WO2022244767A1 - Cosmetic material including bright pigment - Google Patents

Cosmetic material including bright pigment Download PDF

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Publication number
WO2022244767A1
WO2022244767A1 PCT/JP2022/020519 JP2022020519W WO2022244767A1 WO 2022244767 A1 WO2022244767 A1 WO 2022244767A1 JP 2022020519 W JP2022020519 W JP 2022020519W WO 2022244767 A1 WO2022244767 A1 WO 2022244767A1
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Prior art keywords
pigment
flake
cosmetic
zirconium oxide
film
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PCT/JP2022/020519
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French (fr)
Japanese (ja)
Inventor
治子 堀口
伸路 三上
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日本板硝子株式会社
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Priority to JP2023522671A priority Critical patent/JPWO2022244767A1/ja
Publication of WO2022244767A1 publication Critical patent/WO2022244767A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/28—Zirconium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/12—Face or body powders for grooming, adorning or absorbing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds

Definitions

  • the present invention relates to cosmetics containing pigments, particularly makeup cosmetics containing pigments.
  • Appropriate pigments are added to cosmetics according to their type.
  • base makeup cosmetics typified by foundations contain extender pigments, color pigments, white pigments, pearlescent pigments, and the like.
  • Extender pigments are used to impart spreadability, depositability, and even gloss, and are also used as extenders.
  • Color pigments are used to impart basic shades.
  • White pigments are used to impart hiding power and whiteness.
  • Pearlescent pigments are used to give pearl luster (pearl effect).
  • a typical pearlescent pigment is a flake-like substrate having an optical interference film on its surface. Glass, mica, etc. are used as the flake substrate. A titanium oxide film is usually used as the optical interference film.
  • Patent Document 1 proposes obtaining strong color development by using a light interference film and metal fine particles.
  • red coloration is enhanced by adhering fine gold particles onto a titanium oxide film.
  • the enhanced color development is highly useful in imparting local conspicuous bright spots to cosmetics.
  • the amount of the pearlescent pigment to be blended varies depending on the application of the cosmetic, but for base makeup cosmetics, it is at most about 8% by mass of the entire cosmetic.
  • the glossiness of the entire base makeup cosmetic is adjusted with extender pigments.
  • extender pigments there is a limit to how much gloss can be improved only by adjusting with extender pigments.
  • conventional pearlescent pigments although they can locally improve gloss on the basis of their high brightness, are not designed to suit the purpose of adjusting the properties of the cosmetic as a whole.
  • an object of the present invention is to provide new cosmetics containing improved pigments.
  • Luminescent pigments are pigments that can provide brightness enhancement, with or without pearl luster.
  • a cosmetic containing a glitter pigment comprises a flake-shaped substrate and a coating containing zirconium oxide on the flake-shaped substrate, Provided is a cosmetic, wherein the thickness of the film is 40 nm or more and 120 nm or less.
  • a cosmetic containing a glitter pigment comprises a flake-shaped substrate and a coating containing zirconium oxide on the flake-shaped substrate, further comprising an extender pigment different from the luster pigment,
  • a cosmetic containing the luster pigment in a range of 15 to 60% by mass based on the total amount of the luster pigment and the extender pigment.
  • a cosmetic that can provide a bright and natural appearance when applied to the skin is provided by an improved luster pigment.
  • MMD is an abbreviation for mean deviation of mean friction coefficient (MIU). MMD is an index corresponding to the smoothness of skin feel. The lower the MMD, the better the smoothness of feel. The details of the method for measuring MMD will be described in the Examples section.
  • the bright pigment of this embodiment comprises a flake-shaped substrate and a coating containing zirconium oxide on the flake-shaped substrate.
  • the film thickness of the coating is 40 nm or more and 120 nm or less.
  • Titanium oxide is known as a film-forming material that can achieve vivid colors due to its high refractive index.
  • pigments having a film containing titanium oxide may give an unnatural appearance due to excessive brightness and its characteristic interference color when a considerable amount is blended in cosmetics.
  • the titanium oxide-containing film is highly colored, making its complementary color easily visible, and the cosmetic may appear slightly dull.
  • Coatings containing zirconium oxide are inferior to titanium oxide-containing films in color development and brightness, but are suitable for providing a bright appearance while alleviating the above-described unnaturalness.
  • the zirconium oxide-containing film is also suitable for imparting “natural” coloring, specifically, coloring close to human skin, in base makeup cosmetics such as foundation.
  • the bright pigment according to the present embodiment has an L* of 30 or more and less than 70, further 35 or more and 68 or less, particularly 40 or more and 65 or less when the reflected color is displayed based on the L * a * b * color system .
  • can have The L * of the color reflected by the titanium oxide film is usually above 70.
  • the zirconium oxide-containing film can achieve a desired color development particularly for base makeup cosmetics, specifically a color development ranging from silver to yellow to orange. A method for measuring the reflected color will be described in the Examples section.
  • a bright pigment having a zirconium oxide-containing film can provide cosmetics with better properties than a bright pigment having a titanium oxide-containing film in terms of feeling on the skin.
  • Skin feel is a property that is emphasized in base makeup cosmetics. This favorable property provides a particularly advantageous effect when the bright pigment is blended into the base makeup cosmetic in a substantial amount, for example, at a content of 10% by mass or more.
  • the effect of the bright pigment according to the present embodiment is, for example, 1.5 or less, preferably 1.2 or less, more preferably 1.0 or less, still more preferably 0.8 or less, particularly preferably 0.6 or less, and in some cases 0 May have an MMD of 0.5 or less.
  • the lower limit of MMD is not particularly limited, it is, for example, 0.01 or more.
  • Effect pigments according to this embodiment may have, for example, an MIU of 2.1 or less, preferably 2.0 or less, more preferably 1.5 or less, and in some cases 1.0 or less.
  • the lower limit of MIU is not particularly limited, it is, for example, 0.01 or more.
  • the amount of the bright pigment to be blended can be, for example, 10% by mass or more, 12% by mass or more in some cases, and 14% by mass or more if necessary, based on the total amount of the cosmetic.
  • the bright pigment of the present embodiment may be blended in the cosmetic in a blending amount outside the above range, for example, 3% by mass or more, further 5% by mass or more, particularly 7% by mass or more.
  • the upper limit of the compounding amount is not particularly limited, but is, for example, 30% by mass or less, and further 35% by mass or less.
  • the flake-like substrate and the coating that constitute the bright pigment will be described below.
  • the flake-like substrate is a minute plate-like thin piece, which is also called a scale-like substrate or the like.
  • the flaky substrate is, for example, at least one selected from the group consisting of flaky glass, flaky alumina, flaky graphite, flaky iron oxide, flaky titania, bismuth oxychloride, mica, talc, and sericite.
  • the flake substrate is preferably flake glass, flake alumina or mica. Mica may be natural mica or synthetic mica. Glass flakes, which are particularly preferred flake substrates, are described below.
  • the glass composition that constitutes the glass flakes contains silicon oxide and a metal oxide other than silicon oxide, and is specifically selected from the group consisting of silicon oxide, aluminum oxide, calcium oxide and sodium oxide. At least one may be included. Silicon oxide may be the main component in the glass composition.
  • the content of silicon oxide in the glass composition is not particularly limited, but is, for example, 40% by mass or more, 45% by mass or more, and may be 75% by mass or less.
  • the glass composition may have a transmission of greater than 60%, or even greater than 70% over the wavelength range of 400-800 nm when converted to a thickness of 100 ⁇ m.
  • the glass composition may correspond to at least one selected from the group consisting of soda lime glass, A glass, C glass, E glass, borosilicate glass and aluminosilicate glass. Glass flakes composed of these multi-component glass compositions are suitable for production by a melting method with excellent mass productivity.
  • the preferred average particle size of the glass flakes is 1-160 ⁇ m, 2-120 ⁇ m, further 3-100 ⁇ m, and in some cases 5-90 ⁇ m.
  • the average particle size of the glass flakes is determined by the particle size (D50) corresponding to 50% of the volume accumulated from the smaller particle size side in the particle size distribution of the light scattering equivalent diameter measured by the laser diffraction method. do.
  • a preferred thickness of the glass flakes is 0.1 to 10 ⁇ m, further 0.2 to 3 ⁇ m, and sometimes 0.25 to 2 ⁇ m. If the average particle size and thickness are too large, it will be difficult to obtain a photovolatile pigment with a sufficiently good tactile feel.
  • a very good tactile sensation may be obtained from flake-like glass having a thickness of 1 to 2 ⁇ m.
  • These numerical ranges are also preferred average particle diameters and thicknesses of flake-shaped substrates other than flake-shaped substrates.
  • Glass flakes can be produced, for example, by a blow method.
  • the blow method melts the raw material cullet, continuously extracts the molten glass from a circular slit, and inflate the molten glass by blowing gas such as air from the blow nozzle provided inside the circular slit.
  • the glass is formed into a balloon shape, and the expanded and thinned glass is pulverized into flakes (scales).
  • the glass flakes it is possible to use, for example, commercially available products sold as Glass Flakes (registered trademark) series by Nippon Sheet Glass Co., Ltd.
  • glass flakes are superior in smoothness compared to crystalline particles such as mica. For this reason, glass flakes are particularly suitable for achieving a sufficiently low MMD.
  • the bright pigment comprises glass flakes and a single-layer zirconium oxide-containing film directly formed on the surface thereof.
  • a base film may be formed on the surface of the flake-shaped substrate.
  • a coating containing zirconium oxide is formed on the surface of the underlying film.
  • the underlayer may be a single layer or multiple layers.
  • the underlying film may be a film containing an oxide.
  • the zirconium oxide-containing film contains at least zirconium oxide.
  • the zirconium oxide-containing film may contain zirconium oxide as a main component.
  • a preferred thickness of the zirconium oxide-containing film is 40 to 120 nm, more preferably 60 to 110 nm, especially 80 to 100 nm. If the film thickness is too thin, the brightness will decrease. Color development by the zirconium oxide-containing film can be appropriately adjusted by controlling the film thickness, but as the film thickness increases, it usually shifts from silver to yellow, orange, red, and purple. Color development from silver to orange via yellow is suitable for base makeup cosmetics such as foundations. From this point of view, the film thickness is preferably 120 nm or less. In one preferred form, the surface of the zirconium oxide-containing film is exposed.
  • a liquid phase deposition method is suitable for forming a zirconium oxide-containing film on a flake-shaped substrate.
  • This liquid phase film forming method is usually carried out by dispersing the flaky substrates in a liquid containing a zirconium-containing salt and stirring the liquid.
  • the liquid may be an aqueous solution in which a zirconium-containing salt is dissolved.
  • Zirconium-containing salts are, for example, zirconium sulfate, zirconium oxychloride, zirconium ammonium carbonate.
  • a pH adjuster such as an acid may be added to the liquid, if necessary. The pH can be adjusted, for example, in the range of 1.9-4.0, further 2.0-3.5.
  • the surface on which the film is to be deposited may be pretreated.
  • This pretreatment is preferably contact with a liquid containing a tin-containing salt.
  • This pretreatment facilitates obtaining a sufficiently low MMD from the zirconium oxide-containing film.
  • the liquid containing the tin-containing salt may be an aqueous solution in which the tin-containing salt is dissolved.
  • Tin-containing salts are, for example, tin chloride, more particularly tin(II) chloride, tin(IV) chloride, tin(II) chloride dihydrate, tin(IV) chloride pentahydrate.
  • Cosmetics The cosmetic of this embodiment contains the bright pigment of this embodiment.
  • Cosmetics are not particularly limited, and include basic cosmetics such as skin lotions, milky lotions, and creams, hair care cosmetics such as hair styling agents, body care products such as body creams, body powders, antiperspirants, and sunscreens, bath salts, and the like. but preferably makeup cosmetics such as foundation, mascara, eyeshadow, eyeliner, lipstick, gloss, blush, and manicure.
  • Makeup cosmetics may be point makeup cosmetics such as lipsticks and blushes, or may be base makeup cosmetics such as concealers, foundations, and finishing powders.
  • the form of cosmetics is not particularly limited, and examples include powders, sticks, pencils, creams, emulsions, dispersions, oils, tablets, capsules, liners, paints, gels, and others.
  • the foundation may be cake type, powder type, cream type or liquid type.
  • Cosmetics may contain conventionally used components as components other than bright pigments. Components other than the bright pigment are appropriately selected according to the type of cosmetic. Cosmetics may contain pigments other than luster pigments.
  • foundations contain extender pigments, coloring pigments, white pigments, and pearlescent pigments.
  • the amount of the pearl luster pigment, which only needs to locally impart luster, to the foundation is at most about less than 8% by mass of the total amount of the foundation.
  • an extender pigment is usually blended in an amount larger than the above in order to adjust the characteristics of the foundation as a whole.
  • Cosmetics may contain the bright pigment of the present embodiment in a small amount, in other words, to the extent that the bright pigment functions as a pearlescent pigment, or in a substantial amount, in other words, the bright pigment is substantially an extender pigment or It may be contained to the extent that it functions as a pigment similar to it.
  • the content of the luster pigment may be, for example, 10% by mass or more, particularly 12 to 18% by mass, based on the total amount of the cosmetic.
  • the cosmetic may further contain an extender pigment that is different from the bright pigment of the present embodiment.
  • the bright pigment may be contained in an amount of 15 to 60%, preferably 20 to 35% by mass, based on the total amount of the bright pigment and the extender pigment.
  • the extender pigment is, for example, at least one selected from talc, sericite, mica, calcium carbonate, barium sulfate, magnesium silicate, cerium oxide, magnesium oxide, zeolite, and bentonite.
  • the luster pigment of the present embodiment can compensate for the luster that is lacking with these extender pigments alone, while avoiding unnecessary coloring. Blending of the bright pigment of the present embodiment within the above range is suitable for realizing cosmetics capable of providing a bright and natural appearance.
  • the luminance L * of reflected light was measured using a colorimeter "CR-400" manufactured by Konica Minolta.
  • the sample to be measured is a composition in which a bright pigment is added to a transparent acrylic resin (Nippe Acrylic "Autoclear Super” manufactured by Nippon Paint Co., Ltd. so that it becomes 10% by mass and mixed).
  • the composition was applied so that the thickness of the coating film was 9 mil (about 228.6 ⁇ m), and the thickness of the coating film after drying was 70 to 80 ⁇ m.
  • the light source used was D65.
  • the light source and the measurement surface are black-coated surfaces, and the reflected light measured is vertical reflected light, which is observed using the CIE 2° visual field color matching function.
  • the film thickness of the coating and the thickness of the substrate were measured by observing the cross section of the luster pigment using a scanning electron microscope (SEM).
  • Average particle size D50 The average particle size of the flake-like substrate was obtained by dispersing the flake-like substrate to be measured in water and measuring the diameter corresponding to cumulative 50% volume (D50) with "MT3300" manufactured by Microtrac.
  • Example 1 Pretreatment of Flake-shaped Substrate
  • glass flakes having an average particle size (D50) of 80 ⁇ m and a thickness of 1.3 ⁇ m were used as the flake-shaped substrate.
  • the glass flakes used in this example and the following examples are glass flakes (registered trademark) manufactured by Nippon Sheet Glass Co., Ltd., and are composed of multi-component glass.
  • This multi-component glass contains SiO2 , Al2O3 , MgO and CaO, and further contains an alkali component (at least one selected from Li2O, Na2O and K2O ).
  • 150 g of flaky substrates were mixed with 1.5 L of water and stirred.
  • zirconium oxide-containing film 150 g of the pretreated flake-like substrate and 1.5 L of water were mixed, and the temperature was raised to 75 ⁇ 3°C. Hydrochloric acid and sodium hydroxide were then added thereto to adjust the pH to 2.0-3.5. Subsequently, an aqueous zirconium sulfate solution with a concentration of 20% by mass and an aqueous sodium hydroxide solution with a concentration of 10% by mass were simultaneously added dropwise for 3.5 hours while maintaining the above pH to coat the zirconia oxide film. The powder and liquid were then separated by filtration.
  • the separated powder is dispersed in an aqueous solution adjusted to pH 2.0 to 3.5 with hydrochloric acid, stirred, and then filtered twice, and then dispersed in water, stirred, and then filtered twice. Carried out. Finally, the powder was dried in an atmosphere of 180°C for 12 hours and calcined at 600°C for 2 hours. Thus, a flaky substrate having a zirconium oxide-containing film formed on the surface was obtained.
  • Example 2 A zirconium oxide-containing film was formed on the surface in the same manner as in Example 1, except that glass flakes having an average particle size (D50) of 18 ⁇ m and a thickness of 1.3 ⁇ m were used as the flake substrates. A flaky substrate was obtained.
  • D50 average particle size
  • Example 3 A zirconium oxide-containing film was formed on the surface in the same manner as in Example 1, except that glass flakes having an average particle size (D50) of 8 ⁇ m and a thickness of 0.3 ⁇ m were used as the flake substrates. A flaky substrate was obtained.
  • D50 average particle size
  • Example 4 A zirconium oxide-containing film was formed on the surface in the same manner as in Example 1, except that glass flakes having an average particle size (D50) of 120 ⁇ m and a thickness of 1.3 ⁇ m were used as the flake substrates. A flaky substrate was obtained.
  • D50 average particle size
  • Example 5 A zirconium oxide-containing film was formed on the surface in the same manner as in Example 1, except that glass flakes having an average particle size (D50) of 160 ⁇ m and a thickness of 1.3 ⁇ m were used as the flake substrates. A flaky substrate was obtained.
  • D50 average particle size
  • Example 6 A flaky substrate having a zirconium oxide-containing film formed on its surface was obtained in the same manner as in Example 1, except that the dropping time was set to 4 hours and 30 minutes in the step of forming the zirconium oxide-containing film.
  • Example 7 A zirconium oxide-containing film was formed as follows without performing pretreatment of the flake-shaped substrate.
  • the flake-like substrate used is the same as in Example 1. Formation of Zirconium Oxide-Containing Film Hydrochloric acid was added to 150 mL of water to adjust the pH to 2.0 to 3.5. 0.5 g of urea and 21 g of zirconium sulfate were sequentially added thereto. Subsequently, 6 g of flaky substrate was added thereto and stirred for another 10 minutes. The powder and liquid were then separated by filtration. After that, the obtained powder was washed with water, dried at 90° C. for 1.5 hours, and further calcined at 800° C. for 1 hour. Thus, a flaky substrate having a zirconium oxide-containing film formed on the surface was obtained.
  • Example 1 A flaky substrate having a zirconium oxide-containing film formed on its surface was obtained in the same manner as in Example 1, except that the dropping time in the step of forming the zirconium oxide-containing film was 4 hours and 45 minutes.
  • Example 2 A flaky substrate having a zirconium oxide-containing film formed on its surface was obtained in the same manner as in Example 1, except that the dropping time was changed to 6 hours in the step of forming the zirconium oxide-containing film.
  • a foundation was prepared based on the recipe in Table 1 using a bright pigment.
  • a foundation was applied to the skin, and its appearance was evaluated based on the following indices. 4 points: The skin looks naturally bright. No glare. 3 points: The skin looks bright but has a little glare. 2 points: The color of the skin is slightly unnatural. 1 point: Unnatural glare is observed on the skin. The evaluation results are shown in Table 2 together with the properties of the bright pigment.
  • L * of the bright pigment of each example was in the range of 40 or more and 65 or less.
  • L * of the bright pigment of Comparative Example 3 exceeded 70.
  • Example 8 Flakes having a zirconium oxide-containing film formed on the surface in the same manner as Sample 1, except that synthetic mica manufactured by Nihon Koken Kogyo Co., Ltd. having an average particle diameter (D50) of 10 ⁇ m was used as the flake-shaped substrate. A similar substrate was obtained. The thickness of the synthetic mica was several ⁇ m or less.
  • Table 3 shows the properties of the bright pigment.
  • the zirconium oxide-containing film formed in each example is superior to the titanium oxide-containing film not only in appearance but also in terms of smoothness provided by the luster pigment.
  • the improvement in smoothness was remarkable when glass flakes were used as the flake substrates and when tin pretreatment was performed on the flake substrates.
  • Reflected light and brightness by the zirconium oxide-containing film are suitable for cosmetic pigments, especially pigments for adjusting the overall cosmetic properties.
  • FIGS. 1 and 2 show the results of observing the flake-shaped substrates on which the zirconium oxide-containing films were formed using SEM.
  • the section shown in FIG. 1 shows a zirconium oxide-containing film with a thickness of 90 nm.
  • the zirconium oxide-containing film was densely composed of particles with a size of about several tens of nanometers.

Abstract

An objective of the present disclosure is to provide a novel cosmetic material including an improved pigment. The present disclosure provides a cosmetic material including a bright pigment, wherein the bright pigment includes a flake-shaped substrate and a coating film including zirconium oxide on the flake-shaped substrate, and the thickness of the coating film is 40-120 nm.

Description

光輝性顔料を含む化粧料Cosmetics containing luster pigments
　本発明は、顔料を含む化粧料、特に、顔料を含むメイクアップ化粧品に関する。 The present invention relates to cosmetics containing pigments, particularly makeup cosmetics containing pigments.
　化粧品には、その種類に応じて適切な顔料が配合されている。例えば、ファンデーションに代表されるベースメイクアップ化粧品には、体質顔料、着色顔料、白色顔料、真珠光沢顔料等が配合される。体質顔料は、進展性、付着性、さらには光沢を付与するために使用され、増量剤としても使用されている。着色顔料は、基本的な色調を付与するために使用される。白色顔料は、隠蔽力、白さを付与するために使用される。 Appropriate pigments are added to cosmetics according to their type. For example, base makeup cosmetics typified by foundations contain extender pigments, color pigments, white pigments, pearlescent pigments, and the like. Extender pigments are used to impart spreadability, depositability, and even gloss, and are also used as extenders. Color pigments are used to impart basic shades. White pigments are used to impart hiding power and whiteness.
　真珠光沢顔料は、真珠光沢（パール効果）を付与するために使用される。代表的な真珠光沢顔料は、表面に光干渉膜を有するフレーク状基体である。フレーク状基体としては、ガラス、マイカ等が用いられている。光干渉膜としては、通常、酸化チタン膜が用いられている。 Pearlescent pigments are used to give pearl luster (pearl effect). A typical pearlescent pigment is a flake-like substrate having an optical interference film on its surface. Glass, mica, etc. are used as the flake substrate. A titanium oxide film is usually used as the optical interference film.
　真珠光沢顔料は、より強くより鮮やかな発色を実現するために開発が進められている。例えば特許文献１には、光干渉膜と共に金属微粒子を用いて強い発色を得ることが提案されている。特許文献１では、酸化チタン膜の上に金微粒子を付着させることにより、赤色の発色が強化されている。強化された発色は、化粧料に局所的に目立つ輝点を付与する上で利用価値が高い。 Pearlescent pigments are being developed to achieve stronger and more vivid colors. For example, Patent Document 1 proposes obtaining strong color development by using a light interference film and metal fine particles. In Patent Literature 1, red coloration is enhanced by adhering fine gold particles onto a titanium oxide film. The enhanced color development is highly useful in imparting local conspicuous bright spots to cosmetics.
　真珠光沢顔料の配合量は、化粧品の用途によって異なるが、ベースメイクアップ化粧品については、多くても化粧料全体の８質量％程度である。 The amount of the pearlescent pigment to be blended varies depending on the application of the cosmetic, but for base makeup cosmetics, it is at most about 8% by mass of the entire cosmetic.
特開２００６－２９９０５１号公報JP 2006-299051 A
　例えば、ベースメイクアップ化粧品全体の光沢は、体質顔料により調整される。しかし、体質顔料による調整のみでは光沢の向上には限界がある。一方、従来の真珠光沢顔料は、その高い輝度に基づいて光沢を局所的に向上させ得るものではあるが、化粧料全体の特性を調整する目的に適合するようには設計されていない。 For example, the glossiness of the entire base makeup cosmetic is adjusted with extender pigments. However, there is a limit to how much gloss can be improved only by adjusting with extender pigments. On the other hand, conventional pearlescent pigments, although they can locally improve gloss on the basis of their high brightness, are not designed to suit the purpose of adjusting the properties of the cosmetic as a whole.
　そこで、本発明は、改善された顔料を含む新たな化粧料の提供を目的とする。 Therefore, an object of the present invention is to provide new cosmetics containing improved pigments.
　本発明者は、鋭意検討を進めた結果、フレーク状基体と酸化ジルコニウムを含む被膜とを有する顔料を用いることにより、上述の目的が達成できることを見出した。なお、本明細書では、改善された顔料が真珠光沢の発現を主目的としていないことを考慮し、以降、これを光輝性顔料と呼ぶ。光輝性顔料は、真珠光沢の有無によらず、輝度の向上をもたらしうる顔料である。 As a result of intensive studies, the present inventor found that the above-mentioned objects can be achieved by using a pigment having a flake-like substrate and a coating containing zirconium oxide. In the present specification, considering that the improved pigment is not mainly aimed at developing pearl luster, it is hereinafter referred to as a luster pigment. Luminescent pigments are pigments that can provide brightness enhancement, with or without pearl luster.
　本発明は、その一側面から、
　光輝性顔料を含む化粧料であって、
　前記光輝性顔料は、フレーク状基体と、前記フレーク状基体上の酸化ジルコニウムを含む被膜と、を備え、
　前記被膜の膜厚が４０ｎｍ以上１２０ｎｍ以下である、化粧料、を提供する。 From one aspect of the present invention,
A cosmetic containing a glitter pigment,
The bright pigment comprises a flake-shaped substrate and a coating containing zirconium oxide on the flake-shaped substrate,
Provided is a cosmetic, wherein the thickness of the film is 40 nm or more and 120 nm or less.
　本発明は、その別の一側面から、
　光輝性顔料を含む化粧料であって、
　前記光輝性顔料は、フレーク状基体と、前記フレーク状基体上の酸化ジルコニウムを含む被膜と、を備え、
　前記光輝性顔料とは異なる体質顔料をさらに含み、
　前記光輝性顔料と体質顔料との合計量に対し、前記光輝性顔料を、質量基準で１５～６０％の範囲で含有する、化粧料、を提供する。 From another aspect of the present invention,
A cosmetic containing a glitter pigment,
The bright pigment comprises a flake-shaped substrate and a coating containing zirconium oxide on the flake-shaped substrate,
further comprising an extender pigment different from the luster pigment,
Provided is a cosmetic containing the luster pigment in a range of 15 to 60% by mass based on the total amount of the luster pigment and the extender pigment.
　本発明によれば、改善された光輝性顔料により、肌に塗布した際に、明るく自然な外観を提供できる化粧料が提供される。 According to the present invention, a cosmetic that can provide a bright and natural appearance when applied to the skin is provided by an improved luster pigment.
光輝性顔料の一例の断面を走査型電子顕微鏡（ＳＥＭ）で観察した結果である。It is the result of having observed the cross section of an example of a luster pigment with a scanning electron microscope (SEM). 光輝性顔料の一例の表面をＳＥＭで観察した結果である。It is the result of having observed the surface of an example of a luster pigment by SEM.
　以下、本発明の実施形態を説明するが、以下の説明は、本発明を特定の実施形態に制限する趣旨ではない。 Embodiments of the present invention will be described below, but the following description is not intended to limit the present invention to specific embodiments.
　本明細書において、「主成分」は、含有率が最も高い成分を意味する。ＭＭＤは、平均摩擦係数（ＭＩＵ；ｍｅａｎ　ｆｒｉｃｔｉｏｎ　ｃｏｅｆｆｉｃｉｅｎｔ）の平均偏差（ｍｅａｎ　ｄｅｖｉａｔｉｏｎ　ｏｆ　ｍｅａｎ　ｆｒｉｃｔｉｏｎ　ｃｏｅｆｆｉｃｉｅｎｔ）の略称である。ＭＭＤは、肌感触の滑らかさに対応する指標である。ＭＭＤが低いほど、感触の滑らかさは向上する。ＭＭＤの測定方法の詳細は実施例の欄において説明する。 As used herein, "main component" means the component with the highest content. MMD is an abbreviation for mean deviation of mean friction coefficient (MIU). MMD is an index corresponding to the smoothness of skin feel. The lower the MMD, the better the smoothness of feel. The details of the method for measuring MMD will be described in the Examples section.
（光輝性顔料）
　本実施形態の光輝性顔料は、フレーク状基体と、フレーク状基体上の酸化ジルコニウムを含む被膜と、を備えている。被膜の膜厚は４０ｎｍ以上１２０ｎｍ以下である。 (Luminous pigment)
The bright pigment of this embodiment comprises a flake-shaped substrate and a coating containing zirconium oxide on the flake-shaped substrate. The film thickness of the coating is 40 nm or more and 120 nm or less.
　酸化チタンは、その高い屈折率により鮮やかな発色を実現しうる被膜形成材料として知られている。しかし、酸化チタンを含む被膜（酸化チタン含有膜）を有する顔料は、化粧料に相当量を配合した際に、強すぎる輝度とその特徴的な干渉色により、不自然な外観をもたらすことがある。また、酸化チタン含有膜による顕著な発色によってその補色が視認されやすくなり、化粧料がややくすんで観察されることがある。酸化ジルコニウムを含む被膜（酸化ジルコニウム含有膜）は、発色や輝度の強さでは酸化チタン含有膜に劣るが、上述の不自然さを緩和しつつ明るい外観を提供上では適している。酸化ジルコニウム含有膜は、ファンデーション等のベースメイクアップ化粧品における「自然な」発色、具体的には人肌に近い発色、を付与することにも適している。 　Titanium oxide is known as a film-forming material that can achieve vivid colors due to its high refractive index. However, pigments having a film containing titanium oxide (titanium oxide-containing film) may give an unnatural appearance due to excessive brightness and its characteristic interference color when a considerable amount is blended in cosmetics. . In addition, the titanium oxide-containing film is highly colored, making its complementary color easily visible, and the cosmetic may appear slightly dull. Coatings containing zirconium oxide (zirconium oxide-containing films) are inferior to titanium oxide-containing films in color development and brightness, but are suitable for providing a bright appearance while alleviating the above-described unnaturalness. The zirconium oxide-containing film is also suitable for imparting “natural” coloring, specifically, coloring close to human skin, in base makeup cosmetics such as foundation.
　本実施形態による光輝性顔料は、その反射色をＬ＊ａ＊ｂ＊表色系に基づいて表示したときに、３０以上７０未満、さらに３５以上６８以下、特に４０以上６５以下のＬ＊を有し得る。酸化チタン膜による反射色のＬ＊は、通常、７０を上回る。本実施形態において、酸化ジルコニウム含有膜は、特にベースメイクアップ化粧品に望ましい発色、具体的にはシルバーから黄色、さらに橙色にかけての発色、を実現することができる。なお、反射色の測定方法は実施例の欄において説明する。 The bright pigment according to the present embodiment has an L* of 30 or more and less than 70, further 35 or more and 68 or less, particularly 40 or more and 65 or less when the reflected color is displayed based on the L * a * b * color system . can have The L * of the color reflected by the titanium oxide film is usually above 70. In the present embodiment, the zirconium oxide-containing film can achieve a desired color development particularly for base makeup cosmetics, specifically a color development ranging from silver to yellow to orange. A method for measuring the reflected color will be described in the Examples section.
　酸化ジルコニウム含有膜を有する光輝性顔料は、肌に与える感触においても、酸化チタン含有膜を有する光輝性顔料よりも、化粧料に優れた特性を付与しうることが見い出された。肌感触は、ベースメイクアップ化粧品において重視される特性である。この好ましい特性は、相当量、例えば１０質量％以上の含有率でベースメイクアップ化粧品に光輝性顔料を配合する際に、特に有利な効果をもたらす。 It was found that a bright pigment having a zirconium oxide-containing film can provide cosmetics with better properties than a bright pigment having a titanium oxide-containing film in terms of feeling on the skin. Skin feel is a property that is emphasized in base makeup cosmetics. This favorable property provides a particularly advantageous effect when the bright pigment is blended into the base makeup cosmetic in a substantial amount, for example, at a content of 10% by mass or more.
　本実施形態による光輝性顔料は、例えば１．５以下、好ましくは１．２以下、より好ましくは１．０以下、さらに好ましくは０．８以下、特に好ましくは０．６以下、場合によっては０．５以下のＭＭＤを有し得る。ＭＭＤの下限は、特に制限されないが、例えば０．０１以上である。本実施形態による光輝性顔料は、例えば２．１以下、好ましくは２．０以下、より好ましくは１．５以下、場合によっては１．０以下のＭＩＵを有し得る。ＭＩＵの下限は、特に制限されないが、例えば０．０１以上である。 The effect of the bright pigment according to the present embodiment is, for example, 1.5 or less, preferably 1.2 or less, more preferably 1.0 or less, still more preferably 0.8 or less, particularly preferably 0.6 or less, and in some cases 0 May have an MMD of 0.5 or less. Although the lower limit of MMD is not particularly limited, it is, for example, 0.01 or more. Effect pigments according to this embodiment may have, for example, an MIU of 2.1 or less, preferably 2.0 or less, more preferably 1.5 or less, and in some cases 1.0 or less. Although the lower limit of MIU is not particularly limited, it is, for example, 0.01 or more.
　本実施形態において、光輝性顔料の配合量は、化粧料全体に対し、例えば１０質量％以上、場合によっては１２質量％以上、必要があれば１４質量％以上とすることができる。ただし、本実施形態の光輝性顔料は、配合量が上述の範囲外、例えば３質量％以上、さらに５質量％以上、特に７質量％以上の範囲で化粧料に配合してもよい。配合量の上限は、特に制限されないが、例えば３０質量％以下、さらに３５質量％以下である。 In the present embodiment, the amount of the bright pigment to be blended can be, for example, 10% by mass or more, 12% by mass or more in some cases, and 14% by mass or more if necessary, based on the total amount of the cosmetic. However, the bright pigment of the present embodiment may be blended in the cosmetic in a blending amount outside the above range, for example, 3% by mass or more, further 5% by mass or more, particularly 7% by mass or more. The upper limit of the compounding amount is not particularly limited, but is, for example, 30% by mass or less, and further 35% by mass or less.
　以下、光輝性顔料を構成するフレーク状基体と被膜とを説明する。
・フレーク状基体
　フレーク状基体は、鱗片状基体等とも呼ばれる微小な板状の薄片である。フレーク状基体は、例えば、フレーク状ガラス、フレーク状アルミナ、フレーク状グラファイト、フレーク状酸化鉄、フレーク状チタニア、オキシ塩化ビスマス、マイカ、タルク、及びセリサイトからなる群より選ばれる少なくとも１種である。フレーク状基体は、好ましくはフレーク状ガラス、フレーク状アルミナ又はマイカである。マイカは天然マイカであっても合成マイカであってもよい。以下、特に好ましいフレーク状基体であるフレーク状ガラスについて説明する。 The flake-like substrate and the coating that constitute the bright pigment will be described below.
- Flake-like Substrate The flake-like substrate is a minute plate-like thin piece, which is also called a scale-like substrate or the like. The flaky substrate is, for example, at least one selected from the group consisting of flaky glass, flaky alumina, flaky graphite, flaky iron oxide, flaky titania, bismuth oxychloride, mica, talc, and sericite. . The flake substrate is preferably flake glass, flake alumina or mica. Mica may be natural mica or synthetic mica. Glass flakes, which are particularly preferred flake substrates, are described below.
　フレーク状ガラスを構成するガラス組成物は、酸化ケイ素と共に、酸化ケイ素以外の金属酸化物をさらに含むもの、具体的には、酸化ケイ素と共に、酸化アルミニウム、酸化カルシウム及び酸化ナトリウムからなる群より選ばれる少なくとも１つを含むものであってもよい。ガラス組成物において、酸化ケイ素は主成分であってもよい。ガラス組成物における酸化ケイ素の含有率は、特に制限されないが、例えば４０質量％以上、４５質量％以上であり、７５質量％以下であってもよい。ガラス組成物は、１００μｍの厚さに換算したときに、４００～８００ｎｍの波長域にわたって６０％、さらには７０％を超える透過率を有するものであってもよい。ガラス組成物は、具体的には、ソーダライムガラス、Ａガラス、Ｃガラス、Ｅガラス、ホウケイ酸ガラス及びアルミノケイ酸ガラスからなる群より選択される少なくとも１種に該当するものであってもよい。これらの多成分ガラス組成物により構成されたフレーク状ガラスは、量産性に優れた溶融法により製造することに適している。 The glass composition that constitutes the glass flakes contains silicon oxide and a metal oxide other than silicon oxide, and is specifically selected from the group consisting of silicon oxide, aluminum oxide, calcium oxide and sodium oxide. At least one may be included. Silicon oxide may be the main component in the glass composition. The content of silicon oxide in the glass composition is not particularly limited, but is, for example, 40% by mass or more, 45% by mass or more, and may be 75% by mass or less. The glass composition may have a transmission of greater than 60%, or even greater than 70% over the wavelength range of 400-800 nm when converted to a thickness of 100 μm. Specifically, the glass composition may correspond to at least one selected from the group consisting of soda lime glass, A glass, C glass, E glass, borosilicate glass and aluminosilicate glass. Glass flakes composed of these multi-component glass compositions are suitable for production by a melting method with excellent mass productivity.
　フレーク状ガラスの好ましい平均粒径は、１～１６０μｍ、２～１２０μｍ、さらに３～１００μｍ、場合によっては５～９０μｍである。なお、フレーク状ガラスの平均粒径は、レーザ回折法により測定した光散乱相当径の粒度分布において、粒径が小さい側からの体積累積が５０％に相当する粒径（Ｄ５０）により定めることとする。フレーク状ガラスの好ましい厚さは、０．１～１０μｍ、さらに０．２～３μｍ、場合によっては０．２５～２μｍである。平均粒径及び厚さが大きすぎると、十分に良好な触感を有する光揮性顔料が得られにくくなる。ただし厚さに関しては、厚さ１～２μｍのフレーク状ガラスから極めて良好な触感が得られることがある。なお、これらの数値範囲は、フレーク状ガラス以外のフレーク状基体の好ましい平均粒径及び厚さでもある。 The preferred average particle size of the glass flakes is 1-160 μm, 2-120 μm, further 3-100 μm, and in some cases 5-90 μm. The average particle size of the glass flakes is determined by the particle size (D50) corresponding to 50% of the volume accumulated from the smaller particle size side in the particle size distribution of the light scattering equivalent diameter measured by the laser diffraction method. do. A preferred thickness of the glass flakes is 0.1 to 10 μm, further 0.2 to 3 μm, and sometimes 0.25 to 2 μm. If the average particle size and thickness are too large, it will be difficult to obtain a photovolatile pigment with a sufficiently good tactile feel. However, as for the thickness, a very good tactile sensation may be obtained from flake-like glass having a thickness of 1 to 2 μm. These numerical ranges are also preferred average particle diameters and thicknesses of flake-shaped substrates other than flake-shaped substrates.
　フレーク状ガラスは、例えばブロー法により製造することができる。ブロー法とは、原料カレットを溶融し、溶融したガラスを円形スリットから連続的に取り出し、その際に円形スリットの内側に設けられたブローノズルから空気等の気体を吹き込んで溶融したガラスを膨らませてバルーン状とし、膨張して薄くなったガラスを粉砕してフレーク状（鱗片状）とする方法である。フレーク状ガラスとしては、例えば日本板硝子社よりガラスフレーク（登録商標）シリーズとして販売されている市販品を使用することが可能である。 Glass flakes can be produced, for example, by a blow method. The blow method melts the raw material cullet, continuously extracts the molten glass from a circular slit, and inflate the molten glass by blowing gas such as air from the blow nozzle provided inside the circular slit. In this method, the glass is formed into a balloon shape, and the expanded and thinned glass is pulverized into flakes (scales). As the glass flakes, it is possible to use, for example, commercially available products sold as Glass Flakes (registered trademark) series by Nippon Sheet Glass Co., Ltd.
　フレーク状ガラスの表面は、マイカ等の結晶性粒体と比較して平滑性に優れている。このため、フレーク状ガラスは、十分に低いＭＭＤの実現に特に適している。 The surface of glass flakes is superior in smoothness compared to crystalline particles such as mica. For this reason, glass flakes are particularly suitable for achieving a sufficiently low MMD.
　好ましい一形態において、光輝性顔料は、フレーク状ガラスと、その表面に直接形成された単層の酸化ジルコニウム含有膜とを備えている。ただし、フレーク状基体の表面には下地膜が形成されていてもよい。この場合、酸化ジルコニウムを含む被膜は、下地膜の表面上に形成される。下地膜は、単層であっても多層であってもよい。下地膜は、酸化物を含む膜であってもよい。 In a preferred embodiment, the bright pigment comprises glass flakes and a single-layer zirconium oxide-containing film directly formed on the surface thereof. However, a base film may be formed on the surface of the flake-shaped substrate. In this case, a coating containing zirconium oxide is formed on the surface of the underlying film. The underlayer may be a single layer or multiple layers. The underlying film may be a film containing an oxide.
・酸化ジルコニウム含有膜
　酸化ジルコニウム含有膜は、少なくとも酸化ジルコニウムを含む。酸化ジルコニウム含有膜は、酸化ジルコニウムを主成分としていてもよい。酸化ジルコニウム含有膜の好ましい膜厚は、４０～１２０ｎｍ、さらに６０～１１０ｎｍ、特に８０～１００ｎｍである。膜厚が薄すぎると輝度が低下する。酸化ジルコニウム含有膜による発色は、膜厚の制御により適宜調整されうるが、膜厚が大きくなるにつれ、通常、シルバーから黄、橙、赤、紫へと移行していく。ファンデーション等のベースメイクアップ化粧品には、シルバーから、黄を経由して橙までの発色が適している。この観点から、膜厚は１２０ｎｍ以下が好適である。好ましい一形態において、酸化ジルコニウム含有膜の表面は露出している。 - Zirconium oxide-containing film The zirconium oxide-containing film contains at least zirconium oxide. The zirconium oxide-containing film may contain zirconium oxide as a main component. A preferred thickness of the zirconium oxide-containing film is 40 to 120 nm, more preferably 60 to 110 nm, especially 80 to 100 nm. If the film thickness is too thin, the brightness will decrease. Color development by the zirconium oxide-containing film can be appropriately adjusted by controlling the film thickness, but as the film thickness increases, it usually shifts from silver to yellow, orange, red, and purple. Color development from silver to orange via yellow is suitable for base makeup cosmetics such as foundations. From this point of view, the film thickness is preferably 120 nm or less. In one preferred form, the surface of the zirconium oxide-containing film is exposed.
　フレーク状基体上への酸化ジルコニウム含有膜の形成には、液相成膜法が適している。この液相成膜法は、通常、ジルコニウム含有塩を含む液体にフレーク状基体を分散させ、この液体を攪拌することにより実施される。液体は、ジルコニウム含有塩が溶解した水溶液であってもよい。ジルコニウム含有塩は、例えば、硫酸ジルコニウム、酸塩化ジルコニウム、炭酸ジルコニウムアンモニウである。液体には、必要に応じ、酸等のｐＨ調整剤を投入してもよい。ｐＨは、例えば、１．９～４．０、さらには２．０～３．５の範囲に調整することができる。 A liquid phase deposition method is suitable for forming a zirconium oxide-containing film on a flake-shaped substrate. This liquid phase film forming method is usually carried out by dispersing the flaky substrates in a liquid containing a zirconium-containing salt and stirring the liquid. The liquid may be an aqueous solution in which a zirconium-containing salt is dissolved. Zirconium-containing salts are, for example, zirconium sulfate, zirconium oxychloride, zirconium ammonium carbonate. A pH adjuster such as an acid may be added to the liquid, if necessary. The pH can be adjusted, for example, in the range of 1.9-4.0, further 2.0-3.5.
　酸化ジルコニウム含有膜の成膜に先立ち、膜を析出させるべき表面に前処理を実施してもよい。この前処理は、好ましくは、錫含有塩を含む液体による接触である。この前処理により、酸化ジルコニウム含有膜から十分に低いＭＭＤが得られやすくなる。この前処理によるＭＭＤ低下の機構は現段階では明らかではないが、生成する酸化ジルコニウムの表面や密度が影響を受け、その結果、ＭＭＤが低下している可能性がある。錫含有塩を含む液体は、錫含有塩が溶解した水溶液であってもよい。錫含有塩は、例えば塩化錫、より具体的には塩化錫（ＩＩ）、塩化錫（ＩＶ）、塩化錫（ＩＩ）二水和物、塩化錫（ＩＶ）五水和物である。 Prior to forming the zirconium oxide-containing film, the surface on which the film is to be deposited may be pretreated. This pretreatment is preferably contact with a liquid containing a tin-containing salt. This pretreatment facilitates obtaining a sufficiently low MMD from the zirconium oxide-containing film. Although the mechanism of the reduction in MMD due to this pretreatment is not clear at this stage, it is possible that the surface and density of the zirconium oxide produced are affected, resulting in the reduction in MMD. The liquid containing the tin-containing salt may be an aqueous solution in which the tin-containing salt is dissolved. Tin-containing salts are, for example, tin chloride, more particularly tin(II) chloride, tin(IV) chloride, tin(II) chloride dihydrate, tin(IV) chloride pentahydrate.
（化粧料）
　本実施形態の化粧料は、本実施形態の光輝性顔料を含む。化粧料は、特に限定されず、化粧水、乳液、クリーム等の基礎化粧品、ヘアスタイリング剤等のヘアケア化粧品、ボディクリーム、ボディパウダー、制汗剤、サンスクリーン剤等のボディケア製品、入浴剤等であってもよいが、好ましくは、ファンデーション、マスカラ、アイシャドウ、アイライン、口紅、グロス、チーク、マニュキュア等のメイクアップ化粧品である。メイクアップ化粧品は、口紅、チーク等のポイントメイクアップ化粧品であってもよく、コンシーラー、ファンデーション、仕上げ用パウダー等のベースメイクアップ化粧品であってもよい。 (cosmetics)
The cosmetic of this embodiment contains the bright pigment of this embodiment. Cosmetics are not particularly limited, and include basic cosmetics such as skin lotions, milky lotions, and creams, hair care cosmetics such as hair styling agents, body care products such as body creams, body powders, antiperspirants, and sunscreens, bath salts, and the like. but preferably makeup cosmetics such as foundation, mascara, eyeshadow, eyeliner, lipstick, gloss, blush, and manicure. Makeup cosmetics may be point makeup cosmetics such as lipsticks and blushes, or may be base makeup cosmetics such as concealers, foundations, and finishing powders.
　化粧料の形態は、特に限定されず、例えば、粉末、スティック、ペンシル、クリーム、エマルジョン、ディスパーション、オイル、タブレット、カプセル、ライナー、ペイント、ゲルその他である。例えばファンデーションは、ケーキタイプ、パウダータイプ、クリームタイプ、リキッドタイプのいずれであってもよい。化粧料は、光輝性顔料以外の成分として、従来から使用されてきた成分を含み得る。光輝性顔料以外の成分は、化粧料の種類に応じて適宜選択される。化粧料は、光輝性顔料以外の顔料を含んでいてもよい。 The form of cosmetics is not particularly limited, and examples include powders, sticks, pencils, creams, emulsions, dispersions, oils, tablets, capsules, liners, paints, gels, and others. For example, the foundation may be cake type, powder type, cream type or liquid type. Cosmetics may contain conventionally used components as components other than bright pigments. Components other than the bright pigment are appropriately selected according to the type of cosmetic. Cosmetics may contain pigments other than luster pigments.
　例えばファンデーションには、体質顔料、着色顔料、白色顔料、真珠光沢顔料等が配合される。局部的に光沢を与えればよい真珠光沢顔料のファンデーションへの配合量は、多くてもファンデーション全量の８質量％未満程度である。これに対し、体質顔料は、ファンデーション全体の特性を調整するために、通常、上記よりも多い量が配合される。 For example, foundations contain extender pigments, coloring pigments, white pigments, and pearlescent pigments. The amount of the pearl luster pigment, which only needs to locally impart luster, to the foundation is at most about less than 8% by mass of the total amount of the foundation. On the other hand, an extender pigment is usually blended in an amount larger than the above in order to adjust the characteristics of the foundation as a whole.
　化粧料は、本実施形態の光輝性顔料を、少量、言い換えると光輝性顔料が真珠光沢顔料として機能する程度に含んでいてもよく、相当量、言い換えると光輝性顔料が実質的に体質顔料又はそれに類似する顔料として機能する程度に含んでいてもよい。後者の場合は、化粧料全量に対する光輝性顔料の含有量を、例えば１０質量％以上、特に１２～１８質量％としてもよい。 Cosmetics may contain the bright pigment of the present embodiment in a small amount, in other words, to the extent that the bright pigment functions as a pearlescent pigment, or in a substantial amount, in other words, the bright pigment is substantially an extender pigment or It may be contained to the extent that it functions as a pigment similar to it. In the latter case, the content of the luster pigment may be, for example, 10% by mass or more, particularly 12 to 18% by mass, based on the total amount of the cosmetic.
　化粧料は、本実施形態の光輝性顔料と共に、これとは異なる体質顔料をさらに含んでいてもよい。この場合、光輝性顔料と体質顔料との合計量に対し、光輝性顔料は、質量基準で、１５～６０％、好ましくは２０～３５の範囲で含まれていてもよい。体質顔料は、例えば、タルク、セリサイト、マイカ、炭酸カルシウム、硫酸バリウム、珪酸マグネシウム、酸化セリウム、酸化マグネシウム、ゼオライト、及びベントナイトから選ばれる少なくとも１つである。これらの体質顔料のみでは不足する光沢を、不要な着色を避けながら、本実施形態の光輝性顔料は補いうる。本実施形態の光輝性顔料の上記範囲での配合は、明るく自然な外観を提供できる化粧料の実現に適している。 The cosmetic may further contain an extender pigment that is different from the bright pigment of the present embodiment. In this case, the bright pigment may be contained in an amount of 15 to 60%, preferably 20 to 35% by mass, based on the total amount of the bright pigment and the extender pigment. The extender pigment is, for example, at least one selected from talc, sericite, mica, calcium carbonate, barium sulfate, magnesium silicate, cerium oxide, magnesium oxide, zeolite, and bentonite. The luster pigment of the present embodiment can compensate for the luster that is lacking with these extender pigments alone, while avoiding unnecessary coloring. Blending of the bright pigment of the present embodiment within the above range is suitable for realizing cosmetics capable of providing a bright and natural appearance.
　以下、実施例により本発明の具体例を説明するが、以下の実施例も本発明を制限する趣旨で提示するものではない。以下の実施例及び比較例から得た光揮性顔料の特性は、以下のように評価した。 Specific examples of the present invention will be described below with reference to examples, but the following examples are not intended to limit the present invention. The properties of the photovolatile pigments obtained from the following examples and comparative examples were evaluated as follows.
（触感；ＭＩＵ及びＭＭＤ）
　すべり性に対応するＭＩＵ及び滑らかさに対応するＭＭＤは、カトーテック社製の摩擦感テスター「ＫＥＳ－ＳＥ」を用いて測定した。摩擦子には１０ｍｍ角のシリコーン素子を用い、測定条件は、静荷重５０ｇ、測定速度１ｍｍ／秒とした。測定対象試料は、光輝性顔料を黒色人工皮革（イデアテックスジャパン社製「プロテインレザー（登録商標）サプラーレ」）の上に単位面積あたり質量が１．３ｍｇ／ｃｍ２となるように均一に散布して作製した。なお、測定時の相対湿度は５４％であった。 (Tactile sensation; MIU and MMD)
MIU corresponding to slickness and MMD corresponding to smoothness were measured using a friction tester "KES-SE" manufactured by Kato Tech. A 10 mm square silicone element was used as the friction element, and the measurement conditions were a static load of 50 g and a measurement speed of 1 mm/sec. For the sample to be measured, a bright pigment was evenly dispersed on a black artificial leather ("Protein Leather (registered trademark) Suprale" manufactured by Ideatex Japan Co., Ltd.) so that the mass per unit area was 1.3 mg/cm 2 . was made. The relative humidity at the time of measurement was 54%.
（反射光；輝度及び色）
　反射光の輝度Ｌ＊は、コニカミノルタ社製の測色計「ＣＲ－４００」を用いて測定した。測定対象試料は、光輝性顔料を透明アクリル樹脂（日本ペイント社製ニッペアクリル「オートクリヤスーパー」に１０質量％となるように添加し混合した組成物を白地／黒地の隠蔽率測定用紙上に塗布して作製した。組成物は塗膜の厚さが９ｍｉｌ（約２２８．６μｍ）となるように塗布したが、乾燥後の塗膜の厚さは７０～８０μｍとなった。用いた光源はＤ６５光源、測定面は黒地塗布面である。測定した反射光は垂直反射光とした。反射光はＣＩＥ２°視野等色関数を用いて観測した。 (reflected light; brightness and color)
The luminance L * of reflected light was measured using a colorimeter "CR-400" manufactured by Konica Minolta. The sample to be measured is a composition in which a bright pigment is added to a transparent acrylic resin (Nippe Acrylic "Autoclear Super" manufactured by Nippon Paint Co., Ltd. so that it becomes 10% by mass and mixed). The composition was applied so that the thickness of the coating film was 9 mil (about 228.6 μm), and the thickness of the coating film after drying was 70 to 80 μm.The light source used was D65. The light source and the measurement surface are black-coated surfaces, and the reflected light measured is vertical reflected light, which is observed using the CIE 2° visual field color matching function.
（膜厚、基体厚さ）
　被膜の膜厚及び基体の厚さは、走査型電子顕微鏡（ＳＥＭ）を用いて光輝性顔料の断面を観察することにより測定した。 (film thickness, substrate thickness)
The film thickness of the coating and the thickness of the substrate were measured by observing the cross section of the luster pigment using a scanning electron microscope (SEM).
（平均粒子径Ｄ５０）
　フレーク状基体の平均粒子径は、測定対象とするフレーク状基体を水に分散させ、マイクロトラック社製「ＭＴ３３００」で体積累積５０％相当径（Ｄ５０）を測定した。 (Average particle size D50)
The average particle size of the flake-like substrate was obtained by dispersing the flake-like substrate to be measured in water and measuring the diameter corresponding to cumulative 50% volume (D50) with "MT3300" manufactured by Microtrac.
（実施例１）
・フレーク状基体の前処理
　実施例１では、フレーク状基体として、平均粒径（Ｄ５０）が８０μｍ、厚さが１．３μｍのフレーク状ガラスを用いた。本実施例及び以降の実施例で使用したフレーク状ガラスは、いずれも日本板硝子社製ガラスフレーク（登録商標）であり、多成分ガラスにより構成されている。この多成分ガラスは、ＳｉＯ2、Ａｌ2Ｏ3、ＭｇＯ及びＣａＯを含み、さらにアルカリ成分（Ｌｉ2Ｏ、Ｎａ2Ｏ及びＫ2Ｏから選ばれる少なくとも１種）を含んでいる。まず、フレーク状基体１５０ｇを水１．５Ｌと混合して攪拌した。次いで、これに塩酸を添加し、ｐＨを１．４５～１．５５に調整した。引き続き、これに濃度１．３質量％の塩化錫（ＩＶ）水溶液９．０６ｍＬを加えた。その後、さらに攪拌を継続し、ろ過により粉末と液体とを分離した。分離した粉末を水に分散させ、再度ろ過して、前処理済みフレーク状基体を得た。 (Example 1)
Pretreatment of Flake-shaped Substrate In Example 1, glass flakes having an average particle size (D50) of 80 μm and a thickness of 1.3 μm were used as the flake-shaped substrate. The glass flakes used in this example and the following examples are glass flakes (registered trademark) manufactured by Nippon Sheet Glass Co., Ltd., and are composed of multi-component glass. This multi-component glass contains SiO2 , Al2O3 , MgO and CaO, and further contains an alkali component (at least one selected from Li2O, Na2O and K2O ). First, 150 g of flaky substrates were mixed with 1.5 L of water and stirred. Hydrochloric acid was then added thereto to adjust the pH to 1.45-1.55. Subsequently, 9.06 mL of tin (IV) chloride aqueous solution with a concentration of 1.3% by mass was added thereto. After that, stirring was further continued, and powder and liquid were separated by filtration. The separated powder was dispersed in water and filtered again to obtain pretreated flaky substrates.
・酸化ジルコニウム含有膜の形成
　前処理済みフレーク状基体１５０ｇと水１．５Ｌとを混合し、７５±３℃に昇温した。次いで、これに塩酸及び水酸化ナトリウムを添加し、ｐＨを２．０～３．５に調整した。引き続き、濃度２０質量％の硫酸ジルコニウム水溶液と濃度１０質量％の水酸化ナトリウム水溶液とを同時に上記ｐＨを維持しながら３．５時間滴下し、酸化ジルコニア膜を被覆した。その後、ろ過により粉末と液体とを分離した。分離した粉末は、塩酸でｐＨ２．０～３．５に調整した水溶液に分散させて攪拌し、その後ろ過する操作２回と、水に分散させて攪拌し、その後ろ過する操作２回とを順次実施した。最後に、粉末を１８０℃、１２時間の雰囲気で乾燥させ、６００℃で２時間焼成した。こうして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。 - Formation of zirconium oxide-containing film 150 g of the pretreated flake-like substrate and 1.5 L of water were mixed, and the temperature was raised to 75±3°C. Hydrochloric acid and sodium hydroxide were then added thereto to adjust the pH to 2.0-3.5. Subsequently, an aqueous zirconium sulfate solution with a concentration of 20% by mass and an aqueous sodium hydroxide solution with a concentration of 10% by mass were simultaneously added dropwise for 3.5 hours while maintaining the above pH to coat the zirconia oxide film. The powder and liquid were then separated by filtration. The separated powder is dispersed in an aqueous solution adjusted to pH 2.0 to 3.5 with hydrochloric acid, stirred, and then filtered twice, and then dispersed in water, stirred, and then filtered twice. Carried out. Finally, the powder was dried in an atmosphere of 180°C for 12 hours and calcined at 600°C for 2 hours. Thus, a flaky substrate having a zirconium oxide-containing film formed on the surface was obtained.
（実施例２）
　フレーク状基体として、平均粒径（Ｄ５０）が１８μｍ、厚さが１．３μｍのフレーク状ガラスを用いたことを除いては、実施例１と同様にして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。 (Example 2)
A zirconium oxide-containing film was formed on the surface in the same manner as in Example 1, except that glass flakes having an average particle size (D50) of 18 μm and a thickness of 1.3 μm were used as the flake substrates. A flaky substrate was obtained.
（実施例３）
　フレーク状基体として、平均粒径（Ｄ５０）が８μｍ、厚さが０．３μｍのフレーク状ガラスを用いたことを除いては、実施例１と同様にして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。 (Example 3)
A zirconium oxide-containing film was formed on the surface in the same manner as in Example 1, except that glass flakes having an average particle size (D50) of 8 μm and a thickness of 0.3 μm were used as the flake substrates. A flaky substrate was obtained.
（実施例４）
　フレーク状基体として、平均粒径（Ｄ５０）が１２０μｍ、厚さが１．３μｍのフレーク状ガラスを用いたことを除いては、実施例１と同様にして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。 (Example 4)
A zirconium oxide-containing film was formed on the surface in the same manner as in Example 1, except that glass flakes having an average particle size (D50) of 120 μm and a thickness of 1.3 μm were used as the flake substrates. A flaky substrate was obtained.
（実施例５）
　フレーク状基体として、平均粒径（Ｄ５０）が１６０μｍ、厚さが１．３μｍのフレーク状ガラスを用いたことを除いては、実施例１と同様にして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。 (Example 5)
A zirconium oxide-containing film was formed on the surface in the same manner as in Example 1, except that glass flakes having an average particle size (D50) of 160 μm and a thickness of 1.3 μm were used as the flake substrates. A flaky substrate was obtained.
（実施例６）
　酸化ジルコニウム含有膜の形成工程において、滴下時間を４時間３０分としたことを除いては、実施例１と同様にして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。 (Example 6)
A flaky substrate having a zirconium oxide-containing film formed on its surface was obtained in the same manner as in Example 1, except that the dropping time was set to 4 hours and 30 minutes in the step of forming the zirconium oxide-containing film.
（実施例７）
　フレーク状基体の前処理を実施することなく、酸化ジルコニウム含有膜を以下により形成した。用いたフレーク状基体は実施例１と同様である。
・酸化ジルコニウム含有膜の形成
　水１５０ｍＬに塩酸を添加してｐＨを２．０～３．５に調整した。これに尿素０．５ｇと硫酸ジルコニウム２１ｇとを順次添加した。引き続き、これにフレーク状基体６ｇを添加し、さらに１０分間攪拌した。その後、ろ過により粉末と液体とを分離した。その後、得られた粉末を水で洗浄し、９０℃、１．５時間乾燥させ、さらに８００℃で１時間焼成した。こうして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。 (Example 7)
A zirconium oxide-containing film was formed as follows without performing pretreatment of the flake-shaped substrate. The flake-like substrate used is the same as in Example 1.
Formation of Zirconium Oxide-Containing Film Hydrochloric acid was added to 150 mL of water to adjust the pH to 2.0 to 3.5. 0.5 g of urea and 21 g of zirconium sulfate were sequentially added thereto. Subsequently, 6 g of flaky substrate was added thereto and stirred for another 10 minutes. The powder and liquid were then separated by filtration. After that, the obtained powder was washed with water, dried at 90° C. for 1.5 hours, and further calcined at 800° C. for 1 hour. Thus, a flaky substrate having a zirconium oxide-containing film formed on the surface was obtained.
（比較例１）
　酸化ジルコニウム含有膜の形成工程において、滴下時間を４時間４５分としたことを除いては、実施例１と同様にして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。　 (Comparative example 1)
A flaky substrate having a zirconium oxide-containing film formed on its surface was obtained in the same manner as in Example 1, except that the dropping time in the step of forming the zirconium oxide-containing film was 4 hours and 45 minutes.
（比較例２）
　酸化ジルコニウム含有膜の形成工程において、滴下時間を６時間としたことを除いては、実施例１と同様にして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。 (Comparative example 2)
A flaky substrate having a zirconium oxide-containing film formed on its surface was obtained in the same manner as in Example 1, except that the dropping time was changed to 6 hours in the step of forming the zirconium oxide-containing film.
（比較例３）
　日本板硝子社製「メタシャイン（登録商標）ＭＴ１０８０ＲＳ」を用いた。 (Comparative Example 3)
"Metashine (registered trademark) MT1080RS" manufactured by Nippon Sheet Glass Co., Ltd. was used.
　光輝性顔料を用い、表１の処方に基づいてファンデーションを調製した。ファンデーションを肌に塗布し、その外観を以下の指標に基づいて評価した。
４点：肌が自然に明るく見える。ギラツキもない。
３点：肌は明るく見えるが、少しギラツキがある。
２点：肌がやや不自然な色味である。
１点：肌に不自然なギラツキが見られる。
　評価の結果を光輝性顔料の特性と共に表２に示す。 A foundation was prepared based on the recipe in Table 1 using a bright pigment. A foundation was applied to the skin, and its appearance was evaluated based on the following indices.
4 points: The skin looks naturally bright. No glare.
3 points: The skin looks bright but has a little glare.
2 points: The color of the skin is slightly unnatural.
1 point: Unnatural glare is observed on the skin.
The evaluation results are shown in Table 2 together with the properties of the bright pigment.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　なお、各実施例の光輝性顔料のＬ＊は、４０以上６５以下の範囲にあった。これに対し、比較例３の光輝性顔料のＬ＊は、７０を超えていた。 In addition, L * of the bright pigment of each example was in the range of 40 or more and 65 or less. On the other hand, L * of the bright pigment of Comparative Example 3 exceeded 70.
（実施例８）
　フレーク状基体として、平均粒径（Ｄ５０）が１０μｍの日本光研工業株式会社製合成マイカを用いたことを除いては、試料１と同様にして、表面に酸化ジルコニウム含有膜が形成されたフレーク状基体を得た。なお、合成マイカの厚さは数μｍ以下であった。 (Example 8)
Flakes having a zirconium oxide-containing film formed on the surface in the same manner as Sample 1, except that synthetic mica manufactured by Nihon Koken Kogyo Co., Ltd. having an average particle diameter (D50) of 10 μm was used as the flake-shaped substrate. A similar substrate was obtained. The thickness of the synthetic mica was several μm or less.
（比較例４）
　フレーク状基体である合成マイカの表面に酸化チタン含有膜が形成されたメルク社製「Ｔｉｍｉｒｏｎ　Ｉｃｅ　Ｃｒｙｓｔａｌ」を用いた。 (Comparative Example 4)
"Timiron Ice Crystal" manufactured by Merck Co., Ltd., in which a titanium oxide-containing film is formed on the surface of synthetic mica, which is a flake substrate, was used.
　光輝性顔料の特性を表３に示す。 Table 3 shows the properties of the bright pigment.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２及び表３より、各実施例で形成した酸化ジルコニウム含有膜は、酸化チタン含有膜よりも、外観のみならず、光輝性顔料が与える滑らかさの点でも優れていることが理解できる。滑らかさの改善は、フレーク状基体としてフレーク状ガラスを用いた場合、さらにフレーク状基体に錫前処理を実施した場合、に顕著となった。酸化ジルコニウム含有膜による反射光及び輝度は、化粧品の顔料、特に化粧品全体の特性を調整するための顔料に適している。 From Tables 2 and 3, it can be understood that the zirconium oxide-containing film formed in each example is superior to the titanium oxide-containing film not only in appearance but also in terms of smoothness provided by the luster pigment. The improvement in smoothness was remarkable when glass flakes were used as the flake substrates and when tin pretreatment was performed on the flake substrates. Reflected light and brightness by the zirconium oxide-containing film are suitable for cosmetic pigments, especially pigments for adjusting the overall cosmetic properties.
　ＳＥＭを用いて酸化ジルコニウム含有膜を形成したフレーク状基体を観察した結果を図１及び図２に示す。図１に示した断面には、膜厚９０ｎｍの酸化ジルコニウム含有膜が示されている。図１及び図２に示したように、酸化ジルコニウム含有膜は、数十ｎｍ程度の大きさの粒子により緻密に構成されていた。
 
  1 and 2 show the results of observing the flake-shaped substrates on which the zirconium oxide-containing films were formed using SEM. The section shown in FIG. 1 shows a zirconium oxide-containing film with a thickness of 90 nm. As shown in FIGS. 1 and 2, the zirconium oxide-containing film was densely composed of particles with a size of about several tens of nanometers.

Claims (9)

  1. 　光輝性顔料を含む化粧料であって、
    　前記光輝性顔料は、フレーク状基体と、前記フレーク状基体上の酸化ジルコニウムを含む被膜と、を備え、
    　前記被膜の膜厚が４０ｎｍ以上１２０ｎｍ以下である、化粧料。     A cosmetic containing a glitter pigment,
    The bright pigment comprises a flake-shaped substrate and a coating containing zirconium oxide on the flake-shaped substrate,
    A cosmetic, wherein the film thickness of the film is 40 nm or more and 120 nm or less.
  2. 　前記光輝性顔料の平均摩擦係数の平均偏差（ＭＭＤ）が１．５以下である、請求項１に記載の化粧料。 The cosmetic according to claim 1, wherein the average deviation (MMD) of the average coefficient of friction of the bright pigment is 1.5 or less.
  3. 　前記ＭＭＤが０．６以下である、請求項２に記載の化粧料。 The cosmetic according to claim 2, wherein the MMD is 0.6 or less.
  4. 　前記フレーク状基体の平均粒径（Ｄ５０）が１８０μｍ以下である、請求項１～３のいずれか１項に記載の化粧料。 The cosmetic material according to any one of claims 1 to 3, wherein the average particle size (D50) of the flake-like substrate is 180 µm or less.
  5. 　前記フレーク状基体がフレーク状ガラスである、請求項１～４のいずれか１項に記載の化粧料。 The cosmetic material according to any one of claims 1 to 4, wherein the flake-like substrates are flake-like glass.
  6. 　前記光輝性顔料を１０～３５質量％の範囲で含有する、請求項１～５のいずれか１項に記載の化粧料。 The cosmetic composition according to any one of claims 1 to 5, containing the luster pigment in the range of 10 to 35% by mass.
  7. 　前記光輝性顔料とは異なる体質顔料をさらに含み、
    　前記光輝性顔料と前記体質顔料との合計量に対し、前記光輝性顔料を、質量基準で１５～６０％の範囲で含有する、請求項１～６のいずれか１項に記載の化粧料。     further comprising an extender pigment different from the luster pigment,
    The cosmetic according to any one of claims 1 to 6, wherein the bright pigment is contained in a range of 15 to 60% by mass based on the total amount of the bright pigment and the extender pigment.
  8. 　ベースメイクアップ化粧品である、請求項１～７のいずれか１項に記載の化粧料。 The cosmetic according to any one of claims 1 to 7, which is a base makeup cosmetic.
  9. 　ファンデーションである、請求項８に記載の化粧料。 The cosmetic according to claim 8, which is a foundation.
PCT/JP2022/020519 2021-05-17 2022-05-17 Cosmetic material including bright pigment WO2022244767A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06116507A (en) * 1992-10-06 1994-04-26 Nippon Sheet Glass Co Ltd Iridescent luster pigment
JP2002038051A (en) * 2000-07-31 2002-02-06 Nippon Sheet Glass Co Ltd Glass flake and cosmetic material brended with the same
WO2003011235A1 (en) * 2001-08-01 2003-02-13 Nippon Sheet Glass Co., Ltd. Cosmetic
WO2011013654A1 (en) * 2009-07-30 2011-02-03 富士フイルム株式会社 Cosmetic

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06116507A (en) * 1992-10-06 1994-04-26 Nippon Sheet Glass Co Ltd Iridescent luster pigment
JP2002038051A (en) * 2000-07-31 2002-02-06 Nippon Sheet Glass Co Ltd Glass flake and cosmetic material brended with the same
WO2003011235A1 (en) * 2001-08-01 2003-02-13 Nippon Sheet Glass Co., Ltd. Cosmetic
WO2011013654A1 (en) * 2009-07-30 2011-02-03 富士フイルム株式会社 Cosmetic

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