JP2017171655A - Skin external composition for blocking near infrared radiation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a skin external composition that exhibits sufficient near infrared radiation blocking action to prevent adverse effect on skin.SOLUTION: A skin external composition for blocking near infrared radiation comprises zinc oxide and titanium oxide having specific average primary particle diameters.SELECTED DRAWING: None

Description

  The present application relates to a near-infrared shielding skin external composition containing zinc oxide and titanium oxide having a specific average primary particle size.

Sun rays that reach the earth's surface are classified into three types of electromagnetic waves, ultraviolet rays (290 to 400 nm), visible rays (400 to 760 nm), and infrared rays (760 nm to 1 mm), depending on the wavelength. In general, ultraviolet rays are ultraviolet A waves (UVA) (320 to 400 nm) and ultraviolet B waves (UVB) (290 to 320 nm), infrared rays are near infrared rays (760 to 3000 nm), mid infrared rays (3,000 to 30000 nm) and far infrared rays ( 30000 nm to 1 mm).
It is known that ultraviolet rays increase the expression of collagen degrading enzyme MMP-1 and cause skin aging such as wrinkles and sagging. In recent years, it has been reported that among the near-infrared rays, particularly in the IRA (760 to 1400 nm) region, the expression of MMP-1 is enhanced, thereby being involved in skin aging as in the case of ultraviolet rays (non-native). Patent Document 1).
Moreover, it has been reported that near-infrared rays reduce cell proliferation in the mouse epidermis (Non-patent Document 2) and promote changes in elastin fiber structure, angiogenesis and inflammatory reaction in human dermis (Non-patent Document 2). 3) It is considered that it affects a wide range of skin tissues.

Zinc oxide and titanium oxide are known as near-infrared shielding materials used in cosmetics (Patent Document 2, Patent Document 3, and Patent Document 4).
Although patent document 5 discloses the hexagonal plate-like zinc oxide used as an infrared reflective material, there is no specific description about the cosmetics using the said hexagonal plate-like zinc oxide.

  As mentioned above, zinc oxide and titanium oxide are known as near-infrared shielding materials used in cosmetics. However, when cosmetics containing a large amount of these are applied to the skin, whitening occurs or powder There is a problem such as increased sharpness and elongation. The makeup base is a makeup cosmetic that is applied on the skin before applying the foundation. Must be avoided in particular. Moreover, when sold as a sunscreen agent, since it is used not only by women but also by children and men, the problem of whitening and powderiness that impairs the feeling of bare skin must be avoided.

JP2015-86183A International Publication No. 2012/036082 JP-A-2015-86157 JP 2005-162695 A International Publication No. 2015/118777 International Publication No. 2012/147886

Photodermatol Photoimmunol Photomed 2003; 19: 228-234 Photodermatol Photoimmunol Photomed. 1996; 12 (6): 233-6 J Investig Dermatol Symp Proc. 2009; 14 (1): 15-9

  The disclosures of the prior art documents cited in this specification are all incorporated herein by reference.

  The subject of this application is providing the skin external composition which has sufficient near-infrared shielding effect in order to prevent the bad influence to skin, especially the aging by the light of skin.

As a result of intensive studies to solve the above-mentioned problems, the present inventors show that a combination of zinc oxide having a specific average primary particle diameter and titanium oxide having a specific average primary particle diameter exhibits a high near-infrared shielding effect. As a result, the present invention was reached.
That is, the present invention
An external composition for skin comprising zinc oxide having an average primary particle size of 0.3 to 4 μm and titanium oxide having an average primary particle size of 0.3 to 3.3 μm.

  The inventors of the present application have also found that near-infrared (IRA) enhances MMP-1 expression synergistically with ultraviolet rays, and further blocks 67% or more of near-infrared (IRA) of outdoor natural light, thereby blocking near-infrared rays. It was found that the enhancement of MMP-1 expression by (IRA) can be suppressed. By suppressing the increased expression of MMP-1, it is possible to prevent adverse effects on the skin such as wrinkles and sagging. Therefore, this invention provides the composition for external use of skin which contains the said component and the near-infrared (IRA) shielding rate at the time of apply | coating to skin is 67% or more.

  The external composition for skin of the present invention preferably further contains an ultraviolet absorber and / or an ultraviolet scattering agent. By having both the ultraviolet protection effect and the near-infrared shielding effect, the external composition for skin of the present invention can more reliably suppress the increase in intracellular MMP-1 expression and exhibit a high skin aging inhibitory effect.

That is, the present invention provides the following:
[1] Zinc oxide having an average primary particle size of 0.3 to 4 μm; and titanium oxide having an average primary particle size of 0.3 to 3.3 μm;
A composition for external use comprising the skin.
[2] The composition according to [1], comprising 10 to 100 parts by weight of the titanium oxide with respect to 100 parts by weight of the zinc oxide.
[3] The composition according to [1] or [2], comprising 1 to 7% by weight of the zinc oxide and the titanium oxide.
[4] The composition according to any one of [1] to [3], comprising 0.3 to 3% by weight of the titanium oxide.
[5] The composition according to any one of [1] to [4], comprising 1 to 6% by weight of the zinc oxide.
[6] The composition according to any one of [1] to [5], wherein the zinc oxide has a hexagonal plate shape.
[7] The composition according to any one of [1] to [6], wherein the near infrared (IRA) shielding rate is 67% or more.
[8] The composition according to any one of [1] to [7], further comprising an ultraviolet absorber and / or an ultraviolet scattering agent.
[9] The composition according to any one of [1] to [8], wherein sweating can be suppressed.
[10] The composition according to any one of [1] to [9], which is used as a makeup base.

  The composition for external use of the skin of the present application provides a sufficient near-infrared shielding effect, and when applied to the skin as a makeup base, for example, has a conventional near-infrared shielding action such as whitening, powderiness, and poor elongation. The inconvenience peculiar to the cosmetics to have was suppressed.

  The inventors of the present application have found that blocking the near-infrared (IRA) of outdoor natural light by 67% sufficiently prevents the adverse effects of near-infrared rays on the skin, so that the external composition for skin of the present application is unnecessarily close. Without increasing the content of the infrared shielding material, it is possible to effectively prevent the adverse effects of near infrared rays on the skin. That is, it is considered that not only the increase in the expression of MMP-1 is suppressed but also an effect on cell proliferation, angiogenesis, inflammatory reaction, oxidative stress, and the like. This is considered to contribute to the suppression of skin aging symptoms such as wrinkles, sagging, redness, hot flashes, dullness, reduced turnover, spots, dryness, and skin irritation. Furthermore, the composition of the present application can effectively prevent near-infrared rays (IRA and IRB), thereby suppressing an increase in skin temperature and suppressing sweating. Thereby, it can prevent that the composition apply | coated to skin flows down with sweat, and can prevent the bad influence of sunlight more effectively.

The graph which shows the expression level of the collagenase MMP-1 mRNA in Test Example 1 The graph which shows the sweating amount of the left forearm bending side part in Test Example 6 The graph which shows the sweating amount of the right forearm bending side part in Test Example 6

The present invention is described in detail below.
In the present specification, unless otherwise specified, the terms “zinc oxide” and “titanium oxide” mean zinc oxide and titanium oxide used as near-infrared shielding agents.
In the present specification, unless otherwise specified, the terms “particulate zinc oxide” and “particulate titanium oxide” mean zinc oxide and titanium oxide used as an ultraviolet scattering agent.

In the present specification, “primary particles” refer to the smallest particles that constitute a powder.
In this specification, “average primary particle size” means the average particle size of primary particles.

  In this specification, the average primary particle diameter of zinc oxide and fine particle zinc oxide can be calculated by a conventional method. For example, it can be calculated by a conventional method such as a method of analyzing a transmission electron micrograph or a scanning electron micrograph or a laser diffraction method. For example, the unidirectional diameter of primary particles can be measured with a transmission electron microscope, and the average value of the cumulative distribution can be used as the average primary particle diameter. Or it is good also considering the value measured according to the measuring method of the nominal value of the hexagonal plate-shaped zinc oxide (Sakai Chemical Industry Co., Ltd. XZ-1000F) by Sakai Chemical Industry Co., Ltd. as an average primary particle diameter in this specification.

  In this specification, the average primary particle diameter of titanium oxide and fine particle titanium oxide can be calculated by a conventional method. For example, it can be calculated by a conventional method such as a method of analyzing a transmission electron micrograph or a scanning electron micrograph or a laser diffraction method. For example, the diameter can be measured with a transmission electron microscope to analyze the image, and the calculated weight average diameter can be used as the average primary particle diameter. Or it is good also considering the value measured in accordance with the measuring method of the nominal value of the particle size of zinc oxide (MP-100) made by Teika Co., Ltd. as the average primary particle size in this specification.

  The shape of zinc oxide in the present application is not particularly limited, but a hexagonal plate shape, an irregular shape with a rounded corner, and a shape close to a spherical shape are desirable. Hexagonal zinc oxide is particularly preferred. A plurality of zinc oxides having different shapes may be used in combination.

The zinc oxide in the present application may be subjected to a surface treatment. The surface treatment is not particularly limited, and a surface treatment that forms a film with at least one compound selected from the group consisting of silicon oxide, hydrate of silicon oxide, aluminum oxide, and aluminum hydroxide, Examples thereof include surface treatment with a water-repellent organic compound, surface treatment with a coupling agent such as a silane coupling agent and a titanium coupling agent.
The zinc oxide in the present application may be conductive zinc oxide doped with a dopant component such as aluminum or gallium.
You may perform combining these 2 or more types of processes.

A commercial item may be sufficient as the zinc oxide in this application.
Preferable examples of commercially available hexagonal plate-like zinc oxide include hexagonal plate-like zinc oxide manufactured by Sakai Chemical Industry Co., Ltd., XZ-300F (particle size 0.3 μm), XZ-500F (particle size 0.5 μm), XZ-1000F ( Particle size 1 μm), XZ-2000F (particle size 2 μm), XZ-300F-LP (particle size 0.3 μm), XZ-500F-L (particle size 0.5 μm), XZ-1000F-L (particle size 1 μm) , XZ-2000F-L (particle diameter 2 μm).
Examples of commercially available amorphous and rounded zinc include large particle zinc oxide, LPZINC-2 (particle diameter 2 μm), LPZINC-2-KS (particle diameter 2 μm) manufactured by Sakai Chemical Industry Co., Ltd.
If the average primary particle diameter of each zinc oxide is within the predetermined range of the present invention, two or more zinc oxides can be used in combination.

  Although the shape of the titanium oxide in this application is not specifically limited, For example, a rutile type and an anatase type are mentioned. A plurality of zinc oxides having different shapes may be used in combination.

  The titanium oxide in the present application may be subjected to a surface treatment. The surface treatment is not particularly limited, and examples include surface treatment with inorganic compounds such as silica and alumina, surfactants such as stearic acid, isostearic acid and sodium alginate, silicone compounds such as silicone oil, and the like. A combination of these two or more surface treatments may be used.

The titanium oxide in the present application may be a commercial product.
Preferred examples of commercially available titanium oxide include JR-1000 (particle diameter 1 μm) and MP-100 (particle diameter 1 μm) (both manufactured by Teika Co., Ltd.).
If the average primary particle diameter of each titanium oxide is within the predetermined range of the present invention, two or more types of titanium oxide can be used in combination.

The average primary particle diameter of zinc oxide in the present application is 0.3 to 4 μm, preferably 0.5 to 3.3 μm, more preferably 0.8 to 2.2 μm, and further preferably 0.8 to 1.2 μm. .
Examples of the upper limit of the average primary particle diameter of zinc oxide in the present application are 4 μm, 3.5 μm, 3.3 μm, 3 μm, 2.7 μm, 2.5 μm, 2.2 μm, 2 μm, 1.5 μm, 1.1 μm, And 1 μm.
Examples of the lower limit of the average primary particle diameter of zinc oxide in the present application include 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, and 0.9 μm.

The content of zinc oxide contained in the composition of the present application is preferably 1 to 6% by weight, more preferably 1.5 to 5% by weight, still more preferably 1.5 to 4% by weight, and still more preferably 1.8. -3.5 wt%.
Examples of the upper limit of the content of zinc oxide contained in the composition of the present application are 6 wt%, 5.5 wt%, 5 wt%, 4.5 wt%, 4 wt%, 3.5 wt%, 3 wt% %.
Examples of the lower limit of the content of zinc oxide contained in the composition of the present application include 1% by weight, 1.3% by weight, 1.5% by weight, 1.8% by weight, 2% by weight, and 2.5% by weight. Can be mentioned.

The average primary particle diameter of titanium oxide in the present application is 0.3 to 3.3 μm, preferably 0.5 to 2.5 μm, more preferably 0.8 to 1.7 μm, and still more preferably 0.8 to 1. 2 μm.
Examples of the upper limit of the average primary particle diameter of titanium oxide in the present application include 3.3 μm, 3 μm, 2.5 μm, 2 μm, 1.7 μm, 1.5 μm, 1.2 μm, and 1 μm.
Examples of the lower limit value of the average primary particle diameter of zinc oxide in the present application include 0.3 μm, 0.4 μm, 0.5 μm, 0.7 μm, 0.8 μm, and 0.9 μm.

The content of titanium oxide contained in the composition of the present application is preferably 0.3 to 3% by weight, more preferably 0.4 to 2% by weight, still more preferably 0.5 to 1.5% by weight, and still more preferably. Is 0.6 to 1.3% by weight.
Examples of the upper limit of the content of titanium oxide contained in the composition of the present application include 3% by weight, 2.5% by weight, 2% by weight, 1.5% by weight, 1.3% by weight and 1% by weight. .
Examples of the lower limit of the content of titanium oxide contained in the composition of the present application include 0.3% by weight, 0.4% by weight, 0.5% by weight, and 0.6% by weight.

In this application, the weight part of titanium oxide contained with respect to 100 parts by weight of zinc oxide is preferably 10 to 100 parts by weight, more preferably 15 to 80 parts by weight, still more preferably 20 to 70 parts by weight, and still more preferably. Is 45 to 70 parts by weight.
In the present application, examples of the upper limit value of parts by weight of titanium oxide included with respect to 100 parts by weight of zinc oxide include 100 parts by weight, 80 parts by weight, 70 parts by weight, 60 parts by weight, and 50 parts by weight.
In this application, as an example of the lower limit of the weight part of titanium oxide contained with respect to 100 weight part of zinc oxide, 10 weight part, 15 weight part, 20 weight part, 30 weight part, 40 weight part, and 45 weight part are Can be mentioned.

In the present application, the total content of zinc oxide and titanium oxide is preferably 1 to 7% by weight, more preferably 2 to 6% by weight, still more preferably 2.5 to 5.5% by weight, and even more preferably 2.5%. -3.5 wt%.
In the present application, examples of the upper limit value of the total content of zinc oxide and titanium oxide include 7 wt%, 6 wt%, 5.5 wt%, 5 wt%, 4.5 wt%, 4 wt%, and 3.5 wt%. % By weight.
In the present application, examples of the lower limit of the total content of zinc oxide and titanium oxide include 1% by weight, 1.5% by weight, 2% by weight, and 2.5% by weight.

In the present specification, the near-infrared shielding rate is distinguished by IRA (760-1400 nm) and IRB (1400-3000 nm), and is measured by the following method.
(1) The composition is weighed so as to be ² mg / cm ^{2 at} the center of a 22 × 22 mm cover glass.
(2) Another sheet of cover glass is overlaid on the composition, and the composition is stretched evenly so as to be pressed, and then horizontally separated to form a film sample (one set of two cover glasses).
(3) Three to five sets of coating film samples are prepared for each composition.
(4) Let stand for 30 to 60 minutes in a dark place to completely dry the coating film.
(5) Irradiate a 250 W infrared lamp from 15 cm above the coating film sample.
(6) A light receiving probe is installed below the center of the coating film sample. The light receiving probe is connected to the spectroscope, and here, the light quantity of each wavelength transmitted through the coating film sample is measured.
(7) Transmittance is measured using a spectroscope with an optimal measurement range. For example, MAYA is used for transmittance measurement at 300-1100 nm, and NIRQuest is used for transmittance measurement at 880-2520 nm.
(8) The wavelength at which the transmittance is measured is every 0.5 nm (1,601 points for MAYA and 3,281 points for NIRQuest).
(9) The transmittance of each wavelength is measured for a pair of cover glasses not coated with the composition, and this average value is taken as a blank value.
(10) Next, the transmittance of the coating film sample is measured (becomes the transmittance from the blank value).
(11) When calculating the average transmittance of IRA (760-1400 nm), measurement points (total 1,281 points) measured every 0.5 nm were obtained from 3 to 5 sets of coating film samples. Calculate the average value. When calculating the average transmittance of IRB (1400-3000 nm), the measurement points (total 2,201 points) measured every 0.5 nm are averaged for the values obtained from 3 to 5 sets of coating film samples. Calculate the value.
(12) The average value (1,281 or 2,201 points) of the calculated measurement points is further averaged, and this value is averaged (%) of IRA (760-1400 nm) or IRB (1400-3000 nm). And
(13) Each near-infrared shielding rate (%) is calculated by the following equation.
Near-infrared shielding rate (%) = 100-average transmittance (%)

Although the near-infrared shielding rate exhibited by the composition of the present application is not particularly limited, the near-infrared (IRA) has an adverse effect on the skin by blocking 67% of the near-infrared (IRA) of outdoor natural light as found by the present inventors. Sufficiently blocked. Therefore, it is desirable that the composition of the present application exhibits a near infrared (IRA) shielding rate of 67% or more.
In view of the fact that zinc oxide and titanium oxide are desirably as small as possible in order to avoid problems such as white floating, the composition of the present application achieves a near infrared (IRA) shielding ratio of 67% or more while achieving zinc oxide. Most preferably, the content of titanium oxide is small.

  The composition of the present application contains an ultraviolet absorber and / or an ultraviolet scattering agent, thereby suppressing adverse effects of not only near infrared rays but also ultraviolet rays, and can be a more suitable composition for protecting the skin. The composition of the present application preferably has a near infrared (IRA) shielding rate of 67% or more, and preferably achieves an ultraviolet B wave shielding rate of SPF 15 or more, more preferably SPF 24 or more, SPF 30 or more, Or what achieves ultraviolet A wave shielding rate more than PA ++ is preferable, and what achieves both of the above-mentioned SPF value and the above-mentioned PA value is still more preferred.

  The near infrared (IRB) shielding rate of the composition of the present application is not particularly limited, but is preferably 50% or more, and more preferably 60% or more. The composition of this application can suppress perspiration by shielding near infrared rays (IRB), and can prevent the bad influence on the skin by near infrared rays (IRB).

The ultraviolet absorber in this application will not be specifically limited if it is used for the skin external preparation of cosmetics. Two or more ultraviolet absorbers may be used in combination.
Examples of UV absorbers include ethylhexyl methoxycinnamate (2-ethylhexyl paramethoxycinnamate), octocrylene (2-ethylhexyl 2-cyano-3,3-diphenyl-2-propenoate), t-butylmethoxydibenzoylmethane (4-tert-butyl 4′-methoxydibenzoylmethane), bisethylhexyloxyphenol methoxyphenyltriazine (2,4-bis-[{4- (2 ethylhexyloxy) -2-hydroxy} -phenyl] -6- ( 4-methoxyphenyl) -1,3,5-triazine), methylenebisbenzotriazolyltetramethylbutylphenol, hexyl diethylaminohydroxybenzoylbenzoate, ethylhexyltriazine (2,4,6-tris [4- (2-ethylhexyloxy) Carbonyl) anili No] -1,3,5-triazine, phenylbenzimidazolesulfonic acid, polysilicone 15 (dimethicodiethylbenzalmalonate), 2 [{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl]- 2H-benzotriazole, diethylhexylbutamide triazine, and octyl dimethoxybenzylidene dioxoimidazolidine propionate.

  Although content of the ultraviolet absorber in the composition of this application is not specifically limited, For example, it is 0.001 to 20 weight%, Preferably it is 0.1 to 15 weight%, More preferably, it is 1 to 10 weight%. When ethylhexyl methoxycinnamate is used, its content is preferably 2 to 8% by weight, more preferably 3 to 7% by weight.

  The ultraviolet scattering agent in this application will not be specifically limited if it is used for the skin external preparation of cosmetics. Two or more ultraviolet light scattering agents may be used in combination.

  Although content of the ultraviolet-ray scattering agent in the composition of this application is not specifically limited, For example, it is 1 to 20 weight%, Preferably it is 3 to 15 weight%, More preferably, it is 5 to 12 weight%.

  Examples of the ultraviolet scattering agent in the present application include fine particle zinc oxide and fine particle titanium oxide.

In the present application, the particulate zinc oxide is preferably highly transparent while having an ultraviolet scattering effect. The average primary particle diameter of the fine particle zinc oxide preferred in the present application is less than 0.3 μm, more preferably 0.05 to 0.2 μm, and still more preferably 0.01 to 0.1 μm.
The fine particle zinc oxide in the present application may be subjected to a surface treatment. Examples of the surface treatment include those described above for zinc oxide. Conductive zinc oxide doped with a dopant component as described above may be used.

The fine particle zinc oxide in the present application may be a commercially available product or a combination of a plurality of commercially available products.
As a preferable example of commercially available fine particle zinc oxide, Sakai Chemical Industry Co., Ltd., FINEX-50S-LP2, FINEX-30S-LP2, FINEX-50W, FINEX-30W, FINEX-50W-LP2, FINEX-52W-LP2, FINEX -30W-LP2, FINEX-33W-LP2, FINEX-50-LPT, FINEX-25-LPT, FINEX-50S-LPT, FINEX-30S-LPT, FINEX-50, FINEX-30, FINEX-25, FINEX-33W -LPF1, CANDY ZINC 100, and XZ-100F-LP.

In the present application, the fine titanium oxide is preferably highly transparent while having an ultraviolet scattering effect. The average primary particle diameter of the fine particle titanium oxide preferable in the present application is less than 0.3 μm, more preferably 0.05 to 0.2 μm, and still more preferably 0.01 to 0.1 μm.
The fine particle titanium oxide in the present application may be subjected to surface treatment. Examples of the surface treatment include those described above.

The fine particle titanium oxide in the present application may be a commercially available product or a combination of a plurality of commercially available products.
As examples of commercially available fine particle titanium oxide, STR-100C-LP, STR-100A-LP, STR-100W, STR-100W-LP, STR-100W-LF, STR-40-LP, manufactured by Sakai Chemical Industry Co., Ltd. Examples thereof include STR-100N, MKR-1, MKR-1S, and MT-100TV and MT-700B manufactured by Teika Corporation.

The dosage form of the composition of this application will not be specifically limited if it is a dosage form used as skin external cosmetics. Examples include lotions, oil-in-water emulsifier forms, water-in-oil emulsifier forms, and sprays, which can be prepared by methods well known to those skilled in the art. Preferably the composition of the present application is in the form of a water-in-oil emulsifier.
Although the specific use of the composition of this application is not specifically limited, For example, a lotion, a milky lotion, a cream, a cosmetic liquid, a makeup base, a sunscreen agent, and a liquid foundation are mentioned, for example. In particular, when used as a makeup base or sunscreen agent, the effects of the present invention can be effectively utilized, and therefore the composition of the present application is desirably used in these applications.

The composition of the present application essentially contains zinc oxide and titanium oxide, and the other components are not particularly limited, and can be appropriately selected based on the dosage form and application. As described above, an ultraviolet absorber and an ultraviolet scattering agent may be contained.
Examples of other ingredients included in the composition of the present application:
Silicone compounds such as dimethyl silicone oil, volatile silicone, methylphenyl silicone oil, amino-modified silicone, highly polymerized dimethiconol, polyether-modified silicone oil, polyglycerin-modified silicone oil, silicone gel, acrylic silicone, and trimethylsiloxysilicate; Specific examples of compounds include: siloxane alginate triol, ethyltrisiloxane, octamethyltrisiloxane, carboxydecyltrisiloxane, carboxydecyltrisiloxane zinc, cyclotetrasiloxane, cyclohexasiloxane, cycloheptasiloxane, cyclo Pentasiloxane, tetrahydrotetramethylcyclotetrasiloxane, tetraphenyldimethyldisiloxane, trisiloxy , Trifluoropropylcyclotetrasiloxane, trimethylpentaphenyltrisiloxane, PCA dimethicone, PEG-10 dimethicone, PEG-10 methyl ether dimethicone, PEG-11 methyl ether dimethicone, PEG-12 dimethicone, PEG-12 methyl ether lauroxy PEG -5 amidopropyl dimethicone, PEG-32 methyl ether dimethicone, PEG-3 dimethicone, PEG-7 dimethicone, PEG-8 dimethicone, PEG-9 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, PEG-9 methyl ether dimethicone, PEG / PPG-10 / 3 oleyl ether dimethicone, PEG / PPG-14 / 4 dimethicone, PEG / PPG-18 / 18 dimethicone, PEG / PPG-19 / 19 Methicone, PEG / PPG-20 / 15 dimethicone, PEG / PPG-20 / 20 dimethicone, PEG / PPG-30 / 10 dimethicone, PPG-2 dimethicone, aminopropyl dimethicone, amodimethicone, alkyl (C20-28) perfluorodecyl Ethoxy dimethicone, alkyl (C26-28) methicone, alkyl (C30-45) dimethicone, alkyl (C30-45) methicone, caprylyl trimethicone, caprylyl methicone, glyceryl undecyl dimethicone, cyclomethicone, diphenyl dimethicone, simethicone, dimethicone , Diphenylsiloxyphenyl trimethicone, stearyl dimethicone, stearoxy dimethicone, cetyl PEG / PPG-10 / 1 dimethicone, cetyl diglyceryl tris (trimethylsiloxy) Silylethyl dimethicone, cetyl dimethicone, cetyl dimethicone copolyol, cetyl PEG / PPG10-1 dimethicone, triethoxysilylethyl polydimethylsiloxyethyl dimethicone, triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone, trifluoromethylalkyl (C1-4) dimethicone , Trimethylsiloxyphenyl dimethicone, trimethoxysilyl dimethicone, perfluoroalkyl (C4-14) ethoxy dimethicone, hydrogen dimethicone, bis (PEG / PPG-14 / 14) dimethicone, bis (PEG / PPG-16 / 16) PEG / PPG -16/16 dimethicone, bis (PEG / PPG-20 / 5) PEG / PPG-20 / 5 dimethicone, bis (glyceryl / lauryl) glyceryl la Rildimethicone, bis (hydroxy / methoxy) amodimethicone, bisPEG-15 methyl ether dimethicone, phenyltrimethicone, phenylmethicone, behenoxy dimethicone, polyglyceryl-3 disiloxane dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, methicone, Methyl trimethicone, methoxy PEG / PPG-25 / 4 dimethicone, methoxy PEG / PPG-7 / 3 aminopropyl dimethicone, lauryl PEG-10 tris (trimethylsiloxy) silylethyl dimethicone, lauryl PEG-8 dimethicone, lauryl PEG-9 poly Dimethylsiloxyethyl dimethicone, lauryl PEG / PPG-18 / 18 methicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, (PE -10 / lauryl dimethicone) crosspolymer, (PEG-10 dimethicone / vinyl dimethicone) cross polymer, (PEG-12 dimethicone / PPG-20) cross polymer, (PEG-15 / lauryl dimethicone) cross polymer, (PEG-15 / Lauryl polydimethylsiloxyethyl dimethicone) crosspolymer, (PEG-15 / lauryl polydimethylsiloxyethyl dimethicone) cross polymer, (crotonic acid / vinyl isoalkyl (C8-12) esters / VA / bisvinyl dimethicone) cross polymer, (diphenyl) Dimethicone / vinyldiphenyldimethicone / silsesquioxane) crosspolymer, (diphenylmethylsiloxyphenylmethicone / phenylsilsesquioxane) crosspolymer, (dimethicone / (PE G-10 / 15)) cross polymer, (dimethicone / PEG-10) cross polymer, (dimethicone / bisisobutyl PPG-20) cross polymer, (dimethicone / vinyl dimethicone) cross polymer, (dimethicone / phenyl vinyl dimethicone) cross polymer , (Dimethicone / polyglycerin-3) cross polymer, (trifluoropropyl dimethicone / trifluoropropyl divinyl dimethicone) cross polymer, vinyl dimethicone / methicone silsesquioxane) cross polymer, (vinyl dimethicone / methicone silsesquioxane) cross Polymer, (vinyl dimethicone / lauryl dimethicone) cross polymer, (vinyl dimethyl / trimethylsiloxysilicate / dimethicone) cross polymer, (polyglyceryl-3 / lauryl poly) (Dimethylsiloxyethyl dimethicone) cross polymer, (lauryl dimethicone / polyglycerin-3) cross polymer, (lauryl polydimethylsiloxyethyl dimethicone / bisvinyl dimethicone) cross polymer, PEG-10 dimethicone cross polymer, PEG-12 dimethicone cross polymer, alkyl (C30-45) cetearyl dimethicone cross polymer, dimethicone cross polymer, dimethicone copolyol cross polymer, cetearyl dimethicone cross polymer, (PEG methicone / oleyl PPG methicone / dimethicone) copolymer, (acrylic acid / stearyl methacrylate / dimethicone methacrylate) ) Copolymer, (Acrylates / Ethylhexyl acrylate / Dimethicone methacrylate) Copolymer, (Acrylates / Stearyl acrylate / dimethicone methacrylate copolymer, (acrylates / tridecyl acrylate / triethoxysilylpropyl methacrylate / dimethicone methacrylate) copolymer, (acrylates / behenyl acrylate / dimethicate acrylate) copolymer, (dimethicone / vinyltrimethylsiloxysilicate) Acid) crosspolymer, (vinyldimethyl / trimethylsiloxysilicic acid / dimethicone) crosspolymer, (vinyldimethyl / trimethylsiloxysilicate stearyldimethicone) crosspolymer, trifluoroalkyldimethyltrimethylsiloxysilicic acid, trimethylsiloxysilicic acid, phenylpropyldimethyl Siloxysilicic acid, polymethylsilsesquioxane, bisPEG-18 methyl ether dimethylsilane);
Fatty acid esters such as isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, cetyl ethylhexanoate, isononyl isononanoate, diethyl sebacate, diisopropyl adipate, diisopropyl sebacate, diisostearyl malate; inulins such as inulin stearate Derivatives; dextrin derivatives such as dextrin palmitate, (palmitic acid / ethylhexanoic acid) dextrin; (behenic acid / eicosanedioic acid) glyceryl; dibutylethylhexanoylglutamide; ozokerite, ceresin, polyethylene; disteardimonium hectorite;
Macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hydrogenated oil, mallow, hydrogenated castor oil, beeswax, Oils and waxes such as candelilla wax, carnauba wax, microcrystalline wax, synthetic wax, lanolin, reduced lanolin, hard lanolin, jojoba wax;
Hydrocarbons such as liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, microcrystalline wax;
Higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid;
Higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyl decanol, myristyl alcohol, cetostearyl alcohol, etc .;
Anionic surfactants such as sodium laurate, sodium palmitate, potassium lauryl sulfate;
Cationic surfactants such as stearyltrimethylammonium chloride and benzalkonium chloride;
Amphoteric surfactants such as betaine surfactants (alkyl betaines, amide betaines, sulfobetaines, etc.), acylmethyl taurines;
Sorbitan fatty acid esters (such as sorbitan monostearate, sorbitan sesquioleate), glycerin fatty acids (such as glyceryl monostearate), propylene glycol fatty acid esters (such as propylene glycol monostearate), hardened castor oil derivatives , Polyglycerol alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerol monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyl) Decyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE • POP alkyl ethers (POE • POP2-decyltetradecyl ether, etc.), Tetronic Nonionic surfactants such as POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), sucrose fatty acid esters, alkyl glucosides;
Moisturizing ingredients such as sodium pyrrolidonecarboxylate, lactic acid, sodium lactate;
Powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, Al hydroxide, etc. whose surface may be treated;
Inorganic pigments such as iron oxide, the surface of which may be treated;
Pall agents such as fish phosphorous foil and bismuth oxychloride whose surface may be treated;
Red 202, Red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, which may be laked Organic pigments such as Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204;
Organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer;
Lower alcohols such as ethanol and isopropanol;
Vitamin E such as tocopherol and tocopherol acetate, vitamin D, vitamin H, pantothenic acid, pantethine, pyrroloquinoline quinone and the like;
Extracts such as miwillow extract and scallop extract;
Phenoxyethanol, methylparaben, benzoic acid Na, BHT, sorbic acid K
Water, glycerin, 1,3-butylene glycol;
Alkyl benzoates,
Citric acid, Na citrate, sodium chloride and the like can be mentioned.

Examples of combinations of ingredients included in the composition of the present application include the following combinations:
Cyclopentasiloxane, dimethicone, diphenylsiloxyphenyl trimethicone, diethyl sebacate, PEG-9 polydimethylsiloxyethyl dimethicone, (dimethicone / (PEG-10 / 15)) crosspolymer, inulin stearate, disteardimonium hectorite, (Vinyl dimethicone / methicone silsesquioxane) crosspolymer, (dimethicone / vinyl dimethicone) crosspolymer, trimethylsiloxysilicic acid, polyethylene, tocopherol, iron oxide, ethylhexyl methoxycinnamate, BHT, fine particle zinc oxide, hydrogen dimethicone, PEG- 10 Dimethicone, Titanium oxide, Al hydroxide, Hexagonal zinc oxide, Water, Glycerin, Sodium chloride, Methylparaben, Myrtle extract, Sorbic acid K, Benzoic acid a, Pleurotus cornucopiae extract, 1,3-butylene glycol, citric acid, citric acid Na, and ethanol.

  When the composition of the present application is used as an emulsifier-type cosmetic base or sunscreen agent, it is desirable to include a silicone compound, and its content is preferably 20% to 80% by weight, more preferably. Is 25% to 70% by weight, more preferably 25% to 50% by weight.

<Test Example 1: Total solar radiation, near-infrared (IRA) dose>
The total solar radiation was measured from 9:00 to 17:00 in fine weather in the summer (July 2012) in Nago City, Okinawa Prefecture. A dosimeter LP PYLA03 (Delta Ohm) was used to measure the intensity of global solar radiation.
Based on the intensity of global solar radiation measured from 10:00 to 16:00, the total solar radiation amount (6 hours): 2136.0 (J / cm ² ) was obtained from the following formula.
Irradiance (W / m ² ) / 10000 × second (sec) = irradiation dose (J / cm ² ).
Table 1 shows the measurement results of the intensity of global solar radiation and the amount of global solar radiation.

Generally, the amount of near-infrared rays (IRA) of sunlight reaching the ground surface is reported as 30% (Non-Patent Document 1). Based on this report, the amount of near infrared rays (IRA) per 6 hours (10: 0 to 16:00) on the measurement day was calculated to be 640.8 J / cm ² from the total solar radiation amount.

In Test Example 1, the result was that the amount of near infrared rays per day for 6 hours was “640.8 J / cm ² ”. This near infrared ray amount was obtained under severe conditions for a long time of 6 hours in midsummer and sunny days. Since the situation where the makeup base and sunscreen are actually used is generally considered not to be so severe, the maximum value of the near-infrared amount under natural light outdoors is about 600 J / s slightly lower than that value. The following tests were conducted with the setting of cm ² .

<Test Example 2: Collagenase MMP-1 mRNA expression analysis by near infrared (IRA) and ultraviolet A wave irradiation>

<Test method>
(1) Normal human fibroblasts derived from newborns (NHDF, LIFELINE), growth medium (FibroLife S2 Comp kit, LIFELINE), and maintenance medium (FibroLife Basal Medium, LIFELINE) were purchased from Kurabo Industries. Gentamicin / Amphotericin Solution (Gibco) was added as an antibiotic to both media. To the maintenance medium, 200 mmol / L L-Glutamine Solution (Wako) was added so that the L-glutamine concentration was equal to the growth medium. A 37 ° C. CO ₂ incubator was used for the culture.
(2) NHDF was seeded in a 35 mmφ Collagen Type I coated dish (IWAKI) at a density of 5 × 10 ⁵ cells / dish, and cultured in 2 mL of growth medium per petri dish for 24 hours.
(3) Thereafter, the culture medium was replaced with a maintenance medium containing no growth factor, and further cultured for 24 hours. The amount of the maintenance medium was 2 mL per petri dish.
(4) The radiation of the infrared lamp (IR100 / 110V100WR, TOSHIBA) of the near-infrared irradiation device has a cooling water layer shielding the wavelength of 1400 nm or more (the water level during irradiation kept 5 mm) and a wavelength of 700 nm or less. The filter was passed through a shielding acrylic filter (Mitsubishi Rayon, IR 70) and approximated to the wavelength of near infrared rays (IRA: 760 to 1400 nm). The emission spectrum was measured using Maya2000-Pro (Ocean Optics) below 1000 nm and NIRQuest (Ocean Optics) above 1000 nm. The irradiance was measured using a global solarimeter (Delta OHM, LP PYRA 03), and the irradiance was adjusted by adjusting the number of lamps and the distance from the lamp to the petri dish.
(5) The light radiated from the UVA lamp (TLK40W / 09, Philips) of the ultraviolet A wave irradiation device passes through a 5 mm thick glass plate (Ohwa Shoji Co., Ltd.), and the ultraviolet B wave (280 to 320 nm) The wavelength was completely shielded. The emission spectrum was confirmed using Maya2000-Pro. Irradiance was measured using an ultraviolet A wave probe of a UVX ultraviolet intensity meter (UVP), and the irradiance was adjusted by adjusting the distance from the lamp to the petri dish.
(6) dose of the near infrared is set to three points ^{600J / cm 2, 400J / cm} 2, 200J / cm 2, the dose of ultraviolet A wave was 20 J / cm ^2.
(7) Before starting irradiation, the NHDF maintenance medium was washed with HBSS (Gibco, # 14025-092) and replaced with 1.5 mL of HBSS. Except for the petri dish during irradiation, it was left as a sham group in a 30 ° C. incubator. After the irradiation, HBSS was replaced with 2 mL of maintenance medium per petri dish and cultured in a CO ₂ incubator.
(8) NHDF total RNA was extracted using TRIzol Plus RNA Purification Kit (Ambion) according to the manufacturer's protocol. The concentration of the extracted total RNA was measured using NanoVue Plus (GE Healthcare) and adjusted to a concentration of 100 ng / μL.
(9) 5 μL (500 ng) of total RNA was mixed with PrimeScript RT Master Mix (TAKARA) to prepare a reaction solution, which was subjected to a reverse transcription reaction using Thermal Cycler Dice Touch (TAKARA) according to the manufacturer's protocol. After completion of the reaction, the reaction solution was diluted 10 times with nuclease-free H ₂ O to obtain a cDNA sample.
(10) Primers used for Real-time PCR were purchased from TAKARA. The concentration was adjusted to 20 pmol / μL (10 pmol / μL for each of the forward primer and reverse primer), and this was used as a primer mix.
(11) 1 μL of cDNA and 2 μL of primer mix were mixed with SYBR Premix Ex Taq II (TAKARA) to prepare a reaction solution, and then subjected to PCR reaction using Step One Plus Real-time PCR System. For any of the primers, the reaction was performed according to the following program. Whether or not the target gene was specifically amplified was confirmed by Melt Curve. The comparative Ct method was used for semi-quantification.

<Result>
The results are shown in FIG.
As shown in FIG. 1, the amount of MMP-1 mRNA increased when ultraviolet A wave (20 J / cm ² ) alone was irradiated.
Compared with ultraviolet A wave (20 J / cm ² ) alone, ultraviolet A wave (20 J / cm ² ) + near infrared (400 J / cm ² ), and ultraviolet A wave (20 J / cm ² ) + near infrared (600 J / In cm ² ), the amount of mRNA increased significantly.
Compared with ultraviolet A wave (20 J / cm ² ) alone, ultraviolet A wave (20 J / cm ² ) + near infrared (200 J / cm ² ) showed no significant difference in the amount of mRNA.
That is, when the near-infrared irradiation amount was 200 J / cm ² or less, the expression amount of MMP-1 due to irradiation with ultraviolet A waves did not increase.
From this test, if the amount of near infrared rays is set to 200 J / cm ² , which is a 67% decrease of 600 J / cm ² set in Test 1, it is possible to prevent an increase in the amount of MMP-1 mRNA caused by near infrared rays. It was confirmed that it was possible. Therefore, the inventors of the present application set the 67% or more as a near-infrared shielding rate that can surely suppress the adverse effects on the skin caused by the near-infrared rays.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

<Prescription Examples 1 to 17>
Each component shown in Table 1 was prepared by separately preparing an oil phase component and an aqueous phase component and mixing them to prepare Formulation Examples 1 to 17 of the makeup base agent.
The oil phase component is cyclopentasiloxane, dimethicone, diphenylsiloxyphenyltrimethicone, alkyl benzoate (C12-15), diethyl sebacate, PEG-9 polydimethylsiloxyethyl dimethicone, cetyl dimethicone copolyol, cetyl PEG / PPG10- 1 dimethicone, (dimethicone / (PEG-10 / 15)) crosspolymer, ethylhexyl methoxycinnamate, particulate zinc oxide, (vinyl dimethicone / methicone silsesquioxane) crosspolymer, (dimethicone / vinyl dimethicone) crosspolymer / D5, Tocopherol, talc, polyethylene, disteardimonium hectorite, inulin stearate, trimethylsiloxysilicic acid (50) / D5, polymethylsilsesquioxane, bisPEG-18me Ether dimethyl silane, stearyl dimethicone large particles of titanium oxide (1um), large particle zinc oxide (2um), hexagonal plate-like zinc oxide (2um), hexagonal plate-like zinc oxide (1um), iron oxide.
The aqueous phase components are sodium chloride, preservatives, water, glycerin, butylene glycol, and ethanol.

<Test Example 3: Near-infrared shielding rate>
About each prescription example, it measured by said method.
The results are shown in Tables 2 and 3.

<Test Example 4: SPF value>
The SPF value of each formulation example was measured using SPsphere Analyzer UV-2000S manufactured by Labsphere.
The results are shown in Tables 2 and 3.

<Test Example 5: White float / powder / Nobi>
Two panelists apply each prescription example (0.5g) to the face, and for each of white floatation, powderiness, and spread, 0 points are good, 5 points are bad, 0 points to 5 points It was evaluated in 6 stages.
The results are shown in Table 3.

Fine particle zinc oxide (0.04 μm) ¹ : Daito Kasei Kogyo Fine particle titanium oxide Large particle titanium oxide (1 μm) ² : MP-100 manufactured by Teika Co., Ltd.
Large particle zinc oxide (2 μm) ³ : Sakai Chemical Industry Co., Ltd. LPZINC-2
Hexagonal plate-like zinc oxide (2 μm) ⁴ : Sakai Chemical Industry Co., Ltd. XZ-2000F
Hexagonal plate-like zinc oxide (1 μm) ⁵ : Sakai Chemical Industry Co., Ltd. XZ-1000F

<Test Example 6: Antiperspirant effect>
One adult performed a step-up / down movement for 10 minutes in the sunlight (outdoor, sun, temperature 23.9 ° C. to 25.1 ° C., from the Japan Meteorological Agency temperature data) without applying Formulation Example 17. . The amount of perspiration was measured by attaching a probe of a portable perspiration meter (OKS-04HM) to the left and right forearm flexion sides. After resting for 10 minutes, one adult must apply Formulation Example 17 (2 mg / cm ² , application area is 280 cm ² ) on the left forearm flexion side and right forearm flexion side and leave for 30 minutes. The coated preparation was completely dried. The platform was moved up and down under the same conditions, and the amount of sweat was measured by the same method.
A reduction in the amount of perspiration was confirmed when Formulation Example 17 was applied (post) compared to Formulation 17 without application (pre). The decrease in the amount of perspiration is thought to be due to the fact that the composition of the present application shielded not only IRA but also IRB.
The results are shown in FIGS.

Claims (10)

Zinc oxide having an average primary particle size of 0.3-4 μm; and titanium oxide having an average primary particle size of 0.3-3.3 μm;
A composition for external use comprising the skin.   The composition according to claim 1, comprising 10 to 100 parts by weight of the titanium oxide with respect to 100 parts by weight of the zinc oxide.   The composition according to claim 1 or 2, comprising 1 to 7% by weight of the zinc oxide and the titanium oxide.   The composition according to any one of claims 1 to 3, comprising 0.3 to 3% by weight of the titanium oxide.   The composition according to any one of claims 1 to 4, comprising 1 to 6% by weight of the zinc oxide.   The composition according to any one of claims 1 to 5, wherein the zinc oxide has a hexagonal plate shape.   The near infrared (IRA) shielding rate is 67% or more, The composition of any one of Claims 1-6 characterized by the above-mentioned.   The composition according to any one of claims 1 to 7, further comprising an ultraviolet absorber and / or an ultraviolet scattering agent.   The composition of any one of Claims 1-8 which can suppress sweating.   The composition according to any one of claims 1 to 9, which is used as a makeup base.