JP2020066599A - Composite powder, external composition for skin, and method for enhancing fluorescence intensity of inorganic fluorescent powder - Google Patents

Abstract

To provide a novel method for enhancing fluorescence intensity of an inorganic phosphor, and an inorganic phosphor having enhanced fluorescence intensity, obtained by using the method, and an external composition for skin containing the same.SOLUTION: At least a part of the surface of inorganic fluorescent powder is coated with non-fluorescent powder, to enhance fluorescence intensity of the inorganic fluorescent powder.SELECTED DRAWING: Figure 1

Description

  TECHNICAL FIELD The present invention relates to a composite powder of an inorganic fluorescent powder and a non-fluorescent powder, a composition for external skin containing the same, and a method for enhancing the fluorescent intensity of the inorganic fluorescent powder.

  Various powders are contained in cosmetics depending on the purpose. Particularly in makeup cosmetics and sunscreen cosmetics, it is general to impart effects such as luster, soft focus, color correction, and ultraviolet ray protection ability by powder.

  Among powders, fluorescent powders are generally used for applications such as displays, lighting, playground equipment and paints, but are also used in cosmetics for the purpose of enhancing the makeup effect. For example, by using a fluorescent powder in a cosmetic material, not only soft focus property and the like but also color correction effect by fluorescent color can be provided.

  Patent Document 1 discloses a cosmetic material having improved soft focus properties by containing an aluminate complex oxide which is an inorganic fluorescent powder. Patent Document 2 discloses a blue fluorescent powder containing amorphous silica particles, and describes application to cosmetics. However, since the fluorescent powders described in Patent Document 1 and Patent Document 2 do not have sufficient emission intensity, it is necessary to increase the blending amount in order to exert the effect as a cosmetic. Further, since these fluorescent powders have a high soft focus property, they are unsuitable for cosmetics having an effect of enhancing a glossy feeling.

  Under such circumstances, a technique for enhancing the makeup effect by enhancing the fluorescence intensity of fluorescent powder has been developed. For example, Patent Document 3 discloses a cosmetic in which the emission intensity is more effectively increased by containing an inorganic fluorescent powder and another powder. However, in the technique described in this document, the effect of enhancing the fluorescent intensity of the fluorescent powder may be insufficient.

  On the other hand, various composite powders are used in the cosmetics field, and it is known that various cosmetic effects can be obtained by combining powders to be composited. For example, Patent Document 4 discloses a composite powder in which silica is compounded on an inorganic powder by a specific method to enhance the soft focus effect. Patent Document 5 discloses a composite powder in which the gloss is enhanced by compounding boron nitride with a metal oxide.

  However, in Patent Documents 4 and 5, there is no description about the fluorescent powder, and the problem of increasing the fluorescent intensity of the fluorescent powder cannot be solved even by referring to these documents. Further, there is no description about the color correction effect.

JP, 2014-5255, A JP, 2016-141780, A International Publication No. 2017/142057 JP, 2005-113306, A JP, 2011-236137, A

  It is an object of the present invention to provide a novel method for enhancing the fluorescence intensity of an inorganic phosphor, an inorganic phosphor with enhanced fluorescence intensity obtained using this method, and a cosmetic containing the same.

  As a result of intensive studies for solving the above-mentioned problems, the present inventor has found that the fluorescent intensity is enhanced by coating at least a part of the surface of the inorganic fluorescent powder with the non-fluorescent powder.

That is, the gist of the present invention is as follows.

[1] A composite powder characterized in that at least a) a part of the surface of an inorganic fluorescent powder is covered with b) a non-fluorescent powder.
[2] a) The composite powder according to [1], wherein the fluorescent wavelength of the inorganic fluorescent powder is in the range of 440 nm to 520 nm or 640 nm to 700 nm.
[3] a) The inorganic fluorescent powder is a crystal matrix and / or an activator of Al (aluminum), Zn (zinc), Mg (magnesium), Si (silicon), Mn (manganese), Ca (calcium), Ti. (Titanium), Ce (Cerium), Ba (Barium), O (Oxygen), P (Phosphorus), S (Sulfur) at least one element selected from the above is contained. The composite powder according to [1] or [2].
[4] a) The inorganic fluorescent powder is selected from the group consisting of oxides (Al / Ca / manganese), oxides (Mg / manganese / titanium), zinc oxide phosphors, and phosphoric acid (Ca / cerium). The composite powder according to any one of [1] to [3], which is at least one kind.
[5] b) The non-fluorescent powder is at least one selected from the group consisting of titanium oxide, non-fluorescent zinc oxide, iron oxide, aluminum oxide (alumina), and silica [ The composite powder according to any one of 1] to [4].
[6] a) The composite powder according to any one of [1] to [5], wherein the particle size of the inorganic fluorescent powder is 1 μm or more and 200 μm or less.
[7] b) The composite powder according to any one of [1] to [6], wherein the non-fluorescent powder has a particle size of 1 nm or more and 100 nm or less.
[8] The ratio of the a) inorganic fluorescent powder to the b) non-fluorescent powder in the composite powder is as follows: a component: b component = 95 (wt%): 5 (wt%) to 70 (wt%): 30 ( % By weight), The composite powder according to any one of [1] to [7].
[9] The composite powder according to any one of [1] to [8], which is for an external composition for skin.
[10] A composition for external use for skin, containing the composite powder according to any one of [1] to [9].
[11] A method for enhancing the fluorescence intensity of an inorganic fluorescent powder, characterized in that a) a part of the surface of the inorganic fluorescent powder is covered with b) a non-fluorescent powder.

  According to the present invention, a) a composite powder in which at least a part of the surface of the inorganic fluorescent powder is coated with b) a non-fluorescent powder, a) the fluorescent intensity of the inorganic fluorescent powder is significantly improved. Can be made. In addition, since a) the composite powder of the present invention in which at least a part of the surface of the inorganic fluorescent powder is coated with b) the non-fluorescent powder exhibits excellent luminescent properties, it is more preferable to include it in a cosmetic composition. It is possible to provide cosmetics having a high makeup effect.

2 is a scanning electron microscope image of the inorganic fluorescent composite powder of Example 1. 5 is a scanning electron microscope image of the inorganic fluorescent powder mixture of Comparative Example 2.

  Hereinafter, the present invention will be described in detail. It should be noted that the terms used in the present specification have the meanings commonly used in the art unless otherwise specified.

  Further, as used herein,% means% by weight unless otherwise specified.

<Composite powder>
The composite powder of the present invention is characterized in that at least a) a part of the surface of the inorganic fluorescent powder is covered with b) a non-fluorescent powder. Here, the coating means that a) at least a part of the surface of the inorganic fluorescent powder is covered by b) a non-fluorescent powder, and a) a part of the surface of the inorganic fluorescent powder is covered. In this case, a) includes the case where the entire surface of the inorganic fluorescent powder is covered. The coverage of the composite powder of the present invention is preferably 30% or more, more preferably 40% or more, still more preferably 50% or more.

The coverage in the present invention is the ratio of the difference between a) the surface area of the inorganic fluorescent powder and the surface area of the uncoated surface of the composite powder to the surface area of the inorganic fluorescent powder. Can be expressed as

  As a method of obtaining the coverage, for example, the surface of the composite powder is observed in a scanning electron microscope observation image, and the entire surface of the composite powder and b) the surface area of the surface not coated with the non-fluorescent powder are imaged. It is possible to obtain the coverage of each composite powder by the above formula, obtained by analysis or the like, and use the average value of the coverage of the plurality of composite powders as the coverage of the composite powder in the present invention.

  The a) inorganic fluorescent powder used in the present invention may be any inorganic powder having fluorescent properties, and its shape and size are not limited.

  a) As the inorganic fluorescent powder, any inorganic powder having fluorescent properties may be used. Even if the inorganic fluorescent powder does not include an activator having a fluorescent property in a single crystal host, it is composed of a crystalline host and an activator (impurity). An activated phosphor may be used. The crystalline matrix in the present specification may be a crystalline body or an amorphous body. Further, it may or may not contain an activator and the like other than the above, and is used in the same meaning as a crystalline substance and an amorphous substance which are usually used even when the activator and the like are not included. Examples of the crystal matrix include metal oxides, phosphoric acid compounds, metal sulfides, metal sulfates, halophosphoric acid compounds, and the like, and metal oxides or phosphoric acid compounds are preferable.

  The crystal matrix of the a) inorganic fluorescent powder used in the present invention includes Al (aluminum), Ti (titanium), Zn (zinc), Ge (germanium), Si (silicon), Fe (iron), Zr (zirconium). ), Mn (manganese), Mg (magnesium), Ca (calcium), and Zn (zinc) are preferably contained. Among them, Al (aluminum), Zn (zinc), Mg (magnesium), Ca (calcium), Ti (titanium), Ba (barium), O (oxygen), P (phosphorus), and S (sulfur) are selected. It is preferable to contain one or more kinds of elements, particularly O (oxygen) and / or P (phosphorus), and Al (aluminum), Zn (zinc), Mg (magnesium), Ca (calcium). ), Ti (titanium), and Ba (barium).

  Examples of the activator for the a) inorganic fluorescent powder containing the activator used in the present invention include Mn (manganese), Eu (europium), Cr (chromium), Ce (cerium), Pr (praseodymium), La (lanthanum). , Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), Fe (iron), Zn (zinc), Ti (titanium). Etc. are used, but are not particularly limited thereto.

  The a) inorganic fluorescent powder used in the present invention is Al (aluminum), Zn (zinc), Mg (magnesium), Si (silicon), Mn (manganese), Ca (calcium) as a crystal matrix and / or activator. , Ti (titanium), Ce (cerium), Ba (barium), O (oxygen), P (phosphorus), and S (sulfur) are preferable. In particular, oxide (Al / Ca / manganese), oxide (Mg / manganese / titanium), zinc oxide phosphor, phosphoric acid (Ca / cerium) are preferable.

  The a) inorganic fluorescent powder used in the present invention may emit fluorescent light of any color, and red fluorescent powder, green fluorescent powder and blue fluorescent powder are particularly preferable.

  a) The maximum fluorescence wavelength of the inorganic fluorescent powder is preferably 440 nm to 520 nm or 640 nm to 700 nm.

  Examples of commercially available a) inorganic fluorescent powder used in the present invention include Lumate R (manufactured by Sakai Chemical Industry Co., Ltd.), Lumate G (manufactured by Sakai Chemical Industry Co., Ltd.) and Lumate B (manufactured by Sakai Chemical Industry Co., Ltd.). However, the present invention is not limited to these.

  The particle size of the a) inorganic fluorescent powder used in the present invention is not particularly limited, but is preferably 0.5 μm or more, more preferably 1 μm or more. The particle size of the a) inorganic fluorescent powder is 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and further preferably 100 μm or less. The particle size of the a) inorganic fluorescent powder used in the present invention is 1 μm or more and 200 μm or less from the viewpoint of obtaining sufficient fluorescence intensity and being excellent in feeling when used in cosmetics and the like. It is preferably 2 μm or more and 100 μm or less.

  The particle diameter used in the present invention refers to the average diameter of primary particles when observed with a transmission electron microscope.

  The non-fluorescent powder b) used in the present invention is not particularly limited as long as it has no fluorescent property, and may be an inorganic powder or an organic powder, and its shape and size are not limited.

  Examples of the inorganic powder include titanium oxide, non-fluorescent zinc oxide, iron oxide (red iron oxide, yellow iron oxide, black iron oxide), silica, aluminum oxide, aluminum hydroxide, cesium oxide, chromium oxide, chromium hydroxide, barium sulfate. , Synthetic phlogopite, mica, talc, sericite, kaolin, gunjou, konjou, carbon black, calcium carbonate, magnesium carbonate, silicone, magnesium silicate, magnesium aluminum silicate, boron nitride and the like, but are particularly limited to these. Not done.

  Examples of commercially available inorganic powders include MP-1133AQ (manufactured by Teika), MP-1133WP (manufactured by Teika), MT-100WP (manufactured by Teika), MT-100SA (manufactured by Teika), MT-500B. (Manufactured by Teika), MZ-300 (manufactured by Teika), MTZ-3040TSW (manufactured by Teika), MZ-500 (manufactured by Teika), FINEX-30 (manufactured by Sakai Chemical Industry), FINEX-50 (Sakai Chemical Industry). Industrial Co., Ltd.), FINEX-30W (Sakai Chemical Industry Co., Ltd.), FINEX-50W (Sakai Chemical Industry Co., Ltd.), FINEX-50W-LP2 (Sakai Chemical Industry Co., Ltd.), AEROSIL 200 (Japan Aerosil Co., Ltd.), AEROSIL Alu C (manufactured by Nippon Aerosil Co., Ltd.), LL-100HP (manufactured by Titanium Industry Co., Ltd.), R-516HP (manufactured by Titanium Industry Co., Ltd.), BL-100HP ( Tan Kogyo Co., Ltd., Sericite FSE (Sanshin Mining Co., Ltd.), Silica Micro Bead P-1500 (JGC Catalysts Co., Ltd.), KSP-100 (Shin-Etsu Chemical Co., Ltd.), KSP-300 (Shin-Etsu Chemical Co., Ltd.) Manufactured) and the like, but are not particularly limited thereto.

  Examples of the organic powder include polyethylene, polyamide, crosslinked polystyrene, polymethylmethacrylate, cellulose, carbamate, fluororesin, polyolefin, epoxy resin, phenol resin, wheat starch, silk, long-chain fatty acid salt, ceramide, phospholipid and the like. However, the present invention is not limited to these.

  Examples of commercially available organic powders include GANTZ Pearl GMX-0610 (manufactured by Aika Kogyo Co., Ltd.), GANTZ Pearl GMX-0610AQ (manufactured by Aika Kogyo Co., Ltd.), SP-500 (manufactured by Toray Co., Ltd.), and Ceramide I (manufactured by Evonik Co.). ), Ceramide III (manufactured by Evonik), Ceramide VI (manufactured by Evonik), Phytopresome Care-V (manufactured by Nippon Seika Co., Ltd.), Ceramide TIC-001 (manufactured by Takasago International Corporation), SLP-PC70 (manufactured by Tsuji Seiyu Co., Ltd.). ), SLP-PC92H (manufactured by Tsuji Seiyu Co., Ltd.), NIKKOL Recinol S-10 (manufactured by Nikko Chemicals Co., Ltd.) and the like, but are not particularly limited thereto.

  The non-fluorescent powder used in the present invention is preferably an inorganic powder, and among them, a metal oxide, a metal hydroxide and a silicate are preferable. Further, metal oxides and silica oxides are preferable, and titanium oxide, non-fluorescent zinc oxide, iron oxide, aluminum oxide (alumina), and silica are particularly preferable.

  The particle size of b) the non-fluorescent powder used in the present invention is preferably smaller than the particle size of the inorganic fluorescent powder used in the present invention, preferably 250 nm or less, and 100 nm or less of fine particles. More preferably. Further, from the viewpoint of the effect of improving the fluorescence intensity of the composite particles of the present invention, it is preferably 0.1 nm or more, more preferably 1 nm or more. The particle size of the non-fluorescent powder used in the present invention is preferably 0.1 nm or more and 150 nm or less, more preferably 1 nm or more and 100 nm or less.

  The a) inorganic fluorescent powder and / or b) non-fluorescent powder used in the present invention improves the adhesion between the powders by combining the powders to be composited, and the fluorescence intensity of the resulting composite powder. Surface treatment may be performed for the purpose of further increasing the temperature. This surface treatment may be performed on each powder before compounding, or may be performed on the obtained composite powder.

  The types of substances used for the surface treatment include silica, alginic acid, aluminum oxide (alumina), POE / dimethicone copolymer, polyethylene glycol, aluminum hydroxide, amino acid, metal soap, perfluoroalkylethyl phosphate diethanolamine acid. , Fluoroalkyl acrylate / polyalkylene glycol acrylate polymer, perfluoropolyether phosphoric acid, anionic or cationic polymer having perfluoropolyether chain, hydrogenated lecithin, acylated amino acid, α-tocopherol phosphate ester acid, methyl Hydrogen polysiloxane, α-monoalkoxy polydimethyl siloxane, α-dialkoxy polydimethyl siloxane, triethoxysilylethyl polydimethylsiloxyethyl dimethicone Amodimethicone, triethoxy caprylyl silane, aminopropyltriethoxysilane, perfluorooctyl ethyl triethoxysilane, perfluorooctyl triethoxysilane, but and the like, without limitation. Among them, hydrophilic surface treatment is preferable, and silica, alginic acid, aluminum oxide (alumina), POE / dimethicone copolymer, polyethylene glycol, and aluminum hydroxide are particularly preferable.

  The a) inorganic fluorescent powder and / or the b) non-fluorescent powder may be subjected to a plurality of surface treatments, such as surface treatment rate (ratio of surface treatment agent amount to powder) and surface treatment. The method is also not particularly limited.

  The surface of the a) inorganic fluorescent powder and / or b) non-fluorescent powder used in the present invention is hydrophilic in that it has high adhesiveness in the wet treatment in the method for preparing a composite powder described below. Is preferred. Among them, at least one or more hydrophilic surface treatments are preferable, and it is particularly preferable that the outermost surface is hydrophilic surface treatment. Here, examples of the hydrophilic surface treatment include, but are not particularly limited to, silica, alginic acid, aluminum oxide (alumina), aluminum hydroxide, amino acid, polyethylene glycol, and POE / dimethicone copolymer treatment.

  The method for preparing the composite powder in the present invention is not particularly limited, but wet processing is preferable.

  In the wet treatment, it is preferable that a) the inorganic fluorescent powder and b) the non-fluorescent powder are dispersed in a dispersion medium, and b) the non-fluorescent powder is coated on at least a part of the surface of the a) the inorganic fluorescent powder. . Further, it is preferable to sufficiently disperse a) the inorganic fluorescent powder and / or b) the non-fluorescent powder by a mechanical stirring force and a crushing force, specifically, a magnetic stirrer, a mixer, an ultrasonic wave, a homogenizer, a high-pressure homogenizer. , Disperser mixer, bead mill, colloid mill, roller mill, triple roller mill, stamp mill, rod mill, ball mill, jaw crusher, kneader, planetary mixer, etc., but are not particularly limited to these, and two or more may be used. I do not care.

  Moreover, you may add processes, such as filtration, centrifugation, and drying. The drying method is also not particularly limited. The obtained composite powder may be used as a dispersion or a paste, or may be used as a powder.

  The dispersion medium used in the wet treatment is not particularly limited, and examples thereof include water, alcohols, hydrocarbon oils, ester oils, silicone oils and organic solvents, and the dispersion medium contains components such as surfactants, salts and chelating agents. You may let me.

  The dispersion medium used in the wet treatment is preferably a hydrophilic dispersion medium, and preferably contains at least water, for the reason that the adhesion between powders is improved.

  The weight ratio of a) the inorganic fluorescent powder and b) the non-fluorescent powder in the composite powder of the present invention is appropriately adjusted according to the shape and size of each of the a) the inorganic fluorescent powder and the b) the non-fluorescent powder. However, it is preferable that a component (wt%): b component (wt%) = 95: 5 to 70:30, particularly 90:10 to 70:30. Further, the above ratio may be, for example, the ratio of the charged amounts (% by weight) of the components a) and b) when preparing the composite powder.

  Since the composite powder of the present invention has strong fluorescence intensity, it can be suitably used for various external compositions for skin such as cosmetics. Further, it can be suitably used in the fields of lighting, playground equipment, paints, etc. that can utilize fluorescence.

<External composition for skin>
The composition for external use of the present invention contains the above-described composite powder of the present invention. Since the composite powder of the present invention has strong fluorescence intensity and exhibits excellent light emitting property and color correction effect, the composition for external use for skin containing the same makes the scars inconspicuous or adjusts the skin tone, and has a makeup effect. It can be used for general external preparations for skin such as pharmaceuticals, quasi drugs, and cosmetics for the purpose of imparting In particular, since it has an excellent makeup effect, it can be suitably used as a cosmetic product.

  The content of the composite powder in the external composition for skin of the present invention is 0.0001% by weight or more and 50% by weight or less, preferably 0.001% by weight or more and 30% by weight or less, and 0.01% by weight. % Or more and 20% by weight or less is more preferable, 0.01% by weight or more and 10% by weight or less is further preferable, and 0.01% by weight or more and 5% by weight or less is particularly preferable.

  The external composition for skin of the present invention may contain, in addition to the composite powder of the present invention, other components as long as the effects of the present invention are not impaired.

  Other components include oils, lipophilic nonionic surfactants, hydrophilic nonionic surfactants, other surfactants, sequestering agents, natural water-soluble polymers, and semi-soluble polymers according to various purposes. Synthetic water-soluble polymer, synthetic water-soluble polymer, inorganic water-soluble polymer, various extracts, various powders, moisturizing ingredients, polyhydric alcohols, scrubbing agents, ultraviolet scattering ingredients, astringent ingredients, peptides or the like Derivative, amino acid or its derivative, washing component, keratin softening component, cell activating component, anti-aging component, blood circulation promoting component, whitening component, component having DNA damage preventing and / or repairing action, anti-inflammatory component, anti-inflammatory component Other components such as oxidizing components, vitamins, sebum-adsorbing components, antibacterial components and the like may be contained within a range that does not impair the effects of the present invention. In the external composition for skin of the present invention, these components may be blended alone or in combination of two or more. It should be noted that each of these components is not particularly limited as long as it can be used in the fields of pharmaceuticals, quasi drugs, cosmetics, etc., and any component can be appropriately selected and used.

  The external composition for skin of the present invention may contain a non-composited fluorescent powder in addition to the composite powder of the present invention.

  The method for producing the external composition for skin of the present invention is not particularly limited, and the composite powder of the present invention which is an essential component, and components appropriately selected from the above-mentioned other components and the like are blended and mixed by a conventional method. Can be manufactured.

  Specific applications of the external composition for skin of the present invention include, for example, basic cosmetics such as lotion, moisturizer, emulsion, beauty essence, pack, hand cream, body lotion, body cream and lip balm; Makeup remover, cleaning cosmetics such as body shampoo; makeup cosmetics such as foundation, makeup base, eye color, eye shadow, eyeliner, eyebrow, highlight, control color, cheek, mascara, lipstick, face powder; It can be used for cosmetics such as sunscreen cosmetics. In addition, a multifunctional preparation in which the functions of these cosmetics are combined into one preparation is also included. Furthermore, it can also be used in medicines, quasi drugs, such as ointments for wounds and external preparations for acne.

  Among them, makeup cosmetics such as foundation, makeup base, eye color, eye shadow, eye liner, eyebrow, highlight, control color, cheek, mascara, lipstick, face powder; sunscreen cosmetics, etc. preferable.

<Method for enhancing fluorescent intensity of inorganic fluorescent powder>
The present invention also includes a method of enhancing the fluorescence intensity of inorganic fluorescent powder, characterized in that a) a part of the surface of the inorganic fluorescent powder is coated with b) non-fluorescent powder. In addition, the composite powder of the present invention obtained by coating a) a part of the surface of the inorganic fluorescent powder with b) a non-fluorescent powder exhibits excellent luminescent properties, so that it can be incorporated into a cosmetic composition. It is possible to provide a cosmetic having a higher makeup effect. In addition, in the method for enhancing the fluorescent intensity of the inorganic fluorescent powder, the description of a) the inorganic fluorescent powder, b) the non-fluorescent powder, and the specific description of the composite powder prepared using these are given in "Composite Powder". The explanation in the section can be applied.

  Next, a detailed description will be given with reference to examples of the composite powder in which a) at least a part of the surface of the inorganic fluorescent powder is coated with b) the non-fluorescent powder, but the present invention is not limited thereto. is not.

(Example 1)
Silica-treated oxidation (Al / Ca / manganese) (plate-like, particle size 40 μm, aluminum hydroxide treatment 4.5%, silica treatment 1.0%, fluorescence wavelength 660 nm) 4.5 g in water 45.5 g It was put in and sufficiently dispersed by a disper mill to obtain an oxidized (Al / Ca / manganese) aqueous dispersion. Next, 0.5 g of alumina-treated fine particle titanium oxide (needle-shaped, particle diameter 15 nm, Al hydroxide treated 6%) was put in 49.5 g of water and dispersed sufficiently with a disper mill to obtain an alumina-treated fine particle titanium oxide aqueous dispersion. Got The alumina-treated fine particle titanium oxide aqueous dispersion was mixed with the oxidized (Al / Ca / manganese) aqueous dispersion, thoroughly dispersed with a Dispermill, filtered, and dried at 60 ° C. overnight. After drying, the aggregate was crushed with a mill grinder to obtain an inorganic fluorescent composite powder.

(Comparative Example 1)
4.5 g of silica-treated oxide (Al / Ca / manganese) (plate-like, particle size 40 μm, aluminum hydroxide treated 4.5%, silica-treated 1.0%, fluorescence wavelength is 660 nm) 4.5 g, and alumina-treated fine particle titanium oxide 0.5 g (needle-shaped, particle diameter 15 nm, treated with Al hydroxide 6%) was pulverized with a mill grinder to obtain an inorganic fluorescent powder mixture.

(Comparative example 2)
As Comparative Example 2, silica-treated oxidation (Al / Ca / manganese) (plate-like, particle size 40 μm, aluminum hydroxide treatment 4.5%, silica treatment 1.0%, fluorescence wavelength 660 nm) was used.

<Confirmation of compounding>
The inorganic fluorescent composite powder of Example 1 and the inorganic fluorescent powder mixture of Comparative Example 2 were observed using a scanning electron microscope VE-8800 (manufactured by Keyence Corporation). The respective micrographs are shown in FIG. 1 (Example 1) and FIG. 2 (Comparative Example 2).

  Comparing FIG. 1 and FIG. 2, obviously, in Example 1, the alumina-treated fine particle titanium oxide adheres to the surface of the silica-treated oxide (Al / Ca / manganese), and the alumina-treated fine particle titanium oxide which is a non-fluorescent powder, It was confirmed that the surface of silica-treated oxide (Al / Ca / manganese), which is an inorganic fluorescent powder, was coated.

<Test 1 Evaluation of fluorescence intensity>
A double-sided tape is attached to a plate (50 mm x 50 mm HELIOPLATE HD6, made by HelioScreen Labs), and the sample is evenly applied with a brush. Using a spectrophotometric color difference meter GC-5000 (manufactured by Nippon Denshoku Industries Co., Ltd.), light was applied to the surface of the plate coated with the sample at an incident angle of 45 ° to measure the reflection intensity at the regular reflection angle. Regarding the intensities at the fluorescence wavelength of the component a), the intensities at the fluorescence wavelength of each sample were compared, where the intensity at a) only the inorganic fluorescent powder was 1.

  Comparative Example 2: a) Inorganic fluorescent powder alone, Comparative example 1: a) Inorganic fluorescent powder and b) Non-fluorescent powder are simply mixed, and the reflection intensity at a fluorescent wavelength of 660 nm is compared. The fluorescence intensity increased about 9 times by simply mixing the body and b) the non-fluorescent powder. Example 1: The composite powder of a) an inorganic fluorescent powder and b) a non-fluorescent powder showed about 14 times the strength of Comparative Example 1, and it was confirmed that the composite further increases the fluorescence strength. .

  Further, comparing the fluorescence intensities in the case of the fluorescence wavelength (660 nm) and in the case of the fluorescence wavelength (400 nm), the fluorescence intensity is higher at the fluorescence wavelength (660 nm), and the fluorescence wavelength of the component a) In, a more remarkable increase in strength was confirmed. Since the fluorescence intensity at the fluorescence wavelength of 660 nm was remarkably enhanced, the powder became reddish.

(Example 2)
Silica treatment Oxidation (Al / Ca / manganese) (plate-like, particle size 40 μm, aluminum hydroxide treatment 4.5%, silica treatment 1.0%, fluorescence wavelength 660 nm) 0.95 g in water 49.05 g Then, it was sufficiently dispersed with a Dispermill to obtain an oxidized (Al / Ca / manganese) aqueous dispersion. Next, 0.05 g of alumina-treated fine particle titanium oxide (needle-shaped, particle diameter 15 nm, Al hydroxide treated 6%) was put in 49.9 g of water, and dispersed sufficiently by a disper mill to obtain an alumina-treated fine particle titanium oxide aqueous dispersion. Got The alumina-treated fine particle titanium oxide aqueous dispersion was mixed with the oxidized (Al / Ca / manganese) aqueous dispersion, thoroughly dispersed with a Dispermill, filtered, and dried at 60 ° C. overnight. After drying, the aggregate was crushed with a mill grinder to obtain an inorganic fluorescent composite powder.

(Example 3)
Silica treatment Oxidation (Al / Ca / manganese) (plate-like, particle size 40 μm, aluminum hydroxide treatment 4.5%, silica treatment 1.0%, fluorescence wavelength 660 nm) 0.80 g in water 49.20 g Then, it was sufficiently dispersed with a Dispermill to obtain an oxidized (Al / Ca / manganese) aqueous dispersion. Next, 0.20 g of alumina-treated fine particle titanium oxide (needle-shaped, particle diameter 15 nm, Al hydroxide-treated 6%) was put in 49.80 g of water and sufficiently dispersed by a disper mill to obtain an alumina-treated fine particle titanium oxide aqueous dispersion. Got The alumina-treated fine particle titanium oxide aqueous dispersion was mixed with the oxidized (Al / Ca / manganese) aqueous dispersion, thoroughly dispersed with a Dispermill, filtered, and dried at 60 ° C. overnight. After drying, the aggregate was crushed with a mill grinder to obtain an inorganic fluorescent composite powder.

(Example 4)
Silica treatment Oxidation (Al / Ca / manganese) (plate-like, particle size 40 μm, aluminum hydroxide treatment 4.5%, silica treatment 1.0%, fluorescence wavelength 660 nm) 0.70 g is put in water 49.30 g. Then, it was sufficiently dispersed with a Dispermill to obtain an oxidized (Al / Ca / manganese) aqueous dispersion. Next, 0.30 g of alumina-treated fine particle titanium oxide (needle-shaped, particle size 15 nm, Al hydroxide treated 6%) was put in 49.70 g of water and dispersed sufficiently with a disper mill to give an alumina-treated fine particle titanium oxide aqueous dispersion. Got The alumina-treated fine particle titanium oxide aqueous dispersion was mixed with the oxidized (Al / Ca / manganese) aqueous dispersion, thoroughly dispersed with a Dispermill, filtered, and dried at 60 ° C. overnight. After drying, the aggregate was crushed with a mill grinder to obtain an inorganic fluorescent composite powder.

  The fluorescence intensities of Examples 1 to 4 which were subjected to the composite treatment were compared, with the intensity of Comparative Example 2 which was a) the inorganic fluorescent powder before the composite being set as 1. The results are shown in Table 2.

(Example 5)
The silica-treated oxidation (Al / Ca / manganese) of Example 1 was treated with silica having a particle diameter of 10 μm (Al / Ca / manganese) (plate-like, particle diameter 10 μm, aluminum hydroxide treatment after 4.5%, silica treatment). 3.0% / fluorescence wavelength of 660 nm) to obtain an inorganic fluorescent composite powder.

(Example 6)
The silica-treated oxidation (Al / Ca / manganese) of Example 3 was treated with silica-treated oxidation (Al / Ca / manganese) having a particle diameter of 10 μm (plate-like particle diameter 10 μm-aluminum hydroxide treatment after 4.5%, silica treatment). 3.0% / fluorescence wavelength of 660 nm) to obtain an inorganic fluorescent composite powder.

(Example 7)
The silica-treated oxidation (Al / Ca / manganese) of Example 4 was treated with silica having a particle diameter of 10 μm (Al / Ca / manganese) (plate-like, particle diameter 10 μm, aluminum hydroxide treatment after 4.5%, silica treatment). 3.0% / fluorescence wavelength of 660 nm) to obtain an inorganic fluorescent composite powder.

(Comparative example 3)
As Comparative Example 3, silica-treated oxidation (Al / Ca / manganese) (plate-like, particle size 10 μm, aluminum hydroxide treatment 4.5%, silica treatment 3.0%, fluorescence wavelength 660 nm) was used.

  The fluorescence intensities of Examples 5 to 7 that were subjected to the composite treatment were compared, with the intensity of Comparative Example 3 which was a) the inorganic fluorescent powder before the composite being set as 1. The results are shown in Table 3.

  From Examples 1 to 4 and Comparative Example 2, even if the ratio of the component a) and the component b) was changed, it was confirmed that the fluorescence intensity was enhanced by the compounding.

  Further, even if the particle diameter of the component a) was changed (Examples 5 to 7), similarly, it was confirmed that the fluorescence intensity was enhanced by the combination. In particular, the fluorescence intensity remarkably increased at a: b = 90: 10 to 70:30.

(Example 8)
The silica-treated oxidation (Al / Ca / manganese) of Example 1 was changed to alginic acid-treated oxidation (Al / Ca / manganese) (plate-like, particle size 40 μm, alginic acid treatment 3%, fluorescence wavelength was 660 nm), and the inorganic fluorescent composite powder was used. Got the body

(Example 9)
The alumina-treated fine particle titanium oxide of Example 8 was changed to silica-treated fine particle titanium oxide (needle-like, particle diameter 15 nm, silica-treated 30%) to obtain an inorganic composite powder.

(Example 10)
The alumina-treated fine particle titanium oxide of Example 1 was changed to alumina (substantially spherical, particle diameter 13 nm, no surface treatment) to obtain an inorganic fluorescent composite powder.

(Example 11)
The silica-treated oxidation (Al / Ca / manganese) of Example 1 was changed to alginic acid-treated oxidation (Al / Ca / manganese) (plate-shaped, particle size 40 μm, alginic acid-treated 1%, fluorescence wavelength was 660 nm), and further alumina-treated fine particles. The titanium oxide was changed to silica (substantially spherical, particle diameter 12 nm, no surface treatment) to obtain an inorganic fluorescent composite powder.

(Example 12)
The silica-treated oxidation (Al / Ca / manganese) of Example 3 was changed to alginic acid-treated oxidation (Al / Ca / manganese) (plate shape, particle size 40 μm, alginic acid treatment 1%, fluorescence wavelength was 660 nm), and further alumina treated fine particles. The titanium oxide was changed to a silica-treated pigment-grade titanium oxide (substantially spherical, particle size 250 nm, Al hydroxide treated 2.6% and silica treated 5.0%) to obtain an inorganic composite powder.

(Example 13)
The silica-treated pigment-grade titanium oxide of Example 12 was treated with POE / dimethicone copolymer-treated fine particle zinc oxide (substantially spherical / particle diameter 35 nm / triethoxycaprylylsilane treatment 3.6%, followed by polyoxyethylene / methylpolysiloxane copolymerization). The coalescence treatment was changed to 10.0%) to obtain an inorganic fluorescent composite powder.

(Comparative example 4)
As Comparative Example 4, alginic acid-treated oxidation (Al / Ca / manganese) (plate-like particle size 4 μm, alginic acid-treated 3%, fluorescence wavelength 660 nm) was used.

(Comparative example 5)
As Comparative Example 5, alginic acid-treated oxidation (Al / Ca / manganese) (plate-like particle size 4 μm, alginic acid-treated 1%, fluorescence wavelength 660 nm) was used.

  The inorganic fluorescent composite powders obtained in the respective examples were compared with the non-composite a) inorganic fluorescent powder with a fluorescent intensity of 1, and the results are shown in Table 4 (Comparing Examples 8 and 9). The strength ratios of Example 4 and Example 10 were found in Comparative Example 2 and Examples 11 to 13 were found in Comparative Example 5).

(Example 14)
The silica-treated oxidation (Al / Ca / manganese) of Example 1 was changed to phosphoric acid (Ca / cerium) (Lumate B (manufactured by Sakai Chemical Industry Co., Ltd., maximum fluorescence wavelength 460 nm)) to obtain an inorganic fluorescent composite powder.

(Example 15)
The silica-treated oxide (Al / Ca / manganese) of Example 1 was changed to a zinc oxide phosphor (Lumate G (manufactured by Sakai Chemical Industry Co., Ltd., maximum fluorescence wavelength: 500 nm)), and the alumina-treated fine particle titanium oxide (silica-treated fine particle titanium oxide ( Inorganic fluorescent composite powder was obtained by changing to needle-like particles, particle diameter 15 nm, silica treatment 30%).

(Example 16)
The silica-treated oxidation (Al / Ca / manganese) of Example 1 was changed to oxidation (Mg / manganese / titanium) (Lumate R (produced by Sakai Chemical Industry Co., Ltd., maximum fluorescence wavelength 660 nm)), and the alumina-treated fine particle titanium oxide was treated with silica. Inorganic fluorescent composite powder was obtained by changing to fine particle titanium oxide (acicular, particle size 15 nm, silica treated 30%).

(Comparative example 6)
As Comparative Example 6, phosphoric acid (Ca / cerium) (Lumate B (manufactured by Sakai Chemical Industry Co., Ltd., maximum fluorescence wavelength 460 nm)) was used.

(Comparative Example 7)
As Comparative Example 7, a zinc oxide phosphor (Lumate G (manufactured by Sakai Chemical Industry Co., Ltd., maximum fluorescence wavelength 500 nm)) was used.

(Comparative Example 8)
As Comparative Example 8, oxide (Mg / manganese / titanium) (using Lumate R (manufactured by Sakai Chemical Industry Co., Ltd., maximum fluorescence wavelength 660 nm)) was used.

  Results of comparison of the fluorescence intensity at 460 nm of Example 14 and Comparative Example 6, comparison of the fluorescence intensity at 500 nm of Example 15 and Comparative Example 7, and comparison of the fluorescence intensity at 660 nm of Example 16 and Comparative Example 8, respectively. Is shown in Table 5. In each case, the strength of the comparative example was set to 1, and the strength ratio was calculated.

<Application example to cosmetics>
Next, formulation examples of the external composition for skin (cosmetics) containing the inorganic fluorescent composite powder are shown, but the formulation is not limited thereto.

[Powder foundation]
Ingredient name Mixing amount [%]
Silicone treated talc Residual fluorine treated sericite 5
Silicone treated pigment grade titanium oxide 5
Silicone treated fine particles titanium oxide 5
Boron nitride 3
(Vinyl dimethicone / methicone silsesquioxane) crosspolymer 2
Nylon powder 1
Stearic acid Mg 1
Inorganic fluorescent composite powder of Example 1 3
Methylphenyl polysiloxane 7
2-Ethylhexyl paramethoxycinnamate 5
Bisethylhexyloxyphenol methoxyphenyl triazine 1
Sorbitan isostearate 0.5
Color pigment Suitable amount
Preservative Suitable amount
Total 100

  A powder foundation having an excellent makeup effect was obtained.

[Loose powder]
Ingredient name Mixing amount [%]
Silicone treated talc Residual fluorine treated sericite 5
Polymethylsilsesquioxane 7
Inorganic fluorescent composite powder of Example 1 5
Silicone treated pigment grade titanium oxide 3
Mica titanium 3
Color pigment Suitable amount
Preservative Suitable amount
Total 100

[Makeup base]
Ingredient name Mixing amount [%]
Water residual BG 10
1,3-pentanediol 1
Xanthan gum 0.1
Hydroxypropyl methylcellulose 0.2
(Hydroxyethyl acrylate / acryloyl dimethyl taurine Na) copolymer
0.5
Polysorbate 60 1.5
Glyceryl stearate 1.5
2-Ethylhexyl paramethoxycinnamate 8
Isostearic acid treated fine particle zinc oxide 2
Hexyl diethylaminohydroxybenzoate 3
Isononyl isononanoate 3
Methyl polysiloxane 3
Inorganic fluorescent composite powder of Example 3 1
Mica titanium 1
Color pigment Suitable amount
Preservative Suitable amount
Total 100

  A makeup base with an excellent makeup effect was obtained.

[sunscreen]
Ingredient name Mixing amount [%]
Cyclopentasiloxane Residual methylphenylpolysiloxane 5
2-Ethylhexyl paramethoxycinnamate 6
Bisethylhexyloxyphenol methoxyphenyl triazine 3
Isononyl isononanoate 7
Silicone treated fine particles zinc oxide 3
Lauryl PEG-9 polydimethylsiloxyethyl dimethicone 2
Sorbitan isostearate 1
Inorganic fluorescent composite powder of Example 1 treated with stearic acid 1
Water 25
DPG 5
Xanthan gum 0.1
Ethanol 5
Preservative Suitable amount
Total 100

  A sunscreen with an excellent makeup effect was obtained.

  According to the present invention, it is possible to provide a composite powder in which the fluorescent intensity originally possessed by the inorganic fluorescent powder is remarkably improved. In addition, since the composite powder of the present invention exhibits excellent luminescent properties, when incorporated into a cosmetic, various forms of cosmetic with a higher makeup effect can be provided. Further, it can be used not only in cosmetics but also in the fields of lighting, playground equipment, paints and the like.

Claims (11)

  At least a) a part of the surface of the inorganic fluorescent powder is covered with b) a non-fluorescent powder, which is a composite powder.   The composite powder according to claim 1, wherein a) the fluorescent wavelength of the inorganic fluorescent powder is in the range of 440 nm to 520 nm or 640 nm to 700 nm. a) Inorganic fluorescent powder is Al (aluminum), Zn (zinc), Mg (magnesium), Si (silicon), Mn (manganese), Ca (calcium), Ti (titanium) as a crystal matrix and / or activator. 2. At least one element selected from the group consisting of C, Ce (cerium), Ba (barium), O (oxygen), P (phosphorus) and S (sulfur) is contained. Or the composite powder according to 2.   a) The inorganic fluorescent powder is at least one selected from the group consisting of oxide (Al / Ca / manganese), oxide (Mg / manganese / titanium), zinc oxide phosphor, and phosphoric acid (Ca / cerium). The composite powder according to any one of claims 1 to 3, wherein   b) The non-fluorescent powder is at least one selected from the group consisting of titanium oxide, non-fluorescent zinc oxide, iron oxide, aluminum oxide (alumina), and silica. 4. The composite powder according to any one of 4 above.   a) The particle size of the inorganic fluorescent powder is 1 μm or more and 200 μm or less, and the composite powder according to claim 1.   b) The composite powder according to any one of claims 1 to 6, wherein the non-fluorescent powder has a particle diameter of 1 nm or more and 100 nm or less.   The ratio of a) the inorganic fluorescent powder and b) the non-fluorescent powder in the composite powder is as follows: a component: b component = 95 (wt%): 5 (wt%) to 70 (wt%): 30 (wt%) The composite powder according to any one of claims 1 to 7, wherein   The composite powder according to any one of claims 1 to 8, which is for an external composition for skin.   A composition for external skin application, which comprises the composite powder according to claim 1.   a) A method for enhancing the fluorescence intensity of an inorganic fluorescent powder, which comprises coating a part of the surface of the inorganic fluorescent powder with b) a non-fluorescent powder.