FIELD OF THE INVENTION
The present invention relates to an organic silicone resin powder comprising a copolymer produced by polymerization reaction between a reactive group-containing organopolysiloxane and at least one kind of monomer or oligomer capable of reacting to the reactive group, which can improve the feel of cosmetics, wax, coating color and like materials when the powder is mixed therewith, specifically which can elevate spreadability of such materials as cited above, that is, enables the materials to be applied more evenly and more thinly, and further can ensure gloss in their outward appearance.
Further, the invention is concerned with a cosmetic material which contains an organic silicone resin powder comprising a copolymer produced by the polymerization reaction between an organopolysiloxane having reactive group(s) and at least one kind of monomer or oligomer capable of reacting to the foregoing reactive group(s) to improve adhesiveness as well as impressions created by the application thereof, such as a dry feel and a feeling of refreshment, and application characteristics, such as spreadability.
BACKGROUND OF THE INVENTION
The cosmetic materials currently in use comprise a composition containing an inorganic powder, such as titanium oxide, mixed with a resin of hydrocarbon type or silicone type for the purpose of improving the characteristics required therefor and advancing such improvements. The characteristics required for cosmetic materials, as mentioned above, include pleasant feels upon application, such as a dry feel and a feeling of refreshment, spreading properties, such as even and thin application, and texture, such as gloss and color.
For instance, the cosmetic material containing a hydrocarbon type of synthetic resin powder, such as powder of polyethylene resin, polyamide resin, acrylic resin, vinyl chloride resin or epoxy resin, is disclosed in Japanese Tokkai Sho 52-99236 (the term “Tokkai” as used herein means an “unexamined published patent application”).
As examples of a cosmetic material into which a resin of silicone type is compounded, mention may be made of the cosmetic material disclosed in Japanese Tokkai Hei 1-268615, which contains a powder of polyorganosilsesquioxane as a three-dimensionally cross-linked silicone, and the cosmetic material containing finely pulverized silicone rubber having elasticity as disclosed in Japanese Tokko Hei 7-53646 (the term “Tokko” as used herein means an “examined patent publication”).
As to the inorganic powder, on the other hand, red iron oxide and titanium oxide have hitherto been used as pigment, and tabular powders, such as mica and sericite, have so far been used as an essential component of nail color, nail coat, face powder, mascara or eyeliner.
Those inorganic powders have hydroxyl groups on their surfaces, so that they are generally used after undergoing silicone, fluoropolymer, metallic soap or activator treatment for weakening their surface activity and the cohesiveness thereof or making the surfaces hydrophobic.
However, the cosmetic materials containing the hydrocarbon type of synthetic resins as recited above are generally apt to have high hardness, and so the application thereof occasionally arises a uncomfortable feeling, such as a hard feel, in the users.
On the other hand, the cosmetic materials containing finely pulverized silicone rubber can wipe away a hard feel, but they are not easy to handle because of lack in fluidity and sometimes difficult to homogeneously mix with other ingredients because of their strong cohesiveness and their inferiority in compatibility.
In general those conventional fine silicone particles are prepared by an emulsion polymerization method. As a result, such particles have a spherical shape or a shape close thereto. While the spherical particles are used in a cosmetic material for the purpose of improving the sliding properties and reducing a tacky feel at the time the cosmetic material is applied to the skin, they lower the adhesiveness of the cosmetic material to the skin because of their shape. Therefore, it is usually tried to improve the adhesiveness by compounding an inorganic tabular powder, such as mica or sericite powder, into a cosmetic material.
However, those inorganic tabular powders have their specific gravity in the range of 2-3, and so their specific gravity is greater than those of other ingredients to constitute a cosmetic material. In addition, they contain impurities because of natural materials, and so they are dull in color. Accordingly, when such heavy inorganic tabular powders are compounded into a liquid cosmetic material, they cause a problem of precipitation. Further, as the color of such powders become much darker when wetted by oil, compounding with them lowers the color saturation of the resultant cosmetic material.
SUMMARY OF THE INVENTION
The present invention is made aiming chiefly at dissolving the aforementioned problems. More specifically, a first object of the invention is to provide an organic silicone powder which, when it is compounded with other ingredients into a composition, does not arise in users of the composition an uncomfortable feeling, such as a hard feel or a tacky touch, which is the problem of conventional resin powders of hydrocarbon or silicone type, and forms no sediment because of its low specific gravity, and further can improve the texture of the composition, including the gloss and the touch thereof, and the impressions that the users have upon application thereof, such as spreadability and feels.
A second object of the invention is to provide a method of producing the organic silicone resin powder as mentioned above.
A third object of the invention is to provide a cosmetic material comprising a powder which can impart improved moist or dry feel, and enhanced refreshing effect to the cosmetic material, can elevate not only application characteristics, including spreadability, but also adhesiveness, and further has improved specific gravity, compatibility and dispersibility to form no deposit.
One of the subject matters of the invention is an organic silicone resin powder that has a tabular shape the aspect ratio of which is greater than about 1 and comprises a copolymer produced by polymerization reaction between an organopolysiloxane containing at least one reactive group and at least one kind of monomer or oligomer capable of reacting to the reactive group. Therein, the reactive group may be a radical polymerizable group, while the monomer or oligomer may have radical polymerizability. This organic silicone resin powder may further comprise an inorganic powder.
Another subject matter of the invention is a method of producing an organic silicone resin powder having a tabular shape the aspect ratio of which is greater than about 1, with the method comprising the steps of forming a film from a copolymer produced by polymerization reaction between an organopolysiloxane containing at least one reactive group and at least one kind of monomer or oligomer capable of reacting to the reactive group, grinding the film into a powder, and then putting the powder through a sieve. Therein, the film may be formed using a biaxial extruder.
Still another subject matter of the invention is a cosmetic material which contains an organic silicone resin powder having a tabular shape the aspect ratio of which is greater about 1 and comprising a copolymer produced by polymerization reaction between an organopolysiloxane containing at least one reactive group and at least one kind of monomer or oligomer capable of reacting to the reactive group. In such a cosmetic material, the foregoing organic silicone resin powder may be contained in a proportion of from about 0.01 to about 50 weight %. In addition, the number average molecular weight of the foregoing copolymer may be from about 2,000 to about 100,000. Further, the cosmetic material may further contain at least one ingredient selected from the group consisting of oils, surfactants and powders.
Herein, the term “aspect ratio” is defined as the b/a ratio, when the thickness of a resin powder particle is taken as “a” and the major axis thereof is taken as “b”. Therefore, the particles are regarded as more tabular the greater their aspect ratio is.
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiments of the present invention are illustrated below. However, the invention should not be construed as being limited to these embodiments.
The particles constituting the present organic silicone resin powder have a tabular shape, and the thickness thereof is in the range of about 0.1 μm to about 2 μm. Considered from the standpoints of easiness of handling and impressions created by the application thereof, it is desirable that their average particle diameter on a volume equivalent basis (DP50) be from about 0.1 to about 100 μm, particularly preferably from 1 to 50 μm. A reason therefor is in that when the thickness and diameter of particles are smaller than the foregoing range the gloss, which is characteristic of powder, tends to be lost; while the particles having greater thickness and diameter than the foregoing range tend to give a rough feel.
Although the organic silicone resin powder having an aspect ratio greater than about 1 can serve the present purpose, it is desirable for the powder to have its aspect ratio in the range of 5 to 50 in order to further enhance its effects and make them more certain.
The reactive group-containing organopolysiloxanes and the monomers or oligomers capable of reacting to the reactive groups contained in such organopolysiloxanes, which are usable in producing copolymers according to the present invention, are illustrated below.
The reactive group-containing organopolysiloxanes usable in the invention are represented by the following formula;
wherein A is a reacive group, R is a univalent hydrocarbon group containing 1 to 10 carbon atoms, x is from 0.002 to 1.5 and y is from 0 to 3.0, provided that 1.5≦x+y≦2.5.
The R groups which constitute the foregoing organopolysiloxane molecule may be the same or different.
The reactive group represented by A is intended to include functional groups having chemical reactivity. Suitable examples of such a functional group include an amino group, a hydroxyl group, an epoxy group, a carboxylic acid group, and radical polymerizable groups, such as vinyl, styryl, α-methylstyryl, acryl and methacryl groups.
Specifically, the reactive group-containing organopolysiloxanes are, e.g., amino-modified silicones, alcohol-modified silicones, epoxy-modified silicones, carboxylic acid-modified silicones, vinyl-modified silicones, styrene-modified silicones, bisphenol A-modified silicones, acrylic-modified silicones, methacrylic-modified silicones, or maleic anhydride-modified silicones.
Of the reactive group-modified silicones as recited above, the modified silicones having acrylic reactive groups, such as acrylate or methacrylate groups, are preferred over the others because of their high reactivity, easiness of reaction control and easy availability of raw materials.
As far as organopolysiloxanes have at least one reactive group in their respective organopolysiloxane skeletons, they can serve the present purpose. And, considering the reactivity, it is desirable for the reactive group to be situated at a terminal position of organopolysiloxane molecule.
Also, the organopolysiloxanes containing two or more of reactive groups per molecule can be used in the invention, as seen from the definition of x and y in the formula illustrated above, and those reactive groups may be the same or different. In addition, the organopolysiloxane used in the invention may have not only a linear skeleton but also a branched skeleton.
Further, the organopolysiloxane used in the invention may be a mixture of two or more of reactive group-containing organopolysiloxanes differing in molecular weight.
As far as the reactive group-containing organopolysiloxane selected from the aforementioned range is employed, the resultant organic silicone resin powder can have improved spreadability and give desirable impressions, e.g., a moist feel, to users.
The reactive monomers or oligomers usable for the production of copolymers according to the present invention are monomers or oligomers which each have a functional group capable of reacting to the reactive groups contained in the organopolysiloxanes mentioned above. More specifically, when the reactive group contained in an organopolysiloxane used in copolymerization is an amino group, an alcoholic group, an epoxy group, a carboxylic acid group or a radical polymerizable group, the reactive group of the monomer or oligomer to be selected for the copolymerization is a functional group as a counterpart of the above-recited reactive group, namely an epoxy group, a carboxylic acid group, an amino group, an alcoholic group or a radical polymerizable group respectively.
In view of high reactivity, easy control of reaction and easy availability of raw materials, similarly to the case of the foregoing reactive group-containing organopolysiloxanes, it is desirable for the reactive monomer or oligomer to be a monomer containing a radical polymerizable group or an oligomer thereof. Suitable examples of such a monomer or oligomer include a-olefins (such as ethylene, propylene, butene, pentene, 4-methylpentene, hexene, heptene, octene, vinylcyclohexene, styrene, a-methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, p-t-butylstyrene and α-methyl-p-methylstyrene), acrylonitrile, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl methacrylate, N,N-diemthylacrylamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactame, acryloylmorpholine, N-vinylimidazole, maleic anhydride, phenylimide, and oligomers of the monomers as recited above.
Also, the reactive monomer may be a polyfunctional monomer, such as tricyclodecanedimethanol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate or polyethylene(propylene) glycol diacrylate.
The reactive group-containing organopolysiloxane and the reactive monomer or oligomer are properly selected from their respective exemplifications as recited above, and subjected to copolymerization reaction. In a special case where organopolysiloxanes are grafted onto an organic resin by copolymerization of a radical polymerizable monomer and a radical polymerizable group-containing organopolysiloxane, it is advantageous to use an organopolysiloxane having a radical polymerizable group at one end of the siloxane chain.
The foregoing radical polymerizable monomer and radical polymerizable group-containing organopolysiloxane can be copolymerized in a conventional manner using a radical initiator, such as benzoyl peroxide or azobisisobutyronitrile. As to the method for copolymerization, any method of emulsion polymerization, solution polymerization and block polymerization may be adopted therein.
When the thus produced copolymer has hydroxyl groups, it may be further reacted with a dibasic acid anhydride to convert a part of the hydroxyl groups into carboxyl groups, thereby producing a modified copolymer.
Further, the modified copolymer thus produced can be neutralized with an alkali solution to be further converted into the carboxylic acid salt.
The copolymers produced using the aforementioned methods have their individual weight average molecular weight in the range of 2,000 to 100,000, preferably 5,000 to 60,000.
When the copolymer has a weight average molecular weight lower than 2,000, the powder thereof is brittle, and the cosmetic material mixed therewith tends to have a tacky feel. When the copolymer has a weight average molecular weight higher than 100,000, on the other hand, the powder thereof is apt to have high hardness, and so the cosmetic material mixed therewith tend to have a rough feel. Therefore, it is desirable for the present copolymers to have their individual molecular weight within the foregoing limits. Additionally, the aforementioned drawbacks are certain to be removed as far as the weight average molecular weight is from 5,000 to 60,000.
Further, it is desirable that the compounding ratio of reactive group-containing organopolysiloxanes to reactive monomers or oligomers be in the range of 0.1/99.9 to 50/50, particularly from 5/95 to 30/70, by weight.
When the reactive group-containing oranopolysiloxane is compounded in a proportion lower than 0.1 weight %, the resultant copolymer sometimes fails to exhibit marked characteristics of organopolysiloxanes, including slipping properties; while, when it is compounded in a proportion higher than 50 weight %, the glass transition temperature thereof is liable to drop, the composition containing the resultant copolymer, such as a cosmetic material, tends to arise an uncomfortable feeling, e.g., a stiff feel, in users.
Then, if the foregoing compounding ratio is selected from the range of 5/95 to 30/70 by weight, it becomes certain that the resultant copolymer can exhibit marked characteristics of organopolysiloxanes, such as slipping properties, and can have a glass transition temperature of at least 40° C. to arise no uncomfortable feeling.
For raising the molecular weight of the present copolymers, various methods can be adopted, with examples including a method of controlling the compounding ratio upon copolymerization, a method of carrying out copolymerization using at least two kinds of compounds for either or both of copolymerizable monomers (namely a reactive monomer or oligomer and a reactive group-containing organopolysiloxane), a method of carrying out copolymerization using a polyfunctional group-introduced compound for either of copolymerizable monomers, and a method of carrying out the copolymerization of a reactive monomer or oligomer and a reactive group-containing organopolysiloxane in the presence of compounds reactive to the monomer or the oligomer and/or the organopolysiloxane.
More specifically, when an olefin monomer containing a carboxylic acid group is chosen as the reactive monomer, the olefin monomer can undergo not only the dehydration condensation reaction with an organopolysiloxane having alcoholic group(s) reactive to the carboxylic acid group and a polyhydric alcohol, such as glycol, but also radical polymerization, thereby producing a copolymer.
In another case of copolymerization, the olefin monomer containing an epoxy group instead of the carboxylic acid group in the foregoing case is chosen as the reactive monomer, and the addition reaction may be carried out using such an olefin monomer in combination with an organopolysiloxane containing amino group(s) instead of the alcoholic group(s) in the foregoing case and an amino compound.
Instead of using polyfunctional reactive monomers in the copolymerization reaction, the organopolysiloxane used therein maybe chosen from polyfunctional organopolysiloxanes.
In the next place, the method of preparing the present organic silicone resin powder having a tabular shape and an aspect ratio greater than about 1, which can be mixed in cosmetic materials, is illustrated below.
After the copolymer is produced in accordance with any of the aforementioned methods, the resin component is separated by distilling off the solvent, or it is reprecipitated as a powdery matter with methanol or the like and then filtered off.
During, before or after the copolymerization reaction, an inorganic matrix, such as an inorganic powder (e.g., titanium oxide, mica or titanium mica), a pearl brightener or an inorganic pigment, and general additives for synthetic resins, such as a lubricant (e.g., silicone oil), an antistatic agent, an ultraviolet absorbent and an antioxidant, can be added to the reaction system.
Thus, the powder having the desired outward appearance, which was impossible for conventional inorganic powders to have, can be obtained.
The resin component thus obtained is made into a tabular powder in a manner as described below: For instance, the resin component is dissolved in an organic solvent, made into a thin film, and then ground into a powder. In another manner, the resin component may be formed into a film by means of a biaxial extruder, and further stretched. In still another manner, the powder obtained by reprecipitation may be dried, and then ground into a fine powder. Anyhow, a tabular powder which can make the same impression as mica on users can be formed by coating a solution of resin component on a base in a filmy layer, similarly to the case of preparing release paper, peeling the layer away from the base and then grinding it.
In pulverizing the resin component obtained, hitherto known grinder, such as a primary crusher (e.g., a cutter mill, a hammer mill or a jaw crusher) or a pulverizer (e.g., a stamp mill, a jet mill, a ball mill, a roller mill, a pin-type mill or an impeller mill), may be employed. Additionally, the apparatus as recited above may be used under a cooled or heated condition.
The thus obtained powder is sifted out by means of a classifier to prepare organic silicone resin particles having a tabular shape and the desired diameter and aspect ratio.
Further; the tabular particles thus prepared may undergo a surface treatment using, e.g., metal soap, alumina, silica or phosphoric acid.
The average particle diameter of tabular powder on a volume equivalent basis (Dp50) is determined by a screening method, a laser method or a centrifugal sedimentation method. The average thickness of tabular particles is calculated by selecting several particles arbitrarily from the particles in the visual field of an electron microscope, measuring their respective thicknesses, and calculating the average value of the measured values. And the aspect ratio is calculated from the thus measured average particle diameter and thickness.
The organic silicone resin powder prepared in the manner as mentioned above is mixed as one ingredient of a cosmetic material in a proportion of, e.g., 0.01 to 50 weight %.
When the proportion of the powder mixed is smaller than 0.01 weight %, the resultant cosmetic material cannot have desirable feels, such as a dry feel, in some cases; while the proportion increased beyond 50 weight % tends to impair the applicability of the resultant cosmetic material, such as smooth and even spreadability. Therefore, it is desirable for the porportion of the powder mixed to be in the foregoing range. The more suitable range thereof is from 0.05 to 20 weight %, and this range is certain to remove the foregoing drawbacks.
The cosmetic materials containing the aforementioned organic silicone resin powder can have a remarkable reduction in specific gravity, compared with those containing conventional inorganic powders, so that they can successfully avoid precipitating the powder by aging.
Further, even an uncomfortable texture, such as a rough or tacky touch, the cosmetic materials tend to have when they contain a conventional resin of hydrocarbon type or silicone type respectively as an ingredient thereof, can be dissolved by adding thereto the present organic silicone resin powder which is made up of a copolymer having improved compatibility and dispersibility, and further has a tabular shape having an aspect ratio greater about 1. Moreover, the addition of the present organic silicone resin powder makes it possible to impart only the advantageous properties each resin has by nature, such as stability and a moist feel, to cosmetic materials.
As mentioned above, the present powder is remarkably improved in not only properties but also easiness of handling, compared with hitherto employed inorganic powders, so that it can be a highly satisfactory substitute for conventional inorganic powders.
In the cosmetic materials according to the invention, other ingredients can be mixed, with examples including the following:
A wide variety of oils can be mixed depending on the intended purpose of the cosmetic material to be prepared. The oils mixed may be in any of solid, semisolid and liquid states.
More specifically, not only natural animal and vegetable fats and oils but also semi-synthetic fats and oils are usable in the present cosmetic material. Examples thereof include avocado oil, linseed oil, almond oil, insect wax, perilla oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candellila wax, beef tallow, beef foot oil, beef bone fat, hydrogenated beef tallow, apricot kernel oil, spermaceti, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, ricebran oil, sugarcanewax, sasanquaoil, saffloweroil, shea butter, Chaisese tung oil, cinnamon oil, jojoba wax, shellac wax, turtle oil, soybean oil, tea seed oil and tsubaki oil.
Other Examples of natural animal and vegetable fats and oils and semi-synthetic fats and oils which can be used herein include evening primrose oil, corn oil, lard, rape seed oil, Japanese tung oil, rice-bran wax, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil, methyl caster oil fatty acid, sunflower oil, grape seed oil, bayberry wax, jojoba oil, macadamia nut oil, beeds wax, mink oil, cottonseed oil, cotton wax, Japan wax, haze kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride, mutton-tallow, peanut oil, anhydrous lanolin, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, polyethylene glycol lanolin fatty acid, POE hydrogenated lanolin alcohol ether, and egg yolk oil.
As examples of hydrocarbon oil which can be added, mention may be made of ozokerite, squalane, squalene, ceresine, paraffin, liquid paraffin, pristane, polyisobutylene, microcrystalline wax and Vaseline.
As examples of a higher fatty acid which can be added, mention may be made of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid and 12-hydroxystearic acid.
As examples of a higher alcohol which can be added, mention may be made of lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, POE cholesterol ester, glycerin monostearyl (batyl alcohol) and monooleyl glycerin ether (cerakyl alcohol).
As examples of ester oil which can be added, mention may be made of diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkylglycol monoisostearates, isocetyl isostearate, trimethylolpropane triisostearic acid ester, ethylene glycol di-2-ethylhexanoic acid ester, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoic acid ester, pentaerythritol tetra-2-ethylhexanoic acid ester, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicapric acid ester, triethyl citrate, 2-ethylhexyl cinnamate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate and butyl stearate.
Other examples of usable esters include diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acid esters, isopropyl myristate, 2-octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethylocanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutaminic acid 2-octyldodecyl ester and diisostearyl malic acid.
As examples of glyceride oil which can be added, mention may be made of acetoglyceride, triisooctanoic acid glycride, triisostearic acid glyceride, triisopalmitic acid glyceride, tri-2-ethylhexanoic acid glyceride, monostearic acid glyceride, di-2-heptylundecanoic acid glyceride and trimyristic acid glyceride.
As examples of silicone oil which can be added, mention may be made of dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, higher alkoxy-modified silicones such as stearoxysilicone, and higher fatty acid-modified silicones.
As examples of fluorine-containing oil which can be added, mention may be made of perfluoropolyether, perfluorodecalin and perfluorooctane.
Additionally, the oils recited above may be added alone or as mixtures of at least two among them.
Further, the present cosmetic material can contain a surfactant, if desired, and has no particular restriction as to the type of surfactant used. In other words, any of anionic, cationic, amphoteric and nonionic surfactants can be used therein.
Examples of a usable anionic surfactant include fatty acid soap, such as sodium stearate and triethanolamine palmitate; polyoxyethylene fatty alcohol ether carboxylic acids and salts thereof; carboxylates, such as condensates of amino acids and fatty acids; alkylsulfonate; alkenesulfonate; sulfonated fatty acid ester; sulfonated fatty acid amide; alkylsulfonic acid-formaldehyde condensate; alkylsulfate; higher secondary alcohol sulfate; alkyl and aryl ether sulfate; fatty acid ether sulfate, fatty acid alkylolamide sulfate; ether sulfate, such as Turkeky red oil; alkyl phosphate; ether phosphate; alkyl aryl ether phosphate; amide phosphate; and active agents of N-acylamino acid type.
Examples of a usable cationic surfactant include amine salts, such as alkylamie salts, polyamines and aminoalcohol fatty acid derivatives, quaternary alkylammonium salts, quaternary arylammonium salts, pyridinium salts and imidazolium salts.
Examples of a usable amphoteric surfactant include betaine, aminocarboxylate and imdazoline derivatives.
Examples of a usable nonionic surfactant include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene phytostanol ehter, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxanes, organopolysiloxanes modified with both polyoxyalkylene and alkyl groups, alkanolamides, sugar ethers and sugar amides.
Furthermore, the following powders can be used in the present cosmetic material.
Such powders are not particularly restricted as to their shape, size and structure, and may have any shape, size and structure as far as the powders used in conventional cosmetic materials have them. Specifically, they may have any of spherical, acicular and tabular shapes, any of haze-particle, fine-particle and pigment-grade sizes and any of structures (e.g., a porous or nonporous structure).
When such a powder is mixed in the present cosmetic material, it is not limited to only one among the powders recited below, but may be used together with another powder equivalent in effect. In addition, the powders recited below may be used as a mixture of two or more thereof. The suitable amount of powders mixed is determined depending on the desired purpose.
Examples of an organic powder include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose powder, silk powder, nylon powder, 12-nylon powder, 6-nylon powder, styrene-acrylic acid copolymer powder, divinylbenzene-styrene copolymer powder, vinyl resin powder, urea resin powder, phenol resin powder, fluororesin powder, silicone resin powder, acrylic resin powder, melamine resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder, rice starch powder and lauroyl lysine.
Examples of a metal salt surfactant powder (metal soap powder) include zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magensium myristate, zinc cetylphosphate, calcium cetylphosphate and zinc sodium cetylphosphate.
Examples of an inorganic powder include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, synthetic mica, muscovite, phlogopite, ruby mica, biotite, lipidolite, silicic acid, silicic acid anhydride, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal salts of tungstic acid, hydroxyapatite, vermiculite, haidilite, bentonite, montmorillonite, hectorite, zeolite, ceramics powder, calcium secondary phosphate, alumina, aluminum hydroxie, boron nitride, silica, titanium mica, iron oxide red, iron oxide black, iron oxide yellow and barium ferrite. The inorganic powder as recited above may be added in advance to the present organic silicone resin powder, and then mixed in a cosmetic material.
The colors include both inorganic and organic pigments. The inorganic powders as recited above are comprised in the inorganic pigment. More specifically, the inorganic pigment includes inorganic red pigments, such as iron oxide iron hydroxide and iron titanate; inorganic brown pigments, such as y-iron oxide; inorganic yellow pigments, such as iron oxide yellow and loess; inorganic black pigments, such as iron oxide black and carbon black; inorganic violet pigments, such as Mango violet and cobalt violet; inorganic green pigments, such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate; inorganic blue pigments, such as Prussian blue and ultramarine blue; lakes of tar pigments; lakes of natural pigments; and synthetic resin powder complexes of the inorganic pigmnents as recited above.
As examples of a pearl pigment, mention may be made of titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scales, and titanium oxide-coated colored mica.
As examples of a metallic powder pigment, mention may be made of aluminum powder, copper powder and stainless powder.
The foregoing tar pigments include Red No. 3, Red No.104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206 and Orange No. 207 (according to the pigment nomenclature method in JIS).
The foregoing natural pigments include carminic acid, laccaic acid, carthamin, bradilin and crocin.
Additionally, complexes of the powders as recited above or those obtained by treating the aforementioned powders with general oil, silicone oil or fluorine-containing compound may be used. Of course, the powders as recited above may be used as a mixture of two or more thereof.
To the present cosmetic material, the ingredients used in general cosmetic materials, such as water, alcohols, water-soluble polymers, film-forming agents, oil-soluble gelling agents, clay minerals modified with organic compounds, resin, ultraviolet absorbents, moisture-holding agents, antiseptics, antibacterial agents, perfume, salts, antioxidants, pH regulators, chelating agents, tonic, skin beautifying components, vitamins, amino acids, nucleic acids, hormones and clathrate compounds, can be added so far as they have no adverse influence on the effects of the present invention.
Examples of usable alcohols include lower alcohols, such as ethanol and isopropanol; sugar alcohols, such as sorbitol and maltose; and sterols, such as cholesterol, phytosterol and lanosterol.
Examples of usable water-soluble polymers include vegetable polymers, such as gum arabic, tragacanth, arabine galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch (rice, corn, potato, wheat), alge colloid, tranto gum and locust bean gum; microbial polymers, such as xanthan gum, dextran, succinoglucan and pullulan; animal polymers, such as collagen, casein, albumin and gelatin; starch polymers, such as carboxymethyl starch and methylhydroxypropyl starch; and cellulose polymers, such as methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, microcrystalline cellulose and powdery cellulose.
As other examples of usable water-soluble polymers, mention may be made of alginic acid polymers, such as sodium alginate and propylene glycol ester of alginic acid; vinyl polymers, such as polyvinyl methyl ether and carboxyvinyl polymer; polyoxyethylene polymers; polyoxyethylene-polyoxypropylene copolymers; acrylic polymers, such as sodium salts of polyacrylic acid, polyethylacrylate and polyacrylamide; polyethyleneimines; cationic polymers; and inorganic water-soluble polymers, such as bentonite, aluminum magnesium silicate, laponite, hectorite and silicic acid anhydride.
Therein, film-forming agents, such as polyvinyl alcohol and polyvinyl pyrrolidine, may be included.
Examples of an oil-soluble gelling agent which can be used herein include metal soaps, such as aluminum stearate, magnesium stearate and zinc myristate; amino acid derivatives, such as N-lauroyl-L-glutamic acid and α,γ-di-n-butylamine; dextrin fatty acid esters, such as dextrin palmitic acid ester, dextrin stearic acid ester and dextrin 2-ethylhexaminic acid palmitic acid ester; sucrose fatty acid esters, such as sucrose palmitic acid ester and sucrose stearic acid ester; benzylidene derivatives of sorbitol, such as monobenzylidene sorbitol and dibenzylidene sorbitol; and clay minerals modified with organic compounds, such as dimethylbenzyldodecyl ammonium montmorillonite clay and dimethyldioctadecyl ammonium montmorillonite clay.
Examples of an ultraviolet absorbent which can be used herein include those of benzoic acid type, uch as p-aminobenzoic acid; hose of anthranilic acid type, uch as methyl anthrarilate; hose of salicylic acid type,such as methyl salicylate; those of succinic acid type, such as octyl p-methoxysuccinate; those of benzophenone type, such as 2,4-dihydroxybenzophenone; and those of urocanic acid type, such as ethyl urocanate.
Examples of a moisture-holding agent which can be used herein include sorbitol, xylitol, polyethylene glycol, hyaluromic acid, chondroitin sulfuric acid and pyrrolidone carboxylic acid.
Examples of an antiseptic which can be used herein include alkyl p-hydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate and phenoxyethanol.
Examples of an antimacrobial agent which can be used herein include benzoic acid, salicylic acid, carbolic acid, sorbic acid, alkyl p-hydroxybenzoates, p-chlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photosensitizer and phenoxyethanol.
Examples of an antioxidant which can be used herein include tocopherol, butylhydroxyanisole, dibutylhydroxy-toluene and γ-oryzanol.
Examples of a pH regulator which can be used herein include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate and ammonium hydrogen carbonate.
Examples of a chelating agent which can be used herein include alanine, sodium ethylenediaminetetraacetate, sodium polyphosphate, sodium metaphosphate and phosphoric acid. Examples of a tonic which can be used herein include L-menthol and camphor.
Examples of an anti-inflammatory agent which can be used herein include allantoin, glycyrrhetinic acid, tranexamic acid and azulene.
Examples of a skin-beautifying component which can be used herein include whitening agents, such as placenta extract, arbutin, glutathione and Ykinoshita extract; cell activators, such as royal jelly, photosensitizer, cholesterol derivatives and calf blood extract; and rough dry skin improvers, including blood circulation improvers such as nonylic acid vanillyl amide, benzyl nicotinate, β-butoxyethyl nicotinate, zingerone, cantharis tincture, ichtammol, caffeine, tannic acid, α-borneol, tocopheryl nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetyl choline, verapamil, cepharanthin and γ-oryzanol, skin astringents such as zinc oxide and tannic acid, and anti-seborrheic agents such as sulfur and thianthol.
Examples of vitamins which can be used herein include vitamin A, such as vitamin A oil, retinol, retinyl acetate and retinyl palmitate; vitamin B2, such as riboflavin, riboflavin buyrate and flavin adenine nucleotide; vitamin B6, such as pyridoxine hydrochloride and pyridoxine dioctanoate; vitamin C, such as L-ascorbic acid, L-ascorbic acid dipalmitic ester, disodium (L-ascorbic acid)-2-sulfate and dipotassium dl-(-tocopherol-L-ascorbic acid phosphoric diester; vitamin D, pantothenic acids, such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether and acetylpantothenyl ethyl ether, ergocalciferol and cholecarciferol; vitamin E, including nicotinic acids such as nicotinic acid, benzyl nicotinate and nicotinic acid amide, dl-α-tocopherol, dl-α-tocopheryl acetate, dl-α-tocopheryl nicotinate and dl-α-tocopheryl succinate; vitamin P; and biotin.
Examples of an amino acid which can be used herein include alginine, aspartic acid, cystine, cysteine, methionine, serine, leucine and tryptopphan; an example of usable nucleic acids is deoxyribonucleic aicd; and examples of usable hormone are estradiol and ethenyl estradiol.
The term “cosmetic material” as used herein are intended to include preparation products in all fields where the feel is regarded as important when they are put on the skin, including not only cosmetics but also medicines for external application, and further enamel for manicure and hairdressing products.
More specifically, the present cosmetic material includes skin care products, such as face lotion, milky lotion, cream, facial pack, massage articles, lip cream, hand cream and cleaning articles; makeup products, such as face powder, foundation, rouge, eye shadow, mascara, eyeliner, eyebrow articles, overcoat articles and lipstick; nail-beautifying articles, such as enamel for manicure; and hairdressing products, such as shampoo, rinse, rinse-in-shampoo, treatment, conditioner, hair cream, hair oil, brushing articles, hair-set articles and hair tonic.
Additionally, the present cosmetic material may have any of forms, including liquid, emulsion, solid, cream, paste, multi-layer, mousse, gel and spray forms, if desired.
Besides the cosmetics, the present organic silicone resin powder can be used in the field of coating, e.g., for a releasable coating agent, a protective coating agent, a water-repellant coating agent, printing ink, coating color or wax.
The present invention will now be illustrated in greater detail by reference to the following examples and comparative examples.
Additionally, the entire disclosure of all applications, patents and publications, cited above and below, and of corresponding Japanese applications No. 11-038039 and 11-039532, filed on February. 17 and February 18 respectively in 1998, is hereby incorporated by reference.