JPH0524885B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a cosmetic containing spherical organic composite clay mineral powder. More specifically, the present invention relates to a cosmetic containing a spherical organic composite clay mineral containing a water-swellable clay mineral and a water-soluble substance and exhibiting excellent feel (smoothness and moisture) and moisturizing properties. [Prior art] Water-swellable clay minerals are used as dispersion stabilizers for paints, pharmaceuticals, and cosmetics by utilizing their swelling and gelling properties, and have particularly high safety and good gelling ability. Therefore, it is preferably used in cosmetics, especially powder dispersion products and emulsion products (eyeliner, mascara, emulsion, cream, nail enamel). It is generally used in the form of a gel dispersed in an aqueous solvent. In addition, water-swollen clay minerals cause interlayer reactions with organic polar molecules and cationic molecules such as various alcohols, amines, and water-soluble polymers, and form clathrate compounds. However, such clathrate compounds have so far only been used in the form of gels dispersed in aqueous solvents. Furthermore, even if the powdered state is incorporated into cosmetics as is, the granules often become amorphous and tend to aggregate due to the filtration and centrifugation processes that take place during powdering. The drawback is that it has a strong rough texture, making it difficult to incorporate it into cosmetics that place particular importance on the feel of the product. On the other hand, water-soluble substances are often incorporated into cosmetics for the purpose of reinforcing moisture in the skin, but when incorporated in large amounts, they often cause stickiness.
Furthermore, any water-soluble substance has poor solubility and compatibility in a formulation system in which water does not exist, and often evaporates over time. Therefore, it could not be incorporated into this type of product. [Problems to be Solved by the Invention] As a result of intensive studies to improve the shortcomings of the prior art, the present inventors have developed a material containing a water-swellable clay mineral and a water-soluble substance, and which has a spherical shape. We discovered that by blending spherical organic composite clay minerals with
Based on this knowledge, we have completed the present invention. [Means for Solving the Problems] That is, the present invention is a cosmetic characterized by blending a spherical organic composite clay mineral powder containing a water-swellable clay mineral and a water-soluble substance. The configuration of the present invention will be described below. The spherical organic composite clay mineral powder (hereinafter referred to as spherical organic clay mineral) blended into the cosmetic in the present invention is a spherical organic composite clay mineral powder containing a water-swellable clay mineral and a water-soluble substance. It is. The water-swellable clay mineral used in the present invention is a layered silicate mineral belonging to the genus smectite, and generally includes montmorillonite, beidellite, nontronite, saponite, and hectorite, and these may be natural or synthetic. It may be hot. Commercially available products include Kunipia, Smecton (all manufactured by Kunimine Industries), Veegum (Vanderbilt),
Laponite (Laporte), fluorine tetrasilicon mica (Topy Industries), etc. can be used. In carrying out the present invention, one or more kinds of these water-swellable clay minerals are arbitrarily selected. The water-soluble substance used in the present invention is any water-soluble substance that is normally used in cosmetics, and specific mucopolysaccharides such as hyaluronic acid, chondroitin sulfate A, chondroitin sulfate B, chondroitin sulfate C, heparan sulfate, heparin Examples of natural water-soluble polymers such as keratan sulfate include gum arabic, gum tragacanth, galactan, guar gum, gum kyalob, gum karaya, carrageenan,
Pectin, agar, quince seed (quince), algae colloid (bonnet extract), starch (rice, corn, potato, wheat)
Microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, semi-synthetic water-soluble polymers such as starch polymers such as carboxymethyl starch, methylhydroxypropyl starch, methyl cellulose, nitro Cellulose polymers such as cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, sodium carboxymethyl cellulose (CMC), crystalline cellulose, cellulose powder, arginine such as sodium alginate, propylene glycol alginate ester, etc. Examples of acidic polymers and synthetic water-soluble polymers include vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxyvinyl polymer (Carbopol), and polyoxylic acids such as polyethylene glycol 20000, 4000000, and 600000. Ethylene (hereinafter referred to as POE) polymers, copolymer polymers such as POE polyoxypropylene (hereinafter referred to as POP) copolymers, acrylic polymers such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, polyethyleneimine,
Examples of polyhydric alcohols such as cationic polymers include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2 -Butene-
Dihydric alcohols such as 1,4-diol, hexylene glycol, octylene glycol, glycerin, trimethylolpropane, 1,2,6-
Trivalent alcohols such as hexanetriol, tetravalent alcohols such as pentaerythritol, pentavalent alcohols such as xylitol, hexavalent alcohols such as sorbitol and mannitol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetrahydric alcohols, etc. Polyhydric alcohol polymers such as ethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol mono Hexyether, ethylene glycol mono2
- Methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether,
Divalent alcohol alkyl ethers such as ethylene glycol diethyl ether and ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc. Dihydric alcohol alkyl ethers, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazibate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate State, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethylene ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.
Hydrolic alcohol ether ester, sorbitol,
Sugar alcohols such as maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch-degrading sugar, maltose, xylitose, starch-degrading sugar-reducing alcohol, glycolide, tetrahydrofurfuryl alcohol, POE tetrahydrofurfuryl alcohol , POP Butyl Ether, POP POE Butyl Ether, Tripolyoxypropylene Glycerin Ether, POP Glycerin Ether, POP
Glycerin ether phosphate, POP POE pentane erythritol ether, etc. Water-soluble proteins such as collagen, casein, albumin,
For example, as a quaternary ammonium salt such as gelatin,
Stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, distearyldimethylammonium chloride, etc. Phospholipids such as lecithin, hydrogenated lecithin, etc. Organic amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-
2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, etc. Amino acids such as glycine, alanine, valine,
Leucine, isoleucine, serine, threonine,
Phenylalanine, tyrosine, tryptophan,
Cystine, cysteine, methionine, proline,
Neutral amino acids such as hydroxyproline and L-Dopa, acidic amino acids such as aspartic acid, glutamic acid, asparagine, and glutamine, araginine,
Basic amino acids such as histidine and lysine, and
Examples of amino acid derivatives include sodium acylsarcosine (sodium lauroylsarcosine),
Examples include acyl glutamate, sodium acyl β-alanine, glutathione, and pyrrolidone carboxylic acid. Among these, polyhydric alcohols and mucopolysaccharides are particularly preferred. In carrying out the present invention, one or more types of these water-soluble substances are arbitrarily selected. The spherical organoclay mineral according to the present invention is a spherical powder containing the water-swellable clay mineral described above and a water-soluble substance, and has a particle size of 2 to 20 μm. The content of water-swellable clay mineral in the total amount of spherical organic clay mineral is 25 to 99.95% by weight, preferably 50 to 99.9% by weight.
The content of the humectant is 0.05 to 70% by weight, preferably 0.1 to 50% by weight based on the total amount of spherical organic clay mineral.
Weight%. Although the method for producing the organic composite clay mineral of the present invention is arbitrary, it is preferable to use the spray drying method as described below because it is the simplest method and an organic clay mineral with a uniform spherical shape can be obtained. That is, the above-mentioned water-soluble substance is dissolved in an aqueous solvent, the above-mentioned water-swellable clay mineral is further dispersed to form a gel, and then these are spray-dried to form the water-swellable clay mineral and the water-soluble substance. This is a method for obtaining a spherical organoclay mineral containing. The concentration of the water-swellable clay mineral in the above-mentioned gel containing a water-soluble substance and the water-swellable clay mineral is preferably 20% by weight or less; if the concentration is higher than that, the gel viscosity becomes too high and the spray nozzle during spray drying becomes difficult. It is difficult to feed the liquid, and the nozzle may become clogged. A particularly preferable concentration range is 1 to 10% by weight.
It is. Also, the concentration of water-soluble substances in the above gel is
0.001 to 5% by weight is preferred. When preparing a gel, it is preferable to stir sufficiently so that water-swellable clay minerals, etc. are sufficiently dispersed and swollen. If the dispersion and swelling are insufficient, the nozzle may become clogged during spray drying, and the resulting spherical shape may be affected. This is not preferable since the organic clay minerals may become uneven. General spray drying methods such as a disk type, a pressure nozzle type, and a two-fluid nozzle type can be applied to the spray drying. In either case, the inlet air temperature during spraying is preferably a temperature at which the humectant is thermally stable, and is 150°C to 200°C.
It is about ℃. Furthermore, the exhaust temperature is regulated by the spray flow rate from the nozzle, etc., but generally speaking, it should be around 100°C. The spherical organoclay mineral thus obtained has a structure in which primary particles of water-swellable clay mineral aggregate.
It is a nearly spherical powder with a particle size of 2 to 20 μm. Furthermore, the more transparent the appearance of the gel prepared in advance and the higher the viscosity (for example, in the case of laponite), the more uniform and smooth the particle surface morphology becomes. When a polyhydric alcohol or the like is selected as a water-soluble substance in producing a spherical organoclay mineral by the above method, the polyhydric alcohol is included between the layers of the water-swellable clay mineral. This can be confirmed by the widening of the long distance in X-ray diffraction. In addition, when mucopolysaccharides are selected as water-soluble substances, they do not penetrate between the layers of these clay minerals.
It is encapsulated in spherical organoclay minerals in a form that is adsorbed onto the surface of primary particles of water-swellable clay minerals. In addition, when a water-soluble substance is dissolved in an organic solvent other than water, another method for producing this spherical organic composite clay mineral is to prepare a spherical water-swellable clay mineral in advance and then include the water-soluble substance therein. There is a way. That is, when a water-dispersed gel containing only a water-swellable clay mineral is spray-dried, a spherical water-swellable clay mineral containing nothing is obtained. If this is dispersed in an organic solvent in which a water-soluble substance has been dissolved in advance, and then the organic solvent is evaporated, the dissolved water-soluble substance will permeate and be included in the spherical water-swellable clay mineral. The spherical organic composite clay mineral thus prepared is exactly the same as the powder obtained by spray-drying a water-dispersed gel of a water-soluble substance and a water-swellable clay mineral in advance. The organic solvent at this time may be any general low boiling point substance other than water, such as methanol, ethanol, acetone, chloroform, etherhexane, etc. Examples of water-soluble substances that dissolve in organic solvents include polyhydric alcohols and quaternary ammonium salts. The amount of the spherical organic clay mineral used in the present invention to be incorporated into the cosmetic is arbitrary depending on the form of the cosmetic, and is generally 0.1 to 80% by weight. In the case of emulsified and dispersed products, the amount is generally 0.1 to 50% by weight, and in the case of powdered or powder-pressed products, it is 0.1% by weight.
~70% by weight is typical. In addition to the above-mentioned spherical organoclay minerals, the cosmetics of the present invention may contain other ingredients commonly incorporated in cosmetics within a qualitative and quantitative range that does not impair the effects of the present invention. . Such ingredients include oils, waxes, pigments, powders, surfactants,
Examples include preservatives, pigments, antioxidants, ultraviolet absorbers, fragrances, humectants such as polyhydric alcohols, chelating agents, acids, alkalis, water-soluble polymers, oil-soluble polymers, and clay minerals. Specific examples of oils, waxes, pigments, and surfactants are listed below. Waxes and oils; animal and vegetable oils such as beef tallow, squalane, olive oil, evening primrose oil, rice bran oil, candelilla wax, and carnauba wax, hydrocarbons, mineral oils such as liquid paraffin and solid paraffin, isopropyl myristate, pentaerythritol tetra-2-ethylhexano Ester oils such as esters, silicone oils such as methylphenyl silicone and dimethyl silicone, alcohols such as 2-octyldodecanol, 2-decyltetradecanol, oleyl alcohol and cetyl alcohol, fatty acids such as behenic acid, oleic acid, and isostearic acid. , higher alcohols such as oleyl alcohol, cetanol, and stearyl alcohol. Surfactant: POE-branched alkyl ether such as PoE-octyldodecyl alcohol, POE-2-decyltetradecyl alcohol, POE-alkyl ether such as POE-oleyl alcohol ether, POE-cetyl alcohol ether,
Sorbitan esters such as sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, POE-sorbitan monooleate, POE-sorbitan monoisostearate, POE-sorbitan monolaurate, etc.
POE-sorbitan ester, glyceryl fatty acid ester such as glyceryl monooleate, glyceryl monostearate, glyceryl monomyristate, POE-glyceryl monooleate,
POE-glycerin fatty acid esters such as POE-glyceryl monostearate, POE-glyceryl monomyristate, POE-dihydrocholesterol ether, POE-hydrogenated castor oil, POE-
POE-hydrogenated castor oil fatty acid esters such as hydrogenated castor oil isostearate, POE-alkylaryl ethers such as POE-octylphenol ether, glycerol ethers such as glycerol monoisostearate, glycerol monomyristate, POE-glycerol monoisostearate POE-glycerol ethers such as POE-glycerol monomyristate; Ionic surfactants, salts of higher fatty acids such as myristic acid, stearic acid, palmitic acid, behenic acid, isostearic acid, oleic acid, potassium, sodium, diethanolamine, triethanolamine, amino acids, etc., the above-mentioned alkali salts of ether carboxylic acids, Anionic surfactants such as N-acylamino acid salts, N-acylsarcosine salts, higher alkyl sulfonates, cationic surfactants such as alkylamine salts, polyamines, aminoalcohol fatty acid organosilicone resins, alkyl quaternary ammonium salts, etc. agent or amphoteric surfactant, etc. Pigments: Inorganic pigments such as talc, mica, kaolin, calcium carbonate, zinc white, titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, deep blue, chromium hydroxide, titanium coated mica, bisma oxychloride, etc. , crystalline cellulose, nylon powder,
organic pigments such as polyethylene powder, etc. [Effects of the Invention] The cosmetic containing the spherical organic clay mineral of the present invention has no roughness, has extremely good slipperiness, and is highly moisturizing. Table 1 lists the spherical organoclay minerals prepared under various conditions. Furthermore, a powder leaf foundation was prepared using powder No. 1 in Table 1 and non-spherical Laponite XLG (amorphous as purchased from Laporte), and its quality characteristics were measured. The results are shown in Table-3. (Table 2 is the prescription)

【table】

[Table] (Production method) No. 1 (No. 2 to No. 9 follow No. 1.) Dissolve 10 g of glycerin in 1 water, and disperse 30 g of Laponite XLG therein while stirring. The obtained gel was dried using a disk-type spray drying experiment device.
Spray drying was carried out at a disk rotation speed of 2000 rpm, an inlet air temperature of 180° C., and an exhaust temperature of approximately 110° C., and 32 g of spherical powder with a diameter of 3 to 15 μm was obtained. This powder contained 25% by weight of glycerin enclosed between layers, and X-ray diffraction revealed that the interlayer distance was 15.5 Å, which was approximately 4 Å wider than the raw material Laponite XLG. (Alternative method) Disperse 30g of Laponite XLG in 1 part of water while stirring. The obtained gel was spray-dried using a disc-type spray drying experiment device at a disc rotation speed of 20,000 rpm, an inlet temperature of 180°C, and an exhaust temperature of about 110°C, yielding 28 g of spherical powder with a diameter of 3 to 15 μm. 15 g of this spherical powder was dispersed in a solution prepared by dissolving 5 g of glycerin in 100 ml of ethanol, and the ethanol was evaporated on a hot water bath. The shape of the powder obtained in this way remains the original spherical shape, and X-ray diffraction reveals that the interlayer distance has increased by about 4 Å, exactly the same as the powder obtained by (manufacturing method) No. 1. It was confirmed that glycerin was present between the layers. Table-2 Powder leaf foundation prescription Laponite XLG 10.0 Talc 20.0 Mica 52.5 Iron oxide red 1.0 Iron oxide yellow 0.5 Iron oxide black 0.5 Titanium oxide 5.0 Liquid paraffin 5.0 Lanolin 5.0 Ethylparaben 0.3 Fragrance 0.2 (Production method) Mix each powder with a Henschel mixer Prepared in
After uniform stirring, the remaining ingredients were added and mixed uniformly. The mixture was pulverized with an atomizer and molded into a medium plate to obtain a powder leaf undation.

【table】

〔Example〕

Next, the present invention will be explained in detail using examples. The present invention is not limited thereby. In addition, the numerical value is weight%. Example 1 Comparative example 1 lipstick

[Table] *-1 No. 2 spherical organoclay mineral in Table-1 (manufacturing method) Oil and wax are heated and dissolved at 85-95℃,
Add pigment to this and disperse. The mixture was immediately degassed under reduced pressure, transferred to a designated container, and cooled and solidified to obtain a lipstick. Example 1 is a stick-like lipstick that spreads very easily and has a score of 4.2 according to the usage test in Table 3.
It was a lipstick that felt moisturizing. Comparative example 1 has a slightly heavy usability and has a score of 2.0.
It didn't feel calm. Example 2 Comparative Example 2 Pressed eye shadow

[Table] (Manufacturing method) After mixing the powders excluding titanium coated mica using a Henschel mixer, oil and surfactant were added and pulverized using a pulverizer. Further, titanium coated mica was added and mixed uniformly using a Henschel mixer. This product was compression molded into a predetermined medium plate to obtain eyeshadow. Example 2 was an eye shadow with good slippage and a moist feel, while Comparative Example 2 had a rough texture and was difficult to spread. Example 3 Baby powder

[Table] *-1 No.4 spherical shape in Table-1
Machine composite clay mineral (manufacturing method) Dissolve citric acid in 99% alcohol, add to talc, mix with Henschel mixer, and remove alcohol at 80℃. Add the remainder and pulverize with an atomizer. Transfer as is to the designated container to obtain baby powder. Example 3 has a soft feel and spreads easily, has little powdery feeling, and has an excellent moisturizing feeling on the skin. Example 4 Emulsified foundation Stearic acid 0.7 Isopropyl myristate 4 Squalane 12 Polyoxyethylene (10) stearyl ether
2 Cetyl alcohol 0.3 Talc 5 Spherical organic complex clay mineral *-1 15 Iron oxide pigment 2.5 Red No. 202 0.5 Preservative 0.09 Triethanolamine 0.42 Propylene glycol 5 Purified water 52.19 Fragrance 0.3 *-1 No.5 in Table 1 Spherical organic clay mineral (manufacturing method) After heating and mixing and dissolving the oil and surfactant, add the pigment part and uniformly disperse. Triethanolamine and propylene glycol dissolved in purified water and heated are added to emulsify. This is stirred and heated and added to emulsify. This was stirred and cooled, a fragrance was added thereto to make it uniform, and the mixture was filled into a container to obtain an emulsified foundation. Example 4 was a foundation that could be applied lightly and smoothly, had a smooth feel, and had a long-lasting moisturizing effect. Example 5 Blush talc 30 Mica 25 Titanium oxide 3 Titanium coated maca 5.5 Red No. 202 0.5 Spherical organoclay mineral *-1 20 Sorbitan diisostearate 1 Squalane 7 Methylphenyl polysiloxane 8 *-1 No. of Table-1 .6 Spherical organic clay mineral (manufacturing method) Mix the pigment part, add the other ingredients by heating and dissolving them, mix and crush. Form this into a medium plate,
A pressed blush was obtained. Example 5 spreads extremely well, has a non-powdery finish, and feels moisturizing on the cheeks. Example 6 Liquid eyeliner isopar H*-1 58.97 Hydrocarbon resin 5 Carnauba wax 1 Candelilla wax 5 Cholesterol 2 Ethyl alcohol 3 Purified water 1 Bentone 38 *-2 3 Iron oxide black 10 Spherical organic clay mineral *-3 10 Sorbitan mono Stearate 1 Fragrance 0.03 *-1 Isoparaffin manufactured by Etsuo Chemical *-2 Organically modified monomorillonite clay manufactured by NL Chemicals *-3 Spherical organoclay mineral No. 7 in Table 1 (manufacturing method) Isopar H Add the activator, water, bentone, and pigment to a portion, mix and disperse uniformly, and keep at 85°C. Add the remainder of Isopar H, resin, and wax to the pot and uniformly dissolve at 90°C. Add the dispersion prepared in advance to this and heat it to 85℃~90℃
Disperse and mix, add fragrance, and slowly cool to 30°C. Fill the designated container to obtain a water-resistant eyeliner. Example 6 was an eyeliner that spread well and had excellent brushability. It also felt moist after removal. Example 7 Dual-use foundation Titanium oxide 15 Mica 22 Iron oxide 3 Spheroidal organoclay mineral* 25 Liquid paraffin 4.5 Methyl polysiloxane 100CS (Silicone KF96 manufactured by Shin-Etsu Chemical) 20 Methylhydrodylene polysiloxane 20CS (Silicon KF96 manufactured by Shin-Etsu Chemical) Silicon KF99) 10 Sorbitan sesquioleate 0.5 * Spherical organic clay mineral No. 8 in Table 1 (manufacturing method) After uniformly mixing the pigment part, add the activator and mix. After pulverizing with an atomizer, it is press-molded into a specified medium plate. Example 7 was a wet/dry foundation that spreads easily and provides a glossy finish even when the sponge is moistened with water or not.

Claims (1)

[Claims] 1. A spherical organic composite containing a water-swellable clay mineral and one or more water-soluble substances selected from mucopolysaccharides, polyhydric alcohols, water-soluble proteins, or amino acids. A cosmetic characterized by containing clay mineral powder. 2. The spherical organic composite clay mineral powder is obtained by dispersing a water-swellable clay mineral and a water-soluble substance in an aqueous solvent, and then spray-drying the dispersion. cosmetics.