JPH0717371B2 - Spherical organic composite clay mineral and its production method - Google Patents

Description

The present invention relates to a spherical organic composite clay mineral and a method for producing the same. More specifically, an organic composite clay mineral containing a water-swelling clay mineral and a water-soluble substance, which has a smooth and moisturizing feel and an excellent moisturizing effect, and is particularly suitable in the fields of cosmetics and pharmaceuticals, and its production. Concerning the law.

[Conventional technology]

It is known that a water-swelling clay mineral causes an inter-layer reaction with various polar organic or cationic molecules such as alcohols, amines and water-soluble polymers to produce an organic composite clay mineral having a new function. However, when the organic composite clay mineral thus obtained is taken out in the form of powder, it is generally subjected to an operation such as filtration or centrifugation, and after taking a step of drying the precipitate and then crushing it with a strong mechanical force,
Most of the particle shape of the obtained powder is indefinite, therefore, the feeling of use has a very rough feeling, and it is swelled and dispersed in an aqueous solvent. It had the drawback of being difficult to mix.

In addition, various water-soluble substances such as polyhydric alcohols are blended in cosmetics mainly for the purpose of retaining water on the skin.

However, among many water-soluble substances, many have excellent moisturizing action, but on the other hand, when they are mixed in a large amount, they have a drawback that they give a sticky feeling to use. Further, the liquid water-soluble substance has a drawback that it is difficult to mix it with a powder cosmetic such as pressed powder.

[Problems to be solved by the invention]

The present inventors have conducted extensive studies to improve the drawbacks of the prior art, and as a result, an organic composite clay mineral containing a water-swellable clay mineral and a water-soluble substance has a smooth and moist feel. The present invention has been completed by discovering that the powder has an excellent moisturizing effect, does not become sticky even if it is blended in a large amount, and can be stably blended in powder cosmetics.

[Means for solving problems]

That is, the first aspect of the present invention is an organic composite clay mineral containing a water-swellable clay mineral and a water-soluble substance.

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, hectorite, etc., which are either natural or synthetic products. It may be.

Commercially available products include Kunipia, Smecton (both Kunimine Industries), Veegum (Vanderbilt), Laponite (Laporte), tetrafluorosilicon mica (Topy Industries) and the like.

In carrying out the present invention, one kind or two or more kinds are arbitrarily selected from these water-swelling clay minerals.

The water-soluble substance used in the present invention is any water-soluble substance usually used, and specifically, as mucopolysaccharides, for example, hyaluronic acid, chondroitin sulfate A, chondroitin sulfate B, chondroitin sulfate C, heparan sulfate, heparin keratan sulfate are used. As a natural water-soluble polymer, for example, gum arabic, tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), arge colloid (cassius extract), starch (rice, corn, potato, As a plant-based polymer such as wheat), a microbial-based polymer such as xanthan gum, dextran, succinoglucan, and pullulan, and a semisynthetic water-soluble polymer such as carboxymethyl starch and methylhydroxypropyl starch. Pung polymers, methyl cellulose, nitrocellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, sodium carboxymethyl cellulose (CM
C), crystalline cellulose, cellulose-based polymers such as cellulose powder, alginic acid-based polymers such as sodium alginate and propylene glycol alginate, and synthetic water-soluble polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, and carboxyvinyl. Vinyl polymers such as polymers (Carbopol), polyethylene glycol 20,000, 4,000,000, 600,0
Polyoxyethylene (hereinafter referred to as POE) -based polymer such as 00, copolymer-based polymer such as POE-polyoxypropylene (hereinafter referred to as POP) copolymer, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc. As the polyhydric alcohol such as acrylic polymer, polyethyleneimine, cationic polymer, etc., for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2 Dihydric alcohols such as 1,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol and octylene glycol, glycerin, trimethylolpropane, 1,2,6-hexanetriol Trivalent alcohol such as
Tetrahydric alcohols such as pentaerythritol, pentavalent alcohols such as xylitol, hexavalent alcohols such as sorbitol and mannitol, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene. Glycol, triglycerin,
Polyhydric alcohol polymers such as tetraglycerin and polyglycerin, ethylene glycol monomethyl ether, ethylene glycol minoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether , Ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and other divalent alcohol alkyl ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Butyl 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 ichpropyl Dihydric alcohol alkyl ethers such as ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Lenglycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadibate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, Dihydric alcohol ether ester such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch Decomposed sugar, maltose, xylitose, starch-decomposing sugar Sugar alcohol such as reducing alcohol, Glysolid, Tetrahydrofurfuryl alcohol, POE Tetrahydrofurfuryl alcohol, POP Butyl ether, POP, PO
E butyl ether, tripolyoxypropylene glycerin ether, POP glycerin ether, POP glycerin ether phosphate, POP POE pentane erythritol ether, etc., as water-soluble proteins, for example, collagen, casein, albumin, gelatin, etc., quaternary ammonium salts, for example, chloride Stearyl trimethyl ammonium,
Lauryltrimethylammonium chloride, distearyldimethylammonium chloride and the like, phospholipids such as lecithin, hydrogenated lecithin and the like, organic amines such as monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2. -Methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol and the like as amino acids such as glycine, alanine, valine, leucine, isoleucine, serine, threonine, phenylalanine, tyrosine, tryptophan, cystine, cysteine, Neutral amino acids such as methionine, proline, hydroxyproline, and L-Dopa; acidic amino acids such as aspartic acid, glutamic acid, asparagine, and gulmine; basic amino acids such as araginine, histidine, and lysine. Further, such as an amino acid derivative, acyl sarcosinate, sodium (sodium lauroyl sarcosinate), acyl glutamates, acyl β- alanine sodium, glutathione, and pyrrolidone carboxylic acid.

Of these, polyhydric alcohols and mucopolysaccharides are particularly desirable.

In carrying out the present invention, one or two or more of these water-soluble substances are arbitrarily selected.

The organic composite clay mineral of the present invention is a spherical powder containing the water-swellable clay mineral and a water-soluble substance, and has a particle size of 2 to 20 μm.

The amount of water-swellable clay mineral in the total amount of organic composite clay mineral is
25 to 99.95% by weight, preferably 50 to 99.9 parts by weight,
The amount of water-soluble substances in the total amount of organic composite clay minerals is 0.05-
It is 75% by weight, preferably 0.1 to 50% by weight.

Although the method for producing the organic composite clay mineral of the present invention is arbitrary, the following spray drying method is preferable because it is the simplest and the organic composite clay mineral having a spherical shape is obtained.

That is, the above-mentioned water-soluble substance is dissolved in an aqueous solvent, and further the above-mentioned water-swellable clay mineral is dispersed to form a gel, which is then spray-dried to form a water-swellable clay mineral and a water-soluble substance. It is a method of obtaining an organic composite clay mineral containing the method, and the manufacturing method constitutes the second aspect of the present invention.

The concentration of the water-swellable clay mineral in the gel containing a water-soluble substance and a water-swellable clay mineral is preferably 20% by weight or less, and at a concentration higher than that, the gel viscosity becomes too high and the spray nozzle is spray-dried. It is difficult to feed the liquid, and the nozzle is clogged. A particularly preferred concentration range is 1 to 10% by weight.

The concentration of the water-soluble substance in the gel is preferably 0.001-5% by weight. At concentrations higher than this, water-soluble substances that cannot be included in the organic composite clay mineral of the present invention also appear,
The amount of the water-soluble substance adsorbed on the surface of the organic composite clay mineral increases, giving a sticky feeling to the use, or the water-soluble substance is powdered by itself, which is not preferable.

In the preparation of the gel, it is preferable that the water-swelling clay mineral is sufficiently dispersed and sufficiently stirred so that it swells. If the dispersion and swelling are insufficient, the nozzle is clogged during spray drying, and the obtained organic substance is obtained. The composite clay mineral may be uneven, which is not preferable.

For spray drying, a general spray drying method such as a disk type, a pressure nozzle type, or a two-fluid nozzle type can be applied.

In either case, the inlet air temperature during spraying is preferably in a temperature range in which the water-soluble substance is thermally stable, and is about 100 to 200 ° C.

The exhaust temperature is regulated according to the flow rate of spray from the nozzle, etc., but roughly 100 ° C is sufficient.

The organic composite clay mineral thus obtained is a substantially spherical powder having a structure in which primary particles of the water-swelling clay mineral are aggregated, and the particle diameter is 2 to 20 μm. Further, the morphology of the particle surface becomes more uniform and smoother as the gel prepared in advance has a transparent appearance and a higher viscosity (for example, in the case of laponite).

When a polyhydric alcohol or the like is selected as the water-soluble substance in the production of the organic composite clay mineral by the method of the second aspect of the present invention, the polyhydric alcohol is clathrated between the layers of the water-swellable clay mineral. This can be confirmed by the widening of the long plane distance in X-ray diffraction.

When mucopolysaccharides, etc. are selected as water-soluble substances, they do not penetrate into the layers of clay minerals and are encapsulated in spherical organic composite clay minerals in the form of being adsorbed on the surface of the primary particles of water-swelling clay minerals. To be done.

Also, when the water-soluble substance is dissolved in an organic solvent other than water,
As another method for producing the spherical organic composite clay mineral, there is a method of preparing the organic composite clay mineral in advance and then infiltrating it with a water-soluble substance. That is, when an aqueous dispersion gel containing only water-swellable clay mineral is spray-dried, an organic composite clay mineral containing no water-soluble substance is obtained. This is dispersed in an organic solvent in which a water-soluble substance is dissolved in advance, and if the organic solvent is subsequently dispersed, it is permeated and contained in the dissolved organic composite clay mineral. The spherical organic composite clay mineral thus prepared becomes a powder which is exactly the same as the powder obtained by spray drying an aqueous dispersion gel of a water-soluble substance and a water-swelling clay mineral. As the organic solvent at this time, any general low boiling point solvent other than water may be used, and, for example, methynol, ethanol, acetone, chloroform, ether hexane, etc. can be used. As a water-soluble substance which is soluble in an organic solvent, a polyhydric alcohol quaternary ammonium salt or the like is fried.

〔The invention's effect〕

Since the spherical organic composite clay mineral of the present invention has a spherical shape, when it is incorporated into a cosmetic product, it gives an extremely smooth, smooth and moisturizing feel without a feeling of roughness.

In addition, when a humectant is included as a water-soluble substance, it exhibits an excellent moisturizing action on the skin, and it is not sticky at all, and the water-soluble substance can be stably added to powder cosmetics.

〔Example〕

Next, for further understanding of the present invention, examples will be given to explain in more detail. The present invention is not limited to this.

Production Example 1 Dissolve 10 g of glycerin in 1,000 ml of water, then add laponite
Disperse 30 g of XLG with stirring. The obtained gel was subjected to a disc-type spray drying experimenter at a disc rotation speed of 20,000 rp.
m, inlet air temperature was about 180 ° C, and exhaust temperature was about 110 ° C. A scanning electron micrograph of this product is shown in FIG.

In this powder, 25% by weight of glycerin was included between layers, and the interlayer distance was expanded by about 4Å by X-ray diffraction.

Production Example 2 0.3 g of sodium hyaluronate is dissolved in 1,000 ml of water, and 50 g of Veegum HV is dispersed with stirring. The gel thus obtained was spray-dried in the same manner as in Example 1 to obtain 46 g of spherical powder which was completely similar in appearance to Example 1.

Production Example 3 Glycerin 10 g and sodium hyaluronate 0.
Dissolve 3 g and disperse 30 g of Laponite XLG with stirring. The gel thus obtained was spray-dried in the same manner as in Example 1 to obtain 32 g of spherical powder which was completely similar in appearance to Example 1.

Comparative Production Example 1 Laponite 10 g was dispersed in 1,000 ml of water while stirring. The gel thus obtained was spray-dried in the same manner as in Example 1 to obtain 24 g of spherical powder which was completely similar in appearance to Example 1.

Production Example 4 15 g of the powder obtained in Comparative Production Example 1 was dispersed in a solution in which 5 g of glycerin was dissolved in 100 ml of ethanol in advance, and ethanol was evaporated on a hot water bath. The powder thus obtained remains spherical, and the interlayer distance has been expanded by X-ray diffraction by about 4Å just like the powder obtained in Example 1, and glycerin is contained between the layers. Was confirmed.

Example 1 Using a powdery foundation untreated laponite and the spherical powders of Production Example 1 and Comparative Production Example 1, a foundation was trial-produced with the following blending amounts.

The numbers are% by weight.

Treated or untreated Laponite 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 Manufacturing method Charge each powder into a Henschel mixer and stir after stirring uniformly. The ingredients were added and mixed uniformly. The mixture was crushed with an atomizer and molded into a medium plate to obtain a powdery foundation.

The table below shows the results of usage tests by 20 panel members of these prototype foundations.

The evaluation was performed by sensory, and the evaluation was performed with the following five-level evaluation of 1 to 5.

1 Poor 2 Slightly bad 3 Normal 4 Fairly good 5 Good results are expressed as average values as follows.

◎ 4.5 to 5.0 ○ 3.5 to 4.4 △ 2.5 to 3.4 × 1.5 to 2.4 Example 5 Eye Shadow Using the spherical powder of Production Example 2, an eye shadow was experimentally manufactured with the following blending amounts.

The numbers are% by weight.

Spherical powder of Preparation Example 25 Mica 18.8 Talc 20 Iron oxide yellow 0.5 Iron oxide black 0.3 Ultramarine blue 15.2 Mica titanium 10 Liquid paraffin 7 Dimethylpolysiloxane (100cs) 3 Paraben 0.2 Perfume Proper amount Production method Mix pigments and coloring pigments with a Henschel mixer. After that, other ingredients are added and further mixed with a Henschel mixer. The mixture was crushed with a pulverizer and press-molded into a predetermined medium dish to obtain eye shadow.

The shadow thus obtained spreads smoothly with a puff and a hand, and remained moist during application and after removal. Example 1
According to the same evaluation method as above, both good sliding and moisturizing were evaluated as ⊚.

Example 6 Lipstick A lipstick was produced using the spherical powder of Production Example 3 in the following amounts.

The numbers are% by weight.

Spherical powder of Production Example 5 Polyethylene wax 8 Ceresin wax 5 Castor oil 35 Stearyl triglyceride 30 Liquid paraffin 16 Iron oxide red 0.5 Red 204 No. 0.5 Fragrance suitable amount Method Wax and oil are charged in a kettle and dissolved by heating at 90 ° C. Further, a pigment, a fragrance and a spherical powder are added, and they are heated and mixed at 85 ° C. After deaeration under reduced pressure, the mixture was filled in a container at 70 ° C., cooled and solidified to obtain lipstick.

The lipstick obtained was a smooth spread, and according to the same evaluation method as in Example 1, both good slipperiness and moistness were ⊚.

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph showing the crystal structure of the spherical organic composite powder according to the present invention containing 25% of glycerin obtained in Production Example 1.

Claims (4)

[Claims] 1. A spherical organic composite clay mineral containing a water-swellable clay mineral and a water-soluble substance. 2. The method according to claim 1, wherein the water-soluble substance is mucopolysaccharide, water-soluble polymer, polyhydric alcohol, organic amine, water-soluble protein, quaternary ammonium salt, phospholipid, amino acid or amino acid derivative. Spherical organic complex clay mineral. 3. A method for producing a spherical organic composite clay mineral, which comprises spray-drying a dissolved dispersion of a water-soluble substance and a water-swellable clay mineral. 4. The spherical organic complex clay mineral according to claim 3, wherein the water-soluble substance is mucopolysaccharide, water-soluble polymer, polyhydric alcohol, organic amine, water-soluble protein, amino acid or amino acid derivative. Manufacturing method.