JP2597494B2 - Makeup cosmetics - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to a novel makeup cosmetic.

Background of the Invention Conventionally, powders such as pigments applied to makeup cosmetics generally provided, particularly loose and solid makeup cosmetics, are usually complex oxides, It has hydroxyl groups on its surface, and the amount of hydroxyl groups varies depending on the type of powder. For example, titanium oxide, which is one of them, contains a small amount of hydroxyl group with weak reactivity or adsorbed water found by analysis of water generated during heating.
As can be seen from the fact that the pigments and the like have a water content of about 35% by weight, the degree of hydrophilicity and the degree of lipophilicity of the surface differ depending on the type of the powder. Furthermore, the secretion of water or sweat, sebum, etc. resulting from the change in particle size and shape deformation due to the mechanical impact force of those fine surfaces, or the difference in the degree of surface activation due to the appearance (production) of a new surface. Differences in the way of wetting by objects, and the amount of oil that has been physically attached or adsorbed to the powder surface with a non-uniform weak force, and the HL of the oil
The difference in B and the segregation of these oils due to the impact force of the machine during the manufacturing process usually causes the decorative film to be transparent, the decorative film to be broken, and the feeling of adhesion to be insufficient.

In addition, among several types of colored pigments mixed with the powder, the pigment surface due to the difference in the degree of hydrophilicity, lipophilicity, crystal form, surface activity, and affinity for sebum and oils on the surface Changes in color (differences in appearance and coating colors) over time due to changes in the wetting phenomenon (for example, changes in the refractive index, aggregation, etc.) of the product, problems with cosmetic effects such as dullness and color unevenness, and the quality of products Was not always satisfactory.

At present, in the case of presqueted make-up cosmetics that are applied to the skin without using water, the puff, which is the applied body, is always placed on the surface of the cosmetic (cake), and the puffs remain dirty with sebum or sweat. By using the oil, the oil, moisture, or oil of the foundation for the base material penetrates between the particles of the cosmetic.

This tends to cause the caking of the cosmetic (the cake becomes a lump and the surface of the cake is partially or entirely in a Tecal state), and significantly impairs the product value. on the other hand,
In the case of presquered makeup cosmetics (eg, pancakes) that are applied to the skin using water (the cosmetics are prepared by mixing an oil agent and a surfactant into a mixture of a normal pigment and other powders). It is composed as an oily system, and by using water for the cosmetic, it is applied to the skin using the fact that it is emulsified on the surface of the cosmetic with water, an oil agent and a surfactant.), At the same time, a solubilization phenomenon occurs due to the interaction with moisture adhering to the surface of the cosmetic or invading the cosmetic,
The oil forms a powder, a hard gel containing pigments, and a kind of hard gel structure.
Caking phenomenon was caused. Also, recently, two-way presqueted make-up cosmetics on the market tend to be poorly miscible with water and ordinary oils, and have some effect in preventing caking.
There are a large number of surfactant-based and oil-based products in product systems, which also tend to cause caking. Furthermore, usually
Silicone oils commonly used in press-type makeup cosmetics may be evenly mixed with one or more oils commonly used in cosmetics. Therefore, when used in a homogeneously mixed state, the oil easily penetrates into the particles on the surface of the cosmetic, which causes caking as described above. Also, since the silicone oil itself has excellent water repellency but no oil repellency, it is a problem that the phenomenon of caking cannot be avoided.

In addition, powder raw materials generally applied to powder cosmetics are mostly composed of scaly (plate-like), needle-like, or irregular shapes. Utilizing its cleaving property, it provided a product that spreads lightly and spreads well. However, as the compounding amount of the oil agent increases, the cleaving property is hindered. In addition, when acicular or amorphous powder is used together It was extremely difficult to seek lightness and ease of spreading.

(Prior Art) Conventionally, there have been various methods and cosmetics as described below as means for improving the disadvantages of such cosmetics.

Surface treatment of powder with metal soap and surfactant Method of surface treatment of powder surface with lecithin or aluminum N-stearoyl-L-glutamate Method of baking treatment of powder surface with methylhydropolysiloxane Alcohol compound, etc. Japanese Patent Publication No. 61-55481 describes a method of treating a powder surface by using a water- and oil-repellent agent comprising a fluorine-containing polymer in a cosmetic comprising a cosmetic powder and a coloring agent as main components. "Cosmetic characterized by blending treated cosmetic powder and / or colorant" and "Composed as main components of cosmetic powder and / or colorant" described in JP-B-61-48803 In cosmetics, cosmetic powder surface-treated with fluorine resin and / or
Or a cosmetic characterized by incorporating a coloring agent) (Problems to be Solved by the Invention) However, the above-described conventional techniques have the following disadvantages.

Method of Surface Treatment of Powder with Metallic Soap / Surfactant Cosmetic treated with metallic soap such as aluminum stearate, zinc stearate, zinc myristate has water repellency but no oil repellency. Therefore, there is no oil resistance to sebum, and the obtained cosmetic is easily disintegrated with secreted sebum. Depending on the choice of surfactant, water repellency is also eliminated. The grease resistance is the same as that of metal soap.

Further, they are physically attached or adsorbed on the surface of the powder, and depending on the production method, they may be unevenly adhered or adsorbed or may have poor water repellency.

Method of surface treatment of powder surface with lecithin or aluminum N-stearoyl-L-glutamate Has good affinity for skin and some water / oil repellency, but its level is low, Since the surface treatment agent is physically attached to the powder, the surface treatment agent is easily desorbed from the powder due to the strong shearing force generated by the mechanical force in the cosmetic manufacturing process. Etc., it is easy to be transparent, and the cosmetic film also floats on sebum.

A method of baking a powder surface with methylhydropolysiloxane Silicon oil such as methylhydropolysiloxane has excellent water repellency but has very poor oil repellency.
Commercially available cosmetics are made by chemically reacting these with hydroxyl groups on the powder surface, but virtually unreacted hydroxyl groups,
Methyl hydropolysiloxane has large residual hydroxyl groups,
It is very little involved in chemical bonding, is actually slightly less water-repellent, and has no oil repellency.

A method of treating the powder surface with an alcohol compound, etc. This method protects the hydroxyl groups on the powder surface, but the resulting cosmetics have improved transparency due to wetting, but have poor adhesion to the skin and lose makeup. Easy to wake up.

The surface-treated cosmetic powders in the cosmetics obtained in JP-B-61-55481 and JP-B-61-48803 are those which are involved in the chemical bond between the powder and the surface treatment agent. It is slight and has poor water and oil repellency. In addition, pigments having almost no hydroxyl groups, such as titanium oxide, hardly participated in chemical bonding, and were very poor in water repellency and oil repellency.

That is, the main object of the present invention is to solve the above-mentioned disadvantages of the conventional technology, to have excellent water repellency and oil repellency, and not to lose makeup.
Prevents the floating of makeup due to aging, changes in color and dullness due to aging, and also prevents caking in product systems.
An object of the present invention is to provide a makeup cosmetic which has a light and easy to spread evenly and does not require any technique.

(Means for Solving the Problems) According to the present invention, the following objects can be achieved by the following.

On the surface of the activated inorganic powder base, there is provided a first coated and baked layer composed of a water-repellent oil-repellent and / or an oil agent and a reactive auxiliary agent. A three-layer structure having a coated and baked second layer composed of one or both of a water-repellent agent and an oil agent and a reactive auxiliary agent (however, if the first layer does not contain a water-repellent oil-repellent agent, the second layer is repellent). Including water and oil repellent)
A make-up cosmetic comprising a coated powder (hereinafter referred to as a three-layer coated powder A).

Coating baking comprising a reactive auxiliary agent and a water / oil repellent or a water / oil repellent and an oil agent on the surface of the activated inorganic powder base.
Coated powder having a three-layer structure and a second layer of a coated and baked film comprising a water repellent and / or an oil agent on the surface of the first baked layer. Make-up cosmetics comprising powder-containing powder B).

(Preferred Embodiment and Function) As the inorganic powder base, an inorganic pigment, another inorganic powder, or a mixture thereof can be used.

The activated inorganic powder base easily reacts with each of the constituents selected from the following first group.

Group 1 (A) water- and oil-repellent and reactive aid, (b) Oil and reactive aid, (c) Water- and oil-repellent, oil and reactive aid, Group 2 (A) Water- and oil-repellent (B) Oil agent, (c) Water-repellent oil-repellent agent and oil agent Examples of means for activating such inorganic powder base include heat treatment, plasma treatment (or corona discharge), and hydrothermal reaction. The activated inorganic powder base is subjected to etching with an alkali or an acid or the like to introduce a functional group, if necessary, to further cause a reaction with each of the constituents selected from the first group. It can be easier to do.

The water-repellent and oil-repellent agents are those having both properties of water repellency and oil repellency. In other words, it usually has no affinity for a hydrophilic substance or a lipophilic substance, and has no affinity for a mixture of a hydrophilic substance and a lipophilic substance. Specific examples thereof include fluorine silanes such as perfluoroalkylsilane and perfluoroalkylsilazane, fluorine silanes having a urethane bond, and fluorine silanes in which silicone is partially modified with fluorine. These water and oil repellents show an affinity for the activated powder.

The reactive assistant is one that is selected from the second group and reacts with the inorganic powder base when the inorganic powder base is coated as a first layer and baked (baking treatment). It binds and promotes the binding of the water- and oil-repellent or oil agent to the inorganic powder base to strengthen the bond. Promotes the bonding of oils or oils (including bonding via reactive aids), and further between water and oil repellents bonded to the inorganic powder base, between oils, between water and oil repellents and oils The coating layer is filled and densified by a crosslinking action.
When the inorganic powder base is coated and baked together with one selected from the group as the coating second layer, the coating first layer of the water- and oil-repellent and the oil agent reacts and binds with the coating first-layer composition. To promote the binding to
Reacts with water and oil repellents and oils to combine and promote the bonding of water and oil repellents and oils to the coating first layer (including bonding via reactive aids), and further to the coating first layer Filled between water- and oil-repellents, between oils, or between a water- and oil-repellent and an oil, and densifies the coating layer by a crosslinking action. The reactive aid must be present at least in the first coating layer, and also in the second coating layer if the first coating layer does not contain a water and oil repellent.

Specific examples of the reactive assistant include organic titanates, aluminum alcoholates, aluminum chelates, cyclic aluminum oligomers, and organic silicates.

Each of the water and oil repellents, oils and reactive auxiliaries can be used in combination of two or more substances.

In the case of the coating first layer, baking (baking treatment) means that each of the layer components and the inorganic powder base are strongly bonded and reacted, and further, the layer components are bonded to the inorganic powder base. The formation of a complicated network structure by causing cross-linking between each other. In the case of the coating second layer, each of the layer components and the component of the coating first layer are strongly bonded and reacted. It means that a cross-link is generated between the layer components bonded to the first coating layer to form a complicated network structure. Baking is carried out by various reactions. Among them, a typical example of the reaction is shown below for the first layer, taking one functional group as an example. However, R "-OH: oil agent (higher alcohol).

(A) Ti (OR) ₄ + H ₂ O → Ti (OR) ₃ · OH + ROH Ti (OR) ₃ · OH + H ₂ O → Ti (OR) ₂ (OH) ₂ ROH The coating layer baked on the inorganic powder base has both water and oil repellency due to the water and oil repellent.

The inorganic powder base surface activated by heat treatment, etc.
The surface of the inorganic powder base is activated, and the solid acid and solid base points are clarified. Therefore, when the activated inorganic powder base is coated with a layer composed of one of the first group, each of the constituents of one of the first group, the functional groups and the active points of the inorganic powder base, Interaction can be enhanced. Therefore,
The first coating layer adheres well to the surface of the inorganic powder base.

The coated powder having a three-layer structure according to the present invention comprises a solid bond between the coated first-layer components comprising one of the first group, an inorganic powder base and each of the first-layer coated components. Has a very tough coating first layer due to the synergistic effect of the interaction with the functional groups and active sites of the above and the adhesion or adsorption force of the coating first layer constituent to the inorganic powder base. Surface activation of the inorganic powder can be easily performed by heating or the like. further,
A strong bond between the coating second layer components comprising one of the first and second groups and each of the coating second layer components and the coating first layer component.
The bonding with each of the layer components results in a tougher coating layer as a whole. Thus, the second coating layer reinforces the first coating layer.

The pigment applied to the coated powders A and B having a three-layer structure according to the present invention preferably has an average particle size of 0.01 to 10 μm.
Inorganic white pigments such as titanium oxide and zinc oxide, iron oxides (petal oxide), inorganic red pigments such as iron titanate, inorganic yellow pigments such as yellow iron oxide and loess, and inorganic purple pigments such as mango violet and cobalt violet Pigment, inorganic green pigments such as chromium oxide, chromium hydroxide, cobalt titanate, etc., inorganic blue pigments such as ultramarine blue and navy blue, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide Examples include pearl luster pigments such as barium sulfate, titanium oxide coated talc, fish phosphor foil, colored titanium oxide coated mica, and metal powder pigments such as aluminum powder and copper powder.

The other inorganic powders preferably have an average particle size of about 1.0 to 20 μm, and are not particularly limited as long as they are used in cosmetics. For example, talc, kaolin, sericite,
Muscovite, synthetic mica, phlogopite, mica, biotite, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, strontium silicate, Inorganic powders such as metal tungstate, α-iron oxide, hydrated iron oxide, silica, hydroxyapatite, etc. can be mentioned. It is preferable to select and use one appropriately, and its content is preferably about 1 to 30% by weight based on the total amount of the inorganic powder base. (If two or more of these are used, it is preferable to pulverize, mix, and disperse them well with a pulverizer in advance.) Also, applied to water- and oil-repellents for coated powders A and B having a three-layer structure Fluorine silanes such as perfluoroalkylsilane and perfluoroalkylsilazane are represented by the following general formulas (1) and (2).

General formula (1) CF ₃ (CF ₂ ) _n CH ₂ —CH ₂ Si—R ₃ (n = 0 to 10) or (C _n F _{2n + 1} ) _m CH ₂ —CH ₂ Si—R ₃ (n = 1-5, m = 1-10) where R ₃ = hydrogen atom (H), hydroxyl group (OH), alkoxy group (OCH ₃ etc.) or phenyl group (OC ₆ H ₅ ) General formula (2) Rf-Si (NH ₂ ) ₃ Or _{Rf = C n F 2n + 1} - (n = 1~10) also or _{Rf = FCF 2 -CF 2 -O n} (n = 1~10) fluorine silane having a urethane bond represented by the following equation.

General formula (3) R = hydrogen atom, phenyl group, hydroxyl group or alkoxy group (OCH ₃ , OC ₂ H ₅ , OC ₃ H ₇ , OC ₄ H ₉ ) Further, a fluorine silane obtained by partially modifying a silicone with fluorine is represented by the following formula.

General formula (4) However, R is the same as that of the general formula (3).

In the above general formula, not only those having a linear structure but also those having a branched structure and optical isomers are included.

As an organic titanate as a reactive auxiliary agent, tetra-i-
Propyl titanate (TPT), tetra-n-butyl titanate (TBT), butyl titanate dimer (DBT), tetrastearyl titanate (TST), triethanolamine titanate (TEAT), titanium acetyl acetate (TAA), titanium ethyl acetoacetate ( TEA
A), titanium lactate (TLA), tetraoctylene glycol titanate (OGT), di-n-butoxy-bis (triethanolaminate) titanium, TBT polymer (n
= 2 to 10), TPT polymer (n = 10) and the like. As the aluminum alcoholate, aluminum ethylate,
Aluminum isopropylate, monosee-butoxyaluminum diisopropylate, aluminum sec-butyrate, and aluminum chelates include ethyl acetoacetate-aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate diisopropylate, and aluminum tris ( Acetylacetonate), cyclic aluminum oligomers include cyclic aluminum oxide isopropylate, and organic silicates include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and 3-glutoxypropyl. Trimethoxysilane, γ-methacryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, N-2 (A Aminoethyl) aminopropyl methyl dimethoxysilane, N-2 (aminoethyl) 3
Examples include aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.

As the oil agent, any oil agent which is applicable to cosmetics and has a water-repellent effect without affinity for water may be used. Squalane, liquid paraffin, vaseline, microcrystalline wax, ozokerite, ceresin, myristic acid,
Harmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, oleyl alcohol, 2-octyl dodecyl myristate, 2-octyl dodecyl gum ester, 2-octyl dodecyl aviate, 2-octyl dodecyl oleate, isopropyl myristate, Various hydrocarbons such as isostearic acid triglycerite, coconut oil fatty acid triglyceride, olive oil, avocado oil, beeswax, myristyl myristate, orica oil, mink oil, lanolin, higher fatty acids, oils and fats, higher alcohols, waxes, etc. are selected. Used.

In the coating powders A and B having a three-layer structure applied in the present invention, the weight composition of the water- and oil-repellent constituting the coating first layer with respect to the inorganic powder base serving as a core is such that the inorganic powder base is 1 1: 0.005 to 1: 0.20, the composition of the oil agent is in the range of 1: 0.005 to 1: 0.10, and the mixture of the water and oil repellent and the oil agent for the inorganic powder substrate 1 is in the range of 1: 0.005 to 1: 0.20. In the second layer of the coating, each of the water repellent oil repellent, the oil agent, and the mixture of the water repellent oil repellent and the oil agent is 1: 0.002 to 1: 0.10, 1:
In the range of 0.002 to 1: 0.05, 1: 0.002 to 1: 0.10, and the entire coating layer including the first coating layer and the second coating layer, the water- and oil-repellent agent is used for one of the inorganic powder bases. , Each of the mixture of the water and oil repellent and the oil agent is 1: 0.007 to 1: 0.20, 1: 0.007 to 1: 0.10,
The range of 1: 0.007 to 1: 0.20 is commonly taken for each three-layer coated powder. In addition, as a pretreatment of the inorganic powder base, the inorganic powder base is washed with isopropyl alcohol (hereinafter referred to as IPA), then with acetone, water, etc., and dried, so that the water adhering to the surface of the inorganic powder base is washed. It is preferable to remove contamination (dirt). The activation heating temperature of the inorganic powder base varies depending on the structural stability of the inorganic powder base and the like, but is desirably performed within the range of 100 to 1000 ° C.

 The points to be noted here are as follows.

One composition in the first group constituting the coating first layer is as follows:
The range required to completely cover the surface of the inorganic powder base serving as the core is to be taken. Therefore, less than 0.4% is not sufficient, and even if it exceeds 20%, there is no significant difference in the effect on quality, and there is no merit of using it.

One composition in the first and second groups constituting the second coating layer is that a range necessary for reinforcing the first coating layer is taken. Therefore, if the composition of one of the first group used in the first coating layer is small, the composition is relatively large, and if it is large, the composition is relatively small.

When the oil agent and the reactive auxiliary agent in the first group are used for the composition of the first coating layer, the oil repellency cannot be imparted by using only the oil agent. Either (a) a water / oil repellent and a reactive aid or (c) a water / oil repellent, an oil and a reactive aid in one group are selected.

When one composition in the first group or one composition in the second group is selected as the composition constituting the coating second layer, it is better to use one composition in the first group. It is relatively superior in terms of the effect of reinforcing one layer.

If both the first and second coating layers are merely coated with the water- and oil-repellent agent and the reactive assistant (no baking treatment), the filmization or water-repellent between the water- and oil-repellent agents by the reactive assistant is applied. The polymerization of the oil agent does not proceed, and the film property becomes very weak.

When both the first and second coating layers are merely coated on the inorganic powder base with the oil agent alone or with the oil agent and the reactive auxiliary agent (without baking treatment), the phenomenon of wetting to other powders may occur. Good, but due to physical adhesion or adsorption, the coating is so weak that it is not practical.

When the mixture of water and oil repellent, oil agent and reactive auxiliary is simply coated on the inorganic powder base for both the first and second coating layers, the reactive auxiliary is effective only after baking. Therefore, in practice, only the effect of simply mixing the oil agent and the water / oil repellent can be obtained. In other words, the coating first layer and the second layer are mixed and cannot be distinguished from each other, and the oil agent and the water / oil repellent are merely attached or adsorbed on the surface of the inorganic powder base.
It merely has the properties of the water and oil repellent and the oil alone.

When the inorganic powder base is not activated in the above, the coating layer is only attached or adsorbed on the surface of the inorganic powder base, and the inorganic powder base and the coating layer composition There is no interaction between them, and these coating layer components are easily detached from the surface of the inorganic powder base by mechanical force, impact force, centrifugal force, shear force, etc., and the object of the present invention is obtained. Absent.

Each of the coated powders of the present invention is subjected to surface activation of inorganic powder base (by heating or the like), clarification of solid acid and solid base points, introduction of functional groups or etching as necessary, Coating and baking such an activated inorganic powder base in the form of (a) bonding between each of the members of the first group, (b) their coating An extremely tough coating film is formed by the interaction between the first layer constituents and the functional groups and the active sites in the inorganic powder base, and (c) further synergistic action with the adhesive force or the adsorptive force. Further, (d) bonding between one of the first and second groups and (e) the coating second layer component and the coating first layer component with respect to the coating film. (F) further synergistic action with adhesion or adhesion to form a more tough coating film. It is to obtain a shall.
The following points should also be noted.

The activation heating temperature of the inorganic powder base varies depending on the type of the inorganic powder base, but may be within a range in which the properties of the inorganic powder base can be exhibited without deteriorating or decomposing.
It is in the range of 0 to 1000 ° C. The heating time is the time for the activation of the surface and the generation of the solid acid / base points as described above.
~ 48 hours. If the time is less than 1 hour, the above-mentioned effect by heating is often not exhibited.

The baking treatment temperature is basically required to be not higher than the boiling point at which the water- and oil-repellent does not decompose and deteriorate and does not evaporate. However, when an oil is used in combination, a temperature at which the oil does not deteriorate or decompose is preferable. Usually, it can be applied within the range of 80 to 180 ° C. The baking treatment time is a time for completing a complex bonding reaction between the coating layer components and between the inorganic powder base and each of the coating layer components, and is usually 1.5 to 48 hours. A baking treatment time longer than this is not necessary in view of the completeness of the reaction, and a baking treatment shorter than this time is incomplete, and the desired strength and cosmetic effect of the coating film cannot be obtained.

The preferred contents of the three-layer coated powders A and B in the makeup cosmetic of the present invention are 1.0 to
40% by weight, 0.5-30% by weight for oil gel type, 15-90% by weight for press type, 10 for loose type
~ 90% by weight is taken. Also, the coated powders A and B having a three-layer structure can be used as it is as 100% by weight as a makeup cosmetic such as face powder, powder eye shadow, dusting powder and the like.

The following is an example of a method for obtaining the coated powders A and B having a three-layer structure applied to the present invention.

In the case of the coated powder A having a three-layer structure, the inorganic powder base is preferably subjected to a pretreatment such as IPA, acetone, water washing and drying (but not essential), and the inorganic powder base is heated. Treatment (if necessary, further alkali treatment or acid treatment), autoclaving or plasma spraying treatment, water and oil repellent and reactive aid, oil and reactive aid, or water and oil repellent and oil and reactive aid The inorganic powder base after the above treatment is poured into an organic solvent in which is dissolved, mixed, stirred, and ground, and then the organic solvent is distilled off (and dried if necessary) to remove the inorganic powder base. Two layers having a core as a first layer of (a) a water / oil repellent and a reactive aid, (b) an oil and a reactive aid, or (c) a water / oil repellent, an oil and a reactive aid The body is baked to increase the film strength, and (a) a water and oil repellent and a reactive aid,
(B) The two-layer body after the baking treatment is poured into an organic solvent in which one of the oil agent and the reactive auxiliary agent, and (c) the water / oil repellent agent, the oil agent and the reactive auxiliary agent are dissolved, and mixed, stirred, After milling, the organic solvent is distilled off, and if necessary, dried. The inorganic powder base having the first coating layer is used as a core and (a) a water and oil repellent and a reactive auxiliary agent.
(A) an oil agent and a reactive auxiliary agent, and (c) a water / oil repellent agent, an oil agent and a reactive auxiliary agent as a coating second layer to form a three-layer structure (where the first coating layer is a water- and oil-repellent agent). If not, the second layer contains a water and oil repellent) and is baked again to obtain the desired composition.

In the case of the coated powder B having a three-layer structure, the two-layer body after the baking treatment obtained by the above method (however, the first layer of the coating is limited to one containing a water- and oil-repellent agent) is replaced by (i) A method for obtaining a target composition, which is the same as the above method except that it is injected into an organic solvent in which one of a water- and oil-repellent, (ii) an oil, and (iii) one of a water- and oil-repellent is dissolved.

The organic solvent used in each of the above steps is xylene, toluene, benzene, n-hexane, butanol,
Examples include ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, petroleum ether, Freon 112, Freon 113, Freon 12, and the like. Also, ammonia water is used as the alkali,
Hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; and carbonates such as sodium carbonate, sodium hydrogencarbonate, lithium carbonate, and potassium carbonate.
On the other hand, examples of the acid include organic acids such as citric acid, malic acid, tartaric acid, and succinic acid.

The coating layer for coating the inorganic powder base only needs to completely cover the outer periphery of the inorganic powder base and adhere to the surface of the inorganic powder base. No need to coat the agent.

Next, an example of a method for producing the coated powders A and B having a three-layer structure in the present invention will be described in more detail.

Production Example 1 One or more inorganic powder bases (preferably
100 parts of an inorganic powder base pretreated with IPA, acetone, water washing, and drying; the same applies hereinafter) 100 to 100 ° C to 100 ° C for 1 to 48 hours (if necessary, 0.1 to 14N alkaline aqueous solution or Mix, stir and grind with 200 to 600 parts of 0.01 to 1N aqueous acid solution for 1 to 24 hours, repeat washing with water until the pH becomes neutral, and dry in a dryer at 40 to 70 ° C for 5 to 48 hours.) Alternatively, using a plasma spray device “Plasmamate N-30”, plasma current 50 to 500 A, discharge pressure 5 to ²⁰ kg / cm ² , cooling water amount 1 to 5 / min, carrier gas 0.2 to 3.0 / min, gas after flow 5 20 seconds, conditions with an atmosphere control device with powder feeder 1～15Rpm, or pressure 1~10atm / cm ^2, temperature 10 to 100 ° C. in an autoclave, ammonia gas 0.2
Activate inorganic powder base by treating at 10 / min. The inorganic powder after the activation treatment is added to a solution in which 0.5 to 20 parts of a water and oil repellent and a reactive auxiliary agent (0.01 to 0.70 part per 1 part of the water and oil repellent) are mixed with 100 to 600 parts of an organic solvent. Mix base and 100 ℃
After mixing, stirring and milling for 1 to 48 hours below, the organic solvent is distilled off (if necessary, dried and coated with a water- and oil-repellent agent and a reactive auxiliary agent using an inorganic powder base as a core). Coat as a single layer, bake at a temperature of 80 to 180 ° C for 1.5 to 48 hours, then cool or return to around room temperature, then an organic solvent in which the baked water and oil repellent does not dissolve (100 parts of inorganic powder base) 100 to 600 parts, 0.2 to 5 parts of oil agent, 0.2 to 10 parts of water and oil repellent, or 0.2 to 10 mixture of water and oil repellent and oil agent
Parts, and in some cases, in addition to any of the above, a reactive auxiliary agent (oil agent, water / oil repellent, or mixture of water / oil repellent and oil 1
Parts), mix the above-mentioned inorganic powder base obtained by baking the first coating layer, mix, stir and grind at a temperature of 100 ° C or less for 1.5 to 48 hours. Evaporate the organic solvent (dry if necessary) and bake at 80 to 180 ° C for 1.5 to 48 hours using a baking device such as an electric furnace or a dryer, or stir at a temperature of 80 to 180 ° C. At the same time, the organic solvent is distilled off and the baking treatment is carried out at the same time, and preferably the mixture is left to cool and cool to obtain a coated powder having a desired three-layer structure.

Production method 2 100 parts of one or more inorganic powder bases at 100 ° C to 1000
Heat treatment in the temperature range of 1 to 48 hours.
~ 14N alkaline aqueous solution or 0.01-1N acid aqueous solution 200-60
After mixing, stirring and grinding in 0 parts for 1 to 24 hours, repeat washing with water until the pH becomes neutral, and dry in a drier at 40 to 70 ° C for 5 to 48 hours) or a plasma spray device “Plasmamate” N-30 ", plasma current 50 ~ 500A, discharge pressure 5 ~ 2
0 kg / cm ² , cooling water amount 1-5 / min, carrier gas 0.2-3.
0 / min, gas afterflow 5-20 seconds, in powder feeder 1~15rpm with atmospheric control conditions, or the pressure 1~10atm / cm ² in an autoclave, the temperature 10 to 100 ° C., ammonia gas 0.2 to 10 / min An inorganic powder base activated under the conditions is obtained. Oil agent 0.5 in 100 to 600 parts of organic solvent
Up to 10 parts and reactive aid (0.01 to 0.70 parts per part of oil)
The inorganic powder base after the above-mentioned activation treatment is mixed in a solution obtained by mixing with the above, and the mixture is mixed, stirred, and ground at 100 ° C. or lower for 1 to 48 hours, and then the organic solvent is distilled off (drying if necessary). ), Then coat the oil and reactive auxiliary agent as the first layer with the inorganic powder base as the core, bake at 80-180 ° C for 15-48 hours, and then cool or return to around normal temperature . Next, 0.2 to 10 parts of a water-repellent oil-repellent or a mixture of a water-repellent oil-repellent and an oil is mixed with 100 to 600 parts of an organic solvent in which the baked oil does not dissolve (based on 100 parts of the inorganic powder substrate) and a reactive auxiliary agent (repellent). 0.01 to 0.70 per part of the water / oil repellent or the mixture of the water / oil repellent and the oil
Part), and the above-mentioned inorganic powder base obtained by baking the first layer of the coating is mixed. The mixture is mixed at a temperature of 100 ° C or less for 1.5 to 48 hours, stirred, ground, and the organic solvent is distilled off. (If necessary, dry) and use a baking treatment device such as an electric furnace or dryer.
Bake at 80-180 ° C for 1.5-40 hours, or 80-18
The organic solvent is distilled off and baked at the same time while stirring at a temperature of 0 ° C., and is preferably left to cool and cool to obtain a coated powder having the desired three-layer structure.

Production Example 3 100 parts of one or more inorganic powder bases at 100 ° C to 1000
Heat treatment in the temperature range of 1 to 48 hours.
~ 14N alkaline aqueous solution or 0.01-1N acid aqueous solution 200-60
After mixing, stirring and grinding in 0 parts for 1 to 24 hours, repeat washing with water until the pH becomes neutral, and dry in a drier at 40 to 70 ° C for 5 to 48 hours) or a plasma spray device “Plasmamate” N-30 ", plasma current 50 ~ 500A, discharge pressure 5 ~ 2
0 kg / cm ² , cooling water amount 1-5 / min, carrier gas 0.2-3.
0 / min, gas afterflow 5-20 seconds, in powder feeder 1~15rpm with atmospheric control conditions, or the pressure 1~10atm / cm ² in an autoclave, the temperature 10 to 100 ° C., ammonia gas 0.2 to 10 / min An inorganic powder base activated under the conditions is obtained. A solution obtained by mixing 0.5 to 20 parts of a mixture of a water-repellent oil-repellent and an oil agent with 100 to 600 parts of an organic solvent and a reactive auxiliary agent (0.01 to 0.70 part per 1 part of the mixture of the water-repellent oil-repellent and the oil agent) is added to the above solution. Mix the inorganic powder base after activation
After mixing, stirring and grinding at a temperature of not more than 1 ° C for 1 to 48 hours, the organic solvent is distilled off (if necessary, dried), and a water- and oil-repellent agent, an oil agent and a reactive auxiliary agent are formed using an inorganic powder base as a core. And a baking treatment at a temperature of 80 to 180 ° C. for 1.5 to 48 hours, and then cooling or returning to around normal temperature. Then add 100 to 600 parts of the baked water and oil repellent and 100 to 600 parts of an organic solvent in which the oil does not dissolve (per 100 parts of the inorganic powder base) to 0.2 to 5 parts of the oil.
Parts, or 0.2 to 10 parts of a water and oil repellent, or 0.2 to 10 parts of a mixture of a water and oil repellent and an oil, and optionally, a reactive auxiliary agent (oil, water and oil repellent, or oil repellent) 0.01 to 0.70 parts per part of a mixture of a water repellent and an oil), and the above-mentioned inorganic powder base obtained by baking the first coating layer is mixed. Time mixing, stirring,
Grind, distill off the organic solvent (dry if necessary), and use an electric furnace or a dryer for baking treatment at 80-180 ° C for 1.5 hours.
Evaporate the organic solvent and bake at the same time while stirring at a temperature of 80 to 180 ° C, or at a temperature of 80 to 180 ° C. Obtain powder.

The coated powder having a three-layer structure obtained as described above may be used as it is for makeup cosmetics, or in combination with a binder oil, or in combination with another powder base, and further with a binder oil and another powder base. It can be easily made into a cake by mixing and pressing it. The loose base is composed of a material with high water / oil repellency and a strong film. It also has an effect of preventing caking without being affected by oil or moisture. In addition, since raw materials with high water and oil repellency are coated as a layer, and the strength of the film is enhanced by the baking treatment effect, they sufficiently withstand crushing power, and are used as loose and presto make-up cosmetics. It completely prevents the change of the makeup with time without change in the wettability of the powder or the pigment at all, especially the change of the appearance color and the application color, and the dullness due to the change of the color with the lapse of time.

In addition, since the surface of the powder is homogenized with a strong film due to a highly water-repellent oil agent or a water-repellent oil-repellent agent, or a mixture of them, the feeling of adhesion is improved. It is hardly affected by the influence of powder and the cleavage action of the powder is not hindered. Especially when a spherical powder is used, the rolling effect of the spherical powder causes the cleavage effect of the powder and the spherical powder even in a system with a large amount of oil. Due to the synergistic effect of the rolling effect of the body, the property that the spread is light and easy to spread is sufficiently exhibited.

What is important in the present invention is that a press-up make-up composition was found in Japanese Patent Application Laid-Open No. 54-14528 as a conventional one using a powder base, a water repellent, and an oil. A simple mixture of the above-mentioned components has been obtained by the usual press-up makeup cosmetic preparation method. In this case, a powder base (in Japanese Patent Application Laid-Open No. Is a water repellent,
Bonding (adsorption, adhesion) with oils is weak. Cosmetic powder, water repellent, and oils are partially separated in the pulverization process, and when water is used, makeup floats and dulls, and adheres to skin. It has been found by the present inventor that it is reduced and the feeling of adhesion is impaired.

It must be further mentioned that silicone oils have the property of having very good water repellency, but they have the property of being very weak in terms of oil repellency, and are strong against moisture secreted from the skin. It is very weak against sebum. As long as these silicone oils are used, the purpose of water- and oil-resistant makeup cosmetics cannot be achieved.

The cosmetics disclosed in JP-B-61-48803, JP-B-61-554.
In the cosmetic disclosed in JP 81, the number of hydroxyl groups in the powder base is limited, and the surface treatment step is carried out with little reaction with hydroxyl groups when the surface activity of the powder is extremely low. I have. Regarding titanium mica containing titanium oxide in the powder base or titanium oxide, even if there are almost no functional groups on the surface or even if there are very few hydroxyl groups in the titanium oxide, they are produced. Based on the finding that the process became very inert from the process, as a result of additional tests of the examples described in JP-B-61-48803 and JP-B-61-55481, the water- and oil-repellency Had no effect.

Further, according to the respective examples described in JP-B-61-48803 and JP-B-61-55481, each treated powder is subjected to a surface treatment, and then washed with an organic solvent to remove the substance by the surface treatment. Most of the powders are desorbed and each treated powder has very little water repellency, but it has no oil repellency. Therefore, most of them are simply adhered or partially adsorbed. Is to be desorbed. or,
It has also been found by the present inventors that when water is used, the makeup is lifted or broken, and the feeling of adhesion is impaired.

(Example) Hereinafter, an example of the present invention will be described.

Example (1) Powder foundation 40 parts of sericite, 15 parts of talc, 10 parts of titanium oxide, 10 parts of kaolin, 20 parts of spherical porous calcium silicate, and 5 parts of petiole were uniformly mixed with a Henschel mixer and pulverized with a pulverizer. 100 g of the mixed powder obtained was placed in a 2000 ml beaker, stirred at room temperature for 60 minutes with 1000 ml of IPA, filtered, and then acetone 50
Stir with 0 ml for 20 minutes and filter. In addition, 3 times with 1000 ml of purified water
After being washed and filtered twice, it is dried at 50 ° C. for 48 hours in a drier to complete the pretreatment step. 100 g of the mixed powder after the above pretreatment is transferred to a crucible and heat-treated at 280 ° C. for 24 hours. Separately, 320 g of xylene and 0.5 g of aluminum tris (ethyl acetoacetate) are dissolved in a weighed amount of 700 g of a bot ball, and the mixed powder after the heat treatment is poured thereinto, and the ball mill is rotated for 5 minutes. Thereafter, 4.5 g of perfluoroalkylsilane (containing 10 fluorine atoms in one molecule) was added, and the mixture was stirred at room temperature for 10 hours.
Bake at ℃ for 20 hours. 100g of this baked powder
In 1.5 g of isopropyl myristate in 300 g of xylene
-1.5 g of octyldodecyl myristate and 2 g of oleic acid
And mixed at room temperature for 10 hours, stirred and then taken out to remove xylene.
Baking treatment is performed at 120 ° C. for 5 hours to obtain a coated powder (a) having a three-layer structure.

Powder foundation A) 93.0 parts of coated powder (a) B) Squalane 6.8 Mix 0.2 A of fragrance for 1 minute with a Henschel mixer, and pulverize with a pulverizer. Transfer the crushed material to Henschel mixer B
Is added, mixed and stirred for 10 minutes, taken out, homogenized with a blower shifter, and filled into a container to obtain a product powder foundation.

Example (2) Powder eye shadow 45 parts titanium oxide, 30 parts muscovite, 4 parts red petal, spherical silica
100 g of the mixed powder consisting of 21 parts was converted to a steam atmosphere using an atmosphere control device, with a plasma current of 400 A and a discharge output of 10 kg / cm.
² , Cooling water amount 2.7 / min, Carrier gas (argon gas)
The powder treated under the conditions of 0.25 / min, gas afterflow of 10 seconds and powder feeder of 3.8 rpm is collected in 200 g of Freon 113. Separately, 2 g of cetyl 2-ethylhexanoate and 0.2 g of tetraisopropyl titanate in 100 g of Freon 113
The mixed powder recovered in the CFC 113 was poured into the mixture while stirring, and the mixture was stirred for 20 hours in a pot containing 600 g of a ball, taken out, CFC was distilled off, and a hot air dryer for baking treatment was used. Bake at 130 ° C for 2 hours. The coated powder was further poured into the above ball mill in which 450 g of a 2% perfluoroalkylsilazane fron solution, 0.2 g of aluminum tris (acetylacetonate) and 2 g of tetraisopropyl titanate were dissolved in Freon 113, and the mixture was stirred for 8 hours. After crushing, taking out and removing the fluorocarbon, baking treatment is performed at 175 ° C. for 10 hours to obtain a coated powder (b) having a three-layer structure.

Powder eyeshadow A) Coated powder (b) 87.0 parts Titanium coated mica 5.0 B) Dimethyl polysiloxane 4.8 Squalane 3.0 Perfume 0.2 A is mixed for 1 minute with a Henschel mixer, and then pulverized with a pulverizer. Transfer this crushed product to Henschel mixer
After mixing and stirring for 8 minutes, take out and homogenize with a crusher to put in a container to obtain a product.

Example (3) Pancake 100 g of a mixed powder consisting of 50 parts of sericite, 10 parts of spherical magnesium silicate, 20 parts of titanium oxide, 10 parts of diatomaceous earth, 5 parts of red stalk, and 5 parts of talc are dispersed in 300 ml of purified water. Put the gas in an autoclave and feed ammonia gas at 0.87 / min.
The pressure is increased to 2 kg / cm ² , the temperature is raised at a rate of 2 ° C./min, set to 60 ° C., treated for 3 hours, taken out, and freeze-dried to obtain a freeze-dried powder.

Oleic acid 0.5 g, monosec-butoxyaluminum diisopropylate 0.3 g, perfluoroalkylsilane (F =
8 g) of 2 g dissolved in 300 g of methyl ethyl ketone was poured into a ball mill pot 1 (ball amount: 700 g), and the freeze-dried powder was added thereto, and the mixture was stirred for 24 hours. Bake at 100 ° C for 15 hours. 100 ml of methyl ethyl ketone, 150 g of a 2% perfluoroalkylsilazane freon liquid and 0.2 g of tetrastearyl titanate were added to the obtained baked powder, and the mixture was stirred in a ball mill pot for 3 hours, taken out, and methyl ethyl ketone and freon were distilled off. For 48 hours to obtain a coated powder (c) having a three-layer structure.

Pancake A) Coated powder (A) 20.0 parts Coated powder (C) 64.0 B) Squalane 5.0 Liquid lanolin 3.0 Dimethyl polysiloxane 4.0 C) 1,3 Butylene glycol 3.3 Ethyl paraben 0.2 Perfume 0.5 A in a Henschel mixer Add B with stirring, stir for 5 minutes, add C, stir for 2 minutes, take out,
The product is made into a container through a blower shifter.

Example (4) Foundation A) Coated powder (b) 20.0 parts Stearic acid 1.0 Cetanol 2.0 Diglycerin triisostearate 3.0 Lanolin 1.0 Squalane 10.0 Activator 5.0 Butylparaben 0.1 BHT 0.1 B) Glycerin 6.0 Thickener 1.5 Purified water 49.3 C) Fragrance 6.0 Dissolve A and B separately, keep at 80 ° C, add B little by little to A, stir well and emulsify. When the emulsification is completed, C is added, the mixture is stirred at 80 ° C for 3 minutes, cooled with water, cooled to 40 ° C, and filled into a container to obtain a product.

(Comparative test) A comparative test was performed using the following samples.

(B) Coated powder having a three-layer structure obtained in Example 1 (b) (b) Coated powder having a three-layer structure obtained in Example 2 (b) (c) ... The obtained coated powder having a three-layer structure (c) (e): Example 1 of Japanese Patent Publication No. 61-55481 (comparative example) (f): Example 1 of Japanese Patent Publication No. 61-48803 (Comparative Example) (g): A sample manufactured in the same manner as in Example 1 except that the oil coating layer of the second coating layer was not baked (Comparative Example) Comparative Test A Comparative Samples (a) to (f) )about,
(A) Specific surface area (SNm ² / g), (b) Water vapor amount (SH ₂ O /
g), (c) Degree of hydrophilicity of powder surface (SH ₂ O / SN ₂ ), (d)
Oleophilizing of the powder surface _{(1- [SH 2 O / SN} 2]) were measured.
0.6 g of each of the comparative test samples (a) to (f) was pretreated at room temperature in a vacuum drier for about 10 hours, pulverized, and crushed under the measurement conditions shown in Table 2 below. (Manufactured by Shimadzu Corporation). The test results are shown in Table 1.

Evaluation In Table 1, in the case of the present invention, the degree of lipophilicity of the powder surface, which is a measure of the fact that the powder surface is completely covered, is substantially equal to 1, and even if the powder is pulverized, the oil agent and the oil repellent are repellent. It can be seen that the water lipophilic agent and the reactive auxiliary are tightly bound. On the other hand, Japanese Patent Publication No. 61-55481 and Japanese Patent Publication No. 61-48803 are about 1/5, which are insufficient bonding, that is, merely adhesion or adsorption. Accordingly, the present invention relates to Japanese Patent Publication No. 61-55481.
It is clear that the structure has a completely different structure from that of Japanese Patent Publication No. 61-48803.

Comparative test B Next, 200 m of xylene solvent was used for each of the above samples.
Put 5 g of the sample in 1 l, stir with a magnetic stirrer at room temperature for 20 minutes, filter and dry. Then, add 5 g of water, nonpolar solvent squalane, and 5 g of polar solvent oleic acid to 20 ml test tubes each with a separate stopper. 0.1 g of each sample was separately injected into the test tube, shaken 100 times, evaluated at room temperature after 2 days, then shaked 100 times, and qualitatively evaluated after 2 days (total of 4 days) The results are shown in Table 3 (however, the results are shown after 4 days).

Comparative test C 5 g of each sample [(a) to (c), (e), (g)] was put into a Soxhlet extractor, and extracted with 100 ml of n-heptane at 80 ° C for 12 hours to elute. Collect the oil as extract. Next, the weight of the oil obtained after distilling off and drying n-heptane was measured, and this was used as the amount of the eluted oil to calculate the elution rate by the following formula. The results are shown in Table 4.

The smaller the dissolution rate, the larger and better the coating strength.

As is clear from the above comparative test data, the coated powder having a three-layer structure in the present invention has a water- and oil-repellent agent, an oil agent, and a powder firmly adhered to each other, and the oil component is hardly eluted in an organic solvent or the like. . This is due to the activation of the powder surface and the interaction between the water and oil repellent, or the oil and the reactive aid, and the interaction between the water and oil repellent, the reactive aid and the oil, etc., so that the solidification is made stronger. I suspected that. On the other hand, what is simply mixed (for example, by spraying) as in the prior art is not fixed, but is merely due to adhesion and is easily extracted into an organic solvent.

(Sensory Evaluation) Sample (X) Powder Foundation of Example (1) (Y) Cosmetic of Example (1) of JP-B-61-48803 (Z) Example (1) of JP-B-61-55481 Fig. 1 shows the results of a sensory evaluation of the cosmetics (1) after 203 months of use destruction for 203 women. The evaluation items are as follows.

1. Lightness of spread 2. Easiness of spreading 3. Adhesion and adhesion to skin 4. Adhesion 5. Uniformity of adhesion 6. Smoothness of skin after makeup 7. Coloring over time after makeup Change 8. Make-up due to change over time of makeup 9. く Make-up dullness 10. く Make-up loss 11. Comprehensive evaluation (simply speaking) As shown in the results of FIG. Compared to the comparative cosmetics, it is much better.

(Effect of the Invention) The cosmetic of the present invention has both water repellency and oil repellency and contains a three-layer structure coated powder having a coating total strongly bonded to the powder base, so that the water repellency, Excellent oil repellency, no makeup loss, prevents makeup floating over time, color change and dulling over time, prevents caking in products, spreads lightly and easily evenly, requires no technique .

[Brief description of the drawings]

FIG. 1 shows the evaluation results of the sensory evaluation comparing the makeup cosmetic of the present invention with the makeup cosmetic of a comparative product. In the figure, (X) shows the powder foundation of Example 1 and Y. Is the embodiment (1) of JP-B-61-48803.
And Z are the cosmetics of Example (1) of JP-B-61-55481.

Claims (2)

(57) [Claims] An activated inorganic powder base having a first coated and baked layer comprising a water repellent and / or an oil agent and a reactive auxiliary agent on the surface of the activated inorganic powder base. A three-layer structure having a coated and baked second layer comprising one or both of a water and oil repellent and an oil agent and a reactive auxiliary agent on the surface of
The second layer contains a water- and oil-repellent agent when the layer does not contain a water- and oil-repellent agent). 2. An activated inorganic powder base having a first coated and baked layer comprising a reactive auxiliary agent and a water and oil repellent or a water and oil repellent and an oil agent on the surface of the activated inorganic powder base. A makeup cosmetic comprising, on the surface of the layer, a coated powder having a three-layer structure having a coated and baked second layer composed of one or both of a water and oil repellent and an oil agent.