CN117042746A - External preparation for skin - Google Patents

External preparation for skin Download PDF

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Publication number
CN117042746A
CN117042746A CN202280020822.9A CN202280020822A CN117042746A CN 117042746 A CN117042746 A CN 117042746A CN 202280020822 A CN202280020822 A CN 202280020822A CN 117042746 A CN117042746 A CN 117042746A
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Prior art keywords
skin
mass
less
component
external preparation
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Inventor
高桥大辉
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Kao Corp
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Kao Corp
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/10—Alcohols; Phenols; Salts thereof, e.g. glycerol; Polyethylene glycols [PEG]; Poloxamers; PEG/POE alkyl ethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/12—Carboxylic acids; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/14—Esters of carboxylic acids, e.g. fatty acid monoglycerides, medium-chain triglycerides, parabens or PEG fatty acid esters
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/16—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing nitrogen, e.g. nitro-, nitroso-, azo-compounds, nitriles, cyanates
    • A61K47/18—Amines; Amides; Ureas; Quaternary ammonium compounds; Amino acids; Oligopeptides having up to five amino acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/24—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing atoms other than carbon, hydrogen, oxygen, halogen, nitrogen or sulfur, e.g. cyclomethicone or phospholipids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • 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
    • A61K8/29—Titanium; Compounds thereof
    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Birds (AREA)
  • Biophysics (AREA)
  • Molecular Biology (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)

Abstract

An external preparation for skin comprising: component (A): 1 or more metal oxides selected from the group consisting of spherical metal oxides (A1) and plate-like metal oxides (A2) having an average particle diameter of 350nm to 2,500 nm; component (B): a non-volatile oil; the content of component (A) in the external preparation for skin is 2% by mass or more and 50% by mass or less, and the viscosity at 25 ℃ is 2,500 mPas or more.

Description

External preparation for skin
Technical Field
The present invention relates to an external preparation for skin.
Background
From the viewpoint of skin protection against sunlight, ultraviolet protection cosmetics such as sunscreen cosmetics are known. On the other hand, in recent years, there has been a demand for external preparations for skin having a protective function against infrared rays due to an increase in health consciousness.
As a technique for preventing damage to tissues in which infrared rays reach deeper parts than skin tissues and damage to these tissues due to infrared rays is prevented, for example, patent document 1 (international publication No. 2009/017104) discloses a near infrared ray damage preventing agent containing a biological tissue containing an infrared ray transmission shielding agent composed of titanium oxide powder and zinc oxide powder. Patent document 2 (japanese patent application laid-open No. 2017-95361) discloses a near infrared ray-proof cosmetic composition comprising titanium oxide powder and zinc oxide powder, which has both excellent near infrared ray-proof effect and high transparency.
Further, patent document 3 (international publication No. 2020/138431), patent document 4 (japanese patent application laid-open publication No. 2020-105175), patent document 5 (japanese patent application laid-open publication No. 2020-105176) and patent document 6 (japanese patent application laid-open publication No. 2020-105177) disclose a skin external preparation containing a plate-like metal oxide having a specific shape, as a skin external preparation having a more excellent infrared ray protection effect.
Disclosure of Invention
The present invention relates to the following.
[1] A skin external agent, wherein the skin external agent contains:
component (A): 1 or more metal oxides selected from the group consisting of spherical metal oxides (A1) and plate-like metal oxides (A2) having an average particle diameter of 350nm to 2,500 nm; a kind of electronic device with high-pressure air-conditioning system
Component (B): a non-volatile oil;
the content of component (A) in the external skin preparation is 2 to 50 mass%, and the viscosity of the external skin preparation at 25 ℃ is 2,500 mPa.s or more.
[2] A method for protecting skin from infrared rays, comprising the step of applying the external preparation for skin according to the above [1] to the skin.
Drawings
FIG. 1 is a photograph (fraction 5) of the observation of the coating uniformity of the external skin preparation of example 9 by an IR microscope.
FIG. 2 is a photograph (fraction 1) of the observation of the coating uniformity evaluation of the external skin preparation of comparative example 2 by an IR microscope.
Detailed Description
[ skin external preparation ]
The external skin preparation of the present invention comprises:
component (A): 1 or more metal oxides selected from the group consisting of spherical metal oxides (A1) and plate-like metal oxides (A2) having an average particle diameter of 350nm to 2,500 nm; a kind of electronic device with high-pressure air-conditioning system
Component (B): a non-volatile oil;
the content of component (A) in the external preparation for skin is 2% by mass or more and 50% by mass or less, and the viscosity at 25 ℃ is 2,500 mPas or more.
The external skin preparation of the present invention has the above-described structure, and is excellent in protective effect against ultraviolet rays, infrared rays, and the like, and is less whitened when applied to the skin.
In order to protect the skin from sunlight, external preparations for the skin are expected to have more improved protection effects, particularly against ultraviolet rays, infrared rays, and the like. Furthermore, as an external preparation for skin, there is also a demand for less tendency to whiten (hereinafter also referred to as "whitening") when applied to skin.
The present invention addresses the problem of providing an external preparation for skin which has excellent protection against ultraviolet rays, infrared rays, etc., and which exhibits little whitening when applied to the skin.
The present inventors have found that the above problems can be solved by an external skin preparation containing a metal oxide having a specific shape and a specific amount, and a nonvolatile oil and having a viscosity of a specific value or more.
According to the present invention, an external preparation for skin which is excellent in protection against ultraviolet rays, infrared rays, etc., and which is less whitened when applied to the skin can be provided. When the external preparation for skin is applied to the skin, the skin can be protected from ultraviolet rays, infrared rays and the like, and further, the effect of suppressing the rise in skin temperature due to irradiation of sunlight and the fatigue suppressing effect can be obtained.
The reason for obtaining the above-described effects by the skin external agent of the present invention is not yet determined, but it is considered as follows.
It is known that when a metal oxide having a large particle diameter is used in an external preparation for skin containing a metal oxide such as titanium oxide, the protective effect against ultraviolet rays, infrared rays, and the like is also improved. However, when only a metal oxide having a large particle diameter is used, the improvement of the infrared ray protection effect is limited, and when a spherical metal oxide having a large particle diameter is blended with an external skin preparation, for example, light scattering of visible light occurs on the surface of particles when the external skin preparation is applied to the skin, and therefore, there is a disadvantage that whitening is easy. Thus, it is difficult to achieve both improvement in the protective effect against ultraviolet rays, infrared rays, etc., and suppression of whitening at the time of application to the skin, simply by adjusting the particle size of the metal oxide used.
Further, although the effect of protecting against ultraviolet rays, infrared rays, etc. can be enhanced by increasing the metal oxide content in the external skin preparation, if the content is increased, the external skin preparation tends to be easily whitened when applied to the skin.
The external preparation for skin of the present invention can obtain a protective effect against ultraviolet rays, infrared rays, etc. and can suppress whitening when applied to the skin by using a metal oxide of a specific size and shape as the component (a) in a specific amount. Further, the present inventors have found that in order to further improve the protective effect against ultraviolet rays, infrared rays, and the like of a skin external agent containing a metal oxide, it is effective to improve the uniform coating property of the skin external agent, and particularly to uniformly arrange the component (a) as an effective component for protecting against ultraviolet rays, infrared rays, and the like on the skin surface, so it is important to control the rheology of the skin external agent.
Specifically, when a low-viscosity external skin preparation is applied to the skin, the component (a) having a high specific gravity is thought to be less likely to remain in the coating film, and therefore the component (a) tends to settle into the skin furrows. In particular, the component (a) having a large particle diameter tends to settle into the skin furrows, and cannot be uniformly disposed on the skin surface, and the protective effect against ultraviolet rays, infrared rays, and the like is also reduced.
The external skin preparation of the present invention contains a component (a) in addition to a component (B), and has a viscosity of a specific value or more, whereby sedimentation of the component (a) on the furrows when applied to the skin can be suppressed, and the uniform application property can be improved, and thus it is considered that the protective effect against ultraviolet rays, infrared rays, and the like can be further improved.
< definition >
In the present invention, ultraviolet means electromagnetic waves having a wavelength of 200nm to 360nm, and infrared means electromagnetic waves having a wavelength of 780nm to 1 mm. Among them, the external skin preparation of the present invention is excellent in near infrared ray protection effect especially at wavelengths of 780nm to 2500 nm. By this near infrared ray protection effect, the effect of suppressing the skin temperature increase due to the irradiation of the sun light and the fatigue suppression effect can be obtained.
In the present specification, the infrared ray protection effect is indicated by the infrared ray protection rate at the wavelength of 825 nm.
< viscosity >
The external skin preparation of the present invention has a viscosity of 2,500mpa·s or more, preferably 3,000mpa·s or more, more preferably 5,000mpa·s or more, still more preferably 8,000mpa·s or more, and still more preferably 10,000mpa·s or more at 25 ℃ from the viewpoint of improving the coating uniformity and suppressing sedimentation of component (a) in the skin to the skin furrows and improving the protective effect against ultraviolet rays, infrared rays, and the like. Further, from the viewpoint of easy spreading on the skin, it is preferably 200,000mpa·s or less, more preferably 150,000mpa·s or less, still more preferably 100,000mpa·s or less, still more preferably 50,000mpa·s or less, particularly preferably 30,000mpa·s or less, and particularly preferably 20,000mpa·s or less.
The external skin preparation of the present invention has a viscosity of 2,500 to 200,000 mPas, preferably 2,500 to 200,000 mPas, more preferably 3 to 200,000 mPas, still more preferably 5 to 150,000 mPas, still more preferably 8 to 100,000 mPas, still more preferably 8,000 to 50,000 mPas, and particularly preferably 10 to 30,000 mPas. In another embodiment, the viscosity of the external skin preparation of the present invention at 25 ℃ is preferably 2,500 to 150,000mpa·s, more preferably 2,500 to 100,000mpa·s, still more preferably 2,500 to 50,000mpa·s, still more preferably 2,500 to 30,000mpa·s, still more preferably 2,500 to 20,000mpa·s.
The viscosity of the external skin preparation at 25℃is a value measured at 25℃using a B-type viscometer, and specifically can be measured by the method described in the examples.
Examples of the means for adjusting the viscosity of the external skin preparation of the present invention to the above range include selection of the type and content of the component (a) used in the external skin preparation, selection of the type and content of the component (B), selection of the use of a thickener, emulsifier, dispersant, aqueous medium and the like, and selection of the content thereof, selection of the dispersion method of the component (a), and the like.
< dosage form etc.)
The formulation of the external skin preparation of the present invention is not particularly limited if the viscosity is within the above range, and is preferably liquid, gel or cream from the viewpoint of easy application to the skin. The external skin preparation of the present invention is preferably in the form of a solid such as a stick (stick) preparation from the viewpoint of infrared ray protection, provided that the viscosity is within the above range. The external skin preparation may be a nonaqueous composition or an emulsified composition, and when used as an emulsified composition, it may be either an oil-in-water emulsified composition or a water-in-oil emulsified composition. In the case of the oil-in-water emulsion composition, the viscosity adjustment is easy; in the case of the water-in-oil emulsion composition, the preparation is easy and the uniformity of application is improved.
The external skin preparation of the present invention is preferably an emulsion composition from the viewpoint of excellent feeling in use, and is preferably a water-in-oil emulsion composition from the viewpoint of excellent protective effect against ultraviolet rays, infrared rays, etc. and excellent feeling in use.
The external skin preparation of the present invention may be a cosmetic composition such as a lotion, cream, emulsion, essence, sun-aid, or base cosmetic, in addition to an external skin preparation for preventing ultraviolet rays or infrared rays.
< component (a): metal oxide ]
The external skin preparation of the present invention contains, as component (A), at least 1 metal oxide selected from the group consisting of spherical metal oxides (A1) and plate-like metal oxides (A2) having an average particle diameter of 350nm to 2,500 nm. The external skin preparation of the present invention contains the component (a), and thus has excellent protective effects against ultraviolet rays, infrared rays, etc., and can also provide an effect of suppressing an increase in skin temperature and an effect of suppressing fatigue, and can also provide an effect of suppressing whitening when applied to the skin.
( Component (A1): spherical metal oxide having average particle diameter of 350nm or more and 2,500nm or less )
The component (A1) used in the present invention is a spherical metal oxide having an average particle diameter of 350nm or more and 2,500nm or less. The term "spherical" as used herein also includes true spherical and slightly true spherical. The component (A1) may be spherical in shape if it is a primary particle or a secondary particle of the metal oxide. When component (A1) is present as secondary particles, the average particle diameter of component (A1) means the average value of the particle diameters of the secondary particles.
The average particle diameter of the component (A1) is 350nm or more, preferably 400nm or more, more preferably 700nm or more, still more preferably 800nm or more from the viewpoint of the protective effect against ultraviolet rays, infrared rays, etc. In addition, from the viewpoint of the protective effect against ultraviolet rays, infrared rays, and the like, and from the viewpoint of suppressing whitening when applied to the skin, it is 2,500nm or less, preferably 2,000nm or less, more preferably 1,800nm or less, still more preferably 1,500nm or less, and still more preferably 1,200nm or less. The average particle diameter of the component (A1) is 350nm to 2,500nm, preferably 400nm to 2,000nm, more preferably 700nm to 2,000nm, still more preferably 700nm to 1,800nm, still more preferably 700nm to 1,500nm, particularly preferably 800nm to 1,200 nm.
The average particle diameter of the component (A1) is the median diameter (d 50 ) This can be obtained, for example, by measuring the particle size distribution by laser diffraction/light scattering. In the measurement, a solvent in which the component (A1) is easily dispersed may be suitably used, for example, purified water may be used for a metal oxide which has not been surface-treated, and silicone oil (for example, methylpolysiloxane, cyclopentasiloxane, etc.) may be used for a metal oxide which has been surface-treated with silicone or the like.
Component (A2) plate-like metal oxide
The component (A2) used in the present invention is a plate-like metal oxide. The component (A2) is plate-shaped, and preferably has a thickness and an aspect ratio in the range described below. Here, if a coating film is formed on the skin surface using the skin external preparation containing the component (A2), the reflectance of light observed on the skin upper surface side becomes high for light having a wavelength in the infrared region and becomes low for light having a wavelength in the visible region due to the light interference effect. Therefore, a higher infrared ray protection effect can be obtained, and whitening when applied to the skin can be easily suppressed.
The thickness of the component (A2) is preferably 30nm or more, more preferably 50nm or more, still more preferably 60nm or more, still more preferably 75nm or more, particularly preferably 90nm or more, and particularly preferably 100nm or more, from the viewpoint of improving the infrared ray protection effect. In addition, from the viewpoint of improving the infrared ray protection effect and suppressing whitening when applied to the skin, the thickness of the component (A2) is preferably 360nm or less, more preferably 330nm or less, still more preferably 310nm or less, still more preferably 280nm or less, still more preferably 270nm or less, particularly preferably 230nm or less, particularly preferably 200nm or less, and most preferably 180nm or less. The thickness of the component (A2) is preferably 30nm to 360nm, more preferably 50nm to 330nm, still more preferably 60nm to 310nm, still more preferably 75nm to 280nm, still more preferably 90nm to 270nm, particularly preferably 100nm to 230nm, particularly preferably 100nm to 200nm, and most preferably 100nm to 180 nm.
In the present invention, the thickness of the component (A2) means the length of the shortest axis in the plate-like metal oxide.
The thickness of the component (A2) can be obtained from an observation image obtained by a Scanning Electron Microscope (SEM). Specifically, the component (A2) was observed by SEM at a magnification of 10,000 times, and the thickness of 50 particles in the observed image was measured, and the average value of the thicknesses was calculated from the number.
The aspect ratio of the component (A2) is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, still more preferably 30 or more, particularly preferably 50 or more, and particularly preferably 55 or more from the viewpoint of improving the infrared ray protection effect and suppressing blushing when applied to the skin; further, it is preferably 300 or less, more preferably 230 or less, still more preferably 200 or less, still more preferably 140 or less, particularly preferably 125 or less, and particularly preferably 120 or less. The aspect ratio of the component (A2) is preferably 3 or more and 300 or less, more preferably 3 or more and 230 or less, still more preferably 10 or more and 230 or less, still more preferably 30 or more and 230 or less, still more preferably 50 or more and 200 or less, particularly preferably 55 or more and 140 or less, particularly preferably 55 or more and 125 or less, and most preferably 55 or more and 120 or less.
The aspect ratio of the component (A2) was observed by SEM under the same conditions as described above, and the length (thickness) of the shortest axis and the length (long diameter) of the longest axis were measured for 50 particles in the observed image, and the aspect ratio (long diameter/thickness) of each particle was calculated and found from the average value thereof. The aspect ratio of component (A2) can be specifically measured by the method described in the examples.
The component (A2) is preferably 30nm to 360nm thick and 3 to 300 nm thick, more preferably 50nm to 330nm thick and 3 to 230nm thick, still more preferably 60nm to 310nm thick, 10 to 230nm thick, still more preferably 75nm to 280nm thick, 30 to 230nm thick, still more preferably 90nm to 270nm thick, 50 to 200nm thick, particularly preferably 100nm to 230nm thick, 55 to 140 nm thick, and 200nm thick, and 55 to 125 nm thick, and most preferably 100nm to 180nm thick, 55 to 120 nm thick, from the viewpoint of improving the infrared ray protection effect and the viewpoint of suppressing whitening when applied to the skin.
The external preparation for skin may contain either one of the component (A1) and the component (A2) as the component (a), or may contain both the component (A1) and the component (A2). In the case where the component (A) contains both the component (A1) and the component (A2), the mass ratio is not particularly limited, and the mass ratio (A1)/(A2) is preferably in the range of 10/90 to 90/10, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30 from the viewpoint of improving the infrared ray protection effect and suppressing whitening when applied to the skin.
The external preparation for skin may contain 2 or more components (A1) as component (a), or may contain 2 or more components (A2).
Examples of the metal oxide of the component (A1) and the component (A2) include titanium oxide, zinc oxide, zirconium oxide, iron oxide, aluminum oxide, cerium oxide, and the like.
Among these, from the viewpoint of the protective effect against ultraviolet rays, infrared rays, and the like, particularly from the viewpoint of the improvement of the protective effect against infrared rays, 1 or more selected from titanium oxide and zinc oxide is preferable, and titanium oxide is more preferable.
The crystalline structure of titanium oxide may be any of rutile type, anatase type and amorphous type, and is preferably rutile type in view of the protective effect against ultraviolet rays, infrared rays and the like.
The component (A1) and the component (A2) may be metal oxides which have not been subjected to surface treatment, or may be metal oxides which have been subjected to surface treatment such as hydrophobic treatment by a known method as needed in order to improve dispersibility in the external preparation for skin. The component (A1) and the component (A2) are different from those obtained by surface-treating the surfaces of particles other than metal oxides with metal oxides.
As the surface treatment agent for surface treatment of the metal oxide, there may be exemplified, for example: a silicone; alkyl alkoxy silane; fluorine-containing compounds such as perfluoroalkyl phosphate esters and perfluoroalkyl alcohols; amino acids such as N-acyl glutamic acid; lecithin; a metal soap; fatty acids such as stearic acid; alkyl phosphates, and the like. Of these, 1 or more selected from silicone and alkylalkoxysilane is preferable.
The silicone as the surface treatment agent is not particularly limited, and examples thereof include: various silicone oils such as methylpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogen polysiloxane (hydrodimethicone), methylcyclopolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, tetradecylhexasiloxane, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxypropylene) siloxane copolymer, dimethylsiloxane-methylhexadecyloxy siloxane copolymer, dimethylsiloxane-methyloctadecyloxy siloxane copolymer, and (alkyl acrylate/polydimethylsiloxane) copolymer (ASC).
The alkylalkoxysilane as the surface treating agent is preferably a branched or linear alkyl group having 6 to 20 carbon atoms, and examples thereof include octyltriethoxysilane and octyltrimethoxysilane.
The surface treatment agent used for the surface treatment of the metal oxide is preferably 1 or more selected from the group consisting of methylpolysiloxane, dimethylpolysiloxane, methylhydrogen polysiloxane, (alkyl acrylate/polydimethylsiloxane) copolymer, and octyltriethoxysilane, from the viewpoint of improving the dispersibility of the component (a) in the external preparation for skin and further improving the protective effect against ultraviolet rays, infrared rays, and the like.
When the component (A1) or the component (A2) is a surface-treated metal oxide, the amount of coating with the surface treatment agent is preferably 1% by mass or more and 9% by mass or less, more preferably 2% by mass or more and 8% by mass or less, relative to the total amount of the component (A1) or the component (A2), from the viewpoint of improving dispersibility in the external preparation for skin.
From the viewpoint of improving the infrared ray protection effect and the viewpoint of suppressing blushing when applied to the skin, it is preferable that the component (a) contains the component (A2).
The metal oxide constituting the component (A2) is a high refractive index material, and a high optical interference effect can be obtained. Therefore, the component (a) preferably contains 1 or more kinds selected from the group consisting of platy titanium oxide and platy zinc oxide as the component (A2), and more preferably contains platy titanium oxide.
When the component (a) contains the component (A2), the content of the component (A2) in the component (a) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass or less, from the viewpoint of improving the infrared ray protection effect and suppressing blushing when applied to the skin.
The content of the component (a) in the external preparation for skin is 2% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more, from the viewpoint of improving the protective effect against ultraviolet rays, infrared rays, and the like. In addition, from the viewpoint of suppressing blushing when applied to the skin, the content is 50 mass% or less.
The content of the component (a) in the external skin preparation is more preferably in the following range from the viewpoint of improving the infrared ray protection effect and the viewpoint of suppressing whitening when applied to the skin.
When the component (A) is spherical titanium oxide having an average particle diameter of 350nm or more and less than 800nm, the content of the spherical titanium oxide in the external preparation for skin is more preferably 5% by mass or more and 30% by mass or less, and still more preferably 5% by mass or more and 25% by mass or less.
When the component (a) is spherical titanium oxide having an average particle diameter of 800nm or more and 2,500nm or less, the content of the spherical titanium oxide in the external skin preparation is more preferably 5 mass% or more and 40 mass% or less, still more preferably 5 mass% or more and 30 mass% or less.
When the component (a) is a platy titanium oxide, the content of the platy titanium oxide in the external skin preparation is more preferably 5 to 30 mass%.
When the component (a) is spherical zinc oxide or plate-like zinc oxide having an average particle diameter of 350nm or more and 2,500nm or less, the content of the spherical zinc oxide or plate-like zinc oxide in the external skin preparation is more preferably 7 mass% or more and 50 mass% or less, still more preferably 10 mass% or more and 50 mass% or less.
The content of the component (a) in the nonvolatile component of the external skin preparation is preferably 3 mass% or more, more preferably 5 mass% or more, and still more preferably 10 mass% or more, from the viewpoint of improving the protective effect against ultraviolet rays, infrared rays, and the like; from the viewpoint of suppressing blushing when applied to the skin, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and still more preferably 20% by mass or less. The content of the component (a) in the nonvolatile component of the external skin preparation is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, still more preferably 10% by mass or more and 30% by mass or less, and still more preferably 10% by mass or more and 20% by mass or less.
The term "nonvolatile component in the external preparation for skin" as used herein means a component in which water, an aqueous medium described later, and a functional oil (oil agent other than the component (B)) are removed from the total amount of the external preparation for skin.
The viscosity (mpa·s) of the external skin preparation is preferably 100 or more, more preferably 250 or more, still more preferably 300 or more, still more preferably 350 or more, still more preferably 25,000 or less, still more preferably 20,000 or less, still more preferably 15,000 or less, still more preferably 10,000 or less, particularly preferably 5,000 or less, and particularly preferably 3,000 or less, from the viewpoint of improving the uniformity of application property and the uniformity of the component (a) on the skin surface by the viscosity which becomes the content of the component (a) in the external skin preparation. Further, [ viscosity (mpa·s) of the skin external agent/content (mass%) of the component (a) in the skin external agent ] is preferably 100 to 25,000, more preferably 250 to 20,000, still more preferably 300 to 15,000, still more preferably 350 to 10,000, particularly preferably 350 to 5,000, particularly preferably 350 to 3,000.
As component (A), commercially available metal oxides can also be used.
Examples of the commercially available spherical titanium oxide as the component (A1) include "ST-750EC" manufactured by Titan Kogyo, ltd., and "R-38L" manufactured by Sakai chemical industry Co., ltd; examples of the commercially available spherical ZINC oxide include "LP-ZINC-2KS" manufactured by Sakai chemical industries, ltd.
Examples of commercially available platy titanium oxides as component (A2) include "Featerleve PT-9001K", "Featerleve PT-7001K", "Featerleve PT-7401K", "Featerleve PT-7801K" and "Featerleve PT-7901K" manufactured by CQV corporation; as a commercially available plate-like zinc oxide, for example, "XZ-1000F-LP" manufactured by Sakai chemical industries, ltd.
< component (B): fixed oil
The external skin preparation of the present invention contains a nonvolatile oil as the component (B) from the viewpoint of easily adjusting the viscosity to a desired level, improving the uniformity of application, and improving the protective effect against ultraviolet rays, infrared rays, and the like. The nonvolatile oil is a nonvolatile oil having an evaporation amount of less than 20% at 25℃for 6 hours, as measured by the following method (1).
Method (1): a glass culture dish having a diameter of 120mm was placed with a filter paper having a diameter of 90mm, 1g of the sample was placed on the filter paper, and the sample was stored in a 65% RH chamber (25 ℃). Then, the residue of the sample after 6 hours was measured, and the evaporation amount was calculated.
The component (B) is preferably in a liquid state at 25℃under 1 atmosphere. More specifically, the viscosity of the component (B) at 25 ℃ is preferably 500mpa·s or less, more preferably 300mpa·s or less, still more preferably 100mpa·s or less, still more preferably 50mpa·s or less, and preferably 5mpa·s or more.
The viscosity was measured using a type B viscometer "TVB-10" (manufactured by DONGCHINESE CORPORATION) under the conditions of rotor No.1, 25℃and 60rpm for 1 minute.
Specific examples of the component (B) include nonvolatile oils which are liquid at 25℃and 1 or more selected from ester oils, silicone oils, hydrocarbon oils, higher fatty acids, and higher alcohols.
Examples of the nonvolatile liquid ester oil include 1 or more selected from monoesters of fatty acids having 8 to 18 carbon atoms and branched alcohols having 2 to 22 carbon atoms, triesters of branched fatty acids having 6 to 18 carbon atoms and glycerin, diesters of dicarboxylic acids having 2 to 18 carbon atoms and branched alcohols having 2 to 18 carbon atoms, diesters of fatty acids having 6 to 18 carbon atoms and diols having 2 to 10 carbon atoms, and alkyl benzoate.
Examples of the monoester of a fatty acid having 8 to 18 carbon atoms and a branched alcohol having 2 to 22 carbon atoms include isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, isopropyl palmitate, ethylhexyl palmitate, and 2-hexyldecyl palmitate.
Examples of the triester of a fatty acid having 6 to 18 carbon atoms and glycerin include tri-2-ethylhexanoic acid glyceride, and tri (caprylic/capric acid) glyceride.
Examples of the diester of a dicarboxylic acid having 2 to 18 carbon atoms and a branched alcohol having 2 to 18 carbon atoms include di-2-ethylhexyl sebacate, diisopropyl sebacate, and diisostearyl malate.
Examples of the diester of a fatty acid having 6 to 18 carbon atoms and a diol having 2 to 10 carbon atoms include diethylene glycol dicaprate, neopentyl glycol dicaprate, and neopentyl glycol di-2-ethylhexanoate.
Examples of the alkyl benzoate include alkyl (C12-C15) benzoate (for example, finsolv TN; manufactured by Innospec Active Chemicals LLC).
Among the ester oils used as component (B), from the viewpoint of easiness of viscosity adjustment, the viewpoint of improvement of solubility of a thickener or the like described later, and the viewpoint of suppression of tackiness at the time of application to the skin, it is preferable that 1 or more selected from the group consisting of monoesters of fatty acids having 12 to 18 carbon atoms and branched alcohols having 2 to 22 carbon atoms, triesters of branched fatty acids having 6 to 18 carbon atoms and glycerin, diesters of dicarboxylic acids having 2 to 18 carbon atoms and branched alcohols having 2 to 18 carbon atoms, diesters of fatty acids having 6 to 18 carbon atoms and branched diols having 2 to 10 carbon atoms, and alkyl benzoate (C12 to C15) esters, more preferably, the compound is 1 or more selected from isopropyl myristate, isocetyl myristate, octyldodecyl myristate, isopropyl palmitate, ethylhexyl palmitate, 2-hexyldecyl palmitate, glyceryl tri-2-ethylhexanoate, diisopropyl sebacate, di-2-ethylhexyl sebacate, diisostearyl malate, neopentyl glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, and alkyl benzoate (C12-C15), and still more preferably isopropyl myristate.
The nonvolatile liquid silicone oil is preferably a methylpolysiloxane, and more preferably a methylpolysiloxane having a viscosity of 20 mPas or less at 25 ℃.
Examples of the nonvolatile liquid hydrocarbon oil include light liquid isoparaffin such as liquid paraffin and hydrogenated polyisobutene, heavy liquid isoparaffin, liquid ceresin, squalane, pristane, squalene, and isohexadecane.
Examples of the non-volatile liquid higher fatty acid include fatty acids having 12 to 22 carbon atoms, and specific examples thereof include oleic acid, isostearic acid, linoleic acid, and linolenic acid.
Examples of the non-volatile liquid higher alcohol include alcohols having 12 to 28 carbon atoms, and specific examples thereof include oleyl alcohol, 2-decyltetradecyl alcohol, dodecyl alcohol, isostearyl alcohol, and octyldodecyl alcohol.
The component (B) is preferably 1 or more selected from ester oils, silicone oils and hydrocarbon oils, more preferably 1 or more selected from ester oils and hydrocarbon oils, and still more preferably ester oils and silicone oils, from the viewpoint of easiness in viscosity adjustment, the viewpoint of improvement in solubility of a thickener or the like described later, and the viewpoint of suppression of tackiness at the time of application to the skin, among the nonvolatile oils which are liquid at 25 ℃.
The content of the component (B) in the external skin preparation of the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, from the viewpoint of easily adjusting the viscosity to a desired level, improving the uniformity of application, and improving the protective effect against ultraviolet rays, infrared rays, and the like. From the viewpoint of suppressing tackiness at the time of application to the skin, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and still more preferably 65% by mass or less.
In the case where the external skin preparation of the present invention is a water-in-oil emulsion composition, the content of the component (B) in the external skin preparation is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, still more preferably 30% by mass or more, and particularly preferably 35% by mass or more, from the viewpoint of making the external skin preparation a water-in-oil type.
In the case where the external skin preparation of the present invention is an oil-in-water emulsion composition, the content of the component (B) in the external skin preparation is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less, from the viewpoint of making the external skin preparation oil-in-water.
In the skin external preparation of the present invention, the mass ratio [ (B)/(a) ] of the content of the component (B) to the content of the component (a) is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.5 or more, still more preferably 1 or more, particularly preferably 2 or more, particularly preferably 3 or more, and most preferably 3.6 or more from the viewpoint of improving the protective effect against ultraviolet rays, infrared rays, etc. by improving the uniformity of coating property and the viewpoint of improving the feel in use; from the viewpoint of suppressing tackiness at the time of application to the skin, it is preferably 60 or less, more preferably 50 or less, still more preferably 30 or less, still more preferably 20 or less, particularly preferably 10 or less, and particularly preferably 8 or less. The mass ratio [ (B)/(a) ] is preferably 0.05 or more and 60 or less, more preferably 0.1 or more and 50 or less, still more preferably 0.2 or more and 30 or less, still more preferably 0.5 or more and 20 or less, still more preferably 1 or more and 10 or less, particularly preferably 2 or more and 10 or less, particularly preferably 3 or more and 10 or less, and most preferably 3.6 or more and 8 or less.
The total content of the component (a) and the component (B) in the external skin preparation is preferably 2% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 45% by mass or more, particularly preferably 47% by mass or more, most preferably 50% by mass or more, and still more preferably 100% by mass or less, from the viewpoint of the protective effect against ultraviolet rays, infrared rays, etc., and the viewpoint of suppressing whitening when applied to the skin.
< tackifier >
The external skin preparation of the present invention preferably contains a thickener from the viewpoints of facilitating viscosity adjustment, improving uniformity of application, and improving the protective effect against ultraviolet rays, infrared rays, and the like. In the present invention, the term "tackifier" means an additive having an effect of thickening a skin external agent.
Examples of the thickener include an oil thickener and a water-soluble thickener, and may be appropriately selected by blending with a formulation of an external skin preparation. For example, in the case where the external skin preparation is a water-in-oil emulsion composition, an oil thickener (oil gelling agent) is preferable from the viewpoint of easy thickening without changing the formulation.
Examples of the oil thickening agent include oil thickening agents used in general skin external preparations, and examples thereof include solid waxes, organomodified clay minerals, fumed silica, colloidal silica, dextrin fatty acid esters, metal soaps, sucrose fatty acid esters, and amino acid gelling agents. Among these, from the viewpoint of easy viscosity adjustment, improvement of uniform coating properties, improvement of protective effects against ultraviolet rays, infrared rays, and the like, 1 or more selected from solid waxes, organomodified clay minerals, dextrin fatty acid esters, and amino acid gelling agents are preferable, and 1 or more selected from solid waxes, organomodified clay minerals, and dextrin fatty acid esters are more preferable.
As the solid wax, there may be mentioned, for example, a wax having a melting point of 61℃or higher. Waxes with melting points above 61 ℃ exhibit solid behavior at 25 ℃.
In the present invention, the melting point is measured by any of the standard of raw materials for quasi drugs, method 1, method 2, and method 3 of general test methods. What method should be adopted is to carry out each component according to the standard of the quasi-drug material when the measurement method is described. If not described, the measurement method is selected in consideration of the melting point. Specifically, when the melting point is significantly higher than 80 ℃, method 1 is generally used; solid fat with melting point lower than that of the case is obtained by the method 2; in the category, etc., solid fats called cream oils are used in method 3; but any method may be used if it is determinable.
The wax having a melting point of 61℃or higher is not particularly limited as long as it is a wax used for a usual external preparation for skin, and examples thereof include mineral waxes such as ceresin and ceresin; petroleum wax such as paraffin wax and microcrystalline wax; synthetic hydrocarbons such as Fischer-Tropsch wax, polyethylene wax, and synthetic hydrocarbon wax; vegetable waxes such as palm wax, candelilla wax, rice wax, and sunflower wax; animal waxes such as beeswax and spermaceti; synthetic waxes such as silica wax and synthetic beeswax; etc.
Among these, from the viewpoint of easy viscosity adjustment, and of improving uniformity of application and improving the protective effect against ultraviolet rays, infrared rays, and the like, 1 or more kinds selected from the group consisting of petroleum waxes and silicone waxes are preferable.
In addition, these waxes are preferably from 65 ℃ to 140 ℃ in melting point, more preferably from 70 ℃ to 110 ℃ in view of easy viscosity adjustment, improved uniformity of application, and improved protection against ultraviolet rays, infrared rays, and the like.
The organomodified clay mineral is not particularly limited as long as it is an organomodified clay mineral used for a usual external skin preparation, and examples thereof include cation modified clay minerals obtained by treating layered clay minerals such as bentonite, laponite, lithium bentonite, montmorillonite and aluminum magnesium silicate with a quaternary ammonium salt type cationic surfactant.
Specifically, it is preferably 1 or more selected from the group consisting of benzyldimethyl stearyl ammonium chloride and dimethyl distearyl ammonium chloride, and more preferably dimethyl distearyl ammonium chloride.
Examples of the commercially available organomodified clay minerals include "BENTONE 38", "BENTONE 38VCG", and "BENTONE 27", which are manufactured by Elementis Japan Co.
The organomodified clay mineral may be used as a premixed gel diluted with a solvent from the viewpoints of improving workability and improving thickening effect.
Specifically, a premixed gel obtained by dispersing an organically modified clay mineral in a solvent in advance is preferable. The solvent is not limited if it can be gelled by an organically modified clay mineral, and is preferably octyldodecanol, mineral oil, or the like from the viewpoint of improving the thickening effect. In addition, from the viewpoint of dispersing the organically modified clay mineral efficiently, it is preferable to further contain polar additives such as propylene carbonate, ethanol, water, various surfactants, and the like.
The content of the organomodified clay mineral in the premix gel is preferably 5 mass% or more, more preferably 8 mass% or more, still more preferably 10 mass% or more, preferably 25 mass% or less, still more preferably 20 mass% or less, still more preferably 18 mass% or less, from the viewpoints of improving workability and improving thickening effect, and suppressing oil separation of the premix gel itself.
Examples of the commercial products of the premixed GEL include "BENTONE GEL EUGV", "BENTONE GEL MIOV", "BENTONE GEL VS-5PCV", "BENTONE GEL PTM V", "BENTONE GEL GTCC V", and the like, which are manufactured by Elementis Japan.
The dextrin fatty acid ester is not particularly limited as long as it is a dextrin fatty acid ester used in a normal external preparation for skin, and is preferably an ester of a fatty acid having 8 to 24 carbon atoms with dextrin, more preferably an ester of a fatty acid having 14 to 20 carbon atoms with dextrin, from the viewpoints of easy viscosity adjustment, improved uniformity of application, and improved protection against ultraviolet rays, infrared rays, etc. The average polymerization degree of dextrin is preferably 3 to 150.
Specific examples thereof include dextrin myristate, dextrin stearate, dextrin palmitate stearate, dextrin oleate, dextrin isopalmitate, dextrin isostearate, dextrin myristate, and dextrin palmitate 2-ethylhexanoate.
Among these, from the viewpoint of easy viscosity adjustment, improvement of uniform coating property, improvement of protective effect against ultraviolet rays, infrared rays, and the like, it is preferable that the dextrin is composed of palmitic acid dextrin, myristic acid dextrin, and palmitic acid 2-ethylhexanoic acid dextrin, and more preferable that at least palmitic acid dextrin is contained.
Examples of the commercial products of the dextrin fatty acid ester include, for example, palmitic acid dextrin ("Rheopearl KL2", "Rheopearl KS2", "Rheopearl TL 2") manufactured by Qianlike powder (Kabushiki Kaisha), palmitic acid 2-ethylhexanoic acid dextrin "Rheopearl TT2", and myristic acid dextrin "Rheopearl MKL 2".
The amino acid gelling agent used as a general external skin preparation may be used without any particular limitation. Specifically, dibutyl lauroyl glutamine and dibutyl ethyl hexanoyl glutamine are preferred.
Examples of commercial products of the amino acid gelling agent include dibutyl lauroyl glutamine "GP-1" and dibutyl ethyl hexanoyl glutamine "EB-21" manufactured by Weisu (Inc.).
From the viewpoints of improving workability and improving the thickening effect, the amino acid gelling agent may be diluted and dissolved in a solvent to form a premixed gel.
Specifically, a premixed gel in which an amino acid gelling agent is dissolved in a solvent in advance is preferable. The solvent is not limited if it can be gelled with an amino acid gelling agent, and is preferably octyldodecanol, isostearic acid, or the like from the viewpoint of improving the thickening effect.
The content of the amino acid gelling agent in the premixed gel is preferably 10 mass% or more, more preferably 15 mass% or more, still more preferably 20 mass% or more, preferably 45 mass% or less, still more preferably 40 mass% or less, still more preferably 36 mass% or less, from the viewpoints of improving workability and improving thickening effect, and suppressing oil separation of the premixed gel itself.
Examples of the commercial products of the premix gel include "AJK-OD2046" (containing 20% by mass of an amino acid gelling agent) and "AJK-IS3613" (containing 36% by mass of an amino acid gelling agent) of higher alcohol industries, inc.
1 or 2 or more tackifiers may be used. When the external skin preparation contains a tackifier, the content of the tackifier in the external skin preparation is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, still more preferably 3% by mass or more, still more preferably 50% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass, from the viewpoint of adjusting the viscosity and improving the uniformity of application and the protective effect against ultraviolet rays, infrared rays, etc. The tackifier content in the external skin preparation is preferably 0.5% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, still more preferably 1% by mass or more and 25% by mass or less, still more preferably 2% by mass or more and 20% by mass or less, and particularly preferably 3% by mass or more and 15% by mass or less.
< emulsifier >
The external skin preparation of the present invention may further contain an emulsifier from the viewpoint of improving the dispersibility of the component (a) and the viewpoint of preparing an emulsified composition. In the present invention, the term "emulsifier" means an additive having emulsifying properties other than the above-mentioned thickener.
The emulsifier used in the present invention may be any of a low-molecular-weight emulsifier and a high-molecular-weight emulsifier, and is preferably a high-molecular-weight emulsifier from the viewpoint of improving the dispersibility of the component (a) and the ease of viscosity adjustment.
The polymer emulsifier is preferably a polymer emulsifier having a hydrophilic site and a hydrophobic site, and examples thereof include alkyl-modified polyacrylic polymers, alkyl-modified polysaccharide polymers, and oxazoline-modified silicones.
Examples of the alkyl-modified polyacrylic acid polymer include (meth) acrylic acid/(meth) acrylic acid alkyl ester copolymers and alkyl acrylate/alkyl methacrylate/polyoxyethylene stearyl ether copolymers.
Examples of the alkyl-modified polysaccharide polymer include hydroxyethyl cellulose, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose, stearyloxy hydroxypropyl methylcellulose, laureth-13 PG hydroxyethyl cellulose, and stearyloxy PG hydroxyethyl cellulose sulfonate.
Examples of the oxazoline-modified silicone include a polymer containing a hydrophilic segment having an N-acylalkylenimine as a repeating unit and an organopolysiloxane segment as a constituent unit, and examples thereof include an N-propionyl polyethyleneimine-methylpolysiloxane copolymer (POLYSILICONE-9).
The emulsifier may be used in an amount of 1 or 2 or more. Among the above, oxazoline-modified silicone is preferable from the viewpoint of improving the dispersibility of the component (a) and the viewpoint of easiness of viscosity adjustment.
In the case where the external skin preparation of the present invention contains an emulsifier, the content of the emulsifier in the external skin preparation is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less, from the viewpoint of the emulsifying performance. The content of the emulsifier in the external skin preparation is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less, still more preferably 0.1% by mass or more and 3% by mass or less, and particularly preferably 0.2% by mass or more and 1% by mass or less.
< dispersant >
The external preparation for skin of the present invention may further contain a dispersing agent from the viewpoint of improving the dispersibility of the component (a). In the present invention, "dispersant" means an additive that mainly contributes to improving the dispersibility of the component (a).
The dispersant used in the present invention is preferably a nonionic surfactant from the viewpoint of improving the dispersibility of the component (a). The nonionic surfactant is not particularly limited as long as it is a nonionic surfactant used for a general skin external preparation, and silicone surfactants, fluorine-containing surfactants, and the like can be used.
Examples of the nonionic surfactant used for the dispersant include alkanolamide, amine oxide, polyoxyethylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, alkyl saccharide, α -monoalkyl glyceryl ether, polyether-modified silicone, and the like, and 1 or 2 or more of these surfactants can be used.
From the viewpoint of further improving the dispersibility of the component (a), the dispersant preferably contains a nonionic silicone surfactant, and more preferably contains a polyether-modified silicone.
Examples of the commercial products of polyether-modified silicones used as dispersants include "KF-6012" (poly (oxyethylene-oxypropylene) methylpolysiloxane copolymer) manufactured by Xinyue chemical industry Co., ltd.), "KF-6015", "KF-6017", "KF-6028", "KF-6038", dow Toray Co., ltd., "SH3775M" (polyoxyethylene-methylpolysiloxane copolymer above), and "SH3772C" manufactured by Dow Toray Co., ltd.
The nonionic surfactant other than the above is preferably a polyoxyethylene alkyl ether type nonionic surfactant. Examples of the commercially available nonionic surfactant include "EMULTEN 121-G" (polyoxyethylene (21) lauryl ether) manufactured by Kagaku Kogyo Co., ltd.), "EMULTEN 1620G" (polyoxyethylene (20) 2-hexyldecyl ether) manufactured by Kagaku Kogyo Co., ltd.), and "EMULTEN 2020G" (polyoxyethylene (20) octyldodecyl ether) manufactured by Kagaku Kogyo Co., ltd.
The dispersant may be used in an amount of 1 or 2 or more. In the case where the external skin preparation of the present invention contains a dispersant, the content of the dispersant in the external skin preparation is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 15% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, from the viewpoint of improving the dispersibility of the component (a). The content of the dispersant in the external skin preparation is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, still more preferably 0.5% by mass or more and 5% by mass or less.
< Water >
The external skin preparation of the present invention preferably further contains water from the viewpoint of imparting a fresh feel to use.
When the external skin preparation contains water, the water content in the external skin preparation is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, depending on the formulation.
< aqueous Medium >
The external skin preparation of the present invention may further contain an aqueous medium other than water from the viewpoint of dispersing or dissolving the component (a) and other compounding ingredients to further improve the uniformity of application. Examples of the aqueous medium include: monohydric alcohols having 4 or less carbon atoms such as ethanol, isopropanol, butanol, etc.; low molecular weight diols and triols having 6 or less carbon atoms such as 1, 3-butanediol, glycerol, ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol. Among these, 1 or more selected from monohydric alcohols having 4 or less carbon atoms is preferable, and ethanol is more preferable.
When the external skin preparation contains an aqueous medium, the content of the aqueous medium in the external skin preparation may be appropriately selected depending on the formulation, and from the viewpoint of dispersing or dissolving the component (a) and dispersing or dissolving other compounding ingredients to further improve the uniform coating property, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less. The content of the aqueous medium in the external skin preparation is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.1% by mass or more and 30% by mass or less, still more preferably 0.1% by mass or more and 20% by mass or less, and still more preferably 0.5% by mass or more and 10% by mass or less.
The total content of water and the aqueous medium in the external skin preparation is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 40% by mass or less, and still more preferably 35% by mass or less, from the viewpoint of improving the fresh feeling in use.
< other ingredients >
The external skin preparation of the present invention may contain, in addition to the above-mentioned components, other components such as ultraviolet absorbers, ultraviolet scattering agents, volatile oils, antiperspirants, fragrances, moisturizers, bactericides, pH adjusters, antioxidants, preservatives and the like, as required.
(ultraviolet absorber)
The external skin preparation of the present invention may further contain an ultraviolet absorber from the viewpoint of improving the ultraviolet protection effect.
The ultraviolet absorber is preferably an organic ultraviolet absorber other than the component (B), and an oil-soluble organic ultraviolet absorber or a water-soluble organic ultraviolet absorber can be used. The ultraviolet absorber is preferably an oil-soluble organic ultraviolet absorber from the viewpoint of improving the ultraviolet protection effect, the viewpoint of suppressing whitening when applied to the skin, and the viewpoint of suppressing tackiness. In the present invention, "oil-soluble" means water-insoluble, specifically, that the solubility in water at 25 ℃ is 1w/w% or less.
Further, from the viewpoint of obtaining the effect of the present invention, the ultraviolet absorber is preferably an inorganic ultraviolet absorber that does not include, for example, an ultraviolet absorber that covers the surface of the inorganic filler with an ultraviolet absorbing material.
As the oil-soluble organic ultraviolet absorber, an oil-soluble organic ultraviolet absorber among salicylic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers, benzoylmethane-based ultraviolet absorbers, and other organic ultraviolet absorbers can be used.
Salicylic acid ultraviolet absorbers such as salicylic acid Gao Mengzhi and octyl salicylate;
cinnamic acid ultraviolet absorbers such as 2-ethylhexyl p-methoxycinnamate (for example, "Uvinul MC80" manufactured by BASF), glycerol di-p-methoxycinnamate mono-2-ethylhexanoate, methyl 2, 5-diisopropylcinnamate, methyl bis (trimethylsiloxy) silylisopentyl trimethoxycinnamate, and mixtures of isopropyl p-methoxycinnamate and diisopropylcinnamate;
4-isopropyl-dibenzylmethane, 4-t-butyl-4' -methoxydibenzoylmethane (e.g., benzoyl methane ultraviolet absorbers such as "PARASOL 1789" manufactured by DSM NUTRITION JAPAN corporation);
Octocrylene (e.g., "PARSOL 340" manufactured by DSM NUTRITION JAPAN Co.), dimethoxybenzylidenedioxyimidazolidinyl propionate 2-ethylhexyl ester (SOFTSHADE DH manufactured by Weisu Co., ltd.), 1- (3, 4-dimethoxyphenyl) -4, 4-dimethyl-1, 3-pentanedione, cinoshanate (Cinoxate), methylparaben, 3- (4-methylbenzylidene) camphor, xin Sanqin, diethylaminohydroxybenzoyl hexyl benzoate (2- (4-diethylamino-2-hydroxybenzoyl) hexyl benzoate, e.g., "Uvinul Aps" manufactured by BASF), bishexyloxyphenoxyphenyl triazine (2, 4-bis { 4- (2-ethylhexyloxy) -2-hydroxy ] phenyl } -6- (4-methoxyphenyl) -1,3, 5-triazine, e.g., "TINOSORB" manufactured by BASF), methylenebisbenzotetramethylbutylphenol (e.g., "BASF" TIRB "2, 6-hydroxybenzoyl") also referred to as "BASF" Uvirol "3, 4-hydroxy" manufactured by BASF "and the like" BASF "3, 6-hydroxy" is also referred to as "BASF" Uviryl "3, 5", etc.
Among the water-soluble organic ultraviolet absorbers, salicylic acid ultraviolet absorbers, cinnamic acid ultraviolet absorbers, benzoylmethane ultraviolet absorbers, and other organic ultraviolet absorbers, organic ultraviolet absorbers having a solubility in water of more than 1w/w% may be used, and examples thereof include triethanolamine salicylate and diethanolamine p-methoxyhydrocinnamate.
Among the above, from the viewpoint of improving the ultraviolet protection effect, the ultraviolet absorber is preferably 1 or more selected from the group consisting of 2-ethylhexyl p-methoxycinnamate, 4-tert-butyl-4' -methoxydibenzoylmethane, octocrylene, 2-ethylhexyl dimethoxybenzylidenedioxyimidazolidinylpropionate, hexyl diethylaminohydroxybenzoate, bisethylhexyloxyphenol methoxyphenyl triazine, methylenebisbenzotriazole-tetramethylbutylphenol, and 2,4, 6-tris [4- (2-ethylhexyloxycarbonyl) anilino ] -1,3, 5-triazine; more preferably, the aromatic amine compound is 1 or more selected from the group consisting of 2-ethylhexyl p-methoxycinnamate, hexyl diethylamino hydroxybenzoate, bisethylhexyl oxyphenoxyphenyl triazine, and 2,4, 6-tris [4- (2-ethylhexyl oxycarbonyl) anilino ] -1,3, 5-triazine; from the viewpoint of protection against both UVA and UVB, it is more preferable to combine 2 or more of these. More preferably 1 or more selected from the group consisting of 2-ethylhexyl p-methoxycinnamate, hexyl diethylaminohydroxybenzoate, and bisethylhexyl oxyphenoxyphenyl triazine, and still more preferably 2 or more of these are combined.
In the case where the external skin preparation of the present invention contains an ultraviolet absorber, the content thereof is preferably 0.2% by mass or more, more preferably 1.5% by mass or more, still more preferably 5% by mass or more, and still more preferably 7% by mass or more in terms of improving the ultraviolet protection effect. From the viewpoint of improving the feel of the skin external preparation, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 15% by mass or less. The specific range of the content of the ultraviolet absorber in the external skin preparation is preferably 0.2% by mass or more and 30% by mass or less, more preferably 1.5% by mass or more and 25% by mass or less, still more preferably 5% by mass or more and 20% by mass or less, and still more preferably 7% by mass or more and 15% by mass or less.
(ultraviolet scattering agent)
The external skin preparation of the present invention may further contain an ultraviolet scattering agent from the viewpoint of improving the ultraviolet ray protection effect.
The ultraviolet scattering agent is preferably inorganic particles, and more preferably metal oxide particles other than the component (a), that is, spherical metal oxide (A1) and plate-like metal oxide (A2) having an average particle diameter of 350nm or more and 2,500nm or less, from the viewpoint of high ultraviolet scattering effect. The metal oxide includes titanium oxide, zinc oxide, iron oxide, zirconium oxide, aluminum oxide, and the like other than the component (a), and more preferably 1 or more selected from titanium oxide and zinc oxide other than the component (a).
The inorganic particles used for the ultraviolet scattering agent are preferably those which are hydrophobized by surface treatment, from the viewpoint of improving dispersibility in the external skin preparation. Examples of the surface treatment method for hydrophobization include silicone treatment with methyl hydrogen polysiloxane (hydrogen polydimethylsiloxane), methyl polysiloxane (polydimethylsiloxane), methyl hydrogen polysiloxane-dimethylpolysiloxane copolymer, and the like; fluorine treatment of perfluoroalkyl phosphate, perfluoroalkyl alcohol, and the like; amino acid treatment such as N-acyl glutamic acid; silane compounds such as hexyl trimethoxysilane, octyl trimethoxysilane, decyl trimethoxysilane, octadecyl trimethoxysilane, octyl triethoxysilane, trifluoropropyl trimethoxysilane, heptadecyl trimethoxysilane, and the like; treatment with a silazane compound such as hexamethyldisilazane and octyldisilazane; lecithin treatment; metal soap treatment; fatty acid treatment with octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachic acid, arachidonic acid, behenic acid, etc.; alkyl phosphate treatment; inorganic compounds such as silica, alumina, and aluminum hydroxide; etc. These surface treatment methods may be used in an amount of 1 or 2 or more.
Examples of the particle shape of the ultraviolet scattering agent include a sphere, a rod, a spindle, a needle, and an indefinite shape having an average particle diameter of less than 350nm, and the particle shape is not particularly limited if the ultraviolet scattering agent has an ultraviolet scattering effect.
The average particle diameter of the ultraviolet scattering agent is usually 1nm or more, and from the viewpoint of improving the ultraviolet protection effect, it is preferably 5nm or more, more preferably 8nm or more, still more preferably 10nm or more. In addition, from the viewpoint of suppressing whitening when applied to the skin, it is preferably less than 350nm, more preferably 300nm or less, still more preferably 100nm or less, and still more preferably 60nm or less.
The average particle diameter can be measured by the same method as the average particle diameter of the component (A1).
The ultraviolet scattering agent may be commercially available ones. Examples of the commercial products of titanium oxide particles used as the ultraviolet scattering agent include "MT-100TV" (aluminum hydroxide, stearic acid treatment) and "MTY-110M3S" (aluminum hydroxide, silica, and hydrodimethicone treatment) manufactured by TAYCA (Inc.).
As the commercial products of zinc oxide particles used as the ultraviolet scattering agent, there may be mentioned, for example, "FINEX-50-LPTM" (polydimethylsiloxane treatment) manufactured by Sa chemical industry Co., ltd., "FINEX-25" (no surface treatment), "FINEX-25LP" (polydimethylsiloxane treatment), and "MZ-300" (no surface treatment) manufactured by TAYCA Co., ltd., "MZ-504R3M" (hydrogen polydimethylsiloxane treatment), "MZY-303S" (hydrogen polydimethylsiloxane treatment), "MZ-306X" (triethoxysilylethyl polydimethylsiloxane treatment), "MZY-200" (no surface treatment), "MZY-203S" (hydrogen polydimethylsiloxane treatment), "MZ-150" (no surface treatment), "MZY-153S" (hydrogen polydimethylsiloxane treatment), "MZ-505S", "MZY-505S", etc.
The ultraviolet scattering agent may be used alone or in combination of 1 or more than 2.
In the case where the external skin preparation of the present invention contains an ultraviolet scattering agent, the content thereof is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, from the viewpoint of improving the ultraviolet protection effect. From the viewpoint of suppressing blushing when applied to the skin, the content is preferably 20 mass% or less, more preferably 18 mass% or less, and still more preferably 15 mass% or less.
< use >
The external preparation for skin of the present invention is useful as an external preparation for skin for preventing ultraviolet rays or infrared rays, suppressing skin temperature rise, or suppressing fatigue.
By applying the external skin preparation of the present invention to the skin, the skin can be effectively protected even when light having a wavelength in the ultraviolet to infrared region such as ultraviolet rays, infrared rays, or sunlight is irradiated to the skin. Thus, the skin can be prevented from photo-aging or skin temperature rise due to irradiation of ultraviolet rays, infrared rays, sunlight, or the like, and the heat insulating effect of the skin can be obtained.
Further, when an animal such as a human is subjected to a long-lasting exercise in a sunlight-irradiated environment, fatigue is likely to occur if the amount of sunlight irradiation is large, but such fatigue due to sunlight irradiation can be suppressed by using the external skin preparation of the present invention.
The fatigue-suppressing effect by using the external skin preparation can be evaluated by the following method, for example.
The skin external preparation is applied at a concentration of 2mg/cm 2 Is applied to the exposed parts (face, chest, back, wrist, back of hand, foot) of the subject, and dried for 15 minutes. Then, artificial solar light sources were placed on the front, rear, left and right sides of the subject, and the upper body of the subject was irradiated with simulated sunlight, and the subject was continuously moved for 30 minutes while maintaining a constant heart rate using a dynamometer (for example, "standard dynamometer 828E (Standard Ergometer 828E)" manufactured by Monark corporation). The test subjects performed a self-evaluation of summer heat sensation and fatigue sensation during exercise, thereby evaluating the effect of exercise performance by using the external skin preparation.
< method for producing skin external preparation >
The method for producing the external preparation for skin of the present invention is not particularly limited, and for example, a known method can be suitably used in the form of a formulation for external preparation for skin. For example, the components (A) and (B) and all other components are mixed uniformly by a disperser or the like. Or may also be used: and a method in which all the components except water and an aqueous medium are mixed uniformly by a disperser or the like, and then the water and the aqueous medium are mixed and stirred by a homogenizer or the like.
When the external preparation for skin is a water-in-oil type emulsion composition or an oil-in-water type emulsion composition, a method of preparing an aqueous phase and an oil phase separately and then mixing the two may be used.
[ method of protecting skin from infrared rays ]
The present invention also provides a method for protecting skin from infrared rays, comprising the step of applying the external skin preparation of the present invention to the skin.
The method of protecting against infrared rays of the present invention is not particularly limited as long as it has a step of applying the external preparation for skin of the present invention to the skin, and examples of the method of applying the external preparation for skin to the skin include coating, spraying, and the like.
In the infrared ray protection method of the present invention, the infrared ray protection rate at the wavelength of 825nm is preferably 35% or more, more preferably 45% or more, and still more preferably 55% or more. In addition, if the infrared ray protection rate at the wavelength of 825nm is 65% or more, the actual feeling of heat insulation of the skin is particularly good. The infrared ray protection rate (%) can be specifically measured by the method of examples.
The present invention further discloses the following external preparations for skin and the like, with respect to the above embodiments.
<1>
A skin external agent, wherein the skin external agent contains:
component (A): 1 or more metal oxides selected from the group consisting of a spherical metal oxide (A1) and a plate-like metal oxide (A2) each having an average particle diameter of 350nm or more, preferably 400nm or more, more preferably 700nm or more, still more preferably 800nm or more and 2,500nm or less, preferably 2,000nm or less, more preferably 1,800nm or less, still more preferably 1,500nm or less, and still more preferably 1,200nm or less; a kind of electronic device with high-pressure air-conditioning system
Component (B): a non-volatile oil;
the content of the component (A) in the external skin preparation is 2% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more and 50% by mass or less, and the external skin preparation has a viscosity of 2,500 mPas or more at 25 ℃.
<2>
The external preparation for skin according to <1>, wherein the metal oxide of the component (A1) and the component (A2) is preferably at least 1 selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, iron oxide, aluminum oxide and cerium oxide.
<3>
The skin external preparation according to <1> or <2>, wherein the viscosity at 25 ℃ is preferably 2,500 to 150,000 mpa-s, more preferably 2,500 to 100,000 mpa-s, still more preferably 2,500 to 50,000 mpa-s, still more preferably 2,500 to 30,000 mpa-s, still more preferably 2,500 to 20,000 mpa-s.
<4>
The external preparation for skin according to any one of <1> to <3>, wherein the viscosity (mpa·s) of the external preparation for skin is preferably 100 or more, more preferably 250 or more, still more preferably 300 or more, still more preferably 350 or more, still more preferably 25,000 or less, still more preferably 20,000 or less, still more preferably 15,000 or less, still more preferably 10,000 or less, particularly preferably 5,000 or less, and particularly preferably 3,000 or less, relative to the content (mass%) of the component (a) in the external preparation for skin.
<5>
The external preparation for skin according to any one of <1> to <4>, wherein the viscosity (mpa·s) of the external preparation for skin is preferably 100 to 25,000, more preferably 250 to 20,000, still more preferably 300 to 15,000, still more preferably 350 to 10,000, particularly preferably 350 to 5,000, particularly preferably 350 to 3,000, relative to the content (mass%) of the component (a) in the external preparation for skin.
<6>
The external preparation for skin according to any one of <1> to <5>, wherein the content of the component (a) in the nonvolatile component of the external preparation for skin is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, and still more preferably 20% by mass or less.
<7>
The external preparation for skin according to any one of <1> to <6>, wherein the content of the component (A) in the nonvolatile component of the external preparation for skin is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, still more preferably 10% by mass or more and 30% by mass or less, particularly preferably 10% by mass or more and 20% by mass or less.
<8>
The external preparation for skin according to any one of <1> to <7>, wherein the average particle diameter of the component (A1) is preferably 400nm or more and 2,000nm or less, more preferably 700nm or more and 2,000nm or less, still more preferably 700nm or more and 1,800nm or less, still more preferably 700nm or more and 1,500nm or less, particularly preferably 800nm or more and 1,200nm or less.
<9>
The external preparation for skin according to any one of <1> to <8>, wherein the component (A) preferably contains a spherical metal oxide having an average particle diameter of 700nm or more and 2,500nm or less as the component (A1), and preferably has a viscosity of 2,500 mPas or more and 20,000 mPas or less at 25 ℃.
<10>
The external preparation for skin according to any one of <1> to <9>, wherein the component (A) preferably contains 1 or more selected from the group consisting of platy titanium oxide and platy zinc oxide as the component (A2).
<11>
The external preparation for skin according to any one of <1> to <10>, wherein the thickness of the component (A2) is preferably 30nm or more, more preferably 50nm or more, still more preferably 60nm or more, still more preferably 75nm or more, particularly preferably 90nm or more, particularly preferably 100nm or more, still more preferably 360nm or less, more preferably 330nm or less, still more preferably 310nm or less, still more preferably 280nm or less, still more preferably 270nm or less, particularly preferably 230nm or less, particularly preferably 200nm or less, and most preferably 180nm or less.
<12>
The external preparation for skin according to any one of <1> to <11>, wherein the thickness of the component (A2) is preferably 30nm to 360nm, more preferably 50nm to 330nm, still more preferably 60nm to 310nm, still more preferably 75nm to 280nm, still more preferably 90nm to 270nm, particularly preferably 100nm to 230nm, particularly preferably 100nm to 200nm, and most preferably 100nm to 180 nm.
<13>
The external preparation for skin according to any one of <1> to <12>, wherein the aspect ratio of the component (A2) is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, still more preferably 30 or more, particularly preferably 50 or more, and particularly preferably 55 or more; further, it is preferably 300 or less, more preferably 230 or less, still more preferably 200 or less, still more preferably 140 or less, particularly preferably 125 or less, and particularly preferably 120 or less.
<14>
The external preparation for skin according to any one of <1> to <13>, wherein the aspect ratio of the component (A2) is preferably 3 or more and 300 or less, more preferably 3 or more and 230 or less, still more preferably 10 or more and 230 or less, still more preferably 30 or more and 230 or less, still more preferably 50 or more and 200 or less, particularly preferably 55 or more and 140 or less, particularly preferably 55 or more and 125 or less, and most preferably 55 or more and 120 or less.
<15>
The external preparation for skin according to any one of <1> to <14>, wherein the content of component (A2) in component (a) is preferably 50 mass% or more, more preferably 60 mass% or more, still more preferably 70 mass% or more, still more preferably 80 mass% or more, particularly preferably 90 mass% or more, and 100 mass% or less.
<16>
The external preparation for skin according to any one of <1> to <15>, wherein the content of spherical titanium oxide having an average particle diameter of 350nm or more and less than 800nm in the external preparation for skin is preferably 5 mass% or more and 30 mass% or less, more preferably 5 mass% or more and 25 mass% or less.
<17>
The external preparation for skin according to any one of <1> to <16>, wherein the content of spherical titanium oxide having an average particle diameter of 800nm to 2,500nm in the external preparation for skin is preferably 5 mass% to 40 mass%, more preferably 5 mass% to 30 mass%.
<18>
The external preparation for skin according to any one of <1> to <17>, wherein the content of the platy titanium oxide in the external preparation for skin is preferably 5% by mass or more and 30% by mass or less.
<19>
The external preparation for skin according to any one of <1> to <18>, wherein the content of the spherical zinc oxide or the plate-like zinc oxide in the external preparation for skin having an average particle diameter of 350nm or more and 2,500nm or less is preferably 7 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 50 mass% or less.
<20>
The external preparation for skin according to any one of <1> to <19>, wherein the viscosity of the component (B) at 25℃is preferably 500 mPas or less, more preferably 300 mPas or less, still more preferably 100 mPas or less, still more preferably 50 mPas or less, and preferably 5 mPas or more.
<21>
The external preparation for skin according to any one of <1> to <20>, wherein the component (B) is preferably in a liquid state at 25 ℃, more preferably 1 or more selected from the group consisting of ester oils, silicone oils, hydrocarbon oils, higher fatty acids, and higher alcohols.
<22>
The external preparation for skin according to any one of <1> to <21>, wherein the content of the component (B) in the external preparation for skin is preferably 1% by mass or more, more preferably 5% by mass or more. Further, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and still more preferably 65% by mass or less.
<23>
The external skin preparation according to any one of <1> to <22>, wherein the external skin preparation is a water-in-oil emulsion composition, and the content of the component (B) in the external skin preparation is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, still more preferably 30% by mass or more, particularly preferably 35% by mass or more.
<24>
The external skin preparation according to any one of <1> to <23>, wherein the external skin preparation is an oil-in-water emulsion composition, and the content of the component (B) in the external skin preparation is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less.
<25>
The external preparation for skin according to any one of <1> to <24>, wherein the mass ratio [ (B)/(A) ] of the content of the component (B) to the content of the component (A) is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.5 or more, still more preferably 1 or more, particularly preferably 2 or more, particularly preferably 3 or more, and most preferably 3.6 or more; preferably 60 or less, more preferably 50 or less, still more preferably 30 or less, still more preferably 20 or less, particularly preferably 10 or less, and particularly preferably 8 or less.
<26>
The external preparation for skin according to any one of <1> to <25>, wherein the mass ratio [ (B)/(A) ] of the content of the component (B) to the content of the component (A) is preferably 0.05 or more and 60 or less, more preferably 0.1 or more and 50 or less, still more preferably 0.2 or more and 30 or less, still more preferably 0.5 or more and 20 or less, still more preferably 1 or more and 10 or less, particularly preferably 2 or more and 10 or less, particularly preferably 3 or more and 10 or less, and most preferably 3.6 or more and 8 or less.
<27>
The external preparation for skin according to any one of <1> to <26>, wherein the total content of the component (A) and the component (B) in the external preparation for skin is preferably 2% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 45% by mass or more, particularly preferably 47% by mass or more, most preferably 50% by mass or more, and still 100% by mass or less.
<28>
The external preparation for skin according to any one of <1> to <27>, wherein the external preparation for skin further preferably contains a tackifier.
<29>
The external preparation for skin according to <28>, wherein the tackifier is preferably an oil tackifier.
<30>
The external preparation for skin according to <28> or <29>, wherein the thickener is preferably at least 1 selected from the group consisting of solid waxes, organically modified clay minerals, dextrin fatty acid esters, and amino acid gelling agents.
<31>
The external preparation for skin according to any one of <28> to <30>, wherein the tackifier content in the external preparation for skin is preferably 0.5 mass% or more, more preferably 1 mass% or more, still more preferably 2 mass% or more, still more preferably 3 mass% or more, still more preferably 50 mass% or less, still more preferably 30 mass% or less, still more preferably 25 mass% or less, still more preferably 20 mass% or less, and particularly preferably 15 mass% or less.
<32>
The external preparation for skin according to any one of <28> to <31>, wherein the tackifier content in the external preparation for skin is preferably 0.5 mass% or more and 50 mass% or less, more preferably 0.5 mass% or more and 30 mass% or less, still more preferably 1 mass% or more and 25 mass% or less, still more preferably 2 mass% or more and 20 mass% or less, and particularly preferably 3 mass% or more and 15 mass% or less.
<33>
The external preparation for skin according to any one of <1> to <32>, wherein the external preparation for skin preferably further contains water; the water content in the external skin preparation is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 10% by mass or more, preferably 50% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less.
<34>
The external preparation for skin according to any one of <1> to <33>, wherein the external preparation for skin is preferably in a liquid, gel, cream or solid form.
<35>
The external preparation for skin according to any one of <1> to <34>, wherein the external preparation for skin is an external preparation for skin for preventing ultraviolet rays or infrared rays, suppressing skin temperature rise, or suppressing fatigue.
<36>
An infrared ray protection method for skin comprising the step of applying the external skin preparation according to any one of <1> to <35> to the skin; preferably, the application method is coating and spraying.
<37>
The method for protecting skin against infrared rays of <36>, wherein the infrared ray protection rate at 825nm is preferably 35% or more, more preferably 45% or more, still more preferably 55% or more, and still more preferably 65% or more.
<38>
The use of the external skin preparation according to any one of <1> to <34> as an ultraviolet light inhibitor, an infrared light inhibitor, an agent for inhibiting skin temperature rise, or an agent for inhibiting fatigue.
Examples (example)
The present invention will be described below by way of examples, but the present invention is not limited to the scope of these examples. In this example, various measurements and evaluations were performed by the following methods.
< viscosity >
The viscosity of each skin external preparation at 25℃was measured on the next day of the preparation of the skin external preparation under the conditions of a rotor rotation speed of 6.0rpm and a rotation time of 60 seconds using a B-type viscometer (model No. TOKI SANGYO VISCOMETER TVB-10M, manufactured by DONGMACHINESE Co., ltd.). The rotors were used in accordance with the viscosities of No.2 to No.4.[ No.2: viscosity 500-5000 mPa.s, no.3: a viscosity of more than 5000 mPas and less than 20000 mPas; no.4: viscosity exceeding 20000 mPa.s ]
< near-infrared ray protection Rate >
50.0mg of each skin external preparation was applied to a polymethyl methacrylate resin (PMMA) substrate (SPF Matser PA-1, manufactured by Session Co., ltd.) of 5 cm. Times.5 cm, and dried for 15 minutes to obtain a sample for measurement. In addition, an uncoated PMMA substrate was used as a control sample. The transmittance at 825nm was measured by a near infrared microscope for each of the measurement sample and the control sample. The transmittance X (%) is obtained by dividing the transmittance of the measurement sample by the transmittance of the control sample, and the near infrared ray protection rate is 100-X (%). The larger this value means that the higher the near infrared ray shielding effect of the skin external agent itself.
Further, regarding the near infrared ray protection effect, 5-stage evaluation was performed based on the following criteria.
5: the near infrared ray protection rate is 65.0% or more
4: the near infrared ray protection rate is 55.0% or more and less than 65.0%
3: the near infrared ray protection rate is more than 45.0% and less than 55.0%
2: the near infrared ray protection rate is more than 35.0% and less than 45.0%
1: the near infrared ray defense rate is less than 35.0%
< coating uniformity >
The skin external preparations of each example were applied to a polymethyl methacrylate (PMMA) substrate of 5cm by 5cm at a rate of 2mg/cm 2 Is uniformly coated by the way of (a) and dried at 25 ℃ for 15 minutes.
The substrate coated with the external skin preparation was subjected to near infrared microscope (IR microscope) to obtain a distribution of transmittance at 825 nm. The distribution image thus confirms the transmittance distribution of the skin portion (convex portion in PMMA plate) and the skin portion (concave portion in PMMA plate), and the uniformity thereof was evaluated at 5 stages, with 1 score when "only skin portion was protected and skin portion was hardly protected" and 5 scores when "both skin and skin were uniformly protected".
(evaluation criterion)
1: only the skin sulcus portion is protected and the skin hillock portion is hardly protected
2: the skin sulcus part is protected and the skin hillock part is slightly protected
3: the skin sulcus portion is protected and the skin hillock portion is protected to some extent
4: the skin sulcus part is protected and the skin hillock part is indeed protected
5: the skin hills and skin furrows are uniformly protected
< whitening upon application to skin >
The whiteness of each example of the skin external preparation immediately after being applied to an area of about 3cm×3cm inside the forearm of a panelist was evaluated at 5 stages, with a whiteness of 1 point when the skin external preparation was quite white and very unnatural, and a whiteness of 5 points when the skin external preparation was natural and no discomfort. The evaluation was performed by 3 panelists, and the average score was used as the evaluation score.
(evaluation criterion)
1: quite white and very unnatural
2: slightly white and unnatural feeling
3: medium and medium
4: is of natural whiteness but slightly uncoordinated feeling
5: is of natural whiteness without discordance
< skin temperature increase inhibition Effect >
The skin external preparations of example 6 and comparative example 5 were uniformly applied to an area of about 4cm×4cm inside the forearm of the panelist, and dried at 25℃under 40% RH for 15 minutes. Thereafter, the coating site was irradiated with simulated sunlight from a distance of 24cm using a solar energy simulator (HAL-320W, manufactured by Niday Spectroscopy Co., ltd.) for 5 minutes.
The skin temperature change during irradiation was measured using a thermal imager (FLIR Co., ltd. "T-420"). In the same manner, the temperature rise when the external skin preparation was not applied was also measured, and the table shows (the temperature rise (DEG C) when the external skin preparation was not applied) ((the temperature rise (DEG C) when the external skin preparation was applied)). The larger this value means the higher the skin temperature increase suppressing effect.
Examples 1 to 23 and comparative examples 1 to 6 (preparation and evaluation of skin external preparations)
Of the components shown in tables 1 to 4, all the components except water were combined and uniformly mixed by a disperser. Then, water was added to the obtained mixture and mixed uniformly by a homogenizer to prepare water-in-oil type skin external preparations having the compositions shown in tables 1 to 4. The obtained external preparation for skin was evaluated by the above-described method. The results are shown in tables 1 to 4. The blending amounts described in the tables are effective component amounts (mass%) of the respective components except "BENTONE GEL PTM V". The amount of "BENTONE GEL PTM V" was the mass% of the label. In the table, the metal oxide not belonging to the component (a) is labeled "component (A1')".
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TABLE 2
TABLE 3
TABLE 4
Examples 24 to 27 (preparation of external preparation for skin)
In examples 24 and 25, all the components except water were mixed and uniformly mixed by a disperser among the components shown in table 5. Then, water was added to the obtained mixture and mixed uniformly by a homogenizer to prepare a water-in-oil type solid skin external preparation having the composition shown in Table 5. In examples 26 and 27, all the components shown in Table 5 were blended and uniformly mixed by a disperser to prepare solid skin external preparations. The blending amounts described in the tables are effective component amounts (mass%) of the respective components.
TABLE 5
The ingredients in the table are as follows.
*1: "R-38L", available from Sakai chemical industry Co., ltd., zrO 2 -Al 2 O 3 Coating spherical titanium oxide with an average particle diameter of 400nm
*2: titan Kogyo, ltd. ST-750EC, aluminum hydroxide-hydrogen polydimethyl siloxane coating treatment spherical titanium oxide with an average particle diameter of 1,000nm
*3: spherical ZINC oxide coated with hydrogen polydimethyl siloxane, manufactured by Sakai chemical industry Co., ltd. "LP-ZINC-2KS", having an average particle diameter of 2,000nm
*4: spherical titanium oxide having an average particle diameter of 270nm was treated with a hydrogen polydimethylsiloxane coating of "JR800s" manufactured by TAYCA Co., ltd
*5: surface ASC treated product of platy titanium oxide (Feateleeve PT-7801K, manufactured by CQV Co., ltd.) having a thickness of 134nm and an aspect ratio of 95
*6: surface ASC treated product of platy titanium oxide (Featerleve PT-7401K, manufactured by CQV Co., ltd.) having a thickness of 112nm and an aspect ratio of 126
*7: surface ASC treated product of platy titanium oxide (Feateleeve PT-7901K, manufactured by CQV Co., ltd.) has a thickness of 191nm and an aspect ratio of 58
*8: XZ-1000F-LP, manufactured by Sakai chemical industry Co., ltd., hydrogen polydimethyl siloxane coated spherical zinc oxide with a thickness of 290nm and an aspect ratio of 3.4
*9: isopropyl palmitate, manufactured by Kabushiki Kaisha
*10: KF-96L-10cs, polydimethyl siloxane, manufactured by Xinyue chemical industry Co., ltd., viscosity of 10 mPa.s
*11: "BENTONE GEL PTM V" by Elementis Japan company, caprylic/capric triglyceride, sela ammonium chloride hectorite and propylene carbonate, 96.8% by mass of nonvolatile component (actual measurement value)
*12: rheopearl KL2 manufactured by Qianli powder manufacturing Co., ltd., and dextrin palmitate
*13: dow Toray Co., ltd. "DOWSIL AMS-C30 COSMETIC WAX", alkyl (C30-45) polymethylsiloxane
14: silicone KF-6028, PEG-9 polydimethylsiloxane ethyl polydimethylsiloxane, manufactured by Xinyue chemical Co., ltd
*15: "OS-88E-TV-E", N-propionyl polyethyleneimine-methyl polysiloxane copolymer (30 mass% -ethanol solution) manufactured by Kagaku Co., ltd
*16: EB-21 manufactured by Weisu (Co., ltd.), dibutyl ethyl hexanoyl glutamine
*17: HNP-9, manufactured by Japanese refined wax Co., ltd., paraffin wax, melting point: 80 DEG C
*18: pure ceresin #810K, manufactured by NIKKO RICA, inc., melting point: 74 DEG C
Tables 1 to 4 show that the external preparations for skin according to the present example have high infrared ray protection effect and high uniformity of coating film, and show little whitening when applied to the skin. In addition, the skin temperature increase suppressing effect is also excellent.
Further, fig. 1 shows a photograph (fraction 5) obtained by an IR microscope in the evaluation of the coating uniformity of the external skin preparation of example 9, and fig. 2 shows a photograph (fraction 1) obtained by an IR microscope in the evaluation of the coating uniformity of the external skin preparation of comparative example 2. In fig. 1 and 2, the white portion indicates the presence of the component (a), and the black portion indicates the absence of the component (a). When the external preparation for skin of example 9 was applied, the component (a) was present in a large amount not only in the skin furrows but also in the skin hills (fig. 1); in contrast, when the external skin preparation of comparative example 2 was applied, the component (a) was almost trapped in the furrows, and the coating uniformity was low (fig. 2).
(industrial applicability)
According to the present invention, an external preparation for skin which is excellent in protection against ultraviolet rays, infrared rays, etc., and which is less whitened when applied to the skin can be provided. When the external preparation for skin is applied to the skin, the skin can be protected from ultraviolet rays, infrared rays, etc., and further, the effect of suppressing the rise in skin temperature due to irradiation of sunlight and the fatigue suppressing effect can be obtained.

Claims (17)

1. A skin external preparation, wherein,
the skin external preparation contains:
component (A): 1 or more metal oxides selected from the group consisting of spherical metal oxides (A1) and plate-like metal oxides (A2) having an average particle diameter of 350nm to 2,500 nm; a kind of electronic device with high-pressure air-conditioning system
Component (B): a non-volatile oil;
the content of component (A) in the external preparation for skin is 2 to 50 mass%,
the viscosity of the external preparation for skin is more than 2,500 mPa.s at 25 ℃.
2. The external preparation for skin according to claim 1, wherein,
the external preparation for skin has a viscosity of 100% or more relative to the content of the component (A) in the external preparation for skin, wherein the unit of viscosity is mPas and the unit of content is mass%.
3. The external preparation for skin according to claim 1 or 2, wherein,
the content of the component (A) in the nonvolatile component of the external skin preparation is 50% by mass or less.
4. The external preparation for skin according to any one of claim 1 to 3, wherein,
the component (A) contains platy titanium oxide as the component (A2).
5. The external preparation for skin according to claim 4, wherein,
the platy titanium oxide content in the external skin preparation is 5 to 30 mass%.
6. The external preparation for skin according to any one of claim 1 to 5, wherein,
the thickness of the component (A2) is 30nm to 360 nm.
7. The external preparation for skin according to any one of claim 1 to 6, wherein,
the aspect ratio of the component (A2) is 3 to 300.
8. The external preparation for skin according to any one of claim 1 to 7, wherein,
the component (A) contains a spherical metal oxide having an average particle diameter of 700nm or more and 2,500nm or less as the component (A1),
the viscosity of the external skin preparation is 2,500 mPas to 20,000 mPas at 25 ℃.
9. The external preparation for skin according to any one of claim 1 to 8, wherein,
the component (B) is 1 or more selected from ester oil, silicone oil, hydrocarbon oil, higher fatty acid, and higher alcohol.
10. The external preparation for skin according to any one of claim 1 to 9, wherein,
the skin external preparation further contains a tackifier.
11. The external preparation for skin according to claim 10, wherein,
the tackifier is an oil tackifier.
12. The external preparation for skin according to claim 11, wherein,
the tackifier is more than 1 selected from solid wax, organic modified clay mineral, dextrin fatty acid ester and amino acid gelling agent.
13. The external preparation for skin according to any one of claim 10 to 12, wherein,
the content of the tackifier in the external skin preparation is 0.5 mass% or more and 50 mass% or less.
14. The external preparation for skin according to any one of claim 1 to 13, wherein,
the skin external preparation further contains water.
15. The external preparation for skin according to any one of claim 1 to 14, wherein,
the external preparation for skin is solid.
16. The external preparation for skin according to any one of claim 1 to 15, wherein,
the external preparation for skin is an external preparation for preventing ultraviolet or infrared rays, inhibiting skin temperature rise, or inhibiting fatigue.
17. A method for protecting skin from infrared rays, wherein,
the method for protecting skin from infrared rays comprising the step of applying the external skin preparation according to any one of claims 1 to 16 to the skin.
CN202280020822.9A 2021-05-14 2022-05-12 External preparation for skin Pending CN117042746A (en)

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JP6676349B2 (en) * 2015-11-18 2020-04-08 花王株式会社 Near infrared protective cosmetic composition
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