JP4774309B2 - Makeup cosmetics - Google Patents

Description

  The present invention relates to a makeup cosmetic, and more particularly to a makeup cosmetic in which amorphous calcium phosphate-coated particles coated with amorphous calcium phosphate are used.

As a pearl agent for imparting pearly luster to makeup cosmetics such as eye shadows, muscovite called mica, which is naturally produced, has been conventionally used. Mica crystals represented by KAl ₂ (Al, Si ₃ ) O ₁₀ (OH) ₂ belong to a monoclinic system and are produced in the form of a pale yellow or green hexagonal plate, which is completely in the (001) plane. Cleavage develops and the cleaved pieces are easily peeled into a thin layer and exhibit surface gloss. Further, a mica titanium pearl having a mica surface coated with a thin film of titanium dioxide is also widely used.

  On the other hand, glass flakes having a so-called pearly luster represented by borosilicate (Ca / Na), in addition to the naturally produced mica titanium-based pearls, have recently been widely used. For example, Patent Document 1 describes that a glass flake having a pearly luster formed by coating a metal oxide on the surface of a flaky glass and having an average particle diameter of 1 to 700 μm is used for cosmetics. ing.

  This glass flake having pearly luster has a high luminance and is excellent in aesthetics as a material for makeup cosmetics and is very effective as compared with mica titanium-based pearls. On the other hand, since the material itself is harder and the crushed pieces are sharper than mica titanium-based pearls, when used in makeup cosmetics, it feels tingling and has a rough feel. It is difficult to adjust makeup cosmetics. In addition, glass flakes with pearly luster have higher surface smoothness compared to titanium mica-based pearls, so the adhesion to the skin is low and the phenomenon of so-called “lame dropping” that peels off the coated surface over time. It is difficult to maintain the durability of the decorative coating film.

  In response to this, it has been studied to further coat the surface of glass flakes having pearly luster with silicone, but it has not been able to solve the above problems.

Japanese Patent Laid-Open No. 2002-128639

  It is an object of the present invention to provide a makeup cosmetic in which the durability of a decorative coating film is improved while using glass flakes having pearly luster.

  As a result of intensive investigations on the improvement of adhesion of glass flakes having pearly luster to the skin, the present inventor has found that the glass flakes having pearly luster are coated with a predetermined amount of amorphous calcium phosphate to adhere to the skin. As a result, the present invention has been completed.

That is, in the present invention, glass flakes having a pearly luster are coated with amorphous calcium phosphate, and the amorphous calcium phosphate is coated in an amount of 1% to less than 10% by mass, and the amorphous calcium phosphate-coated particles, the make-up cosmetic wherein der Rukoto those below (1) to the amorphous calcium phosphate glass flakes having a pearly luster step is carried out in (4) were coated provide.
(1) An acid treatment step of removing acid after mixing glass flakes having pearly luster and an acid having a pH of 2.0 or less to bring the glass flakes having a pearly luster into contact with an acid having a pH of 2.0 or less. .
(2) A suspending step in which glass flakes having pearly luster after the acid treatment step are dispersed in water so as to have a solid content concentration of 0.1 to 50% by mass to prepare a suspension.
(3) An alkali process in which calcium hydroxide is added to the suspension prepared in the suspension process to produce an alkaline suspension having a pH of 12.0 or higher.
(4) A calcium phosphate coating step of coating the surface of glass flakes having pearly luster in the alkaline suspension with amorphous calcium phosphate by adding phosphoric acid to the alkaline suspension prepared in the alkaline step.

  Note that the amorphous calcium phosphate is coated in an amount of 1% or more and less than 10% by mass means that the mass of amorphous calcium phosphate is 1% or more and less than 10% with respect to the total mass of the amorphous calcium phosphate-coated particles. The mass of the amorphous calcium phosphate relative to the mass of the entire amorphous calcium phosphate-coated particle can be confirmed by the method described in the examples.

  According to the present invention, since the amorphous calcium phosphate-coated particles in which the glass flakes having a pearly luster are coated with amorphous calcium phosphate are used in the makeup cosmetics, the coated amorphous calcium phosphate is used for the skin. It is possible to suppress the occurrence of “lame omission” due to an improvement in the adsorptivity to the surface, and the durability of the decorative coating film can be improved.

  Moreover, since the amorphous calcium phosphate is coated in an amount of 1% or more and less than 10% by mass, it is possible to maintain aesthetics such as gloss and color tone of glass flakes having pearly luster.

  In addition, by covering the glass flakes having pearly luster with amorphous calcium phosphate, it is possible to reduce the tingling and rough feeling and improve the feeling of use.

The preferred embodiments of the present invention will be described below.
The makeup cosmetic in the present embodiment uses amorphous calcium phosphate-coated particles using glass flakes having pearly luster as a base material.
First, a method for producing amorphous calcium phosphate-coated particles using the glass flake having pearly luster as a base material will be described.
The amorphous calcium phosphate-coated particles have a pH of 2. on the surface of the base material by mixing the base material and an acid having a pH of 2.0 or less in that the surface of the base material can be more uniformly coated with the amorphous calcium phosphate. An acid treatment step in which acid is removed after contact with 0 or less acid, and the base material after the acid treatment step is dispersed in water to a solid content concentration of 0.1 to 50% by mass and suspended. A suspension process for preparing a liquid, an alkali process for preparing an alkaline suspension having a pH of 12.0 or more by adding calcium hydroxide to the suspension prepared in the suspension process, and a solution prepared in the alkali process. It is manufactured by performing a calcium phosphate coating step in which phosphoric acid is added to the alkaline suspension to coat the surface of the substrate material in the alkaline suspension with amorphous calcium phosphate.

In the acid treatment step, the acid is brought into contact with the surface of the base material. For example, a method of showering a base material with an acid having a pH of 2.0 or less, or a method of immersing the base material directly in an acid with a pH of 2.0 or less. Although a method for treating the granular material can be adopted, it is preferable to perform a method of immersing the substrate material directly in the acid from the viewpoint that the acid can be uniformly and sufficiently brought into contact with the entire substrate material.
The reason why the pH of the acid in this acid treatment is 2.0 or less is that when the pH of the acid used exceeds 2.0, the coverage of the amorphous calcium phosphate on the base material cannot be sufficiently improved. It is.
Moreover, when performing the method of immersing a base material directly as this acid treatment process, it is preferable that it is 0.1-50 mass% as solid content concentration of the base material disperse | distributed to the acid soaked, 1-50 mass % Is more preferable, and 5 to 30% by mass is even more preferable. It is preferable that the solid content concentration is in such a range. If the solid content concentration exceeds 50% by mass, the above-described effects may not be obtained uniformly and sufficiently over the entire base material. Even if the solid content concentration is less than 1% by mass, not only the above-described effects can be expected to be more uniform and sufficient, but also the use of large facilities and the amount of acid used can be obtained. This is because there is a possibility that productivity may be lowered, for example, the amount of the amorphous calcium phosphate-coated particles is reduced.
Moreover, in the point from which the effect similar to the effect mentioned above is acquired, as said acid treatment, a base material is 0.1 to 200 hours, Preferably, it is 1 to 72 hours, More preferably, it is pH 2.0 or less for 1 to 24 hours. It is preferable to immerse in an acid.

As the acid used in this acid treatment step, it is possible to suppress the consumption of calcium ions added in the subsequent alkali step by anions other than phosphate ions, and in the calcium phosphate coating step, It is particularly preferable to use phosphoric acid in that the surface can be covered with phosphoric acid in advance and the amorphous calcium phosphate can be coated more efficiently. In addition, citric acid is preferably used in that it can be coated with amorphous calcium phosphate more efficiently than in the case of using other general acids, although not as much as phosphoric acid.
In addition, one or more of strong acids such as hydrochloric acid, sulfuric acid and nitric acid, and weak acids such as malic acid, acetic acid and oxalic acid may be used in combination with phosphoric acid and citric acid. It can also be used instead of citric acid.

As the glass flakes having pearly luster used as the base material, those made mainly of SiO ₂ and Al ₂ O ₃ can be used as raw glass, and ZnO, CaO, B ₂ O ₃ , Na ₂ O ₃ and K ₂ can be used. Those further containing O, FeO, Fe ₂ O _{3 and the} like can be used. Moreover, as glass used as the raw material of glass flakes, what can be melt-molded can be illustrated, and what is called soda lime glass, S glass, E glass, C glass, etc. can be illustrated.
In addition, such raw glass is melted and stretched to a thin sheet, bead or glass tube, and then crushed into thin pieces, crushed after making a large hollow sphere, Can be formed into flakes by other flake manufacturing methods.

  For glass flakes having a pearly luster, for example, is it possible to coat the flake-shaped glass as described above with a metal such as silver, gold, platinum, palladium, nickel, copper, chromium, molybdenum, tin, magnesium, aluminum and hastelloy? Coated with metal oxides such as titanium oxide and iron oxide, or coated with a coating of Ca and Mg, metal complexes, inorganic pigments such as titanium oxide, iron oxide and ultramarine as color pigments It is possible to use pigments, organic pigments such as tar dyes, and natural pigments.

For example, the glass flakes having the pearly luster have an average thickness of 0.1 to 20 μm and an average particle diameter of 5 to 2000 μm, and iron oxide is formed on the surface of a flaky glass substrate having an A glass composition or an E glass composition. And / or those coated with rutile, anatase and blockite type titanium dioxide can be used.
Furthermore, the glass flakes having a pearly luster are produced by depositing iron oxide and / or titanium dioxide in a solution on the surface of a flaky glass, from the group consisting of calcium ions, magnesium ions and zinc ions. Formed by depositing hydrated tin oxide in the presence of at least one selected material and iron in the presence of hydrated titanium dioxide on a plurality of flaky C or E glasses For example, the first layer is deposited on the surface of a plurality of flaky glasses, and then hydrated titanium dioxide is formed thereon.
More specifically, for example, glass flakes having a pearly luster such as Metashine manufactured by Nippon Sheet Glass Co., Ltd. and Reflex manufactured by Engelhard Inc. are exemplified.
In general, when glass flakes having such a pearly luster are used as the base material, commercially available products can be used as they are, but classification may be performed if necessary.
The average particle size of the glass flakes having pearly luster can be measured using a laser diffraction method, a sedimentation method, a shifter type measuring device, or the like.

In this acid treatment step, the base material and the acid are mixed and the surface of the base material is brought into contact with an acid having a pH of 2.0 or lower, and then the acid is removed. As a method for removing the acid brought into contact with the surface of the substrate material, a general dehydration removal method for removing the liquid material from the mixture of the granular material and the liquid material, such as a method of dewatering by a centrifugal dehydration method or the like is adopted. can do.
In this way, the acid adhering to the base material is removed, and various substances removed from the surface of the base material are discharged out of the system.
At this time, it is preferable to remove the acid to the extent that the acid is slightly attached to the surface of the substrate material, rather than removing the acid completely. By using the substrate material with a slight acid attached thereto in the subsequent suspension step, the amorphous calcium phosphate coating state on the surface of the substrate material can be made uniform in the calcium phosphate coating step.

In the suspension step, the base material after the acid treatment step is dispersed in water so as to have a solid content concentration of 0.1 to 50% by mass to prepare a suspension.
At this time, depending on the type of acid used in the acid treatment step, for example, when phosphoric acid is used, the amount of acid removed in the acid treatment step (attachment of phosphoric acid to the substrate material) Suspended) by adjusting the mixing ratio of the base material to which phosphoric acid is adhered and water within the range of the solid content concentration of 0.1 to 50% by mass. It is preferable to prepare a suspension so that the pH of the liquid is 1 to 7.
In addition, when the acid removal in the acid treatment step or the discharge of various substances removed from the surface of the substrate material by the acid in the acid treatment step to the outside of the system is not sufficient, the substrate material and water are removed. The mixed suspension may be once prepared and then dehydrated to prepare the suspension again.

In the alkaline step, calcium hydroxide is mixed with the suspension prepared in the suspending step to prepare an alkaline suspension in which the base material and calcium hydroxide are mixed. At this time, the pH of the alkaline suspension to be produced is 12.0 or more, and is usually less than 14.0. At this time, it is also possible to prepare an alkaline suspension having a pH of 12.0 or more and less than 14.0 by mixing other ammonia such as sodium hydroxide in addition to calcium hydroxide.
Here, the base material and calcium hydroxide are mixed to bring the suspension to such a pH. If the pH is less than 12.0, the solution is in an acidic state in the calcium phosphate coating step described later. This is because the added phosphoric acid is consumed for the formation of calcium hydrogen phosphate, making it difficult to coat the surface of the base material with amorphous calcium phosphate.
In addition, about this pH, it can measure using common pH measuring instruments, such as a pH meter in which the glass electrode is used.

  In the calcium phosphate coating step, amorphous calcium phosphate is adhered to the surface of the base material by adding phosphoric acid to the alkaline suspension prepared in the alkaline step. At this time, as described above, if the suspension is in an acidic state, in particular, a pH of less than 5.0, the added phosphoric acid is likely to be consumed for the formation of calcium hydrogen phosphate. The addition of phosphoric acid to the alkaline suspension in is preferably performed in a state where the pH is maintained at 5.0 or higher. In addition, if necessary, the pH of the suspension may be maintained at 5.0 or higher to suppress the formation of calcium hydrogen phosphate while alternately adding calcium hydroxide and phosphoric acid. In addition, in the calcium phosphate coating step, the temperature of the suspension is increased by the reaction heat by adding phosphoric acid. Therefore, for example, it is preferable that the suspension is cooled to a temperature of 50 ° C. or lower. . By performing this cooling, the step of adding phosphoric acid can be prevented from being performed in multiple steps, and the method for producing amorphous calcium phosphate-coated particles can be made more efficient.

  At this time, depending on conditions such as the amount and concentration of calcium hydroxide in the alkaline step and the pH of the alkaline suspension, the amount and concentration of phosphoric acid in the calcium phosphate coating step, and the pH after the addition of phosphoric acid, The amount of the amorphous calcium phosphate coated on the crystalline calcium phosphate-coated particles is set to 1% by mass or more and less than 10% by mass.

The coating amount of amorphous calcium phosphate on the amorphous calcium phosphate-coated particles is within such a range when the coating amount of amorphous calcium phosphate is less than 1% by mass, the coating amount of amorphous calcium phosphate. This is because the adsorbability of the amorphous calcium phosphate-coated particles to the skin is not improved, resulting in “lame dropping” or the like.
Further, when the coating exceeds 10% by mass, the glass flakes having a pearly luster such as color tone and luster are concealed by the amorphous calcium phosphate because the glass flakes having a pearly luster as a substrate are concealed originally. This is because of a decrease.
In this respect, the coverage of the amorphous calcium phosphate is preferably 1 to 8% by mass, and particularly preferably 3 to 5% by mass.

The amount of amorphous calcium phosphate coated on the amorphous calcium phosphate-coated particles (amorphous calcium phosphate coverage) is that amorphous acid such as concentrated nitric acid that dissolves amorphous calcium phosphate and hardly dissolves glass is amorphous. The amorphous calcium phosphate coated on the surface of the glass flakes having a pearly luster is dissolved by adding to the calcium phosphate coated particles, and this solution is subjected to inductively coupled plasma (ICP) emission analysis to reduce the Ca concentration in the solution. The Ca content can be obtained from the Ca concentration and the solution amount, and can be obtained from the ratio between the atomic weight of Ca and the molecular weight of amorphous calcium phosphate.
For example, concentrated nitric acid is added to amorphous calcium phosphate-coated particles having a mass M ₁ (mg) to dissolve amorphous calcium phosphate, distilled water is further added, and precipitates (glass flakes having a pearly luster) are obtained by centrifugation or the like. And the supernatant (a solution containing amorphous calcium phosphate), and the filtrate obtained by filtering the supernatant is added with distilled water, centrifuged again, and filtered. The glass flakes having pearly luster and the solution containing amorphous calcium phosphate are sufficiently separated, and the solution containing amorphous calcium phosphate is transferred to a container such as a volumetric flask and distilled water is added. and a constant volume so that the volume V ₁ (ml), the atomic weight of Ca this constant volume liquid sample by measuring the Ca concentrations C ₁ in the liquid sample to ICP emission spectrometry ([mu] g / ml) 0.08 (g / mol), the mass M ₂ (mg) determined in amorphous calcium phosphate which has been coated on the amorphous calcium phosphate-coated particles molecular weight of the amorphous calcium phosphate 1004.64 from (g / mol) by the following formula It can be determined as M ₂ / M ₁ × 100 (%).
M ₂ = C ₁ × V ₁ × 1004.64 / 40.08 / 1000

The amorphous calcium phosphate coated on the surface of the base material in this way is tricalcium phosphate containing crystal water as represented by the general formula: Ca ₃ (PO ₄ ) ₂ .nH ₂ O. In particular, the crystal structure is amorphous. Note that the amorphous crystal structure means that amorphous calcium phosphate has a large amount of water of crystallization, so that the pattern of the powder X-ray diffraction method is illustrated in FIG. 1 as compared to crystalline calcium phosphate. It can be confirmed from the broad.
As long as the effects of the present invention are not impaired, an element such as barium, strontium, zinc, magnesium, sodium, potassium, iron, aluminum, titanium, or the like is dissolved in a part of the calcium of the amorphous calcium phosphate. Alternatively, it may be ion-exchanged or substituted, and a part of PO ₄ may be substituted with one kind of atomic group such as VO ₄ , SiO ₄ , and CO ₄ .
Further, amorphous calcium phosphate may be combined with one or more metal oxides. Although it does not specifically limit as a metal oxide, For example, a titanium oxide, a zinc oxide, a cerium oxide etc. are mention | raise | lifted.

As described above, the produced amorphous calcium phosphate-coated particles can be used in makeup cosmetics as follows after being dried by a general drying method such as freeze drying or cake drying.

As makeup cosmetics in which the amorphous calcium phosphate-coated particles are blended, for example, emulsion foundation, powder foundation, funny, oily foundation, solid emulsion foundation, lipstick, lip gloss, eye shadow, eyeliner, eyebrow, teak, Examples include nail color and body powder.
These makeup cosmetics contain 0.01% by mass or more of the amorphous calcium phosphate-coated particles.

  The blending amount of the amorphous calcium phosphate-coated particles is within such a range that it is difficult to obtain a pearly appearance when the blending amount of the amorphous calcium phosphate-coated particles is less than 0.01% by mass. It becomes. Further, only the amorphous calcium phosphate-coated particles, that is, 100% by mass, can be used as a cosmetic.

  The amorphous calcium phosphate-coated particles to be blended in the makeup cosmetic may be surface-treated in advance. Examples of the surface treatment include fluorine compound treatment, silicone treatment, metal soap treatment, acylated lysine treatment, oil agent treatment, silane treatment, amino acid treatment, wax treatment, metal oxide treatment, etc. Any processing conventionally used can be adopted. Of course, the amorphous calcium phosphate-coated particles may be used in makeup cosmetics without surface treatment.

  In addition to the amorphous calcium phosphate-coated particles, the makeup cosmetics include oils, powders (pigments, pigments), resins, surfactants, stickers, preservatives, and fragrances that are commonly used in makeup cosmetics. , Various components such as ultraviolet absorbers (including organic and inorganic), humectants, physiologically active ingredients, salts, solvents, antioxidants, chelating agents, neutralizing agents, pH adjusting agents and the like can be blended. . Examples of oils include higher alcohols such as cetyl alcohol, isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol, fatty acids such as isostearic acid, undecylenic acid, oleic acid, glycerin, sorbitol, ethylene glycol, Polyhydric alcohols such as propylene glycol and polyethylene glycol, myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, hexyl decyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, oxy Esters such as octyl stearate, hydrocarbons such as liquid paraffin, isoparaffin, petrolatum, squalane, lanolin, reduced Phosphorus, waxes such as carnauba wax, mink oil, cacao butter, coconut oil, palm kernel oil, camellia oil, sesame oil, castor oil, oils and fats such as olive oil and the like.

  Examples of other forms of oil include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, polyether-modified organopolysiloxane, alkyl-modified organopolysiloxane, sugar-modified silicone, glyceryl-modified silicone, and amodimethicone. And silicone compounds such as amino-modified organopolysiloxane, silicone gel, acrylic silicone, trimethylsiloxysilicic acid, and silicone RTV rubber.

  Furthermore, examples of fluorine-based oils include, for example, fluorocarbons such as perfluorodecalin, alcohols such as perfluoropolyether, fluorinated pitch and fluoroalcohol having a perfluoroalkyl chain, and perfluoroalkyl phosphate triethanolamine salts. And phosphoric acid esters such as carboxylic acids having a fluoroalkyl chain, fluoroalkyl-modified silicones, fluorine / polyether co-modified silicones, and fluorinated silicone resins.

  Examples of powders include sericite, mica (muscovite, phlogopite, saucite, mica, lithia mica, synthetic mica), talc, kaolin, vermiculite, smectite, titanium oxide-coated mica (titanium mica), oxidation Pearl pigments such as titanium-coated sericite and titanium oxide-coated talc, fish scale foil and boron nitride, resin powders such as nylon beads, silicone beads, PTFE powder and silicone elastomer, yellow iron oxide, red iron oxide , Black iron oxide, chromium oxide, cobalt oxide, carbon black, ultramarine, bitumen, zinc oxide, titanium oxide, zirconium oxide, silicon oxide, aluminum oxide, cerium oxide, barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate , Silicon carbide, organic dye, lake, fine particle oxidation Tan, particulate zinc oxide, particulate iron oxide, etc. plate-like barium sulfate.

  These powders are fluorine compound treatment, silicone treatment, metal soap treatment, acylated lysine treatment, oil agent treatment, silane treatment, amino acid treatment, wax treatment, metal oxide treatment, silane coupling agent treatment, organic titanate treatment, You may use it in the state which gave surface treatments, such as a fatty-acid treatment. As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and a betaine surfactant can be used.

  Examples of the physiologically active component include anti-inflammatory agents, blood circulation promoters, vitamins, tyrosinase activity inhibitors, urea and the like. Examples of the solvent include purified water, methanol, ethanol, isopropyl alcohol, ether, LPG, volatile silicone, light liquid isoparaffin, and alternative chlorofluorocarbon. Mineral water can also be used instead of purified water.

In this embodiment, the case where the amorphous calcium phosphate-coated particles used in the makeup cosmetics are produced by the above-described method has been described as an example. However, in the present invention, the amorphous calcium phosphate-coated particles are used in the makeup cosmetics. The calcium phosphate-coated particles are not limited to those produced by the above production method.
In addition to the amorphous calcium phosphate-coated particles, various components used in the makeup cosmetics can be appropriately modified within a range that does not impair the effects of the present invention.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.

(Production Example 1 of Amorphous Calcium Phosphate Coated Particles)
It is a glass flake having a silver-white pearl luster with an average particle size of 94 μm formed by coating borosilicate (Ca / Na) with about 1 to 5% by mass of titanium dioxide and 1% by mass or less of tin oxide. Engelhard's product name “Reflecks Pinpoints of Pearl” is used as a base material, 485 g of this base material is put in 1 liter of ion-exchanged water, and 1500 g of 7.5 mass% phosphoric acid aqueous solution is added with stirring and stirred for 10 minutes. After making into a suspension, this suspension was allowed to stand for a whole day and night, and then glass flakes having pearly luster were separated by suction filtration, and an acid treatment step was performed. The pH of the suspension at this time was measured with a pH meter and found to be 0.1. Moreover, said average particle diameter is the value measured using the laser diffraction type dry particle size distribution analyzer by SYMPATEC.
Next, a suspension step was performed in which ion-exchanged water was added to the glass flakes having a pearly luster after the acid treatment step to prepare a suspension having a solid content concentration of 20%.
Further, using a homomixer, a calcium hydroxide suspension in which 11.2 g of calcium hydroxide was dispersed in 1 liter of ion exchange water was prepared, and this calcium hydroxide suspension was added to the suspension prepared in the suspension step. A turbid solution was added to carry out an alkaline step to produce an alkaline suspension.
Furthermore, while maintaining the liquid temperature of this alkaline suspension at 50 ° C. or lower, a 7.5% by mass aqueous phosphoric acid solution was added until the final pH was 6.5 and stirred for 30 minutes, followed by a calcium phosphate coating step. Carried out. This was suction filtered and dried at 80 ° C. for 24 hours to produce amorphous calcium phosphate-coated particles.

(Measurement of amorphous calcium phosphate coverage)
The mass% (amorphous calcium phosphate coverage) of the amorphous calcium phosphate in the produced amorphous calcium phosphate-coated particles was measured as follows.
About 170 mg of amorphous calcium phosphate-coated particles are precisely weighed, 1 ml of concentrated nitric acid is added and shaken gently, and then 5 ml of distilled water is added.
Further, 15 ml of distilled water was added and shaken well, followed by centrifugation at 3000 rpm × 20 minutes using a centrifuge to separate into a supernatant and a precipitate. Filter using 7 filter paper and collect the filtrate in a 50 ml volumetric flask.
After 15 ml of distilled water is added to the centrifuged precipitate and shaken, it is again centrifuged at 3000 rpm for 20 minutes in the same manner as described above. The supernatant obtained by the second centrifugation was designated as No. 1. Filter using 7 filter paper and add the filtrate to the 50 ml volumetric flask in which the first filtrate is collected.
Distilled water is added to the volumetric flask to make a total volume of 50 ml.
This constant volume is measured with an inductively coupled plasma (ICP) emission spectrometer “SPS-4000 (trade name)” manufactured by SEIKO.
As measurement conditions, photometric height: 12.0 mm, integration conditions: 3 times to 2 seconds (1 time of integration), high frequency output: 1.30 kW, gas flow rate: 16.0-1.0-0.5 (l / Min).
From the value of the Ca concentration C ₁ (μg / ml) obtained by this ICP, the mass M ₂ (mg) of the amorphous calcium phosphate coated on the amorphous calcium phosphate-coated particles was measured as follows. The amorphous calcium phosphate coverage of the amorphous calcium phosphate-coated particles was determined by dividing the mass M ₂ (mg) of the solid calcium phosphate by the initial mass of the amorphous calcium phosphate-coated particles (about 170 μg).
M ₂ (mg) = C ₁ (μg / ml) × 50 (ml) × 1004.44 / 40.08 / 1000
As a result, the mass% of the amorphous calcium phosphate in the amorphous calcium phosphate-coated particles was 3% by mass.

(Production Example 2 of Amorphous Calcium Phosphate Coated Particles)
Amorphous calcium phosphate-coated particles were produced in the same manner as in Production Example 1 except that the amount of the base material used was 475 g instead of 485 g, and the amount of calcium hydroxide used was 18.7 g instead of 11.2 g.
The pH in the acid treatment step of Production Example 2 was 0.1 as in Production Example 1.
Moreover, the mass% of the amorphous calcium phosphate in the amorphous calcium phosphate-coated particles of Production Example 2 was 5 mass%.

(Production Example 3 of Amorphous Calcium Phosphate Coated Particles)
Amorphous calcium phosphate-coated particles were produced in the same manner as in Example 1 except that the amount of the base material used was 450 g instead of 485 g, and the amount of calcium hydroxide used was 37.3 g instead of 11.2 g.
The pH in the acid treatment step of Production Example 3 was 0.1 as in Production Example 1.
Moreover, the mass% of the amorphous calcium phosphate in the amorphous calcium phosphate-coated particles of Production Example 3 was 10% by mass.

(Examples 1 and 2, Comparative Examples 1 and 2, Reference Example 1)
Amorphous calcium phosphate-coated particles produced in Production Examples 1 to 3, manufactured by Engelhard, which is not coated with amorphous calcium phosphate, a trade name “Reflecks Pinpoints of Pearl” alone, and an average particle size of 70 μm An eye shadow was prepared according to the formulation shown in Table 1 using a product name “Thimika Extra Large Sparkle” manufactured by Engelhard, which is titanium dioxide-coated mica (titanium mica-based pearl).

(Examples 3 to 4, Comparative Examples 3 to 4, Reference Example 2)
Amorphous calcium phosphate-coated particles produced in Production Examples 1 to 3, manufactured by Engelhard, which is not coated with amorphous calcium phosphate, a trade name “Reflecks Pinpoints of Pearl” alone, and an average particle size of 70 μm An eye shadow was prepared according to the composition shown in Table 2 using a product name “Thimika Extra Large Sparkle” manufactured by Engelhard, which is titanium dioxide-coated mica (titanium mica-based pearl).

(Evaluation)
(Glossiness)
Amorphous calcium phosphate-coated particles of Production Examples 1 to 3, Comparative Example 2 (= Comparative Example 4) of pearlescent glass flakes not coated with amorphous calcium phosphate, Reference Example 1 (= Reference Example 2) The glossiness of mica titanium-based pearls was evaluated.
At this time, a measurement using a gloss checker (“IG-320” manufactured by Horiba, Ltd.) was performed using a sample obtained by applying each particle on artificial leather. The results are shown in Table 3.

Subsequently, the following evaluations were performed using the eye shadows of the examples, comparative examples, and reference examples.
(Evaluation A)
A sensory test was conducted to determine whether or not the eye shadows of the examples, comparative examples, and reference examples had pearl brightness when applied. A case where the pearl luminance was high was judged as “◯”, and a case where the pearl luminance was low was judged as “x”. The results are shown in Table 4.
(Evaluation B)
A sensory test was conducted to determine whether or not a tingling stimulus was felt when the eye shadows of each Example, Comparative Example, and Reference Example were applied. . The results are shown in Table 4.
(Evaluation C)
A sensory test was conducted to determine whether or not smoothness was felt when the eye shadows of Examples, Comparative Examples, and Reference Examples were applied. The results are shown in Table 3.
(Evaluation D)
Artificial leather (“Saplare” manufactured by Idemitsu Techno Fine Co., Ltd.) was lightly pressed on the coated surface of each example, comparative example, and reference example applied at an application amount of 0.1 mg / cm ² , and the eye shadow strikes. Ripped. Further, after the eye shadow was applied at a coating amount of 0.1 mg / cm ² , the coating state after 2 hours in a room temperature room environment was observed. By combining both of these evaluations, the case where no “lame omission” occurred was determined as “◯”, and the case where “lame omission” occurred was determined as “x”. The results are shown in Table 4.

(Oil content adsorption)
Next, the amount of oil adsorbed was measured using the amorphous calcium phosphate-coated particles of Production Example 1 (3% by mass coated product).
In the measurement, a blank sample prepared by drying amorphous calcium phosphate-coated particles under conditions of 350 ° C. × 1 h was prepared. Next, 4.5 g of oleic acid was added to 0.5 g of this blank sample and allowed to stand at 37 ° C. for 24 hours to adsorb oleic acid. Further, the sample was washed three times with 15 ml of diethyl ether and air-dried to obtain an adsorption sample.
About 14 to 17 mg each of the blank sample and the adsorbed sample were collected, and the oil absorption amount was obtained by performing TG-DTA measurement at a heating rate of 20 ° C./min from 30 ° C. to 600 ° C. in a nitrogen gas stream. .
More specifically, the difference between the residual heating rate (%) at 30 to 600 ° C. and the residual heating rate (%) at 30 to 150 ° C. is obtained as a weight loss rate (%), and each of the blank sample and the adsorption sample is obtained. The difference in weight loss rate (%) was taken as the adsorption rate (%), and this adsorption rate (%) was multiplied by 10 to obtain the oil adsorption amount (mg / g).
Similarly, the amount of oil adsorbed was also determined for Engelhard's trade name “Reflecks Pinpoints of Pearl” alone, which was not coated with amorphous calcium phosphate.
The results are shown in Table 5.

As can be seen from the results shown in Tables 3 and 4, the glass flakes having a pearly luster are coated with amorphous calcium phosphate, and the amorphous calcium phosphate is coated in an amount of 1% to less than 10% by mass. The makeup cosmetics characterized in that the amorphous calcium phosphate-coated particles are used, and the coated amorphous calcium phosphate improves the adsorptivity to the skin and causes “lame omission”. It turns out that it is suppressed.
In addition, it can be seen that since the amorphous calcium phosphate is coated in an amount of 1% or more and less than 10% by mass, the aesthetics such as gloss and color tone of the glass flakes having pearly luster can be maintained.
Furthermore, it can be seen that coating the glass flakes having pearly luster with amorphous calcium phosphate can reduce the tingling irritation and rough feeling and improve the feeling of use.

The powder X-ray-diffraction chart of an amorphous calcium phosphate and crystalline calcium phosphate.

Claims (2)

And amorphous calcium phosphate glass flakes having pearl gloss coated, moreover, the amorphous calcium phosphate-coated particles amorphous calcium phosphate is coated in an amount of less than 1% to 10% in the mass have been used , the amorphous calcium phosphate-coated particles are characterized der Rukoto those below (1) to the amorphous calcium phosphate glass flakes having a pearly luster step is carried out in (4) were coated Make-up cosmetics.
(1) An acid treatment step of removing acid after mixing glass flakes having pearly luster and an acid having a pH of 2.0 or less to bring the glass flakes having a pearly luster into contact with an acid having a pH of 2.0 or less. .
(2) A suspending step in which glass flakes having pearly luster after the acid treatment step are dispersed in water so as to have a solid content concentration of 0.1 to 50% by mass to prepare a suspension.
(3) An alkali process in which calcium hydroxide is added to the suspension prepared in the suspension process to produce an alkaline suspension having a pH of 12.0 or higher.
(4) A calcium phosphate coating step of coating the surface of glass flakes having pearly luster in the alkaline suspension with amorphous calcium phosphate by adding phosphoric acid to the alkaline suspension prepared in the alkaline step. The makeup cosmetic according to claim 1 , wherein phosphoric acid is used as an acid in the acid treatment step.

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