JPH02267113A - Organic complex clay mineral - Google Patents

Abstract

PURPOSE:To simply produce organic complex clay minerals uniformly containing an organic substance without using an organic solvent by spray-drying a mixed solution comprising clay minerals, organic solvent-soluble organic substance, surfactant and water. CONSTITUTION:A mixture comprising clay minerals (montmorillonite), an organic substance soluble in an organic solvent, a surfactant (sucrose fatty acid ester) and water is sprayed dried to prepare fine powder of organic complex clay minerals. In the preparation, the total amounts of the organic complex clay minerals have about 25-99.5wt.% clay minerals, about 0.05-75wt.% organic substance and about 0.05-75wt.% surfactant and the temperature of inlet air in spraying is about 150-300 deg.C. Consequently, powder uniformly containing the organic substance in the spherical clay minerals having about 2-20mu particle diameter is prepared and the organic complex clay minerals useful for cosmetic is obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an organic complex clay mineral that is easily obtained and is very useful particularly in the cosmetic and pharmaceutical fields. The present invention relates to an organic composite clay mineral obtained by spray drying a liquid mixture consisting of an organic substance dissolved in water, a surfactant, and water.

[Prior art] It is known that clay minerals undergo interlayer reactions with organic polar molecules and cationic molecules such as various alcohols, amines, and water-soluble polymers, producing organically modified clay minerals with new functions. There is. However, an impregnation method using an organic solvent has been used to produce an organically modified clay mineral consisting of a clay mineral and an organic substance that dissolves in an organic solvent. That is, organically modified clay minerals were obtained by immersing clay minerals in an organic solvent in which an organic substance was dissolved, and then distilling off the solvent. This method has the advantage of being able to uniformly incorporate organic substances into clay minerals in the form of molecules by dissolving them once in an organic solvent, but since it uses a large amount of organic solvent, it There were problems with safety or cost.

[Problems to be Solved by the Invention] The present inventors have conducted extensive research in order to uniformly and easily incorporate organic substances that dissolve in organic solvents into clay minerals without using organic solvents, and as a result, they have found that clay minerals When a mixture of organic substances, surfactants, and water is spray-dried,
Since the organic substance is a fine aggregate, it can be uniformly encapsulated in the powder obtained when spray-drying, and an excellent powder that eliminates the above-mentioned drawbacks has been obtained.

[Means for Solving the Problems] That is, the present invention relates to an organic composite clay mineral obtained by spray drying a liquid mixture consisting of a clay mineral, an organic substance dissolved in an organic solvent, a surfactant, and water. .

When the organic substance of the present invention is an emollient agent, it has a moist feel and excellent emollient effect, and does not become sticky even when blended in a large amount, and when the organic substance is an oil-soluble pigment, it has light resistance. It has excellent color properties and coloring power, and when the organic substance is a fragrance, it has excellent safety and sustained release properties.
When the organic substance is a drug, it increases stability and provides a smooth feel when used, and when incorporated into cosmetics, it has excellent stability and usability.

The configuration of the present invention will be described below.

The clay mineral used in the present invention is a layered silicate mineral belonging to the genus smectite, and generally includes montmorillonite, beidellite, nontronite, sabonite, and hectorite, and these minerals may be natural or synthetic. good. Commercially available products include Kunivia, Smectone (all manufactured by Kunimine Industries), Peagum (Panderbuild), Laponite (Laborte), and Fluorine Tetrasilicon Mica (Toby).
Industrial) etc. can be used. In carrying out the present invention, one or more types of clay minerals are arbitrarily selected from among these clay minerals.

The organic substance that dissolves in the organic solvent used in the present invention may be a liquid oil, a solid oil, a semi-solid oil, or a substance that is sparingly soluble in water, such as avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil,
Olive oil, rapeseed oil, evening primrose oil, egg yolk oil, sesame oil, basic oil, wheat germ oil, sasanquat oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil Liquid oils and fats such as rice bran oil, Shinakiri oil, Japanese tung oil, jojoba oil, germ oil, triglycerin, glycerin trioctanoate, glycerin triisopalmitate, cacao butter, coconut oil, horse tallow, hydrogenated coconut oil, palm oil, Solid fats and oils such as beef tallow, mutton tallow, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, Japanese oak kernel oil, hydrogenated oil, beef leg fat, Japanese oak oil, hydrogenated castor oil, beeswax, candelilla wax, cotton wax, carnauba wax, paiberry Otu, Ibotaro, spermaceti wax, Montan wax, cotton wax, lanolin, kapok wax, acetic acid lanolin, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, Jojo wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE Waxes such as lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, hydrocarbons such as liquid paraffin, osikelite, squalene, pristane, paraffin, montan, squalane, petrolatum, microcrystalline wax, myristin Isopropyl acid, cetyl octoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyl octanoate,
Cetyl lactate, myristyl lactate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, toalkyl monoinstearate glycol, neopentyl glycol capriate, apple Acid glycerin, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaneerythritol tetra-2-ethylhexylate, glycerin tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl-2-ethylhexanoate , 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, cetostearyl alcohol, acetoglyceride, 2-hebutylundecyl palmitate, adipine diisopropyl acid, traurolyl-2-octyldodecyl ester glutamate, 2-hebutyl undecyl adipate, ethyl laurate, di-2-ethylhexyl sepatate, 2-hexyldecyl myristate, 2-to palmitate Synthetic esters such as xyldecyl, 2-hexyldecyl adipate, diisopropyl sebadate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, lauric acid, myristic acid, stearic acid palmitate, behen Higher alcohol fatty acids such as (behenyl) acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tolic acid, lanolin fatty acid, isostearic acid, linoleic acid, sulfuric acid, and eicosapentaenoic acid,
Lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether (batyl alcohol)
, 2-decyltetrazosinol, lanolin alcohol,
Linear and branched higher alcohols such as cholesterol, phytosterols, hexyldodecanol, isostearyl alcohol, octyldodecanol, Red No. 215, Red No. 218, Red No. 223, Red No. 225, Orange 2
Tar pigments such as No. 01, Yellow No. 204, Green No. 202, and Purple No. 201, β-carotene, annatto, and sacro-
Oil-soluble pigments such as yellow, natural pigments such as carminic acid, fragrances such as linalool, linalyl acetate, cinnamic aldehyde, benzyl acetate, citral, limonene, para-aminobenzoic acid, homomenthyl-N-acedelanthranilate, anthranilate , octyl sylate, ultraviolet absorbers such as 2,4-dihydroxybenzophenone, vitamins such as vitamin A and its derivatives, vitamin D and its derivatives, vitamin E and its derivatives, vitamins and their derivatives, sterols, purified Examples include phospholipid-containing substances, hydrogenated products thereof, synthetic glycerin lipid esters, and mixtures thereof.

In addition, poorly soluble substances in water include vitamins such as ubiquinone and vitamin P, bactericidal agents such as chlorhexidine hydrochloride, trichlorocarbanilide, and irgalasan DP300.
Examples include drugs such as dexamethacin acetate.

In the present invention, the surfactant may be either a nonionic surfactant or an ionic surfactant (cationic, anionic, or amphoteric), but preferably a nonionic surfactant commonly used in cosmetics. More specifically, sugar or sugar alcohol fatty acid esters such as sucrose fatty acid esters and maltitol fatty acid esters, sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene sorbitol. Fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether,
Polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene cholestanol ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene beeswax derivative, polyoxy Examples include ethylene lanolin derivatives, polyoxyethylene alkylamines, polyoxyethylene alkylamides, and the like.

In the present invention, the method for producing the liquid mixture is not particularly limited, and for example, a liquid in which clay minerals are dispersed in water is mixed with a liquid mixture consisting of an organic substance soluble in an organic solvent, a surfactant, and water. Examples include a method of dispersing clay minerals in a mixed solution of an organic substance dissolved in an organic solvent, a surfactant, and water while stirring. Note that the mixed liquid consisting of an organic substance dissolved in an organic solvent, a surfactant, and water refers to an emulsion, a solubilized liquid, a lipid bilayer membrane dispersion, and the like.

The emulsion may be either an oil-in-water type or a microemulsion, and may also contain an aqueous solvent such as a lower alcohol such as ethanol or propatool, or a polyhydric alcohol such as glycerin or 1,3-butylene glycol.

The solubilizing liquid is an organic substance dissolved in an aqueous surfactant solution, and may contain an aqueous solvent such as a lower alcohol such as ethanol or propatool, or a polyhydric alcohol such as glycerin or 1,3-butylene glycol.

A lipid bilayer membrane dispersion is a lamellar or vesicular dispersion consisting of a phospholipid, a quaternary ammonium salt type synthetic lipid such as dialkyldimethylammonium chloride, or a mixture of a quaternary ammonium salt and a higher alcohol. It refers to a mixture with a surfactant, and may contain an aqueous solvent such as a lower alcohol such as ethanol or propatool, or a polyhydric alcohol such as glycerin or 1,3-butylene glycol.

The method for preparing these mixtures is arbitrary, and operations such as stirring and heating using a disper, homomixer, Manton Bowlin, etc. may be used as necessary.

Furthermore, these mixed liquids do not need to be stable over a long period of time, since they can be mixed with an aqueous dispersion of clay minerals immediately after production and spray-dried.

The content of clay minerals in the total amount of organic composite clay minerals is 25 to 9
9.5% by weight is preferable, preferably 50-90%
．． The content of organic substances in the total amount of organic composite clay minerals is preferably 0.05 to 75% by weight, more preferably 0.1 to 50% by weight, and the content of surfactants is preferably 0.05 to 75% by weight, more preferably 0.1 to 50% by weight.

In the method for producing an organic composite clay mineral of the present invention, it is preferable to use the following spray drying method because an organic composite clay mineral with a well-shaped spherical shape can be obtained.

That is, clay minerals obtained by dispersing clay minerals in an aqueous solvent to form a gel, mixing it with a liquid mixture consisting of an organic substance dissolved in an organic solvent, a surfactant, and water, and then spray-drying the mixture. This is a method that uses

The concentration of clay mineral in the above gel is preferably 20% by weight or less; if the concentration is higher than that, the gel viscosity becomes too high, making it difficult to feed the liquid through the spray nozzle during spray drying, and causing nozzle clogging. .

A particularly preferred concentration range is 1 to 10% by weight.

When preparing a gel, it is preferable to sufficiently stir the clay minerals, etc. so that they are sufficiently dispersed and swollen. If the dispersion and swelling are insufficient, the nozzle may become clogged during spray drying, and the resulting organic composite may become clogged. Clay minerals may become irregular, which is not preferable.

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 in a temperature range where the organic substance, surfactant, and clay mineral are thermally stable, and is approximately 150 to 300°C.

Further, the exhaust temperature is determined by the flow rate of the spray from the nozzle, etc., and may be around 100°C in large quantities.

The clay mineral obtained in this way is a spherical powder having a structure in which primary particles of clay mineral are aggregated, and the organic substance is uniformly contained inside the powder, and the particle size is 2 to 20 μm.
That's about it. 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.

[Effects of the Invention] The organic composite clay mineral according to the present invention is extremely easy to obtain and can be produced without using organic solvents, so it has excellent safety during production and is also effective in terms of cost reduction. Very advantageous.

When blended into cosmetics, etc., it gives an extremely smooth and moist feel without any roughness. In addition, if the organic substance contained is an oil that has an emollient effect, it will have an emollient effect on the skin but will not be sticky at all.
Oil-soluble pigments have excellent resistance and coloring power, fragrances have excellent stability and sustained release properties, drugs have excellent stability, and all of them are stable for powdered cosmetics. These water-insoluble or sparingly soluble substances can be blended with the water-insoluble or sparingly soluble substances.

[Example] Next, in order to further understand the present invention, the present invention will be described in more detail by giving examples. The present invention is not limited thereby. All compounding amounts are in weight%.

Example 1 ■Liquid paraffin 10.0■Polyoxyethylene (addition of 10 moles) monooleic acid ester 2.0■Methylparaben
0.15 ■ Ion exchange water
Residue (manufacturing method) Dissolve ■ and ■ in ■ heated to 70℃, stir this with a disper, remove the temperature of ■ heated to 70℃, and then cool to room temperature to form an oil-in-water emulsion. Obtained.

On the other hand, add 500ml of the emulsion prepared as above to one cup of water, and add 30g of Laponite XLG.
Disperse while stirring. The obtained gel was dried in a disc-type fuka dryer at a disc rotation speed of 20,000 rpm.
The mixture was spray-dried at an inlet temperature of 180° C. and an exhaust temperature of 110° C. to obtain 87 g of spherical powder with a diameter of 2 to 20 μm.

Example 2 ■ Polyoxyethylene (60 mol addition) hydrogenated castor oil 1.0 ■ Fragrance 0.1 ■ Ethanol 15.0 ■ Methylparaben 0.10 Citric acid
0.1 ■ Sodium citrate 0.30 1.3-butylene glycol 4.0 ■ Ion exchange water
Remains (manufacturing method) Each of ① to ② and ② to ② was dissolved, and both were mixed with stirring to obtain a solubilized liquid.

Next, 50% of the solubilized solution prepared as above was added to 1 part of water.
Add 0 mL and disperse 30 g of Laponite XLG therein with stirring. The gel obtained by rough stirring was spray-dried in the same manner as in Example 1 to obtain 55 g of spherical powder with a diameter of 2 to 20 μm.

Example 3 ■Polyoxyethylene (20 mol addition) 2-ocdildodecyl ether 1.0 ■Hydrogenated soybean resin
1.0■ Methylparahen
0.1 ■ Ion exchange water
Remains (Production method) After mixing Φ to ■, the mixture was heated to 70°C, uniformly dispersed using a homomixer, and then cooled to room temperature to obtain a lipid bilayer membrane dispersion.

Next, 30 g of Laponite XLG was dispersed in one portion of water while stirring. 500 mL of the lipid bilayer membrane dispersion prepared as described above is added to the obtained gel and further stirred. Thereafter, it was spray-dried in the same manner as in Example 1, and the thickness of 2 to 20 μm was obtained.
37g of spherical powder was obtained.

38 g of spherical powder of 2-20 μm was obtained by combining and spray drying.
I got it.

Claims (1)

[Claims] (1) An organic composite clay mineral obtained by spray-drying a mixed solution consisting of a clay mineral, an organic substance dissolved in an organic solvent, a surfactant, and water.