WO2021200781A1 - 粉末含有化粧料 - Google Patents

粉末含有化粧料 Download PDF

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Publication number
WO2021200781A1
WO2021200781A1 PCT/JP2021/013182 JP2021013182W WO2021200781A1 WO 2021200781 A1 WO2021200781 A1 WO 2021200781A1 JP 2021013182 W JP2021013182 W JP 2021013182W WO 2021200781 A1 WO2021200781 A1 WO 2021200781A1
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Prior art keywords
powder
component
titanium oxide
oxide
coated
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PCT/JP2021/013182
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English (en)
French (fr)
Japanese (ja)
Inventor
増渕　祐二
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株式会社コーセー
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Priority to JP2022512183A priority Critical patent/JP7697927B2/ja
Priority to KR1020227000746A priority patent/KR20220161249A/ko
Priority to CN202180005180.0A priority patent/CN114401706B/zh
Publication of WO2021200781A1 publication Critical patent/WO2021200781A1/ja

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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
    • A61K8/26—Aluminium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216—Solid or semisolid forms
    • A61K8/022—Powders; Compacted Powders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/025—Explicitly spheroidal or spherical shape
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A61K8/0254—Platelets; Flakes
    • 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
    • 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
    • A61K8/25—Silicon; Compounds thereof
    • 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
    • A61K8/27—Zinc; Compounds thereof
    • 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
    • A61K8/29—Titanium; 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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/621—Coated by inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/62—Coated
    • A61K2800/623—Coating mediated by organosilicone compounds

Definitions

  • a composite powder having a layered coating of titanium oxide on the surface of mica and further coated with iron oxide, a spherical powder having a specific size, and a specific particle size coated are provided.
  • the powder-containing cosmetics containing titanium oxide more specifically, there is no feeling of burden when spread on the skin, and in particular, stains and color unevenness are uniformly and naturally hidden, and further, it dries over time. It relates to a powder-containing cosmetic that maintains a uniform finish without feeling a feeling and has a high blocking ability in the ultraviolet region.
  • powder-containing cosmetics various concealments have been made for the purpose of naturally and evenly concealing color unevenness such as spots such as chloasma and senile pigment spots and acne scars, which are high concerns for consumers.
  • Powders have been developed and their formulation has been studied.
  • titanium oxide is widely used as a concealing powder because it has a high refractive index and is excellent in whiteness and coloring power, and is also widely used for the purpose of imparting an ultraviolet protection effect.
  • iron oxide is widely used as a coloring pigment for toning to match the skin color of each person.
  • a plate-like powder having an aspect ratio of 10 or more which does not have brilliance, is obtained by coating the surface of mica with two or more of these for the purpose of having an ultraviolet protection effect and excellent moldability.
  • a solid powder cosmetic that protects the skin from ultraviolet rays while naturally hiding stains and uneven color has been developed (see, for example, Patent Document 1).
  • a plate-shaped powder coated with fine particle inorganic powder having a high ultraviolet protection effect and a spherical powder similarly coated with fine particle inorganic powder the ultraviolet protection effect and usability are excellent. Powder cosmetics have been developed (see, for example, Patent Document 2).
  • spherical powders with various particle sizes and compositions have been developed as powders that make skin irregularities such as pores and wrinkles inconspicuous, and spherical cellulose powders that impart a soft focus effect by diffuse reflection of visible light.
  • spherical powders with various particle sizes and compositions have been developed as powders that make skin irregularities such as pores and wrinkles inconspicuous, and spherical cellulose powders that impart a soft focus effect by diffuse reflection of visible light.
  • Cosmetics having a smooth feel without stickiness and excellent long-lasting stability have been developed (see, for example, Patent Document 5).
  • Japanese Patent No. 05558061 Japanese Unexamined Patent Publication No. 2012-240999 Japanese Unexamined Patent Publication No. 2017-081858 JP-A-2007-145778 Japanese Unexamined Patent Publication No. 2013-23120
  • Patent Document 1 As a method of coating plate-shaped mica with titanium oxide, a method of mixing titanium oxide and mica using a bead mill or the like and fixing them is performed, but titanium oxide is used.
  • the surface of the mica may not be uniformly coated, and the UV blocking ability and the feel without a feeling of burden may be inferior, and there is room for further improvement in the coating method and the composition constituting the composite powder.
  • the fine particle inorganic powder coated on the plate-like powder is in the form of specific particles, and the smoothness of the surface is inferior to that of the one coated in the layered form, so that the spread and spread are poor, and oil absorption In some cases, the amount became high and a feeling of dryness was felt, and it was difficult to evenly line up on the skin surface. It has been desired to develop a plate-like powder that maximizes the ability to block ultraviolet rays, has no brilliance, is coated with a metal oxide in a layered manner, arranges smoothly on the skin, and does not give a feeling of dryness.
  • the present inventors have a composite powder having a specific size and a non-brilliant composite powder in which titanium oxide is layer-coated on the surface of mica and further coated with iron oxide.
  • titanium oxide is layer-coated on the surface of mica and further coated with iron oxide.
  • the present invention is based on the technical idea of orienting spherical powder having a specific particle size in the skin groove while orienting iron oxide and titanium oxide-coated plate-like mica in the skin hills, and the following components (A). )-(C), and further (D), the powder-containing cosmetics.
  • Powder-containing cosmetics containing ⁇ 1.2 ⁇ m of titanium oxide and / or zinc oxide [2] The powder-containing cosmetic according to the above [1], wherein the titanium oxide of the component (A) does not take a particle shape on the surface of mica, and the average thickness of the titanium oxide layer is 50 to 100 nm. [3] The powder-containing cosmetic according to the above [1] or [2], wherein the component (A) is further coated with a hydrophobizing agent.
  • the powder according to any one of [1] to [6] above, wherein the coating film obtained by applying a solution in which 40% by mass of the component (A) is dispersed and dried has a transmittance of less than 25% at wavelengths of 300 nm and 360 nm, respectively. It is a contained cosmetic.
  • the powder-containing cosmetic according to any one of the above [1] to [7] which contains 2 to 40% by mass of a powder surface-treated with the component (D) crosslinked silicone.
  • the present technology can additionally adopt the following configurations.
  • the cosmetic film of the solid powder-containing cosmetic according to any one of [1] to [11] is arranged with the component (A) in the skin hill and the component (B) in the skin groove recess. It is a makeup method characterized by.
  • the powder-containing cosmetic of the present invention has a natural and uniform hiding effect against stains and color unevenness while having a high ultraviolet blocking effect, and further, the uniform finish can be achieved for a long time without feeling dry. Can be sustained.
  • Iron oxide / titanium oxide coated sericite of the present invention prepared by the precipitation method (Production Example 5) Conventional titanium oxide / zinc oxide coated sericite prepared by adsorption method (Production Comparative Example 1)
  • the present invention is not limited to the following preferred embodiments, and can be freely changed within the scope of the present invention.
  • the percentage is expressed by mass unless otherwise specified.
  • the range shall include the numerical values at both ends.
  • the "average particle size" in the present invention is measured by observing the surface state using a scanning electron microscope (JSM-7800 prime manufactured by JEOL Ltd.) and measuring with an image analyzer (Luzex AP, manufactured by Nireco). It is a obtained value (median diameter D50) and refers to the major axis of the particles.
  • Component (A) used in the present invention A plate-like composite powder having no brilliance, in which 30 to 50% by mass of titanium oxide is layered on the surface of mica, and 0.1 to 3% by mass of iron oxide is further coated.
  • the resulting composite powder has a uniform finish, lasts for a long time without feeling dry, and has a high ultraviolet blocking effect.
  • the mica used as the mother powder of the plate-shaped composite powder of the component (A) of the present invention has a plate-like shape, and is a natural mica such as phlogopite, muscovite, and sericite among them. Examples thereof include synthetic phlogopite and synthetic mica such as (fluoride / hydroxylation / oxidation) / (Mg / K / silicon).
  • the aspect ratio is preferably 10 to 50, more preferably 10 to 30, and when the aspect ratio is small, the amount of titanium oxide coated is small, so that the ultraviolet blocking effect is inferior and the orientation to the skin hills is poor. It may drop and be inferior to a uniform cosmetic film. Further, when the aspect ratio is large, the bulk specific gravity becomes high, so that the amount to be blended in the powder-containing cosmetic may be limited.
  • those with high whiteness are preferable, and sericite, which does not have brilliance when compounded in layers, and less discoloration when wet with an oil agent, and the surface is treated when coating. Synthetic phlogopite, which can control the brilliance and adhesion of metal oxides, is preferable, and sericite, which can be obtained at low cost, is more preferable.
  • a surface of titanium oxide or iron oxide prepared in advance is mechanochemically surfaced by using mechanical force such as a bead mill, a Henschel mixer or a solventizer.
  • mechanical force such as a bead mill, a Henschel mixer or a solventizer.
  • the method of densely depositing and growing titanium oxide on the surface of mica hereinafter referred to as the precipitation method. (Note).
  • suspending mica in a dilute strong acid solution of titanyl sulfate at ambient temperature rapidly heating to 90-100 ° C., and sustaining this temperature for about 2-3 hours to hydrolyze the titanium sulfate solution.
  • the method of depositing the hydroxide-containing oxide layer on the substrate or by suspending the substrate in boiling water, rapidly adding a strongly acidic concentrated titanyl sulfate solution, and continuing the heating boiling water until the hydrolysis is completed.
  • Examples thereof include a method of causing hydrolysis and precipitation of hydroxide-containing titanium on mica.
  • titanium oxide having an ultraviolet blocking ability can be coated on the entire surface of the plate-shaped mica in a layered manner, so that titanium oxide does not aggregate and feels a burden as compared with the conventional adsorption method. A composite powder with no feel can be obtained.
  • the amount of titanium oxide in the component (A) of the present invention is preferably 30 to 50%.
  • the ultraviolet blocking effect is inferior, and when the blending amount exceeds 50%, the mica surface.
  • the amount is excessive, and it is difficult to form a uniform layer, and the particles cannot be composited and precipitate as particles alone. In that case, the feeling of spreading and spreading is inferior, and the composite powders aggregate with each other, and the ultraviolet blocking ability cannot be effectively obtained. Furthermore, it becomes difficult to arrange them smoothly on the skin, and a uniform hiding effect cannot be expected. You may feel dry.
  • the layered coating means that titanium oxide on the surface of mica does not take a particle shape on the surface of mica.
  • the thickness of the titanium oxide layer is preferably 50 to 100 nm, and the layer is preferably smooth with few irregularities, but the thickness is not particularly limited. Within the thickness range of this layer, the covering power is hard to come out, the ultraviolet blocking effect is high efficiently, it is easy to realize uniform spreading and spreading especially in the skin hills, and there are few irregularities and the oil absorption amount is hard to be high. It is possible to reduce the feeling of dryness in the skin hills where the feeling of dryness is easily felt.
  • the method of further coating the mica coated with the titanium oxide of the component (A) of the present invention with iron oxide is not particularly limited, such as a dry method or a wet method, but for example, a slurry of a coating pigment can be used.
  • a slurry of a coating pigment can be used.
  • the amount of iron oxide in the component (A) of the present invention is not particularly limited, but as a lower limit, 0.1% or more is preferable, 1.0% or more is more preferable, and 1.5% is further. preferable.
  • the upper limit is preferably 5% or less, more preferably 3%, and even more preferably 2.5%. Within this range, the paleness of the composite powder itself can be reduced, and a natural color tone that is more familiar to the skin can be obtained. Further, the amount of iron oxide separately blended in the powder-containing cosmetic can be reduced, the cohesiveness of iron oxide can be reduced, and the ultraviolet blocking effect, particularly the UVA region can be improved.
  • the ultraviolet blocking effect is further enhanced, the antiseptic power is also improved, and it may be easy to react with the surface treatment agent to form a metal soap, which is a preferable effect. Further can be granted. This coverage range is more preferable because the cohesive force of zinc oxide does not hinder uniform spreading and spreading.
  • the amount of the surface treatment of each metal contained in a sample is a sample prepared by using a general method and ICP (Inductively Coupled Plasma; inductively coupled plasma; RACOS; (Germany Spectro)) It can be obtained by measurement by luminescence analysis.
  • ICP Inductively Coupled Plasma; inductively coupled plasma; RACOS; (Germany Spectro)
  • the UV transmittance of the component (A) composite powder of the present invention was evaluated under the following conditions. First, a composite powder of component (A) is added to a nitrocellulose solution containing 43.4% butyl acetate, 21.0% ethyl acetate, 14.6% IPA, and 21.0% nitrocellulose so that the concentration of the composite powder of component (A) is 40%. After the addition, the mixture was dispersed under the conditions of a discharger rotation speed of 3000 rpm and 10 minutes.
  • a coating film was prepared on a quartz plate so that the thickness was the same, and a dried coating film was used as a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.).
  • the transmittance of the coating film in the wavelength range of 250 to 700 nm was measured.
  • a transmittance of 360 nm was used for evaluating the blocking ability of the UVA region of 320 to 400 nm, and a transmittance of 300 nm was used for evaluating the blocking ability of the UVB region of 280 to 320 nm.
  • the transmittance is preferably less than 50%, and more preferably less than 25%.
  • the average particle size of the component (A) of the present invention is not particularly limited.
  • the lower limit is preferably 3 ⁇ m or more
  • the upper limit is preferably 30 ⁇ m or less, and more preferably 20 ⁇ m or less.
  • those having a uniform particle size distribution are more preferable because they tend to form a uniform cosmetic film.
  • the component (A) of the present invention preferably has a low oil absorption amount.
  • the oil absorption amount of the present invention is defined as the oil absorption amount for triethylhexanoin, which is a triglyceride similar to sebum.
  • the end point is the time when triethylhexanoin, which is one of the components, is gradually added to form a slurry.
  • it is not particularly limited, but 100 ml / 100 g or less is preferable, and 70 ml / 100 g or less is preferable.
  • the component (A) of the present invention has a plate shape, it easily adheres to the smooth convex portion of the skin. It is a material that tends to be expensive. If the amount of oil absorbed is too high, the sebum on the surface of the skin is removed, so that a feeling of dryness is easily felt, and it may be necessary to adjust appropriately by excessively blending the amount in the cosmetic or the amount of surface treatment.
  • the component (A) of the present invention can be treated with a hydrophobic surface to reduce smooth spread and dryness and further improve makeup durability.
  • the hydrophobizing agent is not particularly limited, but details will be described later.
  • the lower limit of the blending amount of the component (A) used in the present invention in the powder-containing cosmetic is preferably 1% or more, more preferably 3% or more, still more preferably 5% or more.
  • the upper limit is preferably 50% or less, more preferably 30% or less, still more preferably 15% or less. Within this range, particularly good ones can be obtained in terms of the expression of the ultraviolet blocking effect, the natural finish, and the lack of dryness.
  • the spherical powder of the component (B) used in the present invention has an average particle size of 1 to 40 ⁇ m.
  • the spherical shape has a ratio of major axis to minor axis: major axis / minor axis of 1 to 1.5, and may have fine irregularities on the surface or a hollow inside.
  • the average particle size is preferably 1 ⁇ m or more and 3 ⁇ m or more, and as the upper limit, 40 ⁇ m or less and 30 ⁇ m or less are preferable. If the average particle size is smaller than 1 ⁇ m, the cohesiveness increases in the skin groove and the effect of hiding irregularities such as pores and wrinkles is inferior. Not preferable.
  • the material is not particularly limited, but nylon powder, polystyrene powder, polyethylene powder, polymethylmethacrylate resin powder, silicone resin powder, polyurethane powder, cellulose powder, cellulose acetate powder, silk powder, starch, calcium polyalginate, silicone, urethane, etc.
  • examples thereof include organic powder, silica, and inorganic powder such as calcium carbonate. Due to the background of recent environmental problems of microplastic beads, the blending of spherical cellulose, silica, calcium carbonate and starch is more preferable.
  • a metal oxide may be composited on the surface of the component (B), and even if particles having a diameter of 10 to 1200 nm are precipitated or adsorbed on the surface, they are contained inside the component (B). May be good.
  • the metal oxide is not particularly limited, but titanium oxide, zinc oxide, aluminum oxide, and cerium oxide are preferable, and the component (C) may be compounded with the component (B) in advance.
  • the blending amount of the component (B) of the present invention is not particularly limited, but as a lower limit, 0.5% or more is preferable, 2% or more is more preferable, and 5% or more is further preferable.
  • the upper limit is preferably 30% or less, more preferably 25% or less, still more preferably 20% or less. Within this range, it is possible to enter the concave portion of the skin, make the unevenness inconspicuous, adsorb sebum, and maintain a uniform cosmetic film.
  • the oil absorption of the spherical powder of the component (B) is not particularly limited, but the oil absorption of triethylhexanoin, which is a triglyceride similar to sebum, is preferably 60 ml / 100 g or more, more preferably 70 ml / 100 g or more as the lower limit.
  • As the upper limit 350 ml / 100 g or less is preferable, and 200 ml / 100 g or less is more preferable.
  • the spherical powder oriented in the vicinity of the pores in the skin groove absorbs sebum appropriately, the makeup lasts well, and the sebum is not absorbed more than necessary, so that a feeling of dryness is not felt.
  • a powder having porosity is preferable.
  • silicone resin powder KSP-100 (oil absorption: 80 ml / 100 g) (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • plastic powder CS-400 oil absorption: 90 ml / 100 g)
  • silica manufactured by Negami Kogyo Co., Ltd.
  • Godball D11-796C oil absorption amount 83-89 ml / 100 g
  • Godball E-90C 110-140 ml / 100 g
  • crosslinked poly For methyl methacrylate, for example, MBP-8 (oil absorption amount 140 ml / 100 g
  • the coated titanium oxide and / or zinc oxide of the component (C) is one or two selected from silicon oxide or hydroxide, aluminum oxide or hydroxide, and iron oxide or hydroxide. Titanium oxide and / or zinc oxide coated with.
  • the titanium oxide and / or zinc oxide particles, which are the parent nuclei of the coated titanium oxide and / or zinc oxide of the present invention, are not particularly limited in shape, but titanium oxide alone or titanium oxide contains zinc oxide. Or zinc oxide alone (hereinafter referred to as the mother nucleus).
  • Titanium oxide which is the mother nucleus before coating in the coated titanium oxide and / or zinc oxide of the component (C), can be obtained by using a known method for producing titanium oxide powder, and a commercially available product is used as the mother nucleus. It is also possible to use it. Titanium oxide, which is the mother nucleus, has anatase-type and rutile-type crystal forms, but the rutile-type, which has low photocatalytic activity and high refractive index, is preferable. Alternatively, in order to stabilize the crystal shape, it is preferable to include a small amount of zinc oxide in the titanium oxide powder as the mother nucleus, and the zinc oxide content in the titanium oxide as the mother nucleus is preferably in terms of oxide mass.
  • zinc oxide which is the mother nucleus, can be used alone. This zinc oxide can be obtained by using a known method for producing zinc oxide.
  • titanium oxide and / or zinc oxide which is the parent core of the component (C)
  • the shape of titanium oxide and / or zinc oxide, which is the parent core of the component (C) is not particularly limited, and examples thereof include straw bundle shape, strip shape, spherical shape, needle shape, rod shape, and plate shape.
  • titanium oxide and / or zinc oxide used as the mother nucleus of the present invention preferably has a spherical or plate shape having a relatively smooth surface.
  • the coated titanium oxide and / or zinc oxide of the component (C) is preferably coated with the surface treatment amount of each metal in a specific range as follows. By setting this range, it is possible to obtain a better natural three-dimensional appearance of the skin, and further reduce the paleness and yellowing of the skin, thereby providing a natural and uniform hiding effect. can.
  • the surface treatment amount of aluminum in the coated titanium oxide and / or zinc oxide of the component (C) is preferably 1 to 6%, more preferably 1 to 5%, still more preferably 2 to 5% in terms of oxide mass.
  • the surface treatment amount of silicon is preferably 0.5 to 6%, more preferably 1 to 6%, still more preferably 3 to 6% in terms of oxide mass.
  • the amount of iron surface-treated is preferably 0.5 to 3%, more preferably 0.5 to 2%, and even more preferably 0.5 to 1.5% in terms of oxide mass.
  • the content of the component (C) is preferably 0.5% or more, more preferably 3% or more, still more preferably 5% or more as the lower limit value thereof. Further, as the upper limit value, 30% or less is preferable, 20% or less is more preferable, and 15% or less is further preferable.
  • the component (C) one in which the surface of the mother nucleus is coated with an oxide or hydroxide of silicon is preferable because the dispersibility is improved and a uniform hiding power is imparted.
  • the oxide or water of aluminum is used. More preferably, it is coated with an oxide, or an oxide or hydroxide of iron. Further, it is more preferable that each of these layers (hereinafter, each layer is also referred to as “silicon coating layer”, “aluminum coating layer”, and “iron coating layer”) is provided. It is even more preferable that the surface of the particles in which the silicon coating layer and the aluminum coating layer coexist is coated with an iron oxide or a hydroxide.
  • the component (C) is uniformly dispersed regardless of the unevenness of the skin, and appropriately adheres to the surfaces of the components (A) and (B) without hindering the spread and spread of the components (A) and (B).
  • the presence of an iron-coated layer is preferable because it increases the familiarity with the skin color, has a natural finishing effect even though it has a hiding power, and the collapse of the makeup film is inconspicuous, so that the makeup lasting effect is enhanced.
  • the method of coating the component (C) with the above-mentioned silicon oxide or hydroxide is not particularly limited, and a known coating method can be used.
  • Disperse in water or an alcohol-water mixed solvent, etc. add an alkoxysilane-based metal coupling agent such as tetraethoxysilane, add an acid or base, or heat to remove silica or its hydroxide. Examples thereof include a method of precipitating.
  • the coated powder particles are obtained by washing, filtering, drying and the like.
  • the method of coating the component (C) with the aluminum oxide or hydroxide is not particularly limited, and a known coating method can be used.
  • a method of adding aluminum nitrate, aluminum sulfate, sodium aluminate or the like as it is or as an aqueous solution to an aqueous slurry containing raw material particles, and then adding an acid or alkali to precipitate an aluminum compound and the like can be mentioned.
  • the raw material particles are dispersed in a solvent (alcohol, water, or a mixed solvent of alcohol-water, etc.), an aluminum-based metal coupling agent is added, an acid or a base is added, or the mixture is heated to produce aluminum or hydroxide. Examples thereof include a method of precipitating an object. Then, the coated powder particles are obtained by washing, filtering, drying and the like.
  • the method of coating the component (C) with the iron oxide or hydroxide is not particularly limited, and a known iron oxide coating treatment method can be used.
  • a known iron oxide coating treatment method can be used.
  • an aqueous solution of caustic soda is heated to 30 to 35 ° C., powder particles are dispersed, an aqueous solution containing ferric sulfate is added and stirred, and the reaction is carried out at 90 ° C. for about 2 hours.
  • the obtained composite compound is washed with water, neutralized and dried.
  • the raw material particles and iron oxide or hydroxide can be obtained by firing (for example, about 750 to 900 ° C. for about 1 to 3 hours).
  • iron compound examples include ferric oxide, ferrous oxide, ferric tetraoxide, iron hydroxide, iron organic acid (for example, iron oxalate, iron citrate, etc.), and iron inorganic acid (for example, iron chloride, ferrous sulfate). (Iron, iron sulfate, etc.), etc.), and one or more can be selected from these groups.
  • the iron compound is present in the particles as iron oxide or iron hydroxide.
  • the average particle size D50 by the transmission electron microscope image analysis method is preferably 0.10 ⁇ m or more, more preferably 0.20 ⁇ m or more, and 0 as the lower limit value thereof. More preferably .25 ⁇ m or more.
  • the upper limit is preferably 1.20 ⁇ m or less, more preferably 1.00 ⁇ m or less, further preferably 0.8 ⁇ m or less, and even more preferably 0.50 ⁇ m or less.
  • the components (A), component (B), and component (C) of the present invention may be further surface-treated as long as the effects of the present invention are not impaired.
  • This surface treatment can be performed by using a known powder surface treatment method.
  • surface treatments such as water repellency and / or oil repellency, for example, silicone compounds (for example, dimethylpolysiloxane, methylhydrogenpolysiloxane, etc.), coupling agents (for example, silane-based such as alkylalkoxysilane treatment, aluminum).
  • fluorine compound for example, perfluoroalkylalkoxysilane treatment
  • hydrocarbon for example, lecithin / hydrogenated lecithin, amino acid / peptide, amino acid derivative (for example, as N-acylamino acid treatment, lauroyl lysine treatment, di Treatment with lysine Na lauroyl glutamate, 2Na stearoyl glutamate, Na lauroyl aspartate), polyethylene, wax, fatty acids (eg stearic acid, palmitic acid, myristic acid), fatty acid salts, fatty acid esters, fatty acid amides, metal soaps, etc. be able to.
  • fatty acids eg stearic acid, palmitic acid, myristic acid
  • fatty acid salts fatty acid esters, fatty acid amides, metal soaps, etc. be able to.
  • component (D) further contains a powder treated with dimethiconol and aminopropyltriethoxysilane.
  • Component (D) is represented by the following general formula both terminal reactive diorganopolysiloxane R 1 R 2 2 SiO- represented by (1) (R 2 2 SiO ) L -SiR 1 R 2 2 (1) (In the formula, each R 1 represents a hydroxyl group, each R 2 independently represents a hydrocarbon group having 1 to 20 carbon atoms, and L represents an integer of 3 to 10,000) and.
  • R 3 represents a hydrocarbon group having at least one amino group and having 1 to 20 carbon atoms
  • R 4 represents an alkyl group having 1 to 4 carbon atoms
  • X independently represents 1 carbon number.
  • component (D) a polymer having a fine three-dimensional crosslinked structure of silicone obtained by condensation reaction of the above surface coating treatment agents (1) and (2) (hereinafter, “silicone microcrosslinked”). It is a powder whose surface is coated with (referred to as "thing").
  • the silicone microcrosslinked product may be a compound having no rubber elasticity, and the content mass ratio of (a) and (b) can be obtained in a range of approximately 100: 0.1 to 100: 35.
  • (b) is less than 0.1% by mass, it becomes a viscous silicone oil or gum, and when it is more than 35% by mass, it becomes an elastic silicone elastomer, and the water repellency of the surface-coated powder is lowered.
  • the component (D) it is preferable to contain a polymer having a dimethicone structure having a three-dimensional crosslinked structure in a part obtained by cross-linking an organopolysiloxane.
  • the polymer having a dimethicone structure having a three-dimensional crosslinked structure is not particularly limited, but a polymer having a structure crosslinked with divinyldimethylpolysiloxane or a polymer having a structure crosslinked with an alkyl group having 3 to 20 carbon atoms. Is preferable.
  • the shape is not particularly limited as long as it can cover the powder surface.
  • Examples thereof include a cross-polymer crosslinked with divinyldimethylpolysiloxane (dimethicone / vinyldimethicone) and a dimethicone crosspolymer having an alkyl group in the crosslinked portion. Further, there is no particular limitation on the polymer containing a polyoxyalkylene group in the molecule or the polymer containing a polyoxyalkylene group and a long-chain alkyl group in the molecule.
  • the blending amount of the component (D) is preferably 1 to 50% in the powder-containing cosmetic, and a more preferable range is 2 to 40%. Within this range, particularly good ones can be obtained in terms of expression of effect and finish.
  • the components (A), (B), and (C) may be surface-treated with the surface treatment agent of the component (D).
  • dipropylene glycol, 1,2-alkanediol, ethylhexyl glycerin, and chlorphenesin may be blended as the component (E) preservative.
  • the components (A) to (C) can bring about an antiseptic effect without being hindered from spreading and spreading.
  • the blending amount of the component (E) is preferably 0.001 to 0.5% in the powder-containing cosmetics, and a more preferable range is 0.01 to 0.3%. Within this range, the antiseptic property of the powder-containing cosmetic can be ensured, and the powder-containing cosmetic that does not interfere with the usability, maintains the makeup durability, and further secures the safety to the skin is provided. be able to. In particular, it is more effective in providing powder-containing cosmetics without using parabens.
  • the powder-containing cosmetic of the present invention may contain other arbitrary ingredients depending on the purpose as long as the effects of the present invention are not impaired.
  • oily ingredients pigments, pH regulators, moisturizers, thickeners, surfactants, dispersants, stabilizers, colorants, preservatives, antioxidants, metal sequestering agents, astringents, anti-inflammatory agents, ultraviolet rays.
  • absorbents include absorbents, fragrances, and other pigments.
  • the powder-containing cosmetic of the present invention is not particularly limited as long as it is a dosage form containing a large amount of powder or a dosage form that requires an ultraviolet blocking ability.
  • Preferred examples include powder, powder solid, oily, oily solid, emulsified type and emulsified solid.
  • Applications of the present invention to powder-containing cosmetics include, for example, make-up cosmetics (for example, white powder, base, foundation, concealer, face powder, control color, sunscreen cosmetics, eye shadow, eye liner, mascara, teak. It can be used for color, body powder, perfume powder, baby powder, etc.), body cosmetics, etc. Of these, white powder, foundation, foundation, concealer, face powder, control color, sunscreen cosmetics, body powder, etc. are preferable and can be used for the face because a natural three-dimensional effect can be obtained by using the present invention. Powder-containing cosmetics are more preferred.
  • Table 1 shows the evaluation method of the component (A) as a material and the evaluation result.
  • Production Examples 1 to 9 Manufactured by the precipitation method A.
  • the aspect ratio of the mother body is 20 to 30 for Production Examples 1 to 3, 5 to 8, 10 to 20 for Production Example 4, and 68 for Production Example 9.
  • the amount of oil absorbed in Production Example 4 is 65 ml / 100 g.
  • Production Example 5 is 63 ml / 100 g.
  • Production Comparative Example 1 Manufactured by adsorption method B (mixed at 3000 rpm with a high-speed Henschel mixer and crushed with a palberizer).
  • MT-500B (manufactured by TAYCA), MZ-300 (manufactured by TAYCA), Sanshin Sericite FSE (manufactured by Sanshin Mining Co., Ltd.), and 3% isostearic acid are mixed.
  • Production Comparative Example 2 Manufactured by the same adsorption method B as in Production Comparative Example 1.
  • MT-150EX (manufactured by TAYCA) Average particle size 15 nm Titanium oxide content 40%, TRY-100HP 1%, TRR-100HP 0.5% (manufactured by Titanium Kogyo), Sericite LQ-15 (manufactured by Ochem Trading Co., Ltd.) mixture.
  • Manufacturing Comparative Example 3 Cover Leaf PC-2035M (manufactured by Catalytic Chemical Industry Co., Ltd.)
  • Manufacturing Comparative Example 4 STA-20C (manufactured by Japan Sericite) Mother (Sun Sericite FSE (manufactured by Japan Sericite))
  • Manufacturing Comparative Example 5 Blondii Metallic Gold N-2000S (manufactured by CQV)
  • FIG. 1 shows a photograph of the surface condition observed at a magnification of 5000 to 100,000 times.
  • FIG. 1 a portion where the titanium oxide layer deposited on the surface of the mica of the mother body was partially peeled off was formed, enlarged, and the thickness of the titanium oxide layer was confirmed at 20 places. As a result, the thickness was 50 to 100 nm. ..
  • FIG. 2 shows a zinc oxide / titanium oxide coated mica prepared by the mechanochemical method (Production Comparative Example 1).
  • EDX energy dispersive X-ray analysis
  • UVB transmittance (300 nm), UVA transmittance (360 nm) The ultraviolet blocking ability of the composite powder of the component (A) of the present invention was evaluated under the following conditions. First, a composite powder of component (A) is added to a nitrocellulose solution containing 43.4% butyl acetate, 21.0% ethyl acetate, 14.6% IPA, and 21.0% nitrocellulose so that the concentration of the composite powder of component (A) is 40%. After the addition, the mixture was dispersed under the conditions of a discharger rotation speed of 3000 rpm and 10 minutes.
  • a coating film was prepared on a quartz plate so that the dispersion had the same thickness using a doctor blade (thickness of 12 ⁇ m), and a dried coating film was used as a spectrophotometer (manufactured by U-4100 HITACHI). ), The transmittance of the coating film in the wavelength range of 250 to 700 nm was measured.
  • a transmittance of 360 nm was used, and as an evaluation of the blocking ability of the UVB region of 280 to 320 nm, a transmittance of 300 nm was used to block a wide range of UVB to UVA. I evaluated it in consideration of what I was doing.
  • Table 1 shows the evaluation results of each composite powder and its transmittance and blocking ability. The evaluation level was evaluated at the following levels.
  • the composite powders of Production Examples 1 to 9 are excellent in uniform spreading and lack of covering power, while in Production Comparative Examples 1 and 2, titanium oxide and zinc oxide are formed into particles on the surface of mica. Since it was fixed, the unevenness was large, and it was not possible to obtain a uniform spread and spread with a squeaky and powdery feel, and the particles were also partially aggregated to easily provide covering power. Although the production comparative examples 3, 4, and 5 still have uniform spread and spread, the ultraviolet blocking ability is low, and the production comparative example 5 has a brilliant property, so that the covering power is particularly easy to be obtained.
  • a powder foundation having the composition shown in Tables 2 and 3 was prepared according to the following production method. Regarding the powder foundation obtained together, the following evaluation methods were used to "no burden when spread on the skin”, “effect of evenly hiding stains and uneven color”, “natural finish”, and “natural finish”. We evaluated “no feeling of dryness over time”, “makeup lasting effect”, and “ultraviolet ray blocking effect”.
  • Comparative Example 4 in which the fine particle metal oxide and the component (D) were contained instead of the component (A) had "no burden when spread on the skin", “natural finish”, and “aged time”. It was inferior in “no dryness” and "makeup lasting effect". It is presumed that all of these are due to the fact that the component (A) is not uniformly applied to the skin hills, the component (A) has no concealing effect, and its cosmetic effect is reduced. Comparative Example 5 in which the component (C) was not contained and instead contained a metal oxide, "there was no feeling of burden when spread on the skin”, “the effect of uniformly hiding stains and color unevenness", The effect of "makeup lasting effect" was not satisfied.
  • Comparative Examples 6 and 7 containing no component (B) were inferior in "effect of uniformly concealing stains and color unevenness", “natural finish”, and "makeup lasting effect". It is presumed that this is because the sebum-absorbing ability of the component (B), which is considered to be present in the skin groove, is inferior, and therefore the cosmetic film could not be maintained due to sebum secretion over time. Further, Comparative Example 9 containing particles larger than the component (C) was further inferior in "no feeling of burden when spread on the skin”. In Comparative Example 8 in which the component (C) was not contained and the amount of the component (A) was increased, although the "ultraviolet ray blocking effect" was high, "there was no burden when it was spread on the skin” and "makeup lasting effect”. Was inferior to.
  • Example 17 Solid powder foundation (ingredient) (%) 1.
  • Phospholipid treatment of Production Example 2 2% 10.0 2.
  • Iron oxide 1.5%
  • Aluminum hydroxide 2%
  • Hydrous silicate 3% Dimethicone 0.5%
  • Zinc oxide-containing titanium oxide (average particle size 400 nm) 15.0 3.
  • Mica remaining amount 6.
  • Boron Nitride 5.0
  • Dimethicone-treated low-temperature calcined zinc oxide * 9 5.0
  • Yellow iron oxide 1.5
  • Bengala 0.5
  • Example 17 The solid powder foundation of Example 17 has "no burden when spread on the skin”, “effect of uniformly hiding stains and uneven color”, “natural finish”, and “dryness over time”. It was excellent in “nothing”, “makeup lasting effect”, and “ultraviolet ray blocking effect”.
  • Example 18 Solid powder blusher (prescription) (%) 1.
  • Boron Nitride 10.0 4.
  • N-lauroyl-L-lysine * 14 5.0 5.
  • Mica Titanium 5.0 7. Red No. 226 0.5 8. Yellow No. 4 1.0 9. Blue No. 1 0.1
  • Bengala 0.5
  • Silica anhydride average particle size 20 ⁇ m hollow
  • the solid powder blusher of Example 18 has "no burden when spread on the skin”, “effect of uniformly hiding stains and uneven color”, “natural finish”, and “dryness over time”. It was excellent in “nothing”, “makeup lasting effect”, and “ultraviolet ray blocking effect”.
  • Example 19 Solid powder eyeshadow (ingredient) (%) 1. 1. Synthetic phlogopite (average particle size 20 ⁇ m) 10.0 2. Talc remaining amount 3. Titanium oxide coated mica 20.0 4. Boron Nitride 5.0 5. Polyethylene terephthalate / aluminum / epoxy laminated powder 5.0 6. Iron oxide 1.5% hydrous silicic acid 2% treated plate-shaped zinc oxide (average particle size 300 nm) 2.0 7. Zinc laurate treatment of Production Example 3 2% 5.0 8. Red 202 0.5 9. Cornstarch * 16 5.0 10.1,2-Alkanediol Appropriately 11. Liquid paraffin 3.0 13. Dimethylpolysiloxane 5.0 14.2-Glyceryl ethylhexanoate 3.0 15. Appropriate amount of fragrance * 16: Local cornstarch (manufactured by Japan Corn Starch)
  • the solid powder eyeshadow of Example 19 has "no burden when spread on the skin”, “effect of uniformly hiding stains and uneven color”, “natural finish”, and “aging”. It was excellent in “no dryness”, “makeup lasting effect”, and “ultraviolet ray blocking effect”.
  • Example 20 Solid powder face color (ingredient) (%) 1.
  • Amino modified silicone treated mica 20.0 2.
  • Zinc laurate treated talc Remaining amount 3.
  • Phospholipid treatment Bengala aluminum hydroxide, hydrous silicic acid treatment Titanium oxide (average particle size 400 nm) Table 1 No. 9 3.0 4.
  • Dimethicone 2% treatment of Production Example 6 5.0 5.
  • Ultramarine 0.5 6.
  • Calcium carbonate * 17 1.0 8.3- (4-chlorophenoxy) -1,2-propanediol 0.3
  • Liquid paraffin 2.0 10.
  • Dimethylpolysiloxane 3.0 11.2-Glyceryl ethylhexanoate 3.0 12.
  • the solid powdery face color according to Example 20 has "no burden when spread on the skin”, “effect of uniformly hiding stains and uneven color”, and “natural finish”. It was excellent in “no feeling of dryness over time”, “makeup lasting effect”, and “ultraviolet ray blocking effect”.
  • Example 21 Powdered white powder (ingredient) (%) 1.
  • Crosspolymer 20.0 2.
  • N-lauroyl-L-lysine 10.0 4.
  • Silica average particle size 15 ⁇ m: oil absorption 68 ml / 100 g) 2.0
  • Boron nitride 2.0 7.
  • the white powder according to Example 21 has "no feeling of burden when spread on the skin”, “effect of uniformly hiding stains and uneven color”, “natural finish”, and “no feeling of dryness over time”. , “Makeup lasting effect” and “UV blocking effect” were excellent.
  • Example 22 Foundation (ingredient) (%) in the capillary region 1.
  • Stearoyl glutamic acid 2Na 3% treated yellow iron oxide 2 2.
  • Lauroyl lysine 2 5.
  • Amino-modified silicone 1% treated synthetic phlogopite 5 6.
  • Zinc laurate 2% treated talc Remaining amount 7.
  • Hydrogenated palm kernel oil 2% treatment of Production Example 4 8
  • Spherical silica * 18 4 8.
  • Borosilicate (Ca / Al) 8 10. Treatment with 2% lysine Na dilauroyl glutamate Table 1 No. 11 8 11.
  • the foundation in the capillary region of Example 22 has "no burden when spread on the skin”, “effect of uniformly hiding stains and uneven color”, “natural finish”, and “dryness over time”. It was excellent in “nothing”, “makeup lasting effect”, and “ultraviolet ray blocking effect”.
  • Example 23 Concealer (oil-based solid) (Ingredient) (%) 1. 1. Dextrin palmitate (Leopal TL) 1.0 2. (Palmitic acid / 2-ethylhexanoic acid) Dextrin 2.0 3. 3. (Ethylene / propylene) copolymer (melting point 90-99 ° C) 4.0 4. Glyceryl tri2-ethylcaproate Remaining amount 5. Dextrin isostearate * 20 2.0 6. Crosslinked silicone elastomer 2% treatment of Production Example 8 10.0 7. Trimethylsiloxysilicic acid (30% solid content isododecane solution) 5.0 8. Diisostearyl malate 5.0 9. Jojoba oil 0.1 10. Tribehenin 0.5 11.
  • PEG-9 Polydimethylsiloxyethyl Dimethicone 1.0 12. Lauryl polyglycerin-3 Polydimethylsiloxyethyl dimethicone 0.4 13. (Vinyl Dimethicone / Lauryl Dimethicone) Cross Polymer 4.0 14. Dimethylpolysiloxane (6cs) 5.0 15. Sorbitan sesquioleate 0.3 16. Cross-linked silicone / reticulated silicone block copolymer (average particle size 3-8 ⁇ m) * 4 2.0 17. Spherical polymethyl methacrylate (average particle size 6.5 ⁇ m) 3.0 18. (Vinyl dimethicone / methicone silsesquioxane) Cross polymer 5.0 19.
  • the concealer (oil-based solid) of Example 23 has "no burden when spread on the skin”, “effect of uniformly hiding stains and uneven color”, “natural finish”, and “drying over time”. It was excellent in “no feeling”, “makeup lasting effect”, and “ultraviolet ray blocking effect”.
  • Example 24 W / O solid foundation (ingredient) (%) 1.
  • Polypropylene polymer 0.3 5.
  • Meadowfoam oil 1.0 Ethylhexyl methoxycinnamate 7.0 7.2-Setyl ethylhexanoate 5.0 8.
  • Dimethicone 4% treatment of Production Example 6 5.0
  • Silicone treated iron oxide 1.5 Silicone treated black iron oxide 0.1 15. Purified water 45.0 16.1.3BG 8.0 17. Dipropylene glycol 5.0 18. Xanthan gum 0.05 19. Methyl paraoxybenzoate 0.1 20. Fragrance 0.1 * 21: KF-9021 (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Example 24 has "no feeling of burden when spread on the skin”, “effect of uniformly hiding stains and uneven color”, “natural finish”, and “no feeling of dryness over time”. , “Makeup lasting effect” and “UV blocking effect” were excellent.

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WO2024143443A1 (ja) * 2022-12-28 2024-07-04 株式会社コーセー 固形粉末化粧料
WO2025150549A1 (ja) * 2024-01-12 2025-07-17 花王株式会社 皮膚化粧料

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