JP2023093715A - 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, an external composition for skin containing the same, and a method for enhancing the fluorescence intensity of the inorganic fluorescent powder.

Cosmetics contain various powders depending on the purpose. Especially in makeup cosmetics and sunscreen cosmetics, powders are generally used to impart effects such as luster, soft focus, color correction, and UV protection.

Among powders, fluorescent powders are generally used for applications such as displays, lighting, playground equipment and paints, and are also used in cosmetics for the purpose of enhancing the makeup effect. For example, by using fluorescent powder in cosmetics, it is possible not only to impart soft focus properties, but also to impart color correction effects using fluorescent colors.

Patent Literature 1 discloses a cosmetic having improved soft focus properties by containing an aluminate composite oxide, which is an inorganic fluorescent powder. Patent Document 2 discloses a blue fluorescent powder containing amorphous silica particles, and also describes its application to cosmetics. However, since the fluorescent powders described in Patent Documents 1 and 2 do not have sufficient luminous intensity, it was necessary to increase the amount of the powders to be effective as cosmetics. In addition, since these fluorescent powders have a high soft-focus property, they are not suitable for cosmetics intended to enhance glossiness.

Under such circumstances, techniques have been developed to enhance the makeup effect by increasing the fluorescence intensity of fluorescent powders. For example, Patent Literature 3 discloses a cosmetic in which an inorganic fluorescent powder and other powder are contained to effectively increase the luminous intensity. However, with the technique described in this document, the effect of enhancing the fluorescence intensity of the fluorescent powder may be insufficient.

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

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

JP 2014-5255 A JP 2016-141780 A International Publication No. 2017/142057 JP 2015-113306 A JP 2011-236137 A

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

As a result of intensive studies aimed at solving the above problems, the present inventors have found that the fluorescence intensity is enhanced by coating at least part of the surface of the inorganic fluorescent powder with a non-fluorescent powder.

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

[1] A composite powder, characterized in that at least a) part of the surface of an inorganic fluorescent powder is coated with b) a non-fluorescent powder.
[2] a) The composite powder according to [1], wherein the fluorescence 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 contains Al (aluminum), Zn (zinc), Mg (magnesium), Si (silicon), Mn (manganese), Ca (calcium), Ti as a crystal matrix and/or an activator. (titanium), Ce (cerium), Ba (barium), O (oxygen), P (phosphorus), and S (sulfur). The composite powder according to [1] or [2].
[4] a) the inorganic phosphor powder is 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 [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 [ 1] The composite powder according to any one of [4].
[6] a) The composite powder according to any one of [1] to [5], wherein the inorganic fluorescent powder has a particle size of 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 a) inorganic fluorescent powder and b) non-fluorescent powder in the composite powder is a component: b component = 95 (% by weight): 5 (% by weight) to 70 (% by weight): 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 used as a composition for external use on skin.
[10] A composition for external use on the 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, which comprises a) covering part of the surface of the inorganic fluorescent powder with b) a non-fluorescent powder.

According to the present invention, by forming a composite powder in which at least a part of the surface of a) an inorganic fluorescent powder is coated with b) a non-fluorescent powder, a) the fluorescence intensity of the inorganic fluorescent powder is remarkably improved. can be made In addition, the composite powder of the present invention, in which at least part of the surface of a) the inorganic fluorescent powder is coated with b) the non-fluorescent powder, exhibits excellent luminescence. A cosmetic having a high makeup effect can be provided.

1 is a scanning electron microscope image of the inorganic fluorescent composite powder of Example 1. FIG. 4 is a scanning electron microscope image of the inorganic fluorescent powder mixture of Comparative Example 2. FIG.

The present invention will be described in detail below. In addition, the terms used in this specification are interpreted as meanings commonly used in the technical field unless otherwise specified.

Also, % used in this specification refers to % by weight unless otherwise specified.

<Composite powder>
The composite powder of the present invention is characterized in that at least part of the surface of a) inorganic fluorescent powder is covered with b) non-fluorescent powder. Here, the term “coated” means that a) at least part of the surface of the inorganic fluorescent powder is covered with b) the non-fluorescent powder, and a) part of the surface of the inorganic fluorescent powder is covered. The case a) includes both cases in which 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, even more preferably 50% or more.

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

As a method for 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 covered with the non-fluorescent powder are imaged. The coverage ratio of each composite powder is calculated by the above formula, and the average value of the coverage ratios of a plurality of composite powders can be used as the coverage ratio of the composite powder in the present invention.

The a) inorganic fluorescent powder used in the present invention is not limited in shape and size as long as it is an inorganic powder having fluorescent properties.

a) The inorganic fluorescent powder may be any inorganic powder having fluorescent properties, and even an inorganic fluorescent powder that is a single crystal matrix and does not contain an activator having fluorescent properties is composed of a crystal matrix and an activator (impurity). Activated phosphors may also be used. The crystal matrix in this specification may be a crystalline or amorphous. In addition, it may or may not contain other activators, etc., and even when it does not contain activators, etc., it is used in the same sense as the commonly used crystalline and amorphous bodies. Examples of the crystal matrix include metal oxides, phosphoric acid compounds, metal sulfides, metal sulfates, halophosphoric acid compounds, etc. Metal oxides and phosphoric acid compounds are preferred.

The crystal matrix of 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). Among them, it is selected from Al (aluminum), Zn (zinc), Mg (magnesium), Ca (calcium), Ti (titanium), Ba (barium), O (oxygen), P (phosphorus), and S (sulfur). It preferably contains one or more elements, particularly O (oxygen) and / or P (phosphorus), and Al (aluminum), Zn (zinc), Mg (magnesium), Ca (calcium ), Ti (titanium), and Ba (barium).

Activators for a) inorganic fluorescent powder containing the activator used in the present invention include Mn (manganese), Eu (europium), Cr (chromium), Ce (cerium), Pr (praseodymium), and 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 to these.

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

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

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

Commercially available inorganic fluorescent powder a) used in the present invention includes, for example, Lumate R (manufactured by Sakai Chemical Industry Co., Ltd.), Lumate G (manufactured by Sakai Chemical Industry Co., Ltd.), Lumate B (manufactured by Sakai Chemical Industry Co., Ltd.), and the like. Examples include, but are not limited to, these.

The particle size of a) the 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. In addition, a) the particle size of the inorganic fluorescent powder is 300 μm or less, preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. The particle size of the a) inorganic fluorescent powder used in the present invention is preferably 1 μm or more and 200 μm or less from the viewpoint of obtaining sufficient fluorescence intensity and excellent feeling of use when used in cosmetics and the like. It is preferably 2 μm or more and 100 μm or less, more preferably.

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

The b) non-fluorescent powder used in the present invention is not particularly limited as long as it does not have fluorescent properties, and may be inorganic powder or organic powder, and its shape and size are not limited.

Inorganic powders 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, granite, konjo, carbon black, calcium carbonate, magnesium carbonate, silicone, magnesium silicate, magnesium aluminum silicate, boron nitride, etc., but particularly limited to these not.

Commercially available inorganic powders include, for example, MP-1133AQ (manufactured by Tayca), MP-1133WP (manufactured by Tayca), MT-100WP (manufactured by Tayca), MT-100SA (manufactured by Tayca), and MT-500B. (manufactured by Tayca), MZ-300 (manufactured by Tayca), MTZ-3040TSW (manufactured by Tayca), MZ-500 (manufactured by Tayca), FINEX-30 (manufactured by Sakai Chemical Industry), FINEX-50 (Sakai Chemical Kogyo Co., Ltd.), FINEX-30W (manufactured by Sakai Chemical Industry Co., Ltd.), FINEX-50W (manufactured by Sakai Chemical Industry Co., Ltd.), FINEX-50W-LP2 (manufactured by Sakai Chemical Industry Co., Ltd.), AEROSIL 200 (manufactured by Nippon Aerosil Co., Ltd.), AEROSIL Alu C (manufactured by Nippon Aerosil Co., Ltd.), LL-100HP (manufactured by Titan Kogyo Co., Ltd.), R-516HP (manufactured by Titan Kogyo Co., Ltd.), BL-100HP (manufactured by Titan Kogyo Co., Ltd.), Sericite FSE (manufactured by Sanshin Koko Co., Ltd.), Silica microbeads P-1500 (manufactured by Nikki Shokubai Kasei Co., Ltd.), KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.), KSP-300 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned, but not limited thereto.

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

Commercially available organic powders include, for example, Ganzpearl GMX-0610 (manufactured by Aica Kogyo Co., Ltd.), Ganzpearl GMX-0610AQ (manufactured by Aica Kogyo Co., Ltd.), SP-500 (manufactured by Toray Industries, Inc.), Ceramide I (manufactured by Evonik Co., Ltd.). ), Ceramide III (manufactured by Evonik), Ceramide VI (manufactured by Evonik), Phytopresome Care-V (manufactured by Nippon Fine Chemical Co., Ltd.), Ceramide TIC-001 (manufactured by Takasago International Corporation), SLP-PC70 (manufactured by Tsuji Oil Co., Ltd. ), SLP-PC92H (manufactured by Tsuji Seiyu Co., Ltd.), NIKKOL Resinol 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 these, metal oxides, metal hydroxides and silicic oxides are preferred. Further, metal oxides and silicic oxides are preferred, and titanium oxide, non-fluorescent zinc oxide, iron oxide, aluminum oxide (alumina) and silica are particularly preferred.

In addition, the particle size of the b) 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 fine particles of 100 nm or less. It is more preferable to have In addition, 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 improve the adhesion between the powders or increase the fluorescence intensity of the obtained composite powder depending on the combination of the powders to be composited. For the purpose of, for example, increasing the This surface treatment may be performed on each powder before being combined, or may be performed on the resulting composite powder.

Types of substances used for surface treatment include silica, alginic acid, aluminum oxide (alumina), POE/dimethicone copolymer, polyethylene glycol, aluminum hydroxide, amino acids, metal soap, perfluoroalkylethyl phosphate, diethanolamic acid. , fluorine alkyl acrylate/polyalkylene glycol acrylate polymer, perfluoropolyether phosphate, anionic or cationic polymer having perfluoropolyether chain, hydrogenated lecithin, acylated amino acid, α-tocopherol phosphate acid, methyl Hydrogenpolysiloxane, α-monoalkoxypolydimethylsiloxane, α-dialkoxypolydimethylsiloxane, triethoxysilylethylpolydimethylsiloxyethyldimethicone, amodimethicone, triethoxycaprylylsilane, aminopropyltriethoxysilane, perfluorooctylethyl Examples include, but are not limited to, triethoxysilane, perfluorooctyltriethoxysilane, and the like. 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.

In addition, a) the inorganic fluorescent powder and/or b) the non-fluorescent powder may be subjected to a plurality of surface treatments. The method is also not particularly limited.

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

Although the method for preparing the composite powder in the present invention is not particularly limited, wet processing is preferred.

In the wet treatment, it is preferable to disperse a) inorganic fluorescent powder and b) non-fluorescent powder in a dispersion medium, and b) coat at least part of the surface of a) inorganic fluorescent powder with non-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/disintegrating force. , disper mixers, bead mills, colloid mills, roller mills, three-roller mills, stamp mills, rod mills, ball mills, jaw crushers, kneaders, planetary mixers, etc., but are not particularly limited to these. I do not care.

In addition, steps such as filtration, centrifugation and drying may be applied. The drying method is also not particularly limited. The obtained composite powder may be used as a dispersion, a paste, or as a powder.

The dispersion medium used in the wet treatment is not particularly limited, and includes water, alcohol, hydrocarbon oil, ester oil, silicone oil, organic solvent, etc., and the dispersion medium contains components such as surfactants, salts, and chelating agents. You may let

The dispersion medium used in the wet treatment is preferably a hydrophilic dispersion medium, and preferably contains at least water, for reasons such as improving adhesion between powders.

The weight ratio of a) inorganic fluorescent powder and b) non-fluorescent powder in the composite powder of the present invention is appropriately adjusted depending on the respective shapes and sizes of a) inorganic fluorescent powder and b) non-fluorescent powder. However, component a (% by weight): component b (% by weight) is preferably 95:5 to 70:30, and more preferably 90:10 to 70:30. Moreover, the above ratio may be, for example, the ratio of the charged amount (% by weight) of the components a) and b) when preparing the composite powder.

Since the composite powder of the present invention has a strong fluorescence intensity, it can be suitably used for external skin compositions such as various forms of cosmetics. In addition, it can be suitably used in the fields of lighting, playground equipment, paint, etc., where fluorescence can be utilized.

<Composition for external use on the skin>
The composition for external use of the present invention contains the composite powder of the present invention described above. Since the composite powder of the present invention exhibits high fluorescence intensity, excellent luminescence and color correction effect, the composition for external use on the skin containing it has a make-up effect that makes scars inconspicuous, adjusts skin tone, and has a makeup effect. For the purpose of imparting In particular, it can be suitably used as a cosmetic product because of its excellent makeup effect.

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 wt % or less, more preferably 0.01 wt % or more and 10 wt % or less, and particularly preferably 0.01 wt % or more and 5 wt % or less.

The external composition for skin of the present invention may contain other ingredients in addition to the composite powder of the present invention within a range that does not impair the effects of the present invention.

Other ingredients include oils, lipophilic nonionic surfactants, hydrophilic nonionic surfactants, other surfactants, sequestering agents, natural water-soluble polymers, semi- 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 their Derivatives, amino acids or derivatives thereof, cleansing ingredients, keratin softening ingredients, cell activating ingredients, anti-aging ingredients, blood circulation promoting ingredients, whitening ingredients, ingredients that prevent and/or repair DNA damage, anti-inflammatory ingredients, anti-inflammatory ingredients, Other ingredients such as oxidizing ingredients, vitamins, sebum-adsorbing ingredients, and antibacterial ingredients may be included as long as the effects of the present invention are not impaired. In the composition for external use on skin of the present invention, these components may be blended singly or in combination of two or more. These components are not particularly limited as long as they can be used in the fields of pharmaceuticals, quasi-drugs, cosmetics, and the like, and arbitrary components can be appropriately selected and used.

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

The method for producing the composition for external use on the skin of the present invention is not particularly limited. can be manufactured by

Specific uses of the external composition for skin of the present invention include, for example, basic cosmetics such as lotions, moisturizing liquids, milky lotions, serums, packs, hand creams, body lotions, body creams, and lip balms; cleansing cosmetics such as makeup remover and body shampoo; makeup cosmetics such as foundation, makeup base, eye color, eye shadow, eyeliner, eyebrow, highlighter, control color, blush, mascara, lipstick, face powder; It can be used for cosmetics such as sunscreen cosmetics. In addition, multifunctional preparations in which the functions of these cosmetics are integrated into one preparation are also included. Furthermore, it can also be used for pharmaceuticals and quasi-drugs such as ointments for wounds and external preparations for acne.

Among them, makeup cosmetics such as foundations, makeup bases, eye colors, eye shadows, eyeliners, eyebrows, highlights, control colors, cheeks, mascara, lipsticks, and face powders; preferable.

<Method for Enhancing Fluorescence Intensity of Inorganic Fluorescent Powder>
The present invention also includes a method for enhancing the fluorescence intensity of an inorganic fluorescent powder, which comprises a) coating a portion of the surface of the inorganic fluorescent powder with b) a non-fluorescent powder. In addition, the composite powder of the present invention obtained by coating a part of the surface of a) an inorganic fluorescent powder with b) a non-fluorescent powder exhibits excellent luminescence. , a cosmetic having a higher makeup effect can be provided. In the method for enhancing the fluorescence intensity of inorganic fluorescent powders, a) inorganic fluorescent powders and b) non-fluorescent powders, and specific explanations of composite powders prepared using these are referred to as "composite powders". The explanations in section 3.1.2.1 apply.

Next, examples of composite powders in which a) at least part of the surface of inorganic fluorescent powders is coated with b) non-fluorescent powders will be described in detail, but the present invention is limited to these examples. isn't it.

(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 and sufficiently dispersed with a disper mill to obtain an oxidized (Al/Ca/manganese) aqueous dispersion. Next, 0.5 g of alumina-treated fine titanium oxide particles (acicular, particle size: 15 nm, aluminum hydroxide treatment: 6%) was added to 49.5 g of water and sufficiently dispersed using a disper mill to obtain an aqueous dispersion of alumina-treated fine titanium oxide particles. got Alumina-treated fine-particle titanium oxide aqueous dispersion was mixed with oxidized (Al/Ca/manganese) aqueous dispersion, and after being sufficiently dispersed with a disper mill, the mixture was filtered and dried at 60° C. overnight. After drying, the aggregate was pulverized with a mill grinder to obtain an inorganic fluorescent composite powder.

(Comparative example 1)
4.5 g of 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) and alumina-treated fine titanium oxide (Acicular, particle diameter 15 nm, aluminum hydroxide treatment 6%) 0.5 g 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, after 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 as FIG. 1 (Example 1) and FIG. 2 (Comparative Example 2).

Comparing FIG. 1 and FIG. 2, it is clear that 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 covered.

<Test 1 Evaluation of fluorescence intensity>
Double-sided tape was attached to a plate (50 mm×50 mm HELIOPLATE HD6, manufactured by HelioScreen Labs), and the sample was evenly applied with a brush. Using a spectrogonometric 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°, and the reflection intensity of the regular reflection angle was measured. With respect to the intensity at the fluorescence wavelength of the a) component, the intensity at the fluorescence wavelength of each sample was compared, taking the intensity of the a) inorganic fluorescent powder alone as 1.

Comparative Example 2: Comparison of reflection intensity at a fluorescence wavelength of 660 nm between a) inorganic fluorescent powder alone and Comparative Example 1: simple mixture of a) inorganic fluorescent powder and b) non-fluorescent powder, a) inorganic fluorescent powder Fluorescence intensity increased about 9 times by simply mixing the solid and b) the non-fluorescent powder. Example 1: Composite powder of a) inorganic fluorescent powder and b) non-fluorescent powder showed about 14 times the intensity of Comparative Example 1, and it was confirmed that the fluorescence intensity further increased by compositing. .

Further, when the fluorescence intensity is compared between the fluorescence wavelength (660 nm) and the fluorescence wavelength (400 nm), the fluorescence intensity increases more at the fluorescence wavelength (660 nm), and the fluorescence wavelength of component a) , a more significant increase in strength was confirmed. The fluorescence intensity at a fluorescence wavelength of 660 nm was significantly enhanced, resulting in a reddish powder.

(Example 2)
0.95 g of 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 put into 49.05 g of water. , and a disper mill to obtain an oxidized (Al/Ca/manganese) aqueous dispersion. Next, 0.05 g of alumina-treated fine titanium oxide particles (acicular, particle size: 15 nm, aluminum hydroxide treatment: 6%) was added to 49.9 g of water and sufficiently dispersed using a disper mill to obtain an aqueous dispersion of alumina-treated fine titanium oxide particles. got Alumina-treated fine-particle titanium oxide aqueous dispersion was mixed with oxidized (Al/Ca/manganese) aqueous dispersion, and after being sufficiently dispersed with a disper mill, the mixture was filtered and dried at 60° C. overnight. After drying, the aggregate was pulverized with a mill grinder to obtain an inorganic fluorescent composite powder.

(Example 3)
0.80 g of 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 put into 49.20 g of water. , and a disper mill to obtain an oxidized (Al/Ca/manganese) aqueous dispersion. Next, 0.20 g of alumina-treated fine titanium oxide particles (acicular, particle size: 15 nm, aluminum hydroxide treatment: 6%) was added to 49.80 g of water and sufficiently dispersed using a disper mill to obtain an aqueous dispersion of alumina-treated fine titanium oxide particles. got Alumina-treated fine-particle titanium oxide aqueous dispersion was mixed with oxidized (Al/Ca/manganese) aqueous dispersion, and after being sufficiently dispersed with a disper mill, the mixture was filtered and dried at 60° C. overnight. After drying, the aggregate was pulverized with a mill grinder to obtain an inorganic fluorescent composite powder.

(Example 4)
0.70 g of 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 put into 49.30 g of water. , and a disper mill to obtain an oxidized (Al/Ca/manganese) aqueous dispersion. Next, 0.30 g of alumina-treated fine titanium oxide particles (acicular, particle size: 15 nm, aluminum hydroxide treatment: 6%) was added to 49.70 g of water and sufficiently dispersed by a disper mill to obtain an aqueous dispersion of alumina-treated fine titanium oxide particles. got Alumina-treated fine-particle titanium oxide aqueous dispersion was mixed with oxidized (Al/Ca/manganese) aqueous dispersion, and after being sufficiently dispersed with a disper mill, the mixture was filtered and dried at 60° C. overnight. After drying, the aggregate was pulverized with a mill grinder to obtain an inorganic fluorescent composite powder.

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

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

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

(Example 7)
Silica-treated oxidation (Al/Ca/manganese) of Example 4 was changed to silica-treated oxidation (Al/Ca/manganese) with a particle size of 10 μm (plate-like, particle size of 10 μm, aluminum hydroxide treatment of 4.5%, then silica treatment 3.0% (fluorescence wavelength: 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, after aluminum hydroxide treatment 4.5%, silica treatment 3.0%, fluorescence wavelength 660 nm) was used.

The fluorescence intensities of Examples 5 to 7 subjected to the compounding treatment were compared, with the intensity of Comparative Example 3 (a) inorganic fluorescent powder before compounding being set to 1. Table 3 shows the results.

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

Further, even when the particle size of the component a) was changed (Examples 5 to 7), it was confirmed that the fluorescence intensity was enhanced by the complexing. Especially when a:b was 90:10 to 70:30, the fluorescence intensity increased remarkably.

(Example 8)
Silica-treated oxidation (Al/Ca/manganese) in Example 1 was changed to alginic acid-treated oxidation (Al/Ca/manganese) (plate-like, particle size 40 μm, alginic acid treatment 3%, fluorescence wavelength 660 nm), inorganic fluorescent composite powder got a body

(Example 9)
Inorganic composite powder was obtained by replacing the alumina-treated fine titanium oxide particles of Example 8 with silica-treated fine titanium oxide particles (acicular, particle size: 15 nm, silica treatment: 30%).

(Example 10)
An inorganic fluorescent composite powder was obtained by replacing the alumina-treated fine particulate titanium oxide of Example 1 with alumina (substantially spherical, particle size: 13 nm, no surface treatment).

(Example 11)
Silica-treated oxidation (Al/Ca/manganese) in Example 1 was changed to alginic acid-treated oxidation (Al/Ca/manganese) (plate-like, particle size 40 μm, alginic acid treatment 1%, fluorescence wavelength 660 nm), and alumina-treated fine particles. An inorganic fluorescent composite powder was obtained by replacing titanium oxide with silica (substantially spherical, particle diameter 12 nm, no surface treatment).

(Example 12)
Silica-treated oxidation (Al/Ca/manganese) in Example 3 was changed to alginic acid-treated oxidation (Al/Ca/manganese) (plate-like, particle size: 40 μm, alginic acid treatment: 1%, fluorescence wavelength: 660 nm), and alumina-treated microparticles Titanium oxide was changed to silica-treated pigment-grade titanium oxide (substantially spherical, particle size: 250 nm, treated with Al hydroxide at 2.6%, then treated with silica at 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 zinc oxide particles (substantially spherical, particle size 35 nm, triethoxycaprylylsilane treatment of 3.6%, followed by polyoxyethylene/methylpolysiloxane copolymerization). 10.0%) to obtain an inorganic fluorescent composite powder.

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

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

Table 4 shows the results of comparing the inorganic fluorescent composite powder obtained in each example with the uncombined a) inorganic fluorescent powder with a fluorescence intensity of 1 (Examples 8 and 9 are compared The strength ratio was determined in Comparative Example 2 for Example 4, Example 10, and Comparative Example 5 for Examples 11 to 13).

(Example 14)
The silica-treated oxidation (Al/Ca/manganese) in 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) in 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 was changed to silica-treated fine particle titanium oxide ( needle shape, particle diameter 15 nm, silica treatment 30%) to obtain an inorganic fluorescent composite powder.

(Example 16)
Silica-treated oxidation (Al/Ca/manganese) in Example 1 was changed to oxidation (Mg/manganese/titanium) (Lumate R (manufactured by Sakai Chemical Industry Co., Ltd., maximum fluorescence wavelength 660 nm)), and alumina-treated fine particles of titanium oxide were treated with silica. Inorganic fluorescent composite powder was obtained by changing to fine particles of titanium oxide (acicular, particle size: 15 nm, silica treatment: 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, oxidation (Mg/manganese/titanium) (using Lumate R (manufactured by Sakai Chemical Industry Co., Ltd., maximum fluorescence wavelength: 660 nm)) was used.

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

<Example of application to cosmetics>
Next, formulation examples of external skin compositions (cosmetics) containing the inorganic fluorescent composite powder are shown, but the present invention is not limited to these.

[powder foundation]
Ingredient name Amount [%]
Silicon treated talc Residual fluorine treated sericite 5
Siliconized pigment grade titanium oxide 5
Siliconized microparticle titanium dioxide 5
boron nitride 3
(vinyl dimethicone/methicone silsesquioxane) crosspolymer 2
Nylon powder 1
Mg stearate 1
Inorganic fluorescent composite powder of Example 1 3
Methylphenylpolysiloxane 7
2-ethylhexyl p-methoxycinnamate 5
bisethylhexyloxyphenol methoxyphenyltriazine 1
Sorbitan isostearate 0.5
Appropriate amount of coloring pigment
Appropriate amount of antiseptic
Total 100

A powder foundation with excellent makeup effect was obtained.

[Loose powder]
Ingredient name Amount [%]
Silicon treated talc Residual fluorine treated sericite 5
Polymethylsilsesquioxane 7
Inorganic fluorescent composite powder of Example 1 5
Siliconized pigment grade titanium dioxide 3
Mica Titanium 3
Appropriate amount of coloring pigment
Appropriate amount of antiseptic
Total 100

[Makeup base]
Ingredient name Amount [%]
Water Balance BG 10
1,3-pentanediol 1
Xanthan gum 0.1
Hydroxypropyl methylcellulose 0.2
(Hydroxyethyl acrylate/Na acryloyldimethyltaurate) copolymer
0.5
Polysorbate 60 1.5
Glyceryl stearate 1.5
2-Ethylhexyl p-methoxycinnamate 8
Isostearic acid treated fine zinc oxide 2
Hexyl diethylaminohydroxybenzoate 3
isononyl isononanoate 3
Methyl polysiloxane 3
Inorganic fluorescent composite powder 1 of Example 3
Mica Titanium 1
Appropriate amount of coloring pigment
Appropriate amount of antiseptic
Total 100

A makeup base with excellent makeup effect was obtained.

[sunscreen]
Ingredient name Amount [%]
Cyclopentasiloxane Residual methylphenylpolysiloxane 5
2-Ethylhexyl p-methoxycinnamate 6
bisethylhexyloxyphenol methoxyphenyltriazine 3
isononyl isononanoate 7
Siliconized fine 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
Appropriate amount of antiseptic
Total 100

A sunscreen with excellent make-up effect was obtained.

ADVANTAGE OF THE INVENTION According to this invention, the composite powder which remarkably improved the fluorescence intensity which an inorganic fluorescent powder originally has can be provided. In addition, since the composite powder of the present invention exhibits excellent luminescence, it is possible to provide various forms of cosmetics with higher makeup effects by including the composite powder in cosmetics. Furthermore, it can be used not only in cosmetics but also in the fields of lighting, playground equipment, paints, and the like.

Claims (11)

A composite powder comprising: a) at least part of the surface of an inorganic fluorescent powder, b) coated with a non-fluorescent powder. a) The composite powder according to claim 1, wherein the fluorescence wavelength of the inorganic fluorescent powder is in the range of 440 nm to 520 nm or 640 nm to 700 nm. a) The inorganic fluorescent powder contains Al (aluminum), Zn (zinc), Mg (magnesium), Si (silicon), Mn (manganese), Ca (calcium), Ti (titanium) as a crystal matrix and/or an activator , Ce (cerium), Ba (barium), O (oxygen), P (phosphorus), and S (sulfur). Or the composite powder according to 2. a) At least one inorganic fluorescent powder 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, characterized in that 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. 5. The composite powder according to any one of 4. a) The composite powder according to any one of claims 1 to 5, wherein the inorganic fluorescent powder has a particle size of 1 µm or more and 200 µm or less. b) The composite powder according to any one of claims 1 to 6, wherein the non-fluorescent powder has a particle size of 1 nm or more and 100 nm or less. The ratio of a) inorganic fluorescent powder and b) non-fluorescent powder in the composite powder is a component: b component = 95 (% by weight): 5 (% by weight) to 70 (% by weight): 30 (% by weight) The composite powder according to any one of claims 1 to 7, characterized in that The composite powder according to any one of claims 1 to 8, which is used as a composition for external use on the skin. A composition for external use on the skin, containing the composite powder according to any one of claims 1 to 9. A method for enhancing the fluorescence intensity of an inorganic fluorescent powder, which comprises a) coating a part of the surface of the inorganic fluorescent powder with b) a non-fluorescent powder.

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