JP2020176058A - Clay mineral complex - Google Patents

Abstract

To provide a technique that prevents the attachment of microparticles to a skin surface.SOLUTION: A clay mineral complex is modified with an organic compound, the organic compound having a molecule size that is 100% or less of the inter-charge distance of the clay mineral.SELECTED DRAWING: Figure 1

Description

The present invention relates to clay mineral complexes modified with organic compounds.

It is known that various chemical substances and foreign substances are floating and flying in the atmosphere. Specifically, particulate matter (PM) derived from automobiles, thermal power plants, incinerators, fireplaces, smoke from tobacco, ejecta from volcanic eruptions, soil particles, etc., pollen, dust, sulfur oxides (dioxide) There are microscale particles such as (sulfur, etc.), exhaust gas such as nitrogen oxides (such as sulfur dioxide), and asbestos.

In addition to causing air pollution and adversely affecting the respiratory system by inhaling through the mouth and nose, these fine particles are also taken into the body through the skin, which is the outermost layer of the living body and is constantly exposed to the outside world. There is concern that it may cause trouble or damage to the skin. For example, tobacco smoke is known to reduce wrinkle formation and clarity in the skin through the production of nitrogen oxides or reactive oxygen species, and certain organic compounds are at risk of causing skin irritation. It has also been pointed out that fine particles of dust permeate the skin tissue while adsorbing aromatic hydrocarbons on its surface and affect genes. In addition, pollen such as cedar and cypress causes allergic rhinitis (hay fever).

Therefore, attempts are being made to prevent fine particles from adhering to the skin or entering the body through the skin and having an adverse effect. For example, Patent Document 1 describes that a composition having an α-gel structure is applied to form a film on the surface of the skin to prevent micropollutants from adhering to and permeating the skin. Patent Document 2 describes that an amphoteric and anionic polymer-containing composition is applied to the surface of skin or clothing to prevent pollen from adhering. Non-Patent Document 1 describes that a material for forming a conductive film obtained by polymerizing phosphorylcholine and an acrylic acid monomer is used as a material for suppressing adhesion of fine particles.

By the way, in cosmetics, organically modified clay minerals obtained by modifying clay minerals such as bentonite with organic compounds are widely used as materials for enhancing the dispersion stability and rheology adjustability of the system (Patent Document 3).

Japanese Unexamined Patent Publication No. 2016-88866 Japanese Unexamined Patent Publication No. 2006-2147 Patent No. 50444402

Miyazawa K. “Development of a shield technology to keep off air pollutants --Contribution to healthcare through a biocompatible polymer”, IFSCC Conference, Seoul (2017)

In the materials of Patent Documents 1 and 2 and Non-Patent Document 1, the suppression of adhesion of fine particles to the skin was not always satisfactory, and there was room for improvement.
In view of such a situation, it is an object of the present invention to provide a technique for suppressing adhesion of fine particles to the skin surface.

The present inventors have focused on the fact that the conductive film is effective in suppressing the adhesion of fine particles to the skin surface as in Non-Patent Document 1, and searched for a new material capable of forming such a film. As a result, paying attention to the fact that the powder composed of clay minerals is uniformly arranged on the skin and that the powder is usually negatively charged, the powder is modified with a positively charged organic compound. , It has been found that a complex capable of forming a conductive film on the skin can be obtained. Then, paying attention to the fact that increasing the conductivity of the coating film improves the effect of suppressing the adhesion of fine particles to the skin surface, the modification rate of the organic compound to a powder made of clay mineral is increased in order to increase the conductivity. The present invention was completed on the idea that the above is effective and that the modification rate can be increased by using an organic compound having a predetermined molecular size.

That is, the present invention is as follows.
[1] A clay mineral complex modified with an organic compound.
A complex in which the molecular size of the organic compound is 100% or less of the distance between charges of the clay mineral.
[2] The complex according to [1], wherein the measured modification rate of the organic compound with respect to the clay mineral is 50% or more.
[3] The complex according to [1] or [2], wherein the organic compound is a cationic or amphoteric compound.
[4] The complex according to [3], wherein the organic compound is lecithin.
[5] The complex according to any one of [1] to [4], wherein the clay mineral is selected from the group consisting of bentonite and hectorite.
[6] An external preparation for skin containing the complex according to any one of [1] to [5].
[7] The external preparation for skin according to [6], which is a cosmetic.
[8] The external preparation for skin according to [6] or [7], which is used for suppressing the adhesion of fine particles.

According to the present invention, there is provided a composite as a material capable of forming a film having an excellent effect of suppressing adhesion of fine particles to the skin. The complex of the present invention can be suitably blended in an external preparation for skin such as cosmetics.

The graph which shows the charge amount of the composite which forms the coating film of the composite of this invention, and the charge transfer amount to (free) pollen after peeling from the coating film.

The complex of the present invention is a clay mineral modified with an organic compound.

The clay mineral in the composite of the present invention is usually a plate-like powder. The plate shape makes it easy to arrange evenly on a flat surface when applied to the skin or the like. As will be described later, the composite of the present invention can form a conductive film that is electrically close to neutral. Normally, charged fine particles are likely to adhere to the skin due to static electricity, but the film of the complex of the present invention applied on the skin can suppress the charge on the skin, thus suppressing the adhesion of the fine particles. can do. Clay minerals are preferably arranged on a flat surface in order to facilitate the release of electric charges.

Clay minerals are usually charged and may be positively or negatively charged, but those having a negative charge are preferable.
Examples of clay minerals include scmetite-based hectorite, bentonite, montrilonite, kaolinite, illite, marine clay mineral (sea mud), dessert rose clay mineral, and pascalite, of which bentonite and hectorite are particularly important. preferable. All of these have a negative charge.
The charged parts of the clay mineral are arranged at equal intervals, and in the plate-like powder, they are regularly arranged in the direction parallel to the plate. Usually, the distance between charges can be calculated by the method disclosed in Japanese Patent Application Laid-Open No. 2011-150037. For example, the distance between the anion sites of Na-type montmorillonite, which is the main component of bentonite, is about 1 nm.
Clay minerals having a size that can be usually blended in cosmetics can be used for complex preparation. For example, clay minerals are usually agglomerated during distribution as a raw material, and the volume average particle diameter of such secondary particles is preferably 0.5 to 1000 μm, but is not particularly limited. Clay minerals are generally subjected to treatments such as heating and stirring when blended and dispersed in a composition such as cosmetics, and usually have a smaller particle size. For example, by heating at about 25 to 80 ° C. and stirring at a high shear rate, the volume average particle size can be preferably 5 μm or less, 3 μm or less, and more preferably 1 μm or less. Here, the particle size is a value measured by a laser diffraction / scattering method using a dry particle size distribution measuring device (for example, LS 13 320 manufactured by Beckman Colter).

The organic compound in the composite of the present invention is usually charged in order to efficiently modify the charged clay mineral, and may be positively or negatively charged, but has a positive charge in water. , More specifically, a cationic compound or an amphoteric compound is preferable.
That is, the clay mineral and the organic compound constituting the complex of the present invention are preferably a combination of a clay mineral having a negative charge and a cationic organic compound.

The organic compound in the composite of the present invention has a size that easily fits within the distance between charges of the clay mineral in order to efficiently modify the charged portion of the clay mineral. Specifically, an organic compound having a molecular size of 100% or less, preferably 80% or less, and more preferably 70% or less of the distance between charges of the clay mineral is used. By using an organic compound having such a size, the modification rate of the complex of the present invention is high, and as a result, the neutralization rate described later is also high, so that the effect of suppressing the adhesion of fine particles is exhibited. ..
In the present specification, "molecular size" is a molecule obtained by calculating the surface excess concentration by surface tension measurement using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. and taking the square root of the molecular cross-sectional area which is the inverse number thereof. It can refer to the value of the intermolecular distance. Further, the surface film pressure of the monomolecular film may be measured and a value calculated from the π-A curve (surface pressure-area curve) (Nobuyuki Tsubaki et al., Oil Chemistry, Vol. 41, No. 7, 551). -557, (1992)).

The organic compound in the complex of the present invention may be of natural origin or a synthetic compound, but is preferably of natural origin. It should be noted that the naturally derived substances include not only those obtained from animals, plants, minerals, etc., but also those obtained by artificially producing the compounds.
Lecithin is preferably mentioned as a naturally derived substance. Here, lecithin includes hydrogenated lecithin and non-hydrogenated lecithin, and in the present invention, both can be preferably used as long as they satisfy a predetermined molecular size. In the case of hydrogenated lecithin (distearoylphosphatidylcholine), its molecular size is 0.71 nm.

Further, as the organic compound in the complex of the present invention, a compound having a quaternary amino group is preferably mentioned. Specific examples thereof include stearyltrimethylammonium chloride and dimethyldistearylammonium chloride.

Modes of modification of clay minerals with organic compounds in the complex of the present invention include those via ionic and covalent bonds.
The complexing can be carried out by mixing the organic compound and the clay mineral in an aqueous medium in the pH range where the organic compound used for modification is cationized. For example, when lecithin is used as the organic compound, the pH is preferably 6 or less, more preferably pH 3 or less, still more preferably pH 2 to 3, and the lecithin cationized in the aqueous solution under such pH conditions binds to the clay mineral. To form a complex.

The theoretical modification rate of the organic compound for clay minerals in the composite of the present invention is usually 100%. The measured modification rate is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more.
Here, the modification rate is the molar amount of the charge (usually cation) possessed by the organic compound existing per unit lattice plane of the complexed organic compound and clay mineral, and the exchangeable charge (usually) of the clay mineral. Is a value divided by the molar amount of the anion) site, and represents the rate at which the organic compound is filled in the bond site (usually the charge site) of the clay mineral.
The theoretical modification rate can be calculated from the molecular size of the organic compound and the distance between charges of the clay mineral. Specifically, the surface of a clay mineral is likened to a lattice of intervals between charges, and the clay is densely packed on the lattice so that circles having the molecular size of the organic compound do not overlap. It can be calculated as the ratio of the occupied area of the organic compound molecule to the surface area of the mineral. Further, the theoretical modification rate can also be calculated based on the description relating to the interion distance disclosed in paragraphs 0031 to 0034 of JP2011-150037A.
In addition, the measured modification rate is the modification rate calculated by measuring the change in heating weight of the complex with a thermal analyzer and regarding the amount of weight loss due to oxidative exothermic decomposition as the amount of the compounded organic compound. be able to.

As described above, the complex of the present invention is close to neutral in charge because the clay mineral is usually modified with organic compounds having opposite charges. The "neutralization rate" (the closer to 100%, the greater the degree of neutralization), which indicates the degree to which the resulting complex is electrically neutralized by canceling the charges, is the above-mentioned modification rate. May be synonymous.
In addition, the complex of the present invention is close to neutral in charge, and specifically measured with an Espart analyzer (Hosokawamicron, EST-G) (applied voltage: 100 V, particle count number: 1000, room temperature 25 ° C ± 2). The absolute value of the charge amount of the particles of the complex at ° C., humidity 30% ± 3%, nitrogen gas pressure: 0.02 MPa) is preferably 1.5 μC / g or less, more preferably 1.0 μC / g or less. It is more preferably 0.7 μC / g or less, further preferably 0.5 μC / g or less, and particularly preferably 0.4 μC / g or less.

The complex of the present invention has an action of suppressing adhesion of fine particles.
This is because the conductive film formed by the composite of the present invention avoids normally charged fine particles by charge repulsion. It should be noted that the physical adhesion suppressing action of the coating film is not prevented from occurring at the same time.

In addition, in this specification, fine particles refer to all fine substances, which can usually have an adverse effect on the skin, and are not particularly limited, but are automobiles, thermal power plants, incinerators, fireflies, tobacco. Emissions such as smoke, ejecta from volcanic eruptions, particulate matter (PM) derived from soil particles, pollen, dust, sulfur oxides (sulfur dioxide, etc.), nitrogen oxides (nitrogen dioxide, etc.) Refers to chemical substances such as asbestos and foreign substances. Further, it is usually a microscale particle, for example, a particle having a major axis of 50 μm or less. Further, the shape of the particles is not particularly limited.

In general, it is known that microparticles give a physical stimulus to the skin surface or a stimulus that enters the epidermis and promotes the release of inflammatory factors. Since the complex of the present invention can suppress the adhesion of fine particles to the skin, it can suppress the induction of inflammation by the fine particles, and thus can be preferably used for the prevention of skin damage. Here, "skin damage" refers to any condition in which the skin is unhealthy, for example, a condition in which epidermal cells are stimulated and inflammation occurs due to the release of inflammatory factors, and as a result, wrinkles and pigmentation occur. Inflammation.

Therefore, the composite of the present invention can be preferably blended in the composition, and the composition is preferably in the form of an external preparation for skin, and more preferably in the form of a cosmetic. The cosmetics are not particularly limited, such as skin care cosmetics, make-up cosmetics, and hair care cosmetics.

The dosage form of the composition is not particularly limited, such as an emulsifier type, lotion, oil type, gel type, oil gel type, spray type, sheet mask type and the like.
The composite of the present invention is more preferably an emulsifier type or an oil gel type because it also exhibits excellent dispersibility without adding another surfactant to the composition.

The content of the composite of the present invention in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, based on the total amount of the composition. Further, it is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less. For example, when the composite of the present invention is blended in a water-in-oil emulsifier type composition, it is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 4.0, based on the total amount of the composition. The content is preferably by mass, more preferably 2.0 to 3.5% by mass.
Within such a range, the desired effect can be easily obtained and the degree of freedom in formulation design can be ensured.

In the composition, any component used in ordinary skin external preparations and the like can be arbitrarily contained as long as the effect of the present invention is not impaired. Examples of such an optional ingredient include various active ingredients, oily ingredients, other surfactants, polyhydric alcohols, thickeners, powders, ultraviolet absorbers and the like.

Examples of the active ingredient include a whitening ingredient, a wrinkle improving ingredient, an anti-inflammatory ingredient, and extracts derived from other animals and plants.
The whitening ingredient is not particularly limited as long as it is generally used in cosmetics. For example, 4-n-butyl resorcinol, ascorbic acid glucoside, 3-О-ethylascorbic acid, arbutin, ellagic acid, kojic acid, linoleic acid, nicotinamide, 5,5'-dipropylbiphenyl-2,2'- Examples thereof include diol, disodium 5'-adenylate, potassium 4-methoxysalicylic acid salt, hydroquinone, and pantothenic acid.

The wrinkle improving ingredient is not particularly limited as long as it is generally used in cosmetics. For example, isopropyloxopropylaminocarbonylpyrrolidin carbonylmethylpropylaminocarbonylbenzoylaminoacetate sodium, nicotinic acid amide, vitamin A or derivatives thereof (retinol, retinal, retinoic acid, tretinoin, isotretinoin, tocopherol retinoate, retinol palmitate). , Retinol acetate, etc.), ursolic acid benzyl ester, ursolic acid phosphate ester, bethuric acid benzyl ester, benzylic acid phosphate ester.

Anti-inflammatory components include glycyrrhetinic acid, glycyrrhetinic acid, allantin, isopropylmethylphenol, clarinone, glabridin, salicylic acid, tocopherol acetate, tocopherol nicotinic acid ester, nicotinamide, pantothenic acid, pantothenyl alcohol, and salts or derivatives thereof. And the like, preferably glycyrrhetinic acid and its salt, glycyrrhetinic acid and its salt, pantothenyl alcohol and pantothenic acid and its salt.

The other animal and plant-derived extracts are not particularly limited as long as they are generally used in cosmetics and the like. For example, akebi extract, asunaro extract, asparagus extract, avocado extract, amacha extract, almond extract, arnica extract, aloe extract, aronia extract, apricot extract, ginkgo extract, indokino extract, uikyo extract, udo extract, agetsu extract, elephant kogi extract. , Enmeisou extract, Ogon extract, Oubaku extract, Ouren extract, Otaneninjin extract, Otogirisou extract, Odorikosou extract, Orange extract, Kakyoku extract, Kakon extract, Chamomile extract, Carrot extract, Kawarayomogi extract, Kiwi extract, Cucumber extract, Guava extract, Kujin extract, Kuchinashi extract, Kumazasa extract, Clara extract, Walnut extract, Grapefruit extract, Black rice extract, Chlorella extract, Kuwa extract, Keiketto extract, Gettoyo extract, Gentiana extract, Gennoshoco extract, Tea extract, Gobo extract, Rice extract, Fermented rice extract , Rice bran extract, rice germ oil, moss peach extract, salvia extract, sabonsou extract, sasa extract, sansha extract, sansho extract, shiitake extract, dioe extract, shikon extract, shiso extract, shinanoki extract, shimotsukesou extract, shakuyaku extract, shokyo extract, Shobu root extract, white birch extract, sugina extract, stevia extract, stevia fermented product, sardine extract, sardine extract, sardine extract, sardine extract, sardine extract, sage extract, zenia oyster extract, senkyu extract, senburi extract, sohakuhi Extract, Daiou extract, Soybean extract, Taisou extract, Thyme extract, Dandelion extract, Tea extract, Chouji extract, Chinpi extract, Jincha extract, Togarashi extract, Touki extract, Tokinsenka extract, Tounin extract, Tohi extract, Dokudami extract, Tomato extract, Natto extract , Carrot extract, garlic extract, Novara extract, Hibiscus extract, Bakumondou extract, Hass extract, Parsley extract, Birch extract, Hamamelis extract, Hikiokoshi extract, Hinoki extract, Biwa extract, Fukitanpopo extract, Fukinoto extract, Bukuryo extract, Butcher bloom extract, Grape Extract, grape seed extract, hechima extract, benibana extract, peppermint extract, bodaiju extract, button extract, ho Pup extract, pine extract, mayonara extract, marronnier extract, mizubasho extract, mukuroji extract, melissa extract, mozuku extract, peach extract, yagurumagiku extract, eucalyptus extract, yukinoshita extract, yuzu extract, lily extract, yokunin extract, yomogi extract, lavender extract, green tea extract, apple extract , Louis Boss tea extract, Reishi extract, lettuce extract, lemon extract, lotus extract, lotus extract, rose extract, rosemary extract, roman chamomile extract, royal jelly extract, crackle extract and the like are preferable.

Examples of the oily component include polar oils and volatile hydrocarbon oils.
Polar oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, and lactic acid as synthetic ester oils. Cetyl, myristyl lactate, lanolin acetate, 2-ethylhexyl isononanoate, isosetyl stearate, isosetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-monoisostearate Alkyl glycol, neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptyl undecanoate, trimethyl propane tri-2-ethylhexanoate, trimethyl propane triisostearate, pentane tetra-2-ethylhexanoate Examples thereof include erythritol, glyceryl tri-2-ethylhexanoate, and trimethylolpropane triisostearate.

In addition, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, acetoglyceride,
2-Heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamate-2-octyldodecyl ester, di-2-heptylundesyl adipate, ethyllaurate, di-2-ethylhexyl sebatate, myristic acid Examples thereof include 2-hexyldecyl, 2-hexyldecyl palmitate, 2-hexyldecyl adipic acid, diisopropyl sebatate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, and octylmethoxycinnamate. ..

Also, as natural oils, avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern ka oil, castor oil, flaxseed oil, Saflower oil, cotton seed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese millet oil, jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, glyceryl triisopalmitate And so on.

Examples of the volatile hydrocarbon oil include alkanes having 12 to 16 carbon atoms, which may be straight chains or branched chains, specifically, isododecane, isohexadecane and the like.

Examples of the surfactant include anionic surfactants such as fatty acid sekken (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, triethanolamine alkyl sulfate ether, stearyltrimethylammonium chloride, benzalconium chloride, laurylamine oxide Cationic surfactants such as, betaine-based surfactants (alkylbetaine, amide betaine, sulfobetaine, etc.), imidazoline-based amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy 2) (Sodium salt, etc.), amphoteric surfactants such as acylmethyltaurine, sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.), glycerin fatty acid esters (glyceryl monostearate, etc.), propylene glycol fatty acid esters (Polyethylene glycol monostearate, etc.), hardened castor oil derivative, glycerin alkyl ether, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbit fatty acid esters (POE-sorbit mono) Laurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monoolate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE Alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / cured castor oil derivative (POE castor oil, etc.) , POE cured castor oil, etc.), nonionic surfactants such as sucrose fatty acid ester, alkyl glucoside, etc.

Polyhydric alcohols include polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, martitol, propylene glycol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4. -Hexylene glycol, 1,2-hexanediol, 1,2-octanediol and the like can be mentioned.

As thickeners, guar gum, quince seed, carrageenan, galactan, arabic gum, pectin, mannan, starch, xanthan gum, curdlan, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl hydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, glycogen, Heparan sulphate, hyaluronic acid, sodium hyaluronate, traganth gum, keratane sulphate, chondroitin, mucoitin sulphate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, keratosulfuric acid, locust bean gum, succinoglucan, caronic acid, chitin, chitosan, carboxymethyl Examples thereof include chitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, sodium polyacrylate, polyethylene glycol, bentonite and the like.

As the powders, the surface may be treated, such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic acid anhydride (silica), aluminum oxide, barium sulfate and the like, and the surface. May be treated, red iron oxide, black iron oxide, cobalt oxide, ultramarine, dark blue, titanium oxide, zinc oxide inorganic pigments, surface may be treated, mica titanium, fish phosphorus foil, Pearl agents such as bismuth oxychloride, red 202, red 228, red 226, yellow 4, blue 404, yellow 5, red 505, red 230, red 223, which may be raked. Organic pigments such as No., Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204, Polyethylene powder, Polymethyl methacrylate, Nylon powder, Examples thereof include organic powders such as organopolysiloxane elastomers.

Examples of UV absorbers include paraaminobenzoic acid UV absorbers, anthranylic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers, 2- (2). Examples thereof include ultraviolet absorbers such as'-hydroxy-5'-t-octylphenyl) benzotriazole and 4-methoxy-4'-t-butyldibenzoylmethane.

Hereinafter, the present invention will be described in more detail with reference to examples, but it goes without saying that the present invention is not limited to such examples.

<Test Example 1> Preparation of complex and examination of modification rate (1) Confirmation of cation region For organic compounds used for modification, the pH region cationized in the aqueous solution is measured by zeta potential measurement (ELSZ-2 manufactured by Otsuka Electronics Co., Ltd.). confirmed.

(2) Calculation of molecular size Examples of the organic compounds include lecithin (hydrogenated lecithin Emulmetik 950, manufactured by Lucas Meyer Cosmetics), dimethyldioctadecyl ammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and lauryl betaine (Amphitol 24B,). Kao Corporation) was used.
For dimethyldioctadecyl ammonium chloride and lauryl betaine, the surface excess concentration was calculated by surface tension measurement (automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.). The molecular size was determined from the molecular cross-sectional area, which is the reciprocal of the surface excess concentration.
For the molecular size of lecithin, the literature value calculated from the π-A curve of the monolayer ((Nobuyuki Tsubaki et al., Oil Chemistry, Vol. 41, No. 7, 551-557, (1992)) was adopted.

(3) Preparation of complex Various organic compounds (final concentration 1 to 25 mM), bentonite (Hojun, Wenger A) 8 g, 1N
An appropriate amount of HCl or citric acid (for pH adjustment) and pure water (up to 800 g) were mixed, and the mixture was stirred with a stirrer at 80 ± 5 ° C. for 2 hours. Then, it was washed with an aqueous HCl solution adjusted to pH 2.5 to 3, centrifuged, and then the supernatant was discarded three times. Further, the residue was washed once with pure water, suction-filtered, dried overnight in a vacuum dryer (80 ° C., -0.1 MPa), and then pulverized.

(4) Measurement of modification rate The change in heating weight is measured by a thermal analyzer (TP2-R / TG-DTA manufactured by Rigaku), and the amount of weight loss due to oxidative exothermic decomposition is used as the composite amount of organic compound to determine the degree of neutralization. Was calculated.
Measurement conditions: Temperature range 20 to 500 ° C, temperature rise rate 5 ° C / min., Under air atmosphere Sample container: Aluminum pan The modification rate was the mol ratio of the composite organic compound / bentonite x 100 (%).

Table 1 shows the molecular size and modification rate of each organic compound.
Didecyldioctadecylammonium chloride with a molecular size of 1.12 nm and lauryl betaine with a molecular size of 1.78 nm had low modification rates of 46.4% and 24.7%, respectively. On the other hand, lecithin having a small molecular size of 0.71 nm had a high modification rate of 92.3%, and it can be said that it was almost completely neutralized.

<Test Example 2> Examination of adhesion suppressing effect (1) Sample The following powder particles were used.
Example 1: Lecithin-modified bentonite complex prepared in Test Example 1 Comparative Example 1: Dialkylammonium salt-modified bentonite "Benton 38V" (manufactured by Elementis Japan)
Comparative Example 2: Bentonite Comparative Example 3: Keratin powder

(2) Measurement of Charge Amount of Powder Particles (Base) The powder particles of either Example or Comparative Example were placed in a glass rod bottle and shaken for 3 minutes for pretreatment (forced charging). The charge amount of each charged powder particle was measured using an Espart analyzer (Hosokawa Micron, EST-G). The measurement conditions were: applied voltage: 100 V, particle count: 1000, room temperature 25 ° C ± 2 ° C, humidity 30% ± 3%, nitrogen gas pressure: 0.02 MPa.

(3) Measurement of the amount of charge transfer to pollen The pollen was placed in a glass rod bottle and shaken for 3 minutes to prepare for pre-charging (forced charging).
A 10% by mass ethanol solution of the powder particles of any of the examples and comparative examples was prepared, uniformly applied to the artificial leather (supplere) and dried, and then the charged pollen was sprayed on the artificial leather. The pollen was peeled off by spraying nitrogen gas. The charge amount of 1000 released pollens was measured using an Espart analyzer (measurement conditions are the same as in (2)). The absolute value of (charge amount of pollen after peeling-charge amount of pollen before spraying) was defined as the amount of charge transfer to pollen.

The results are shown in FIG. The horizontal axis is the amount of charge of the powder particles (base), and the smaller the absolute value, the greater the degree of neutralization. The vertical axis is the amount of charge transfer to the liberated pollen when the pollen is peeled from the coating film, and the larger the amount, the more difficult it is for the pollen attached to the coating film to be peeled off. In the coating film formed by the lecithin-modified bentonite complex (Example 1), the amount of charge transfer to pollen was small, and an excellent adhesion suppressing effect was confirmed.

Claims (8)

A clay mineral complex modified with an organic compound
A complex in which the molecular size of the organic compound is 100% or less of the distance between charges of the clay mineral. The complex according to claim 1, wherein the measured modification rate of the organic compound with respect to the clay mineral is 50% or more. The complex according to claim 1 or 2, wherein the organic compound is a cationic or amphoteric compound. The complex according to claim 3, wherein the organic compound is lecithin. The complex according to any one of claims 1 to 4, wherein the clay mineral is selected from the group consisting of bentonite and hectorite. An external preparation for skin containing the complex according to any one of claims 1 to 5. The external preparation for skin according to claim 6, which is a cosmetic. The external preparation for skin according to claim 6 or 7, which is for suppressing the adhesion of fine particles.

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