JPWO2017142057A1 - Skin external composition - Google Patents

Abstract

An object of the present invention is to provide a novel composition for external use on the skin, which further improves the color developability (luminescence) in the composition for external use containing an inorganic phosphor.
The present invention contains (A) powder and (B) inorganic phosphor, and the content of (B) inorganic phosphor is 0.0001 to 9.5% by mass with respect to the entire composition.
It is a composition for external use on the skin. (A) The shape of the powder is preferably plate-shaped or spherical. The (A) powder is more preferably at least one selected from the group consisting of talc, boron nitride, mica, pearl pigment, silicone resin, alkyl polyacrylate, urethane, nylon, and silica.

Description

  The present invention relates to an external composition for skin.

  In general, makeup powders are formulated with various powders for application to the skin to change the texture. For example, in order to cover the dullness of the skin, the hue of the skin is changed using a pigment such as titanium dioxide or iron oxide, a lake pigment or an organic pigment. A pearl pigment such as interference pearl is also used to change the hue of the skin. However, it cannot be said that the effect of changing the skin hue sensation of cosmetics containing the pigments or interference pearls is sufficient (see Patent Document 1).

  In recent years, cosmetics excellent in color developability, in which inorganic phosphors such as specific aluminate complex oxides are blended, have been developed (see Patent Document 2). Since this aluminate complex oxide has higher safety and better color developability than conventional inorganic phosphors, it is expected to be used for various makeup cosmetics, sunscreens and the like.

JP 2002-338424 A International Publication No. 2015/166895

  An object of the present invention is to provide a novel external composition for skin, which further improves the color developability (luminance) in an external composition containing an inorganic phosphor.

  As a result of intensive studies to solve the above problems, the present inventor has enhanced the luminescence intensity of a composition containing an inorganic phosphor by blending powder and an inorganic phosphor in a composition for external use on the skin. I found out that I can.

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

[1] A composition for external use of skin containing (A) powder and (B) inorganic phosphor, and the content of (B) inorganic phosphor is 0.0001 to 9.5% by mass with respect to the entire composition. object.
[2] The external composition for skin according to [1], wherein (A) the powder has a plate shape or a spherical shape.
[3] (A) The powder is at least one selected from the group consisting of talc, boron nitride, mica, pearl pigment, silicone resin, alkyl polyacrylate, urethane, nylon, and silica. [1] Or the composition for external use of skin as described in [2].
[4] (A) Powder is talc, boron nitride, synthetic phlogopite, titanium oxide-coated mica, titanium oxide-coated synthetic phlogopite, titanium oxide-treated mica, titanium oxide-treated talc, (dimethicone / vinyl dimethicone) crosspolymer, Polymethylsilsesquioxane, (diphenyldimethicone / vinyldiphenyldimethicone / silsesquioxane) crosspolymer, (vinyldimethicone / methiconesilsesquioxane) crosspolymer, methylmethacrylate crosspolymer, nylon-12, (HDI / tri The external composition for skin according to any one of [1] to [3], which is at least one selected from the group consisting of (methylolhexyl lactone) crosspolymer and silica.
[5] The external composition for skin according to any one of [1] to [4], wherein (A) the powder comprises a spherical or plate-like powder having a particle size of 5 μm to 300 μm.
[6] Any of [1] to [5], wherein the crystal matrix of (B) the inorganic phosphor includes a metal oxide of any of Al, Ti, Zn, Ge, Si, Fe, Zr, Mn, and Mg. Or a composition for external application to the skin.
[7] The external composition for skin according to [6], wherein (B) the inorganic phosphor is an aluminate phosphor or a titanate phosphor.
[8] The external composition for skin according to any one of [1] to [7], wherein the content of (A) powder is 0.0001 to 100 parts by mass with respect to 1 part by mass of (B) inorganic phosphor. object.
[9] The external composition for skin according to any one of [1] to [8], wherein the composition is for make-up, sunscreen, basic cosmetic, or washing.
[10] (B) A method for enhancing the fluorescence intensity of an external composition for skin containing an inorganic phosphor,
(A) Mixing powder, and (B) content of inorganic fluorescent substance in the whole external composition for skin to be 0.0001-9.5 mass%,
A method characterized by.

  The external composition for skin of the present invention contains (A) powder and (B) inorganic phosphor, so that even if the content of (B) inorganic phosphor is small, excellent color developability (light emitting property). ), It can be suitably used as cosmetics, especially makeup cosmetics such as foundations, eye shadows, and lipsticks, and cosmetics for sunscreen.

It is a figure which shows the emitted light intensity of the composition for external use of skin of embodiment of this invention. It is a figure which shows the emitted light intensity of the composition for external use of skin of embodiment of this invention.

  Hereinafter, the present invention will be described in detail.

[Skin external composition]
The external composition for skin of this invention contains (A) powder and (B) inorganic fluorescent substance. Moreover, the composition for external skin of this invention may contain another component in the range which does not impair the effect of this invention other than these essential components. Hereinafter, each of these components will be described.

<(A) Powder>
The (A) powder in the present invention has an effect of enhancing the light emission intensity of a composition containing the inorganic phosphor (B) described later, among those commonly used in ordinary cosmetics. As one of the reasons why the external composition for skin of the present invention is excellent in color developability (light emitting property), (B) the light emitted when the inorganic phosphor receives external energy such as ultraviolet rays hits the surface of (A) the powder. It is possible to cause irregular reflection. From such a viewpoint, for example, (B) a substance that hardly absorbs light emitted from an inorganic phosphor or a structure in which the powder surface easily causes irregular reflection is preferable as the (A) powder in the present invention. In addition, in this invention, color development means the property in which the color of the composition for external use of skin appears. The color includes not only general colors but also colors that emit light such as fluorescent colors. The light emitting property refers to a property of emitting light such as fluorescence, and is a concept partially shared with the color developing property and affects the color developing property.

  (A) The shape of the powder is not particularly limited as long as it can enhance the emission intensity of the composition containing (B) the inorganic phosphor. For example, the shape is spherical, plate-like, needle-like, spindle-like, hemispherical Etc. (B) From the viewpoint of the effect of enhancing the emission intensity of the composition containing the inorganic phosphor, spherical and plate-like powders are preferable.

  (A) Examples of the powder include spherical or plate-like organic powders such as polymer compounds and organic pigments; spherical inorganic powders such as silica; and plate-like inorganic powders such as mica, talc and boron nitride. A plate-like powder such as a pearl pigment;

  Furthermore, the particle diameter of (A) powder is not particularly limited as long as it is a size that can enhance the emission intensity of the composition containing (B) inorganic phosphor, but as an example, it is 1 μm or more, preferably 2 μm or more, more preferably May be 3 μm or more, more preferably 4 μm or more, and particularly preferably 5 μm or more. (A) Although the upper limit of the particle diameter of the powder is not particularly limited, as an example, it may be 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and particularly preferably 20 μm or less. In particular, when (A) the powder is spherical, the light emission intensity of the composition containing (B) the inorganic phosphor can be more effectively increased by selecting and using one having a particle diameter of 5 μm or more. It has been confirmed that

(Organic powder)
Examples of the organic powder include polymer compounds and organic pigments.

  Examples of the polymer compound include thermoplastic resins such as silicone resin (silicone powder), polyalkyl acrylate, nylon, urethane, styrene resin, polyolefin, fluororesin, and polyester; thermosetting resins such as epoxy resin and phenol resin. Examples thereof include spherical powders of organic polymers such as resins. Of these organic polymer spherical powders, (B) silicone resin (silicone powder), polyalkyl acrylate, nylon and urethane are preferred from the viewpoint of enhancing the light emission intensity of the composition containing the inorganic phosphor (B). .

  Examples of silicone resins include silicone elastomers such as (dimethicone / vinyl dimethicone) crosspolymers; silicone powders such as polymethylsilsesquioxane (also referred to as a methylsiloxane network polymer); (diphenyldimethicone / vinyldiphenyldimethicone / silsesquioxy). (San) cross polymer, silicone composite powder such as (vinyl dimethicone / methicone silsesquioxane) cross polymer, and the like.

  As the silicone resin, commercially available products may be used. For example, Trefil E506S (4 μm), EP-9215 Cosmetic Powder (4 μm), 9701 Cosmetic Powder (4 μm), EP-9801 (4 μm), Trefill E508 (4 μm), 9702 Powder (4 μm), EP-9289LL Cosmetic Powder (4 μm), BY29-129 (4 μm), PF-2001 PIF Emulsion (4 μm), 9546 Silicone Elastomer Blend, FB-9586 Silicone E ); Tospearl 145A (4.5 μm), Tospearl 150KA (5 μm), Tospearl 2000B (6 μm) Tospearl 3000A (6 μm), Tospearl 1100A (11 μm) (made by Momentive Performance Materials Japan); KMP-591 (5 μm), KMP-599 (3 μm), KSP-100 (5 μm), KSP- 105 (2 μm), KSP-300 (5 μm), X-52-1621 (5 μm) (manufactured by Shin-Etsu Chemical Co., Ltd.); Gantz Pearl SI-045C (4.5 μm), Gantz Pearl SIG-070 (7 μm) ( As mentioned above, Aika Kogyo Co., Ltd.) can be cited. Numbers in parentheses indicate particle size.

  The particle diameter of the silicone resin is preferably 3 μm or more and 30 μm or less, more preferably 3 μm or more and 20 μm or less, and even more preferably 5 μm or more and 20 μm or less. When a spherical silicone resin having an average particle size of 2 μm or less is used, the skin external composition of the present invention may cause creaking. Therefore, the average particle size of the silicone resin is preferably a size exceeding 2 μm. Moreover, it is more preferable that it is 5 micrometers or more from a viewpoint that the higher luminous enhancement effect can be anticipated.

  In the present invention, “particle diameter” means any 250 primary particles in an image from a 1,000 times image with a scanning electron microscope (manufactured by JEOL Ltd., JSM840F) unless otherwise specified. The average value (average primary particle diameter) of the values measured on the basis of the major axis of the particles.

  Polyalkyl acrylate is a monomer constituting at least one (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. May be included. Moreover, polyalkyl acrylate may contain the hydrocarbon-type monomer which has carbon-carbon unsaturated bonds other than (meth) acrylic acid ester as a structural monomer. Specific examples of hydrocarbon monomers having a carbon-carbon unsaturated bond include acrylic acid, methacrylic acid, styrene, methylstyrene, vinyltoluene, vinyl acetate, acrylonitrile, vinyl chloride, vinylidene chloride, chloroprene, isoprene, butadiene, and acrolein. Acrylamide, allyl alcohol, vinyl pyridine, vinyl benzoate, allyl benzoate and the like. In addition, the monomer which alkyl acrylate contains is not restricted to 1 type, You may contain 2 or more types as a structural monomer.

  Polyalkyl acrylates include those having a crosslinked structure and those having no crosslinked structure, but those having a crosslinked structure are preferred. The crosslinked structure can be prepared by appropriately utilizing a known method used for polyalkyl acrylate polymers. Examples of the crosslinking agent include divinylbenzene, ethylene dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, allyl methacrylate, and trimethylolpropane trimethacrylate. Is mentioned.

  As the polyalkyl acrylate, cross-linked polymethyl methacrylate (also referred to as methyl methacrylate crosspolymer) is particularly preferable. In addition, there are commercially available powders of methyl methacrylate crosspolymer, for example, Gantzpearl GMX-0610 (6 μm), GMX-0810 (8 μm), GMX-0820 (8 μm), GMX-2001 (20 μm). (Above, manufactured by Aika Kogyo Co., Ltd.), Microsphere M-100 (5 to 20 μm), Microsphere M-305 (5 to 20 μm), Matsumoto Microsphere M-310 and Matsumoto Microsphere M-311 (above And Matsumoto Yushi Seiyaku Co., Ltd.). The numbers in parentheses indicate the particle size.

  As the particle diameter of the polyalkyl acrylate, the average primary particle diameter by microscopic observation is preferably 1 μm or more and 50 μm or less, more preferably 2 μm or more and 30 μm or less, and further preferably 3 μm or more and 30 μm or less. It is even more preferable that it is 5 μm or more and 30 μm or less.

  Examples of urethane include (HDI / trimethylol hexyl lactone) crosspolymer, PLASTIC POWDER D-400 (12 μm to 18 μm), D-800 (5.5 μm to 8.0 μm), CS-400 (12 μm to 18 μm) made of silica. ), D-400HP (12 μm to 18 μm) (manufactured by Toyo Pigment); GRANDPEARL GU-1500 (15 μm) (manufactured by Aika Kogyo Co., Ltd.), which is a cross polymer (HDI / trimethylolhexyl lactone). The numbers in parentheses indicate the particle size.

  Examples of nylon include nylon-12, SP-500 (manufactured by Dow Corning Toray) and GPA-550 (manufactured by Aika Industries). Both have a particle size of 5 μm.

(Inorganic powder)
Inorganic powders include spherical inorganic powders such as silica (including silicic anhydride, hydrous silicic acid, etc.); talc, mica, boron nitride, kaolin, muscovite, synthetic mica, phlogopite, red mica, biotite , Lithia mica, silicic acid, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hector Examples thereof include light, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, glass, and silylated silica. Among these, in the external composition for skin of the present invention, silica, mica, talc and boron nitride are preferable from the viewpoint of enhancing the luminescence intensity of the composition containing (B) the inorganic phosphor, and talc and boron nitride. Is more preferable.

  Specific examples of silicic acid anhydride among the silicas include, for example, SILICA MICRO BEAD P-500 (2 to 20 μm) (manufactured by JGC Catalysts & Chemicals), silica beads SB-150 (5 μm), silica beads SB, which are white silica. -300 (5 μm), silica beads SB-700 (7 μm), silica beads SBNP-810 (10 μm) (manufactured by Miyoshi Kasei Co., Ltd.), God Ball G-6C (3-5 μm) (manufactured by Suzuki Yushi Kogyo Co., Ltd.), etc. Is mentioned. Numbers in parentheses indicate particle size.

  Examples of the mica include PDM-5L (5.0 to 8.5 μm), PDM-10L (10 to 13 μm), PDM-20L (17 to 22 μm), PDM-40L (35 to 44 μm), and PDM-9WA. (10-13 μm), PDM-9WB (10-13 μm), PDM-10S (10-13 μm), PDM-1000 (10-13 μm), PDM-8W (10-13 μm), PDM-FE (5-8 μm) PDM-5L (S) (5.0 to 8.5 μm), PDM-10L (S) (10 to 13 μm), PDM-9WAT (10 to 13 μm), PDM-8W (S) (10 to 13 μm), Synthetic mica such as PDM-1000 (S), PDM-15NR (10-13 μm) (manufactured by Topy Industries, Ltd.); Y-1800 (10 μm), Y-3000 (23 μm), SA-3 10 (26 μm), SA-350 (42 μm), TM-10 (11 μm), TM-20 (18 μm), FA-450 (28 μm), NCC-322 (21 μm), NCF-322 (24 μm), AB-25S Natural mica such as (24 μm) (manufactured by Yamaguchi Mica Co., Ltd.) can be mentioned. The numbers in parentheses indicate the particle size. Among these, synthetic mica is preferable from the viewpoint of the effect of improving the color developability (luminance) of the external composition for skin of the present invention. Compared with natural mica, synthetic mica does not have a dull color of the raw material itself, and, for example, hardly changes in color of the powder itself when mixed with sweat or sebum. Therefore, by adding synthetic mica to the composition for external use of the present invention, it is possible to improve the color developability (luminance), and it is difficult for color change to occur when used on the skin, and the desired hue is maintained for a long time. Can be maintained.

  Examples of the talc include talc JA-46R (7.0 to 11.0 μm), talc MMR (4.4 μm or less), talc JA-13R (5.0 to 8.0 μm), talc JA-24R (6 0.0-9.0 μm), talc JA-68R (9.0-12.0 μm), talc JA-80R (10.0-14.0 μm), talc SW-special, talc SW-A (above, Asada Milling) Etc.). Further, the surface of talc may be treated with silicone or the like, and examples thereof include SA-talc JA-13R, SA-talc JA-46R, SA-talc JA-68R (manufactured by Miyoshi Kasei Co., Ltd.). The numbers in parentheses indicate the particle size.

  Examples of boron nitride include CC6058 (11 μm), CC6097 (5 μm), CC6059 (6 μm), CC6069 (9 μm), CCS102-JA (15 μm), CC6004 (11 μm) (above, manufactured by Momentive Performance Materials). , RonaFair Boroneige SF-3 (2-5 μm), RonaFair Boroneige SF-6 (4.5-8 μm), RonaFair Boroneige SF-9 (6-10.5 μm), RonaFlair BoronageR15 Boroneige SF-15 (9.5 μm or less) (above, manufactured by MERCK) and the like. The numbers in parentheses indicate the particle size.

(Pearl pigment)
The pearl pigment generally refers to a pigment obtained by coating the surface of a plate-like powder with a metal oxide (for example, a colored metal oxide). Depending on the thickness of the coating layer, only a specific color can be seen by thin film interference (interference type), or particles with a different refractive index (generally fine titanium oxide) are attached to the plate-like powder used as a substrate. There is a type that increases the amount of reflected light on the object surface. Further, there is a colored type in which the surface of the interference type is coated with a colored pigment such as iron oxide or an organic dye (for example, a tar dye).

  Examples of the plate powder include mica, mica, sericite, talc, kaolin, synthetic mica, synthetic sericite, synthetic phlogopite, borosilicate, plate titanium dioxide, plate silica, plate aluminum oxide, Examples thereof include boron nitride, barium sulfate, plate-like titania / silica composite oxide, and among these, mica and synthetic mica are preferable. Examples of the colored metal oxide include iron oxide, titanium oxide, copper oxide, cobalt oxide, chromium oxide, nickel oxide, gold, and silver. Among these, titanium oxide is preferable.

  The pearl pigment in the present invention has an average primary particle diameter of 1 μm to 300 μm, usually 2 μm to 300 μm, more preferably 10 μm to 200 μm, and even more preferably 2 μm to 150 μm, as observed with a microscope.

  The pearl pigment changes the brightness of the surface of the object by changing the refractive index of the surface of the substrate material depending on the thickness of the coating layer of the metal oxide (for example, colored metal oxide), and the color of the light is changed by thin film interference. Although it changes, as a pearl pigment which the composition for external use of the skin of the present invention contains silver or interference light, red, yellow, orange and gold are preferable. The pearl pigment in the present invention may be one that has been surface-treated with a silicone compound, a fluorine compound, an amino acid, a fatty acid, or the like.

  The manufacturing method of the pearl pigment in this invention is not specifically limited, It can manufacture by a method well-known to those skilled in the art. For example, it can be obtained by adding an aqueous solution of a colored metal oxide precursor to an aqueous dispersion of a plate-like powder and baking it. Furthermore, surface treatment may be performed with a silicone compound, a fluorine compound, an amino acid, a fatty acid, or the like. Preferred pearl pigments in the present invention include titanium oxide-coated mica, titanium oxide-coated synthetic phlogopite, titanium oxide-treated mica, and titanium oxide-treated talc. In addition, a pearl pigment can also use a commercial item. Commercially available pearl pigments include MERCK's Timiron series (interference type with titanium oxide coating), BASF's Flamenco series (interference type with titanium oxide coating) and Cloisonne series (coloring type with iron oxide or titanium oxide coating), There are FANTASPEARL series (silver type, titanium oxide-coated interference type, titanium oxide and iron oxide coloring type, iron oxide coloring type) manufactured by Nihon Koken Kogyo Co., Ltd. as commercial products of pigments that exhibit red interference light Are, for example, Flamenco Silk Red or SA-Flamenco Silk Red (manufactured by BASF; particle diameter 2-24 μm), Flamenco Spark Red (manufactured by BASF; particle diameter 16 μm to 128 μm), Helios R100R ( P. Industries, Ltd., but the particle diameter 35Myuemu～150myuemu), and the like as preferred but not limited to. Examples of commercially available silver pigments include, but are not limited to, Timilon MP-115 or SA-Timiron MP-115 (manufactured by MERCK; particle diameter of 10 to 60 μm). Commercially available pigments exhibiting yellow, gold, or orange interference light include SILSEEM Misty Pearl YELLOW (manufactured by Nippon Koken Kogyo Co., Ltd .; 5 to 20 μm), Timiron Silk Gold (manufactured by MERCK; 5 to 25 μm), RonaFlair Balance Gold (manufactured by MERCK; particle diameter of 15 μm or less), Flamenco Silk Orange (manufactured by BASF; particle diameter of 16 to 128 μm) and the like are preferable, but are not limited thereto.

  The content of the powder (A) in the external composition for skin of the present invention is not particularly limited as long as the effects of the present invention are exhibited. For example, the powder (A) is 0.0001 to 95 with respect to the entire composition. It is preferable to contain in the ratio of about mass%, and it is more preferable to contain in the ratio of about 0.001-90 mass%. Specifically, when the (A) powder is spherical, the (A) spherical powder is preferably contained in a proportion of 0.01 to 20% by mass with respect to the entire composition. It is more preferable to contain in the ratio of 05-15 mass%, and it is still more preferable to contain in the ratio of 0.1-10 mass%. When (A) powder is plate-shaped, it is preferable to contain (A) plate-shaped powder in the ratio of 0.001-80 mass% with respect to the whole composition, 0.01-70 It is more preferable to contain in the ratio of the mass%, and it is still more preferable to contain in the ratio of 0.1-50 mass%. By containing (A) powder with such a content, the composition for external use of the skin of this invention can show the high luminescence intensity more stably.

<(B) Inorganic phosphor>
The external composition for skin of the present invention contains (B) an inorganic phosphor, and emits red light when it receives external energy such as ultraviolet rays. Furthermore, since the emission intensity of red light emitted from the inorganic phosphor (B) is enhanced by including the powder (A) described above, even if the content of the inorganic phosphor (B) is small, The external composition for skin of the present invention exhibits excellent color development (luminescence).

(B) The inorganic phosphor is preferably an activated phosphor comprising a crystal matrix and an activator. The crystal matrix preferably contains a metal oxide, a metal sulfide, a metal sulfate, a halophosphate compound, or the like. Of these, metal oxides are preferred, and Al (aluminum), Ti (titanium), Zn (zinc), Ge (germanium), Si (silicon), Fe (iron), Zr (zirconium), Mn (manganese), A metal oxide of Mg (magnesium) is more preferable. Among these, metal oxides of Al (aluminum) and Ti (titanium) are more preferable.

  Examples of the activator 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), or the like is used.

(B) As the inorganic phosphor, CaAl ₁₂ O ₁₉ : Mn ⁴⁺ , CaAl ₁₂ O ₁₉ : Cr ³⁺ , Ca ₃ Al ₂ O ₆ : Eu ³⁺ , Ca ₃ (PO ₄ ) ₂ : Mn, NaCl: Mn, Mg ₂ TiO ₄ : red phosphors such as Mn and MnCl _2, and blue phosphors such as CaAl ₂ O ₄ : Eu ²⁺ and Ca ₁₂ Al ₁₄ O ₃₃ : Ce ^3+, and the skin external composition of the present invention is applied to the skin. From the viewpoint of the effect of brightening the skin when used, a red phosphor is preferable. Among these, aluminate phosphors such as CaAl ₁₂ O ₁₉ : Mn ⁴⁺ , CaAl ₁₂ O ₁₉ : Cr ³⁺ , Ca ₃ Al ₂ O ₆ : Eu ³⁺ ; and titanate phosphors such as Mg ₂ TiO ₄ : Mn are more suitable. preferable.

As the aluminate phosphor, calcium aluminate activated with manganese or europium is more preferable,
Following formula (1);
Ca _X Al _y O _{(2X + 3Y + 4Z) / 2} : Mn ⁴⁺ _Z (1)
Particularly preferred is calcium manganese aluminate activated with manganese represented by:

  In the formula, 0.1 <X <1.05, 11.9 <Y ≦ 12, and 0.0005 <Z <0.1.

The compound represented by the above formula (1) is a compound obtained by doping Mn ⁴⁺ into a compound represented by Ca _X Al _y O _{(2X + 3Y + 4Z) / 2} . CaAl ₁₂ O ₁₉ : Mn ⁴⁺ is a red phosphor developed in 1971 (eg, A. Bergstein et al, “Manganese-Activated Luminescence in Sr Al12 O19 and Ca Al12O19” J. Electrochem. Soc., 118 , p116 (1971))). Mn ⁴⁺ is reported to exhibit red emission near 657 nm by replacing the octahedral site of CaAl ₁₂ O ₁₉ .

  Moreover, as said titanate fluorescent substance, the magnesium titanate which activated manganese or europium is more preferable, and the magnesium titanate which activated manganese is especially preferable.

  From the viewpoint that X, Y, and Z in the above formula (1) are excellent in the effects of the present invention, X is more than 0.9 and more preferably less than 1.0. Z is more preferably greater than 0.001 and less than 0.05.

  (B) The particle diameter of the inorganic phosphor is preferably 1 μm to 100 μm, more preferably 1 to 50 μm, further preferably 1 to 20 μm, particularly preferably 1 to 15 μm, and particularly preferably 1 to 6 μm. By setting the particle diameter within this range, the usability of the external composition for skin of the present invention can be improved, and the color developability (luminance) can be made higher. In addition, as for (B) inorganic phosphor, “particle diameter” is an arbitrary value in the image from a 1,000 times image with a scanning electron microscope (JSM840F, manufactured by JEOL Ltd.) unless otherwise specified. The average value (average primary particle diameter) of the values measured on the basis of the major axis of the particles for 250 primary particles.

  (B) In addition to improving the color of the skin, the inorganic phosphor can be expected to have the effect of improving the blood flow of the skin and improving the complexion color because the emitted red light increases the gene expression of the vasodilator. An inorganic phosphor having a dominant wavelength in the region of 600 to 750 nm is preferable.

  (B) Although the manufacturing method of inorganic fluorescent substance is not specifically limited, For example, it aims at the compound (for example, manganese source compound) corresponding to the compound (for example, alkaline source metal etc.) which is a raw material, an aluminum source compound, and the doped ion. It can obtain by baking after making a precursor by mixing in the ratio according to the molar ratio of a compound.

  (B) The inorganic phosphor can be blended in the composition for external use as it is, but if necessary, it may be blended after various surface treatments are carried out by a conventionally known method.

  Moreover, these surface treatments may be one kind, and several kinds may be laminated or mixed.

  The external composition for skin of the present invention preferably contains (B) the inorganic phosphor in a proportion of 0.0001 to 9.5% by mass, and 0.001 to 9.5% by mass with respect to the entire composition. More preferably, 0.01 to 9.5% by mass is further preferable, 0.01 to 7% by mass is even more preferable, 0.01 to 5% by mass is particularly preferable, and 0.01 to 3% by mass is particularly preferable. . The blending ratio (mass ratio) of (A) powder and (B) inorganic phosphor is 0.0001 to 100 parts by mass of (A) powder with respect to 1 part by mass of (B) inorganic phosphor. It is preferably 0.0005 to 50 parts by mass. As an example, the blending ratio (mass ratio) of (A) powder to 1 part by mass of (B) inorganic phosphor may be 0.0001 to 20 parts by mass, or may be 0.001 to 10 parts by mass. The composition for external use of skin of this invention can improve color developability (luminescent property) more by containing (A) powder and (B) inorganic fluorescent substance with the said compounding ratio.

<Other ingredients>
The composition for external use of the skin according to the present invention comprises, in addition to the above essential components, an ultraviolet absorbing component, (B) inorganic particles other than the inorganic phosphor, oil, lipophilic nonionic surfactant, hydrophilic, depending on various purposes. Nonionic surfactants, other surfactants, sequestering agents, natural water-soluble polymers, semi-synthetic water-soluble polymers, synthetic water-soluble polymers, inorganic water-soluble polymers, gelled hydrocarbons Oily bases such as various extracts, moisturizing ingredients, polyhydric alcohols, scrubbing agents, UV scattering ingredients, astringent ingredients, peptides or derivatives thereof, amino acids or derivatives thereof, washing ingredients, keratin softening ingredients, cell activation ingredients Other components such as anti-aging component, blood circulation promoting component, whitening component, component having DNA damage prevention and / or repair activity, anti-inflammatory component, antioxidant component, vitamins, sebum adsorbing component, antibacterial component, etc. , The present invention Effect may be contained in an amount that does not impair the.

  Examples of the ultraviolet absorbing component include B-wave (UV-B) absorbers such as 2-methoxyhexyl paramethoxycinnamate, phenylbenzimidazolesulfonic acid, isopropyl methoxycinnamate, octyl methoxycinnamate, para- Aminobenzoic acid, ethyl PABA, ethyl-dihydroxypropyl PABA, ethylhexyl-dimethyl PABA, homosalate, ethylhexyl salicylate, 3-benzylidene camphor, 4-methylbenzylidene camphor, benzylidene camphor sulfonic acid, camphor benzalkonium methosulfate, polyacrylamide Methylbenzylidene camphor, diethylhexylbutamide triazone, octyl triazone, disodium phenyldibenzimidazole tetrasulfonate, benzalmalonate Polyorganosiloxane having a group; A-wave (UV-A) absorber, 4-tert-butyl-4-methoxybenzoylmethane, 2- [4- (diethylamino) -2-hydroxybenzoyl] benzoic acid hexyl ester 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5 [(Octyl) oxy] -phenol, dimethoxybenzylideneoxoimidazolidinepropionate 2-ethylhexyl, etc .; AB wave absorbers such as 6- (4-methoxyphenyl) -1,3,5-triazine, tetrahydroxybenzophenone, 2 -Hydroxy-4-methoxybenzophenone, 2,4-bis-[{4- (2-ethylhexyloxy) ) -2-Hydroxy} -phenyl] -drometrizole trisiloxane, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) ) Phenol], octocrylene and the like. In addition, as an ultraviolet-absorption component, said ultraviolet absorber may be included individually by 1 type, and 2 or more types may be included.

  When the ultraviolet absorbing component is blended, the amount used can be appropriately selected in consideration of the feeling of use and effects on the skin, but for example 0.01 to 20% by mass with respect to the entire composition for external use of the present invention. Preferably, it is 0.1-15 mass%.

  In the composition for external use of the skin of the present invention, the above-mentioned other components may be used alone 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.

<Method for producing external composition for skin>
The method for producing the composition for external use of the skin of the present invention is not particularly limited, and a component appropriately selected from the essential components (A) powder, (B) inorganic phosphor, and other components is blended, and is usually added. It can be mixed and manufactured by the method.

  The use of the external composition for skin of the present invention is not particularly limited. For example, makeup foundations such as powder foundation, liquid foundation, makeup base, lipstick, lip balm; sunscreen cosmetics; It can be used in basic cosmetics such as moisturizing liquids, milky lotions, cosmetic liquids, packs, hand creams, body lotions and body creams; cleansing cosmetics such as facial cleansers, makeup removers and body shampoos. Moreover, the multifunctional formulation which put together the function of these formulations in one formulation is also mentioned. Among these uses, make-up cosmetics such as liquid foundations, makeup bases, lipsticks, lip balms; sunscreen cosmetics, lotions, moisturizers, emulsions, serums, packs, hand creams, body lotions, body creams Basic cosmetics such as: preferably used in cleansing cosmetics such as face wash, makeup remover, body shampoo, more preferably used in makeup cosmetics or sunscreen cosmetics, and makeup More preferably, it is used in cosmetics. These preparations can be manufactured according to a conventional method.

  The present invention is a method for enhancing the fluorescence intensity of a composition for external use of skin containing (B) an inorganic phosphor, comprising (A) blending powder, and (B) component in the entire composition obtained Also included is a method characterized in that the content is 0.0001 to 9.5% by mass. The present invention also relates to a method for improving the light-emitting property (color-developing property) of the composition for external use of skin containing (B) an inorganic phosphor, wherein (A) the powder is blended, and the whole composition obtained The content of (B) component in is 0.0001-9.5 mass%, The method characterized by the above-mentioned is also included. When the above method is employed, cosmetics, especially foundations, eye shadows, and the like exhibit excellent light emission intensity and light emission (color development) even if the content of the inorganic phosphor (B) in the composition for external use is small. It can be suitably used as makeup cosmetics such as lipsticks and as sunscreen cosmetics. In addition, about (A) powder and (B) inorganic fluorescent substance, the description of the above-mentioned external composition for skin of this invention is applicable.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the unit of the numerical value in each table | surface is the mass% unless there is particular notice.

<Test Example 1>
[Preparation of external composition for skin]
(1) Production of inorganic particles containing aluminate phosphor (calcium manganese aluminate) and titanate phosphor (magnesium manganese titanate) 4.97 g of calcium carbonate (CWS-20 manufactured by Sakai Chemical Industry), manganese carbonate ( Chuo Denki 0.06g), aluminum oxide (Sumitomo Chemical RA-50) 32.0g, flux component calcium fluoride (Wako first grade reagent) 0.18g, magnesium fluoride (Wako special grade reagent) 70.15g Was placed in water and thoroughly mixed using a planetary ball mill at 250 rpm for 30 minutes. The solid obtained by evaporating and drying the mixed slurry at 130 ° C. was crushed in a mortar to obtain a calcined precursor powder. Next, 15 g of the calcined precursor was filled in an alumina crucible, heated to 1600 ° C. at 200 ° C./hour in the atmosphere, held for 3 hours, and then cooled to room temperature at 200 ° C./hour. The obtained fired product was crushed in a mortar to produce inorganic particles containing an aluminate phosphor. Moreover, the titanate phosphor (magnesium manganese titanate) was produced by a method according to the production method of the aluminate phosphor.

(2) Preparation of external composition for skin According to the formulations shown in Tables 1 and 2 below, external compositions for Examples 1 to 14 and Comparative Examples 1 and 2 were prepared by a conventional method. That is, each component was mixed and uniformly dispersed with a stirrer (Awatori Nertaro ARE-310; manufactured by THINKY). Each skin external composition was subjected to the following test to evaluate the luminescence intensity.

  Each composition for external use on the skin was placed on a slide glass (manufactured by Matsunami Glass Industrial Co., Ltd.), and the slide glass was stacked thereon to form a uniform film. The color image obtained by observing and photographing under UV is decomposed into each image of Red (R), Green (G), and Blue (B). Of these, the average luminance in a certain area was calculated. The average luminance of Examples 1 to 10 when the average luminance of Comparative Example 1 is 1.0 is shown in Table 1, and the average luminance of Examples 11 to 12 when the average luminance of Comparative Example 2 is 1.0. Is shown in Table 2. Further, the actual measured values of the average luminance measured for each comparative example and each example are also shown in Tables 1 and 2. The captured images of Comparative Example 1 and Examples 4 and 9 are shown in FIG. 1, and the captured images of Comparative Example 2 and Example 11 are shown in FIG. As a result of the evaluation, as shown in Table 1, compared with the composition for external skin of Comparative Example 1, the composition for external skin of Examples 1 to 10 has high fluorescence intensity (luminance) and excellent color developability (luminance). It was. In addition, as shown in FIG. 1, it was also visually determined that the compositions for external use in Examples 4 and 9 had significantly higher luminance than Comparative Example 1. Similarly, as shown in Table 2 and FIG. 2, the skin external compositions of Examples 11 and 12 have higher fluorescence intensity (luminance) and color developability (luminance) than the skin external composition of Comparative Example 2. It was excellent.

The detail of each component of Table 1 and Table 2 is shown below.
Calcium manganese aluminate (Table 1): Particle size 35 (D50: μm)
Calcium manganese aluminate (Table 2): Particle size 6 (D50: μm)
Methylsiloxane network polymer: Tospearl 2000B * (Momentive Performance Materials) [spherical powder of silicone resin, particle size 6 μm]
(Diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) crosspolymer: KSP-300 (Shin-Etsu Chemical Co., Ltd.) [Silicon resin spherical powder, particle size 5 μm]
Polyalkyl acrylate: Gantzpearl GMX-0610 (Aika Industry Co., Ltd.) [Spherical powder of polyalkyl acrylate, particle size 6 μm]
Silicone-treated talc: SA-talc JA-46R (Miyoshi Kasei Co., Ltd.) [talc plate powder, particle size: 7 to 11 μm]
Silicone-treated mica titanium 1: SA-Timiron MP-115 (Miyoshi Kasei Co., Ltd.) [Pearl pigment plate powder, particle size 10-60 μm]
Silicone-treated mica titanium 2: SA-Flamenco Silk Red (Miyoshi Kasei Co., Ltd.) [Plate pigment powder, particle size 2-24 μm]
Nylon powder: SP-500 (Toray Dow Corning Co., Ltd.) [Nylon spherical powder, particle size 5 μm]
(HDI / trimethylol hexyl lactone) mixture of cross polymer, silicic acid anhydride and methylpolysiloxane: PLASTIC POWDER D-400HP (Toho Pigment Co., Ltd.) [urethane spherical powder, particle size 12-18 μm]
Silicic anhydride: SILICA MICROBEAD P-500 (JGC Catalysts & Chemicals Co., Ltd.) [Silica spherical powder, particle size 2 to 20 μm]
Boron nitride: CC6058 (Momentive Performance Materials) [Boron nitride plate powder, particle size 11 μm]
Silicone-treated synthetic phlogopite: PDM-10L (S) (Topy Industries, Ltd.) [Synthetic mica plate powder, particle size 10 to 13 μm]
Gelled hydrocarbons: Supplementary regulations Gelled hydrocarbons (Bristol-Myers Co., Ltd.)

<Test Example 2>
The light emission intensity was evaluated by the same method as in Test Example 1. The components used in this test were the same as those described in Test Example 1, and calcium manganese aluminate having a particle diameter of 6 (D50: μm) was used. Specifically, Tables 3 and 4 (tests using spherical powder) and Table 5 (plate-like powders are used) together with the formulation of each external composition for skin prepared in this test and the evaluation results thereof. Test).

  As a result, in the same manner as in Test Example 1 above, the composition for external use of the skin containing the combination of various (A) powders was more fluorescent than the comparative example containing (B) only the inorganic phosphor. It was confirmed that the intensity (brightness) was high and the color development (luminescence) was excellent. The fluorescence intensity (brightness) enhancement effect of the present invention is enhanced when (B) the inorganic phosphor has a high content of 10% by mass or more and exhibits high color development (high light emission) by itself. However, when the content of the inorganic phosphor (B) was low, the enhancement effect was remarkable and was very beneficial. Also, from the results in Table 5, when the component (A) is a plate-like powder (boron nitride, talc, synthetic mica), (A) it is stable and hardly affected by the amount of powder added. It was found that high color developability (luminescence) was exhibited.

<Test Example 3>
The light emission intensity was evaluated by the same method as in Test Example 1. The components used in this test are the same as those described in Test Example 1 above. Specifically, the formulation of each composition for external use on skin prepared in this test and the evaluation result are shown in Table 6 below.

  As a result, in the same manner as in Test Example 1, (A) the composition for external use of the skin containing a combination of powder was compared with the comparative example containing only the inorganic phosphor (B) with the fluorescence intensity ( (Brightness) was high, and it was confirmed that the color developability (luminance) was excellent.

<Test Example 4>
The light emission intensity was evaluated by the same method as in Test Example 1. The components used in this test are the same as those described in Test Example 1 except for the (vinyl dimethicone / methicone silsesquioxane) crosspolymer, and the calcium manganese aluminate has a particle size of 35 (D50: μm). Was carried out using Specifically, the formulation of each composition for external use on skin prepared in this test and the evaluation result are shown in Table 7 below.

  (Vinyl dimethicone / methicone silsesquioxane) Crosspolymer: KSP-105 (Shin-Etsu Chemical Co., Ltd.) [Silicon resin spherical powder, particle size 2 μm]

  As a result, in the same manner as in Test Example 1, (A) the composition for external use of the skin containing a combination of powder was compared with the comparative example containing only the inorganic phosphor (B) with the fluorescence intensity ( (Brightness) was high, and it was confirmed that the color developability (luminance) was excellent. From the results of Table 7, it can be seen that, in particular, when a spherical powder is used as the component (A), a larger particle size of 5 μm or more provides a higher fluorescence intensity (brightness) enhancement effect. It was.

  Below, the formulation example (formulation example) of the external composition for skin of this invention is shown below. Any of them can be prepared by a conventional method. The present invention is not limited to these pharmaceutical formulation examples.

<Formulation Example 1 Face Powder>
Talc 60.0 parts by weight Nylon powder 10.0 parts by weight Zinc myristate 15.0 parts by weight (diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) 5.0 parts by weight alkyl polyacrylate 3.0 parts by weight Calcium manganese aluminate 1.0 part by weight 1,3-butylene glycol 1.0 part by weight Coloring pigment Appropriate amount
Preservative appropriate amount
Total 100 parts by mass

<Formulation Example 2 Pressed Powder>
Talc 40.0 parts by weight Sericite 30.0 parts by weight Isotridecyl isononanoate 10.0 parts by weight (diphenyldimethicone / vinyldiphenyldimethicone / silsesquioxane) Crosspolymer 5.0 parts by weight Methylpolysiloxane 3.0 parts by weight Aluminum Calcium manganese oxide 3.0 parts by weight Silica anhydride 3.0 parts by weight Coloring pigment Appropriate amount
Preservative appropriate amount
Total 100 parts by mass

<Formulation Example 3 Foundation>
Water 45.0 parts by mass 1,3-butylene glycol 10.0 parts by mass Methylsiloxane network polymer 8.0 parts by mass Decamethylcyclopentasiloxane 5.0 parts by mass Methylphenylpolysiloxane 5.0 parts by mass Methylpolysiloxane 3 3.0 parts by weight calcium manganese aluminate 3.0 parts by weight boron nitride 3.0 parts by weight sorbitan monoisostearate 2.0 parts by weight dimethyl distearyl ammonium hectorite 1.0 part by weight PEG-9 polydimethylsiloxyethyl dimethicone 1. 0 parts by weight Inulin stearate 0.5 parts by weight Coloring pigment Appropriate amount
Preservative appropriate amount
Total 100 parts by mass

<Formulation Example 4 Makeup Base>
Water 60.0 parts by weight Methylsiloxane network polymer 8.0 parts by weight 1,3-butylene glycol 8.0 parts by weight Concentrated glycerin 5.0 parts by weight (hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer, squalane, polysorbate -60 mixture 3.0 parts by weight methylphenylpolysiloxane 3.0 parts by weight silicone-treated talc 3.0 parts by weight polyoxyethylene sorbitan monostearate 2.0 parts by weight calcium manganese aluminate 1.0 part by weight Coloring pigment
Preservative appropriate amount
Total 100 parts by mass

Claims (10)

  A composition for external use on skin, comprising (A) powder and (B) an inorganic phosphor, wherein the content of (B) inorganic phosphor is 0.0001 to 9.5% by mass relative to the entire composition.   (A) The external composition for skin of Claim 1 whose shape of powder is plate shape or spherical shape.   (A) The powder is at least one selected from the group consisting of talc, boron nitride, mica, pearl pigment, silicone resin, alkyl polyacrylate, urethane, nylon, and silica. Skin external composition.   (A) Powder is talc, boron nitride, synthetic phlogopite, titanium oxide coated mica, titanium oxide coated synthetic phlogopite, titanium oxide treated mica, titanium oxide treated talc, (dimethicone / vinyl dimethicone) crosspolymer, polymethylsil Sesquioxane, (diphenyldimethicone / vinyldiphenyldimethicone / silsesquioxane) crosspolymer, (vinyldimethicone / methiconesilsesquioxane) crosspolymer, methylmethacrylate crosspolymer, nylon-12, (HDI / trimethylolhexyllactone) The external composition for skin according to any one of claims 1 to 3, wherein the composition is at least one selected from the group consisting of a crosspolymer and silica.   The external composition for skin according to any one of claims 1 to 4, wherein the powder (A) comprises a spherical or plate-like powder having a particle diameter of 5 µm to 300 µm.   (B) The crystal matrix of an inorganic phosphor includes the metal oxide of any one of Al, Ti, Zn, Ge, Si, Fe, Zr, Mn, and Mg, according to any one of claims 1 to 5. An external composition for skin.   (B) The external composition for skin according to claim 6, wherein the inorganic phosphor is an aluminate phosphor or a titanate phosphor.   The external composition for skin according to any one of claims 1 to 7, wherein the content of (A) powder is 0.0001 to 100 parts by mass with respect to 1 part by mass of (B) inorganic phosphor.   The external composition for skin according to any one of claims 1 to 8, which is used for makeup, for sunscreen, for basic cosmetics, or for washing. (B) A method for enhancing the fluorescence intensity of a composition for external skin containing an inorganic phosphor,
(A) Mixing powder, and (B) content of inorganic fluorescent substance in the whole external composition for skin to be 0.0001-9.5 mass%,
A method characterized by.

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