt of saturated or unsaturated fatty acid of pine carbon number 10 0.4-9.8%
■ One or more inorganic salts or organic salts with a solubility in water of 2 pi○ and 0.2 ta'100 ta or more 8-54
As polyvalent metal salts of fatty acids with component (%), especially those with a carbon number of 1
2 to 18 are preferred.

Further, examples of the salts include calcium, magnesium, zinc, aluminum salts, etc., and among them, aluminum salts are particularly preferred. Any of the mono-, di- or tri-forms of the polyvalent metal salt can be used, but the mono-form is particularly preferred. These fatty acid polyvalent metal salts may be synthesized in advance by the double decomposition method or the direct method, but
Water-soluble polyvalent metal salts such as calcium chloride,
It may also be produced by subjecting magnesium chloride, magnesium sulfate, zinc chloride, aluminum chloride, aluminum sulfate, alum, etc. to a substitution reaction with a fatty acid monovalent salt.

Preferred fatty acid polyvalent metal salts include aluminum monostearate, aluminum distearate, calcium monostearate, aluminum monooleate, aluminum mono/gulmitate, and aluminum monolaurate.

Inorganic salts or organic acid salts of component ■ include hydrochloric acid, sulfuric acid,
Inorganic acids such as nitric acid; oxycarboxylic acids such as citric acid, tartaric acid, lactic acid, and malic acid; carboxylic acids such as formic acid, acetic acid, and sorbic acid; or alkali metal salts of aromatic carboxylic acids such as salicylic acid and benzoic acid; Examples include metal salts and aluminum salts.

These inorganic salts or organic acid salts may be incorporated into cosmetic compositions in the form of salts, but when manufacturing cosmetics, the corresponding acidic and basic substances are adjusted to the stoichiometry required to form the salt. It may be manufactured by adding the amount.

Preferred inorganic salts or organic salts include potassium sulfate, sodium sulfate, magnesium sulfate, aluminum sulfate, potassium nitrate, sodium nitrate, magnesium nitrate, aluminum nitrate, calcium nitrate, potassium chloride,
Magnesium chloride, sodium chloride, calcium chloride,
Aluminum chloride, potassium carbonate, sodium carbonate, aluminum carbonate, potassium acetate, sodium acetate, calcium acetate, magnesium acetate, sodium formate, potassium formate, magnesium formate, sodium citrate, sodium tartrate, potassium sorbate, sodium sorbate, sodium salicylate , potassium benzoate, sodium benzoate, etc., especially potassium sulfate, magnesium sulfate, potassium chloride, magnesium chloride, aluminum chloride, sodium citrate, sodium tartrate, potassium sorbate, sodium salicylate and sodium benzoate. preferable. The water-insoluble inorganic or organic powder used in the present invention includes the following. In other words, inorganic powders include talc, sericite, titanium oxide, silicon oxide, lead oxide, bentonite, vegum, kaoliso, etc.; organic powders include crystalline cellulose, silk powder, keratin powder from wool, feathers, nails, etc., and nylon powder. , polystyrene powder, polymethyl methacrylate powder, polyoxyethylene powder, ethylene powder, etc., especially talc, sericite, titanium oxide, nylon powder, silk powder, polymethyl methacrylate powder, polystyrene powder, polyethylene. Powders are preferred. These may be used alone or in combination of two or more. Further, the size of the powder is not particularly limited as long as it is 2 to 3 peaks or more, but it is preferably 30 peaks or less in view of the rough feeling during use. The weight ratio of Q-mono(methyl branched alkyl) glyceryl ether and water-impregnable inorganic or organic powder to the emulsified cosmetic is 100:1 to 1:500.
, particularly preferably 10:1 to 1:60.

The emulsified cosmetic of the present invention is produced by a known method except for blending the above two components. For example, in the case of a W/O type emulsified cosmetic, the above two ingredients, water and IQ salmon oil base, and depending on the purpose, a surfactant as an auxiliary emulsifier, a viscosity modifier, a medicinal agent, and a wetting agent. , preservatives, etc. may be appropriately added. Hydrocarbons such as squalane, paraffin oil, and ceresin oil; beeswax, whale wax,
Waxes such as carnauba wax; natural animal and vegetable oils and fats such as olive oil, camellia oil, and lano oil; fatty acids having 10 to 20 carbon atoms; higher alcohols having 10 to 20 carbon atoms; esters thereof; silicone oil; and the like. In addition, as surfactants, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene hydrogenated castor oil, sucrose ester, sorbitan fatty acid Esther,
Glycerin fatty acid esters, fatty acid alkali metal salts, alkyl sulfate esters, alkyl phosphate esters, polyoxyethylene alkyl sulfate esters, polyoxyethylene alkyl phosphate esters, etc. are used as viscosity modifiers, such as polyvinyl alcohol, polyoxyvinyl polymers, etc. 1. Synthetic polymer compounds such as carboxymethylcellulose, polyvinylpyrrolidone, hydroxyethylcellulose, and methylcellulose; natural gums such as gelatin and taracanth gum, and alcohols such as ethanol and inpropyl alcohol; medicinal agents include bactericidal agents; , anti-inflammatory agents, vitamin preparations, etc. Wetting agents include propylene glycol, glycerin, 1,3-butylene glycol, sodium pyrrolidonecarboxylate, sorbitol, etc., and preservatives such as methyl paraoxybenzoate and ethyl paraoxybenzoate. , propyl paraoxybenzoate, butyl paraoxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxychetanol, and the like. The most preferred composition of the emulsified ready-made material of the present invention is as follows.

Blending amount Preferred sardine) Blending amount of water-insoluble inorganic or o.・~5o o. 5-30〈
is organic powder o-mono(methyl branched alkyl) chryceryl 0.1-10 0.5-5
．． 0 Ether fatty acid polyvalent metal salt 001-1.0
002-0.5 water-soluble inorganic salt or o. 1-5. o
o. 2-1.0 Organic acid salt cosmetic oil base 4-
35 8-30 Water Balance Balancing agent 0-10 0-5 Wetting agent 0-30 0-10 Surfactant
0-10 0-5 Viscosity modifier 0-10
0-2 Stabilizer 0-10 0-2 Preservative 0-1 0-0.5 Pigment
Trace amount Trace amount Trace amount Among these compositions, Q-mono (methyl branched alkyl)
When glyceryl ether is less than 0.1%, it is not possible to stabilize the W/O type emulsion, and when it exceeds 10%, it takes on a gel structure and the cream viscosity increases significantly. All of these are not preferred as emulsified IQ saddle materials.

Further, water can be added in any amount, but it is preferable to add 60% or more in order to have a good feeling of use, that is, to reduce oiliness or stickiness on the skin. The emulsified irritants of the present invention can be used in various forms, such as hand creams, nutritional creams, cleansing creams, milky lotions,
It can be in the form of cold cream, hair cream, vanishing cream, foundation cream, etc.

The emulsified cosmetic composition of the present invention obtained as described above not only has significantly improved spreadability by incorporating insoluble inorganic or organic powder, but also has the dispersed powder containing titanium oxide, titanium oxide, In the case of talc, etc., its hiding power blocks out ultraviolet rays that are harmful to the skin, and also provides strong protection to the skin when it comes in contact with water such as sweat in the summer, bathing, or water work.

Furthermore, it is an excellent emulsified makeup that not only retains the original advantages of Q-mono (methyl branched alkyl) glyceryl ether-containing cosmetics, which have a slight oiliness and stickiness, but also actively provides a strong refreshing feeling. You can get a fee. Next, reference examples for producing Q-mo/(methyl branched alkyl) glyceryl ether and examples of the present invention will be described.

Reference Example 1 In a 20mm autoclave, isostearic acid isopropyl ester [Eme 2310 isostearic acid isopropyl ester, commercially available from Emery Company, USA] 4770 and copper chromium catalyst (manufactured by JGC) 2
Prepare 39 evenings.

Next, hydrogen gas is charged at a pressure of 150 k9/kg, and then the reaction mixture is heated to a temperature of 2,790 °C. 1
After hydrogenation at 275° C. for about 7 hours, the reaction product was cooled and the residual catalyst was removed by filtration to obtain 3500 g of crude product.

By distilling the crude product under reduced pressure, the
Colorless and transparent isostearyl alcohol $00 was obtained as a 0.6 fraction. The obtained isostaryl alcohol (methyl branched stearyl alcohol) had an acid value of 0.05, a saponification value of 5.5, and a hydroxyl value of 181.4. Melon (liquid pus) showed absorption at 3340 and 1055 -1, and NMR (CC14 solvent) showed absorption at 6350 (broad triplet; -CH2-OH), respectively.
According to the gas chromatograph, about 75% of the main components of this alcohol have alkyl groups with a total carbon number of 18 (the sum of m and n in formula 1 is 15), and the remaining components have a total carbon number of 14, 16, and it was found that all of the methyl groups in the rind were a mixture of those located near the center of the alkyl main chain. Reference Example 2 (i) In a reaction vessel with a capacity of 5 equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen gas inlet pipe, and a strainer, Reference Example 1 was added.
2444 liters of isostearyl alcohol obtained in step 1 was charged.

Thionyl chloride was added dropwise from a dropping funnel at room temperature while blowing nitrogen gas. The reaction mixture exothermed and evolved gas at the same time. The temperature of the reaction mixture rose to 31°C at the beginning of the reaction, but as the amount of thionyl chloride added increased, it gradually decreased to around 18°C. At this point, the reaction mixture was heated to about 40 qo, and thionyl chloride was continued to be added dropwise. After the gas generation has weakened,
When the reaction mixture was heated to a temperature of 70 to 80 o'clock, the generation of gas became intense again, so thionyl chloride was successively added dropwise. The dropping of thionyl chloride was stopped when no gas was observed to be generated at all. The total amount of thionyl chloride added dropwise was 1,000 ml. The reaction product was cooled and further heated at 70 to 80 degrees for about 1 hour. The reaction product was cooled, and the low-boiling fraction (mainly unreacted thionyl chloride) was distilled off under normal pressure at 40 to 50 oo, the residue was ice-cooled, and ice cubes were added little by little while shaking.

After confirming that the generation of intense gas had stopped, ether was added, then water was added, and the mixture was thoroughly stirred. The ether layer was separated, neutralized with sodium bicarbonate, and the solvent was removed.
Distilled under reduced pressure to give 103~163oo/0.1~1. Isostearyl chloride (formula m, ×=
CI) Shigeru obtained 17 evenings. IR (liquid film): 725 650
-I NMR (CC14): 8 3.50 (triple line -CH2CI) (ii) 7 drops of isopropylidene glycerol in a 5 volume reaction bath equipped with a thermometer, a box frame, a dropping funnel and a Dean-Stark trap. In the evening, 1500 units of xylene,
0 ml of 93% sodium hydroxide milk and 30 ml of water were charged, and heated to reflux at 130 to 140 qo while lighting a candle.

Water was separated from the water/xylene mixture produced in a Dean-Stark trap and removed from the reaction system, and xylene was returned to the reaction system. After heating and refluxing for about 1 hour, when no water was observed to be distilled out, isostearyl chloride 777 produced in Kawasaki was added dropwise over a period of about 30 minutes. After the dropwise addition was completed, the reaction mixture was further heated under reflux at 130 to 140 qo for about 9 hours to complete the reaction. After cooling, the sodium chloride precipitated in the reactor was removed by filtration, and the solvent was removed under reduced pressure.
A fraction of 800 fractions of 0/0.25 to 0.5 Dianyu was obtained.
This is 2,3-○-isopropylidene-1-○-isostearylglyceryl ether (formula W, R=CH3). IR (liquid film): -11200~1260,105
0-1120 (C-○ stretching vibration) NMR (CC14):
63.1-4.2 (multiple line, price) Into a reaction vessel of 5 capacity equipped with a thermometer, a thermometer, and a reflux condenser, 1103 mL of isopropylidene isostearyl glyceryl ether obtained in (ii) was added. Add 1,500 ml of ethanol to this and 2,000 ml of 0.1N sulfuric acid.
' was added.

The mixture was heated to reflux at 80 to 85°C while stirring, and after about 1 hour, it was monitored by gas chromatography, and it was confirmed that the hydrolysis of isopropylidene isostearyl glyceryl ether had been completed. . After being released, it was allowed to stand still and separated into an oil layer and a water layer. The aqueous layer was extracted with ether, combined with the previous oil layer, and an aqueous sodium bicarbonate solution was added to neutralize the remaining acid. After separating the organic layer, the solvent was removed under reduced pressure, and the mixture was further heated and dried at 100° C./0.1 min for 3 hours. Q-mono(isostearyl)glyceryl ether 900 mg was obtained as a colorless transparent liquid. m (liquid film): I00,1050~114 Yamariki-INMR (CC
14): 63.2 to 3.8 (multiple line, acid value: 0.08, saponification value: 0.36, hydroxyl value: 31
3.8 Iodine value: 0.32 Example 1 An anti-day competition cream of the present invention was produced according to the following composition,
A sensory test was conducted on this product by 35 expert female panelists to evaluate its usability.

As control products, sun moth repellent cream A, which was manufactured in the same machine as the product of the present invention except that titanium oxide was not used, and commercial product B were used. The results are shown in Table 1. The results are shown as the average value of the absolute evaluation points. Composition: ■ Titanium oxide 3 (%) ■ Q
- Monoisopalmitylglyceryl ether (m=6, n
= 7) 2 ■ Squalane 10 ■ Aluminum monostearate 0.04 ■ Magnesium sulfate 0.5 ■ Octyl methoxy cinnamate (ultraviolet absorber)
5 ■ Sodium benzoate 0.3 ■
Glycerin 3.5 ■ Propylene glycol 5.0 ■ Purified water Remaining amount Production method: ■ ~ ■ were mixed and heated to 75 qo.

A mixture of (1) and (2) to (2) heated to 7,500 ℃ was added to the mixture, emulsified, and cooled to room temperature to obtain a product. Results: Table 1 (Evaluation Criteria): (Less) ~5 (Desire) (Light) 1~5 (Heavy) As is clear from Table 1, the anti-phosphorus treatment of the present invention The cream had a significantly smoother feel when used than the conventional product, and also had good emulsion stability over a long period of time.

Example 2 A hand cream of the present invention was manufactured according to the following composition.

In addition, a hand cream manufactured in the same manner as the product of the present invention except that talc was not used was used as a comparison product, and 40 expert female panelists compared the feeling of use. The results are shown in Table 2. Composition: ■ Talc 2 (%) ■ Q-Mo/Isostearylglyceryl ether (m=7, n=8
) 2 ■ Isopropyl myristate 10 ■ Dimethylpolysiloxane 3 ■ Aluminum monopalmitate 0.04 ■ Sodium nitrate
0.5■ Methyl paraoxybenzoate 0.2■ Glycerin
50■ Purified water
Remaining amount Production method: ■~■ were heated to 75q0.

A mixture of (1) to (2) heated to 75 qC was added to the mixture, emulsified, and cooled to room temperature to obtain a product. Results: As is clear from Table 2, the hand cream of the present invention had a comparable feeling of use and good emulsion stability over a long period of time.

Example 3 Emulsions and nutritional creams were manufactured according to the following compositions.

All of them were excellent IQ salmon ingredients that had good emulsion stability, were less sticky and oily, and spread easily. (Emulsion) Composition: ■ Polystyrene beads (average particle size 15-) 2 (%) ■
Q-monoisostearylglyceryl ether (mainly m=7, n=8) 1.5■ Beeswax
2■La/Lin 2■Liquid paraffin 20■
Calcium monostearate 0.02■ Sodium citrate 0.5■ Polyoxyethylene (20) sorbitan monooleate 1.0■ Methyl paraoxybenzoate
0.2 ■ Glycerin 5 ■
Purified water Remaining amount Production method: Disperse ■ and ■ in ■~■ and ■ heated and dissolved in 7pi0,
1 and 2 to 3, which had been heated and dissolved at 70 qC, were added to the mixture, emulsified, and cooled to room temperature to obtain a product.

(Nutritional cream) Composition: ■ Chikara Orin 2.5 (%) ■
Q-monoisomyristyl glyceryl ether (m=5
, centered around n=6) 2.0■ Beeswax 4.0■ Vaseline 5.0■ Squalane
20■ Aluminum monooleate 0.04■ Potassium sorbate 0.5■ Glycerin monooleate 3.5■ Polyoxyethylene (2
0) Sorbitan monooleate 1.0
■ Ethyl parabenzoate 0.2■
Propylene glycol 3.0■ Glycerin 50■ Purified water
Remaining amount manufacturing method: Disperse ■ and ■ in ■~■, ■, and ■ heated to 70oo, add ■ and ■~■ heated to 700, emulsify, and cool to room temperature. It was made into a product.

Example 4 A hand cream of the present invention was manufactured according to the following composition.

In addition, a hand cream manufactured in the same manner as the product of the present invention except that sericite was replaced with purified water was used as a comparison product.
The usability was compared in the same manner as in Example 1. The results are shown in Table 3. Composition: ■ Sericite 5 (%) ■ Q-monoisostearyl glyceryl ether (m=7, n=8
) 2 ■ Liquid paraffin 16 ■
Aluminum monostearate 0.04 ■ Magnesium sulfate 0.5 ■ Sodium benzoate 0.3 ■ Glycerin
5 ■ Purified water
Residual amount results: Table 3 Example 5 A face cream of the present invention was manufactured according to the following composition.

In addition, a face cream manufactured in the same manner as the product of the present invention except that the polyethylene powder was replaced with water was used as a comparison product, and the feeling of use was compared in the same manner as in Example 1. The results are shown in Table 4. Composition: ■ Polyethylene powder 4 (%) ■ Q-monoisostearyl glyceryl ether (m=7, n=
8) 2 ■ Octyldodecyl myristate 10 ■ Liquid paraffin 6 ■ Aluminum monostearate 0.04 ■ Magnesium sulfate 0.5 ■ Sodium benzoate 0.3 ■ Glycerin
5) Remaining amount of purified water Results: Table 4 Test Example 1 Add and mix 3 parts by weight of the emulsifier shown in Table 5 to 2 parts by weight of liquid paraffin, and heat to 7-0.

Separately, 70 parts by weight of ion-exchanged water was heated to 70:00, and this was added to the above-mentioned strained mixture to emulsify it. After emulsification, cool to room temperature under a vacuum cleaner, and dry the milk immediately after emulsification and 2yo.
The separation rate was investigated when stored for 7 days. The results are shown in Table 5. Table 5

Claims (1)

[Claims] 1 General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, m is an integer from 2 to 14, and n is 3 to 11
α-mono(methyl-branched alkyl)glyceryl ether represented by (an integer of , the sum of m and n is 9 to 21), a water-insoluble inorganic or organic powder, and a cosmetic oil base. Emulsified cosmetics. 2. The emulsified cosmetic according to claim 1, wherein the water-insoluble inorganic or organic powder is selected from the group consisting of talc, sericite, titanium oxide, kaolin, polystyrene powder, and polystyrene powder. 3. The content of α-mono(methyl branched alkyl) glyceryl ether and water-insoluble inorganic or organic powder is 0.1 to 10% by weight and 0.1 to 20% by weight of the total composition, respectively. The emulsified cosmetic according to item 1 or 2.