CN106389135A - O/W skin external-use agent - Google Patents
O/W skin external-use agent Download PDFInfo
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- CN106389135A CN106389135A CN201610453011.4A CN201610453011A CN106389135A CN 106389135 A CN106389135 A CN 106389135A CN 201610453011 A CN201610453011 A CN 201610453011A CN 106389135 A CN106389135 A CN 106389135A
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- water
- external preparation
- skin external
- oil type
- type skin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- 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
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
- A61K8/602—Glycosides, e.g. rutin
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/67—Vitamins
- A61K8/676—Ascorbic acid, i.e. vitamin C
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/02—Preparations for care of the skin for chemically bleaching or whitening the skin
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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- Birds (AREA)
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- Chemical & Material Sciences (AREA)
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- Dispersion Chemistry (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention provides an O/W skin external-use agent that contains a UV absrober and a whitening composition of which the photo-stability is excellent. The O/W skin external-use agent contains a composite powder composed of titanium oxide and hte UV absrober and the whitening composition.
Description
Technical field
The present invention relates to a kind of water-in-oil type skin external preparation.
Background technology
The reason pigment such as the color spot of skin, freckle Shen is the melanin that transition generates because of the impact of ultraviolet etc.
Calmness is in skin.
In the past, in order to improve pigmentation or the suppression pigmentation of this skin, proposition is various to be combined with whitening chemical combination
The skin preparations for extenal use such as the cosmetic of thing.
For example, have disclosed in patent document 1 containing PAG-whitening such as diisocyanate copolymer, ursin
Compound and the water-in-oil emulsion composition of antiinflammatory.
And, have disclosed in patent document 2 containing the whitening compound such as ascorbic acid derivates, specific polyoxyalkylene
Alkyl co-modified silicone or the water-in-oil emulsion composition of the alkyl co-modified silicone of polyglycerol and ultra-violet absorber.
Patent document 1:Japanese Patent Laid-Open 2012-144444 publication
Patent document 2:Japanese Patent Laid-Open 2014-111584 publication
However, the stability of the light to ultraviolet range for the whitening compound poor must compare many, in order to manifest for a long time whitening effect
Really, improve photostability critically important.Especially in recent years, because LED (Light Emitting Diode) uses in various illuminations
Using in way increases, and therefore as the skin preparations for extenal use containing whitening compound, also becomes important to the stability of LED light
Performance.
But, the water-in-oil emulsion composition of patent document 1 does not have UV resistance ability, exists to whitening compound
The situation of less stable.
On the other hand, though the water-in-oil emulsion composition of patent document 2 contains ultra-violet absorber, through the present invention
The result of the confirmations such as people, distinguishes and inhales only according to only combined with ultraviolet radiation in the water-in-oil type skin external preparation containing whitening compound
Receive agent, the photostability of whitening compound is not enough.
Content of the invention
The present invention completes in view of the foregoing, and its problem is to provide one kind to contain ultra-violet absorber and whitening
Compound and the water-in-oil type skin external preparation having excellent photostability of whitening compound.
For solving the concrete scheme of above-mentioned problem, comprise implementation below.
<1>A kind of water-in-oil type skin external preparation, described water-in-oil type skin external preparation is contained titanium oxide and is inhaled with ultraviolet
Receive composite granule and the whitening compound of agent.
<2>According to<1>Described water-in-oil type skin external preparation, wherein, ultra-violet absorber comprise the 4- tert-butyl group -4 ' -
Methoxy dibenzoyl methane.
<3>According to<1>Or<2>Described water-in-oil type skin external preparation, wherein, whitening compound comprises selected from black bearberry
Glycosides, ascorbic acid or ascorbic acid derivates or their salt and tranexamic acid (ト ラ ネ キ サ Si acid) or derivatives thereof or
At least one in their salt.
<4>According to<1>~<3>Water-in-oil type skin external preparation described in middle either a program, outside described water-in-oil type skin
With agent with respect to the gross mass of the oil phase removing composite granule, comprise the silicone oil of more than 50 mass %.
<5>According to<1>~<4>Water-in-oil type skin external preparation described in middle either a program, wherein, composite granule is contained in
In oil phase.
<6>According to<1>~<5>Water-in-oil type skin external preparation described in middle either a program, outside described water-in-oil type skin
Also contain hydrophilic thickeners with agent.
<7>According to<6>Described water-in-oil type skin external preparation, wherein, hydrophilic thickeners comprise selected from hyaluronic acid
Or at least one in its salt, xanthans and curdlan (ア Le カ リ ゲ ネ ス gives birth to polysaccharide body).
Invention effect
According to the present invention it is possible to provide a kind of composite granule containing titanium oxide and ultra-violet absorber and whitening compound
And the water-in-oil type skin external preparation having excellent photostability of whitening compound.
Specific embodiment
Hereinafter, of embodiment of the water-in-oil type skin external preparation of the application present invention is illustrated.But this
Bright be not limited to following embodiment, in the range of the purpose of the present invention, can suitably be changed and be implemented.
In this specification using "~" number range to represent is to represent, will "~" before and after described numerical value respectively
The scope comprising as minimum of a value and maximum.
In this specification, with regard to the amount of each composition in water-in-oil type skin external preparation, in water-in-oil type skin external preparation
Middle there are multiple materials serving as each composition in the case of, unless otherwise specified then it represents that being present in water-in-oil type skin
The total amount of the many kinds of substance in external preparation.
In this specification, " oil phase " refers to the continuous phase of water-in-oil type skin external preparation, comprise continuous phase liquid medium and
It is dispersed or dissolved in the composition in this liquid medium.
In this specification, " aqueous phase " refers to the dispersion phase of water-in-oil type skin external preparation, comprise dispersion phase liquid medium and
It is dispersed or dissolved in the composition in this liquid medium.
<Water-in-oil type skin external preparation>
The water-in-oil type skin external preparation of present embodiment contains composite granule and U.S. of titanium oxide and ultra-violet absorber
Albefaction compound.
The water-in-oil type skin external preparation of present embodiment for example with the feelings containing titanium oxide and ultra-violet absorber respectively
Condition is compared, and by the composite granule containing titanium oxide and ultra-violet absorber, the light that can significantly improve whitening compound is stable
Property, the especially stability to the light of wavelength 320nm~450nm.As a result, the water-in-oil type skin external preparation of present embodiment
The effect of whitening compound can be manifested for a long time.And, the water-in-oil type skin external preparation of present embodiment contains titanium oxide and purple
The composite granule of ultraviolet absorbers, therefore can isolate the ultraviolet that skin is harmful to.
Hereinafter, the composition that the water-in-oil type skin external preparation of present embodiment can be contained is described in detail.
[composite granule of titanium oxide and ultra-violet absorber]
The water-in-oil type skin external preparation of present embodiment contain titanium oxide and ultra-violet absorber composite granule (with
Under, also referred to as " composite granule ").Water-in-oil type skin external preparation can individually contain a kind of composite granule it is also possible to contain
Two or more.
There is no particular restriction for the titanium oxide of composition composite granule, can appoint for Detitanium-ore-type, rutile-type, brookite type etc.
The titanium oxide of meaning crystal type.From the viewpoint of improving UV resistance ability, the preferred rutile-type of crystal type of titanium oxide.
Titanium oxide can be the titanium oxide being surface-treated using inorganic matters such as aluminium hydroxide, silica, zirconium oxides,
It can be the titanium oxide being surface-treated using aliphatic acid such as stearic acid, isostearic acid, laurate or using inorganic
The titanium oxide that both thing and aliphatic acid are surface-treated.By using inorganic matters such as aluminium hydroxides, surface is carried out to titanium oxide
Process, being capable of passive oxidation titanium.And, by using aliphatic acid such as stearic acid, titanium oxide is surface-treated, can be hydrophobic
Change the surface of titanium oxide.
From the viewpoint of the transparency of UV resistance ability and water-in-oil type skin external preparation, the average grain diameter example of titanium oxide
Preferably such as 1nm~90nm, more preferably 5nm~50nm.The average grain diameter of titanium oxide is following value, that is, utilize transmitted electron to show
Micro mirror shoots more than 1000, using graphical analysis formula particle size distribution device, each captured particle is carried out at image
Reason, and measure the value of equivalent circle diameter.When using commercially available product as titanium oxide, can directly be suitable for described putting down in catalogue etc.
All particle diameters.
As ultra-violet absorber, from the viewpoint of easy and titanium oxide are combined, preferably organic uv absorbers.?
In organic uv absorbers, from the viewpoint of improving the effect of photostability of whitening compound, preferably attached in UVA region
Closely at least one of (wavelength 320nm~450nm) and UVB (wavelength 280nm~320nm) have absorbent organic ultraviolet
Light absorbers, more preferably at least have absorbent organic uv absorbers in UVA areas adjacent.
As the concrete example of ultra-violet absorber, Parsol 1789, diethyl can be enumerated
The own ester of amino oxybenzene formylbenzoate, 2,4- pair-[{ 4- (2- ethyl hexyl oxy) -2- hydroxyl }-phenyl] -6- (4- methoxyl group
Phenyl) -1,3,5-triazines, 2,4,6- tri- (4- (2- ethyl hexyl oxygen carbonyl) anilino-) -1,3,5-triazines, salicylic acid ethyl hexyl
Ester, tetrahydroxybenzophenone, dihydroxy benaophenonel, dihydroxy dimethoxy-benzophenone sodium disulfonate, 2- hydroxyl -4- methoxy
Base benzophenone, Neo-Heliopan HMS, 2-ethylhexylpmethoxycinnamate etc..
In these ultra-violet absorbers, from the viewpoint of easily compound with titanium oxide and cost, it is preferably selected from 4-
The tert-butyl group -4 '-methoxy dibenzoyl methane, Uvinul A Plus and 2,4- be double-[{ 4- (2- second
Base hexyloxy) -2- hydroxyl }-phenyl] at least one in -6- (4- methoxyphenyl) -1,3,5-triazines, from improving whitening
From the viewpoint of the effect of the photostability of compound, more preferably Parsol 1789.
Composite granule preferably has the surface-treated layer containing ultra-violet absorber on the surface of titanium oxide.Surface-treated layer is excellent
Choosing is present in the whole surface of titanium oxide, but in the range of the effect not damaging the present invention, it is possibility to have there is not surface
The part of process layer.The surface of titanium oxide (is surface-treated to titanium oxide using at least one of inorganic matter and aliphatic acid
When, it is configured at the inorganic matter on surface or aliphatic acid) as long as inhaling with ultraviolet with the combination titanium oxide of ultra-violet absorber
Receive agent one to move, then there is no particular restriction, can be that the chemical bond or absorption etc. such as covalent bond non-chemically combine.
In addition, ultraviolet radiation absorption can be confirmed to exist by measuring the reflectance spectrum of composite granule on the surface of titanium oxide
Agent.
There is no particular restriction for the ratio of the titanium oxide in composite granule and ultra-violet absorber.From anti-as composite granule
From the viewpoint of ultraviolet ability, for example, with respect to titanium oxide 1 mass parts, ultra-violet absorber 0.03 mass parts~1 can be set to
Mass parts.
Preferably smaller than 1 μm of the average grain diameter of composite granule.If the average grain diameter of composite granule is less than 1 μm, by composite powder
The coloring of the water-in-oil type skin external preparation that body causes in itself is inhibited, i.e. be not susceptible to whiten.From UV resistance ability and make
From the viewpoint of sense, the average grain diameter of composite granule is more preferably 1nm~500nm, more preferably 3nm~100nm.
The average grain diameter of composite granule can be measured by the average grain diameter identical method with titanium oxide.
Can be using composite granule for example disclosed in International Publication No. 2010/098249 as composite granule.Composite powder
Body can also obtain as commercially available product.Commercially available product as composite granule can enumerate the HXMT- of TAYCA CORPORATION
100ZA etc..HXMT-100ZA is formed on the surface of the titanium oxide being surface-treated using aluminium hydroxide and stearic acid and comprises 4-
The tert-butyl group -4 '-methoxy dibenzoyl methane surface-treated layer.
The containing ratio of the composite granule in water-in-oil type skin external preparation is with respect to total matter of water-in-oil type skin external preparation
Amount is for example preferably 0.1 mass %~50 mass %, more preferably 0.5 mass %~25 mass %, more preferably 1 matter
Amount %~15 mass %.If the containing ratio of composite granule be 0.1 mass % more than, have whitening compound photostability and
The tendency of UV resistance ability all raisings, if the containing ratio of composite granule is below 50 mass %, has raising water-in-oil type skin
The tendency of the dispersion stabilization of the composite granule in skin external preparation.
From the viewpoint of improving the effect of photostability of whitening compound, compound in water-in-oil type skin external preparation
The containing ratio of powder is preferably 0.5 times~10 times of content of whitening compound in terms of quality criteria, more preferably 1 times~5 times.
Composite granule can be contained in any one in the oil phase of water-in-oil type skin external preparation and aqueous phase.From raising Water-In-Oil
The viewpoint of the effect of photostability of the water-resistance of type skin preparations for extenal use, use feeling (smoothness, salubrious sense) and whitening compound
From the point of view of, composite granule is preferably contained in the oil phase of water-in-oil type skin external preparation.
For example, when coordinating composite granule in the oil phase in water-in-oil type skin external preparation, it is possible to use polyether-modified silicon
Ketone, silicone oil etc., to modulate slurry, are coordinated with other compositions in a form of slurry.
There is no particular restriction for the containing ratio of the composite granule in slurry.The containing ratio of the composite granule in slurry is generally preferably
It is set to 10 mass %~80 mass % of the gross mass of slurry, be more preferably set to 20 mass %~60 mass %.If in slurry
The containing ratio of composite granule is above range, then have and can stably coordinate composite granule in water-in-oil type skin external preparation
Tendency.
[whitening compound]
The water-in-oil type skin external preparation of present embodiment contains whitening compound.Water-in-oil type skin external preparation can be single
Solely contain a kind of whitening compound it is also possible to contain two or more.
The concept of " whitening compound " in this specification is not only to comprise the chemical combination with the effect making skin brighten
Thing, but also comprise the compound with the effect of suppression skin melanism.For example, not only have and improve the pigments such as color spot, freckle
The compound of calm effect, and have and suppress the compound of Pigmented effect to be also contained in " whitening compound ".
As whitening compound, known respectively have the compound manifesting whitening effect by following (i)~(iv) method.
I () hinders the effect to melanocyte for the melanocyte activation factor.
(ii) hinder the activity of the tyrosinase protein in melanocyte.
(iii) promote the decomposition of tyrosinase protein.
(iv) oxidation when tyrosine is to B16 cell for the suppression.
As the whitening compound manifesting whitening effect by above-mentioned (i) method, t-AMCHA (trans- 4- ammonia can be enumerated
Methyl-cyclohexyl alkane carboxylic acid) or its salt, tranexamic acid or blood coagulation acid derivative or their salt, chamomile ET (chamomile extraction
Thing) etc..As the whitening compound manifesting whitening effect by above-mentioned (ii) method, can enumerate ursin, ellagic acid or
Its salt, Rucinol (Lucin), ascorbic acid or ascorbic acid derivates or their salt etc..As passing through
Above-mentioned (iii) method, to manifest the whitening compound of whitening effect, can enumerate linoleic acid etc..As by above-mentioned (iv) method
To manifest the whitening compound of whitening effect, ascorbic acid or ascorbic acid derivates or their salt etc. can be enumerated.
Water-in-oil type skin external preparation preferably comprise selected from ursin, ascorbic acid or its salt, ascorbic acid derivates or
At least one in its salt, tranexamic acid or its salt and blood coagulation acid derivative or its salt and as whitening compound.Can as salt
To enumerate alkali metal salt (sodium salt, sylvite etc.), alkali salt (calcium salt, magnesium salts etc.), ammonium salt and alkanolamine etc..
As ascorbic acid derivates or its salt, magnesium ascorbyl phosphate (APM), ascorbic acid phosphoric acid can be enumerated
Ester sodium salt (APS), ascorbyl palmitate, AA2G (AA2G), ethylascorbyl (VC-Et) etc..
As blood coagulation acid derivative or its salt, tranexamic acid lauryl (Tranexamic acid lauryl can be enumerated
Ester), tranexamic acid myristin (Tranexamic acid myristyl ester), tranexamic acid cetyl ester
(Tranexamic acid Cetyl ester), tranexamic acid stearyl (Tranexamic acid Stearyl ester)
Deng.
From the viewpoint of the raising effect of the photostability based on composite granule, water-in-oil type skin external preparation is more preferably
Comprise in ursin, magnesium ascorbyl phosphate (APM), AA2G (AA2G) and tranexamic acid extremely
Few one kind, further preferably comprises selected from ursin, magnesium ascorbyl phosphate (APM) and AA2G
(AA2G) at least one in, particularly preferably comprises at least in ursin and magnesium ascorbyl phosphate (APM)
Kind.
With respect to the gross mass of water-in-oil type skin external preparation, the containing of the whitening compound in water-in-oil type skin external preparation
Rate is had for example to be preferably 0.5 mass %~7 mass %, more preferably 1 mass %~5 mass %, more preferably 2 mass %
~3 mass %.
[polyether modified silicone]
The water-in-oil type skin external preparation of present embodiment can also contain polyether modified silicone.Water-in-oil type skin external application
Agent contains polyether modified silicone, thus has the tendency of the emulsion stability improving water-in-oil type skin external preparation.Water-in-oil type
Skin preparations for extenal use can individually contain a kind of polyether modified silicone it is also possible to contain two or more.
Polyether modified silicone is the polymer having as the silicone chains of main chain and the polyether chain being imported into by modification.
Silicone chains can be the silicone chains of straight-chain or the silicone chains of branched.Polyethylene glycol can be enumerated as polyether chain
(PEG) chain, polypropylene glycol (PPG) chain etc..Polyether modified silicone can have the carbon atom being imported into by modification further
The alkyl chain for 8~22 for the number.
From the viewpoint of the emulsion stability of water-in-oil type skin external preparation, the HLB of polyether modified silicone
(Hydrophile-Lipophile Balance) value is preferably 1~10, more preferably 2~8.In this specification, polyether-modified
The HLB value of silicone is the value obtained from the number of molecular weight and Oxyranyle.When using commercially available product, can directly be suitable for mesh
Described HLB value in record etc..
Can enumerate as polyether modified silicone, PEG-11 methyl ether dimethicone, PEG/PPG-20/22 butyl ether
Dimethyl silicone polymer, PEG/PPG-19/19 dimethyl silicone polymer, PEG-9 dimethyl silicone polymer, PEG-9 methyl ether poly- two
Methylsiloxane, KF6017, PEG-21 methyl ether dimethicone, PEG-9 polydimethylsiloxanes second
Base dimethyl silicone polymer, lauryl KF-6028 etc..
Polyether modified silicone can also obtain as commercially available product.As commercially available product, for example, can enumerate KF-6011, KF-
6011P、KF-6012、KF-6013、KF-6015、KF-6016、KF-6017、KF-6017P、KF-6043、KF-6028、KF-
6028P, KF-6038 (more than, SHIN-ETSU CHEMICAL CO., LTD.) etc..
From the viewpoint of the emulsion stability of water-in-oil type skin external preparation, preferably have as polyether modified silicone
The polyether modified silicone of the silicone chains of branched.Wherein, as polyether modified silicone, more preferably it is selected from PEG-9 poly dimethyl
In silica ethyl dimethyl silicone polymer and lauryl KF-6028 at least one
Kind.
When water-in-oil type skin external preparation contains polyether modified silicone, with respect to total matter of water-in-oil type skin external preparation
Amount, the containing ratio of polyether modified silicone is for example preferably 0.01 mass %~10 mass %, more preferably 0.1 mass %~8 matter
Amount %, more preferably 0.5 mass %~6 mass %.If the containing ratio of polyether modified silicone is more than 0.01 mass %,
There is the tendency of the emulsion stability improving water-in-oil type skin external preparation, if the containing ratio of polyether modified silicone is 10 mass %
Hereinafter, then there is the tendency of the sticky sense after reducing coating water-in-oil type skin preparations for extenal use.
[aliphatic acid]
The water-in-oil type skin external preparation of present embodiment can also contain aliphatic acid.Water-in-oil type skin external preparation contains
Aliphatic acid, thus has the tendency improving viscosity stability and use feeling.Water-in-oil type skin external preparation can individually contain one
Plant aliphatic acid it is also possible to contain two or more.
Can be any one in saturated fatty acid and unrighted acid as aliphatic acid, and can also be straight-chain
And any one in branched.Total carbon atom number as aliphatic acid is not particularly limited, but from viscosity stability and use feeling
From the viewpoint of, preferably total carbon atom number is 8~20, and more preferably total carbon atom number is 10~18.In aliphatic acid, steady from viscosity
From the viewpoint of qualitative and use feeling, the preferably unrighted acid of straight-chain, the saturated fatty acid of branched or branched
Unrighted acid.
As the concrete example of aliphatic acid, octanoic acid, capric acid, laurate, myristic acid, palmitic acid, stearic acid, mountain can be enumerated
Yu acid, oleic acid, linoleic acid, leukotrienes, isostearic acid, coco-nut oil fatty acid, arachidonic acid, undecenoic acid etc..Wherein, from
From the viewpoint of viscosity stability and use feeling, be preferably selected from laurate, myristic acid, palmitic acid, stearic acid, behenic acid,
At least one in oleic acid, linoleic acid, leukotrienes and isostearic acid, is more preferably selected from oleic acid, isostearic acid, stearic acid and palm fibre
At least one in palmitic acid acid.
When water-in-oil type skin external preparation contains aliphatic acid, with respect to the gross mass of water-in-oil type skin external preparation, fat
The containing ratio of acid such as preferably 0.01 mass %~20 mass %, more preferably 0.5 mass %~10 mass %, excellent further
Elect 0.5 mass %~5 mass % as.If the containing ratio of aliphatic acid is more than 0.01 mass %, there is raising water-in-oil type skin
The viscosity stability of skin external preparation and the tendency of use feeling, if the containing ratio of aliphatic acid is below 20 mass %, have raising
The tendency of the dispersiveness of composite granule.
[lipophile thickener]
The water-in-oil type skin external preparation of present embodiment can also contain lipophile thickener.Lipophile thickener refers to
Oil phase can be dispersed or dissolved in and give the composition of viscosity.Water-in-oil type skin external preparation contains lipophile thickener, thus
There is the tendency improving the dispersion stabilization of composition being contained in oil phase.Water-in-oil type skin external preparation can individually contain one kind
Lipophile thickener is it is also possible to contain two or more.
There is no particular restriction for the form of lipophile thickener, can for particle shape, pasty state, pulp-like, glue, liquid,
Arbitrary form in lenticular etc..From the viewpoint of the ageing stability of water-in-oil type skin external preparation, lipophile thickener
Form be preferably particle shape, pasty state or pulp-like, more preferably particle shape." particle shape " refers to either spherical, tabular, no
Any shape in sizing etc. can.The maximum gauge of particle shape lipophile thickener is preferably less than 100 μm.
When lipophile thickener is particle shape, the volume average particle size of lipophile thickener is preferably 0.005 μm~30 μm,
More preferably 0.01 μm~30 μm, more preferably 0.1 μm~30 μm.If the volume average particle size of lipophile thickener is
More than 0.005 μm, then the sense of discomfort with skin during use is suppressed, and improves the tendency of use feeling.And if, lipophile
The volume average particle size of thickener is less than 30 μm, then the surface area with the per unit weight of lipophile thickener will not become
Too small and not impaired to the adhesiveness of skin tendency.
The volume average particle size of lipophile thickener can be measured using commercially available various particle size distribution meters etc..From
Particle size range and mensure easiness consider, dynamic light scattering is preferentially applied in the measurement of the volume average particle size of lipophile thickener
Method.
In this specification, using dense system particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.)
To measure volume average particle size.Specifically, dilute lipophile thickener with dimethyl silicone polymer, so that concentration becomes 1
Quality %, and be measured using quartz cell.The volume average particle size of lipophile thickener as in sample refractive rate is
1.600th, the refractive index of decentralized medium be 1.000 and set dimethyl silicone polymer viscosity as decentralized medium viscosity when
Value and obtain.
As lipophile thickener, cross-linking type silicone powder, polymethyl methacrylate (PMMA) powder can be enumerated, have
Machine modified clay mineral, silicon-dioxide powdery, porous silica powder, cornstarch, dextrin fatty acid ester etc..
As cross-linking type silicone powder, silicone gel powder, silicone rubber powder, silicone resin powder, silicon can be enumerated
Ketone elastomer etc..In cross-linking type silicone powder, from the viewpoint of the dispersion stabilization of water-in-oil type skin external preparation, preferably
Be selected from (Dimethicone/Vinyl Dimethicone) cross-linked polymer, (dimethyl silicone polymer/bis--isobutyl
Base PPG-20) cross-linked polymer, Dimethicone Crosspolymer, (dimethyl silicone polymer (PEG-10)) cross-linked polymeric
Thing, (PEG-10/ lauryl dimethicone) cross-linked polymer, (the poly- diformazan of KF6017/vinyl
Radical siloxane) cross-linked polymer, (dimethyl silicone polymer (PEG-10/15)) cross-linked polymer, (PEG-15/ lauryl poly- two
Methylsiloxane) cross-linked polymer, (PEG-15/ lauryl polydimethylsiloxanes ethyl dimethyl silicone polymer) cross-linked polymeric
Thing, (polyglycereol -3/ lauryl polydimethylsiloxanes ethyl dimethyl silicone polymer) cross-linked polymer, (dimethyl silicone polymer/
Polyglycereol -3) cross-linked polymer, (lauryl dimethicone/polyglycereol -3) cross-linked polymer, (polyglycereol -3/ bay
Base polydimethylsiloxanes ethyl dimethyl silicone polymer) cross-linked polymer, (diphenyl dimethicone/vinyl hexichol
Base dimethyl silicone polymer/silsesquioxane) cross-linked polymer, (dimethyl silicone polymer/couple isobutyl group PPG-20) be crosslinked poly-
Compound, (dimethyl silicone polymer/vinyl trimethyl siloxy esters of silicon acis) cross-linked polymer, (dimethyl silicone polymer/phenyl
Vinyldimethicone) cross-linked polymer, (vinyldimethicone/lauryl dimethicone) hand over
Linked polymer, (vinyldimethicone/polymethyl siloxane silsesquioxane) cross-linked polymer and (lauryl gather
Dimethyl silica ethyl dimethyl silicone polymer/bi-vinyl dimethyl silicone polymer) at least one in cross-linked polymer.
As the commercially available product of silicone gel powder, KSG-15, KSG-16, KSG-1610, KSG-18A, KSP- can be enumerated
100、KSP-101、KSP-102、KSP-105、KSP-300、KSP-441、KSP-411、KSG-41、KSG-42、KSG-43、KSG-
44、KSG-210、KSG-240、KSG-310、KSG-320、KSG-330、KSG-340、KSG-710、KSG-320Z、KSG-350Z
(more than, SHIN-ETSU CHEMICAL CO., LTD.) etc..
As the commercially available product of silicone rubber powder, can enumerate TREFIL (registration mark) E-506C, E-508,
9701Cosmetic Powder、9702Powder、9027/9040/9041/9045/9046/9041/9546Silicone
Elastomer Blend、EP-9215、EP-9216TI、EP-9289 LL、EP-9293 AL、EL-8040 ID Silicone
Organic Blend (more than, DOW CORNING TORAY CO., LTD.), Wacker-Belsil (registration mark) RG 100
(WACKER ASAHI KASEI SILI CONE CO., LTD.), NIKKOL (registration mark) SILBLEND-91 (NIKKO
CHEMIC ALS CO., LTD.) etc..
As PMMA powder, in addition to the powder comprising PMMA, also comprise methyl methacrylate cross-linked polymer,
(methyl methacrylate/ethylene glycol dimethacrylate) cross-linked polymer, (methyl methacrylate/acrylonitrile) copolymer,
(polymethyl methacrylate/dimethyl polysiloxane grafted propylene acid resin) copolymer, (EHA/methyl-prop
E pioic acid methyl ester) powder such as copolymer.
As the commercially available product of PMMA powder, TECHPOLYMER (registration mark) (SEKISUI PLASTICS can be enumerated
CO., LTD.), this microballoon loose (MATSUMOTO YUSHI-SEIYAKU CO., LTD.) etc..
As organo-clay mineral, dimethyl benzyl dodecyl ammonium montmorillonitic clay, dimethyl ten can be enumerated
Eight alkylammonium montmorillonite clays etc..
As silicon-dioxide powdery, silica, silylation silica, dimethylsilyl dioxy can be enumerated
SiClx, dimethyl silicone polymer silicic acid silicon-dioxide powdery etc..
As porous silica powder, the silica of Porous, silylation silica, diformazan can be enumerated
Base silane base silica, dimethyl silicone polymer silicic acid silica etc. are from the viewpoint of viscosity stabilization, preferably many
Hole matter silica.
As the commercially available product of porous silica powder, can enumerate SUNSPHERE (registration mark) H-31, H-32,
H-33, H-51, H-52, H-53, H-121, H-122, H-201 (more than, ASAHI GLASS CO., LTD.), VM-2270
Aerogel Fine Particle (DOW CORNING TORAY CO., LTD.), HDK (registration mark) H2000, H15, H18,
H20, H30 (more than, WACKER ASAHI KASEI SILICONE CO., LTD.), Silo Pure (registration mark) (FUJI
SILYSIA CHEMICAL CO., LTD.), Tokusil (TOKUYAMA CORPORATION manufacture), microsphere silica gel (FUJI
SILYSIA CHEMICAL CO., LTD.) etc..
As the commercially available product of cornstarch, DRY FLO PURE (AKZO NOBEL CO., LTD.) etc. can be enumerated.
As dextrin fatty acid ester, Dextrin palmitate, palmitic acid/2- ethyl hexyl alkanoic acid dextrin, myristic acid can be enumerated
Dextrin, stearic acid dextrin, palmitic acid/stearic acid dextrin, oleic acid dextrin, different Dextrin palmitate, isostearic acid dextrin etc..
And, as lipophile thickener, it is possible to use by styrene/methacrylic acid octadecyl ester/divinylbenzene
Etc. composition Porous polymer, hydrogenation (styrene/isoprene) copolymer, (butylene/ethylene/styrene) copolymer, (benzene
Ethylene/propylene acrylamide) copolymer, (ethylene/propene/styrene) copolymer, clay mineral, bentonite, synthesis phlogopite, polyamides
Polyimide resin, laminar titanium oxide etc..
In these lipophile thickeners, from the viewpoint of the use feeling (smoothness) of water-in-oil type skin external preparation, excellent
It is first selected from (Dimethicone/Vinyl Dimethicone) cross-linked polymer, (dimethyl silicone polymer (PEG-
10/15)) cross-linked polymer, methyl methacrylate cross-linked polymer and (methyl methacrylate/dimethacrylate second two
Alcohol) at least one in cross-linked polymer.
When water-in-oil type skin external preparation contains lipophile thickener, with respect to total matter of water-in-oil type skin external preparation
Amount, the containing ratio of lipophile thickener is for example preferably 0.005 mass %~30 mass %, more preferably 0.01 mass %~20
Quality %, more preferably 0.05 mass %~15 mass %.If the containing ratio of lipophile thickener be 0.005 mass % with
On, then there is the tendency improving the dispersion stabilization in oil phase, if the containing ratio of lipophile thickener is below 30 mass %,
There is the tendency of the use feeling (smoothness) improving water-in-oil type skin external preparation.
[hydrophilic thickeners]
The water-in-oil type skin external preparation of present embodiment can also contain hydrophilic thickeners.Hydrophilic thickeners refer to
Aqueous phase can be dispersed or dissolved in and give the composition of viscosity.Water-in-oil type skin external preparation contains hydrophilic thickeners, thus
There is the precipitation of whitening compound during the moisture evaporation when using be inhibited, and obtain not coarse and inclining of being smooth to the touch
To.And, water-in-oil type skin external preparation contains hydrophilic thickeners, thus there is the photostability improving whitening compound
Tendency.Water-in-oil type skin external preparation can individually contain a kind of hydrophilic thickeners it is also possible to contain two or more.
As hydrophilic thickeners, there is no particular restriction, preferred polysaccharide class.As the concrete example of polysaccharide, can enumerate
Hyaluronic acid or its salt, xanthans, curdlan (Arukashiran), Arabic gum, bassora gum, Karaya Gum, Luo Wang
Seed pectin, guar gum, carragheen, HPG, locust bean gum, gellan gum, natural gellan gum, methylcellulose, hydroxyl second
Base cellulose, hydroxypropyl cellulose, carboxymethylcellulose calcium etc..As the salt of hyaluronic acid, Sodium Hyaluronate etc. can be enumerated.Its
In, from the viewpoint of the raising effect of smooth use feeling and the photostability of whitening compound, it is preferably selected from hyalomitome
At least one in acid or its salt, xanthans and curdlan (Arukashiran).
When water-in-oil type skin external preparation contains hydrophilic thickeners, with respect to total matter of water-in-oil type skin external preparation
Amount, the containing ratio of hydrophilic thickeners is for example preferably 0.01 mass %~2 mass %, more preferably 0.01 mass %~0.5
Quality %, more preferably 0.03 mass %~0.1 mass %.If the containing ratio of hydrophilic thickeners be 0.01 mass % with
On, then there is the tendency of the photostability that can obtain smooth use feeling and improve whitening compound, if hydrophilic thickeners
Containing ratio be 2 mass % below, then have reduce coating water-in-oil type skin preparations for extenal use after sticky sense tendency.
[surfactant]
The water-in-oil type skin external preparation of present embodiment can also contain surfactant.Water-in-oil type skin external preparation
Containing surfactant, thus there is the tendency of the viscosity stability improving water-in-oil type skin external preparation.Water-in-oil type skin
External preparation can individually contain a kind of surfactant it is also possible to contain two or more.
As surfactant, can be any one in nonionic surfactant and ionic surfactant.
As ionic surfactant, alkylsulfonate, alkyl sulfate, MAP, lecithin etc. can be enumerated.As
Nonionic surfactant, can enumerate sorbitan fatty acid ester, fatty acid glyceride, organic monoglyceride, gather
Fatty acid glyceride, methyl glycol fatty acid ester, polyglycereol condensation ricinoleate ester, sucrose fatty ester, polyethylene glycol fatty acid
Ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene
Sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyglyceryl fatty acid ester, polyoxyethylene the third two
Alcohol fatty acid ester, Emulsifier EL-60, polyoxyethylene hardened castor oil etc..
When water-in-oil type skin external preparation contains surfactant, with respect to the gross mass of water-in-oil type skin external preparation,
The containing ratio of surfactant is for example preferably 0.01 mass %~30 mass %, more preferably 0.05 mass %~20 matter
Amount %, more preferably 0.1 mass %~10 mass %.If the containing ratio of surfactant is more than 0.01 mass %,
Have improve water-in-oil type skin external preparation viscosity stability tendency, if the containing ratio of surfactant be 30 mass % with
When lower, then there is the tendency improving use feeling.
[finish]
The water-in-oil type skin external preparation of present embodiment contains finish.Finish is to form water-in-oil type skin external preparation
The composition of oil phase in become the composition of solvent or decentralized medium.As long as being liquid under room temperature (25 DEG C) as finish,
Then there is no particular restriction.As finish, silicone oil, ester oil, hydrocarbon ils etc. can be enumerated.Water-in-oil type skin external preparation can individually contain
There is a kind of finish it is also possible to contain two or more.
As silicone oil, dimethyl polysiloxane (dimethyl silicone polymer), methyl phenyl silicone, methyl can be enumerated
The chain polysiloxanes such as hydrogen polysiloxanes, Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane (cyclopentasiloxane), ten dimethyl
Cyclic polysiloxanes, the octyl group polymethyl siloxanes etc. such as ring six siloxanes, tetramethyl hydrogen cyclotetrasiloxane.
As the commercially available product of silicone oil, KF-96L-0.65cs, KF-96L-1cs, KF-96L-1.5cs, KF- can be enumerated
96L-2cs, KF-96L-5cs, KF-96A-6cs, KF-96-10cs, KF-96-20cs, KF-995 (more than, SHIN-ETSU
CHEMICAL CO., LTD.), SH200 C Fluid 1CS, SH200 Fluid 1.5CS, SH200 C 2CS, SH200 C
Fluid 5CS、SH200 C Fluid 6CS、SH200 C Fluid 10CS、SH200 C Fluid 20CS、2-1184
Fluid, SH245 Fluid, DC246 Fluid, DC345 Fluid, SS-3408 (more than, DOW CORNING TORAY CO.,
LTD.), TSF404, TSF405, TSF4045 (more than, MOMENTIVE PERFORMANCE MATERIALS INC.) etc..
As ester oil, tetraethyl caproic acid pentaerythritol ester, thylhexoic acid cetyl ester, jojoba oil, the moon can be enumerated
Osmanthus acyl glutamic acid two (phytosterol/octyldodecyl) ester, three isostearates, two glyceryl isostearates, three isooctyl acids
Glyceride, dimerization dilinoleic acid (phytosterol/docosyl), dimerization dilinoleic acid (phytosterol/isooctadecane base/ten
Six alkyl/octadecyl/docosyl) ester, isopropyl palmitate, Queensland nut fatty acid phytosterin ester, four (behenyls
Acid/benzoic acid/thylhexoic acid) pentaerythritol ester, ethylhexyl palmitate, myristyl myristate, two neopentanoic acids 3 the third two
Alcohol ester, different tridecanol isononoate etc..
Hydrocarbon ils can be any one in straight-chain and branched.Isodecane, Permethyl 99A, different can be enumerated as hydrocarbon ils
Isoalkane (isoparaffin) of the carbon numbers such as hexadecane 8~16 etc..
With respect to the gross mass of water-in-oil type skin external preparation, the containing ratio example of the finish in water-in-oil type skin external preparation
Preferably such as 5 mass %~80 mass %, more preferably 10 mass %~80 mass %, more preferably 15 mass %~80
Quality %, especially preferably 30 mass %~80 mass %, most preferably 40 mass %~80 mass %.
With respect to the gross mass of the oil phase removing composite granule, water-in-oil type skin external preparation especially preferably comprises 50 matter
The silicone oil of amount more than %.If the containing ratio removing the silicone oil in the oil phase of composite granule of water-in-oil type skin external preparation is 50 matter
Amount more than %, then have the water-resistance improving water-in-oil type skin external preparation and the tendency of use feeling (salubrious sense).
[water]
The water-in-oil type skin external preparation of present embodiment contains water.Water is in the water constituting water-in-oil type skin external preparation
Become the composition of solvent or decentralized medium in the composition of phase.As long as going for the water of skin preparations for extenal use as water, then
There is no particular restriction.
[polyalcohol]
The water-in-oil type skin external preparation of present embodiment can also contain polyalcohol.Water-in-oil type skin external preparation contains
Polyalcohol, thus has the tendency of the use feeling (moisture retention) improving water-in-oil type skin external preparation.Water-in-oil type skin external application
Agent can individually contain a kind of polyalcohol it is also possible to contain two or more.
As polyalcohol, can enumerate glycerine, polyglycereol, ethylene glycol, propane diols, DPG, 1,3-BDO, 1,2-
Pentanediol, 1,2- hexylene glycol, polyethylene glycol, glucose, galactolipin, sucrose, D-sorbite, maltitol, antierythrite, wood sugar
Alcohol, trehalose etc..
[other compositions]
The water-in-oil type skin external preparation of present embodiment can also contain in the range of the effect not damaging the present invention
Other compositions.
As other compositions, the ultra-violet absorber not being combined, water-miscible organic solvent (ethanol can be enumerated with titanium oxide
Deng), preservative (Phenoxyethanol, methyl p-hydroxybenzoate etc.), pH adjusting agent, emollient, NMF, antioxidant, coloring
Agent, spices etc..
<The purposes of water-in-oil type skin external preparation>
The water-in-oil type skin external preparation of present embodiment goes for cosmetic, in the purposes of percutaneous quasi drug.
As cosmetic, color make-up cosmetics such as cosmetic skin-care material, sun-proof cosmetic, foundation make up etc. can be enumerated, but simultaneously
It is not restricted to these.
<The manufacture method of water-in-oil type skin external preparation>
There is no particular restriction for the manufacture method of the water-in-oil type skin external preparation of present embodiment, can be according to known oil
The manufacture method of water-in type skin preparations for extenal use is being manufactured.
For example, when composite granule being coordinated in oil phase, the oil containing composite granule and other oil-phase components can be modulated
Combined thing, and the oil phase composition being obtained and aqueous phase composition are carried out mixing to manufacture water-in-oil type skin external preparation.
And, during by composite granule cooperation in aqueous phase, the water containing composite granule and other water-phase components can be modulated
Combined thing, and the aqueous phase composition being obtained and oil phase composition are carried out mixing to manufacture water-in-oil type skin external preparation.
As the Water-In-Oil being obtained by mixing oil phase composition and aqueous phase composition as water-in-oil emulsion
Emulsification method during type skin preparations for extenal use, there is no particular restriction, can conventionally carry out.
[embodiment]
Below, more specific description is carried out to the present invention by embodiment, but the present invention is without departing from its main idea, then simultaneously
It is not limited to following examples.
[embodiment 1]
At room temperature, using disperser by cyclopentasiloxane, composite granule (HXMT-100ZA, TAYCA
CORPORATION) and dimethyl silicone polymer 10CS fully be stirred mix.Then, add the poly- diformazan of PEG-9 further
Base silica ethyl dimethyl silicone polymer (KF-6028, SHIN-ETSU CHEMICAL CO., LTD.), oleic acid (LUNAC O-V,
Kao Corporation), (Dimethicone/Vinyl Dimethicone) cross-linked polymer (KSG-16, volume
5 μm of average grain diameter, SHIN-ETSU CHEMICAL CO., LTD.) and (dimethyl silicone polymer/(PEG-10/15)) crosslinked poly-
Compound (KSG-210, SHIN-ETSU CHEMICAL CO., LTD.), and carry out mixing mixing and so that it is homogenized, thus obtaining
Oil phase composition.
Then, at room temperature, ethanol, 1,3-BDO, ursin, aqueous solution of sodium hyaluronate 1 mass % and water (are joined
A part for resultant) it is stirred mixing and so that it is homogenized, thus obtaining aqueous phase composition.
Then, using mixer for well-distribution, oil phase composition is stirred, marginally adds aqueous phase composition on one side
To be emulsified.Then add Phenoxyethanol, add remaining water to make it homogenize, be derived from the Water-In-Oil of embodiment 1
Type skin preparations for extenal use.
The composition of the water-in-oil type skin external preparation of embodiment 1 is shown in table 1." % " of becoming in subfield in table 1 represents
" quality % ", "-" represents and does not contain its composition.
[embodiment 2~4]
To replace except adding magnesium ascorbyl phosphate (APM), AA2G (AA2G) or tranexamic acid
Adding beyond ursin, carrying out, thus obtaining the water-in-oil type skin external preparation of embodiment 2~4 same as Example 1ly.Will
The composition of the water-in-oil type skin external preparation of embodiment 2~4 is shown in table 1.
[embodiment 5]
In addition to adding the xanthans 1 mass % aqueous solution and replacing adding the Sodium Hyaluronate 1 mass % aqueous solution, with reality
Apply example 1 to carry out in the same manner, thus obtaining the water-in-oil type skin external preparation of embodiment 5.By outside the water-in-oil type skin of embodiment 5
It is shown in table 1 with the composition of agent.
[embodiment 6~9]
In addition to being not added with the Sodium Hyaluronate 1 mass % aqueous solution, carry out, thus obtaining identically with embodiment 1~4
The water-in-oil type skin external preparation of embodiment 6~9.The composition of the water-in-oil type skin external preparation of embodiment 6~9 is shown in table 1.
[embodiment 10]
In addition to adding cyclopentasiloxane and different tridecanol isononoate and replacing cyclopentasiloxane, with embodiment 1 phase
Carry out together, thus obtaining the water-in-oil type skin external preparation of embodiment 10.Water-in-oil type skin external preparation by embodiment 10
Composition be shown in table 1.
[comparative example 1]
In addition to being not added with ursin, carry out, thus obtaining the water-in-oil type skin of comparative example 1 same as Example 1ly
Skin external preparation.The composition of the water-in-oil type skin external preparation of comparative example 1 is shown in table 1.
[comparative example 2]
Except adding surface treatment titanium oxide (MT-10EX, TAYCA CORPORATION) and the 4- tert-butyl group -4 '-methoxyl group
Beyond dibenzoyl methane is to replace composite granule, carry out, thus obtaining the water-in-oil type of comparative example 1 same as Example 1ly
Skin preparations for extenal use.The composition of the water-in-oil type skin external preparation of comparative example 1 is shown in table 1.In addition, in comparative example 2, the tertiary fourth of 4-
Base -4 '-methoxy dibenzoyl methane do not dissolve and separate out, therefore filter after used.
[comparative example 3]
In addition to adding cyclopentasiloxane and different tridecanol isononoate and replacing adding cyclopentasiloxane, with comparative example
2 are carried out in the same manner, thus obtaining the water-in-oil type skin external preparation of comparative example 3.Water-in-oil type skin external preparation by comparative example 3
Composition be shown in table 1.
[evaluation]
For the water-in-oil type skin external preparation of embodiment 1~10 and comparative example 1~3, carry out following evaluation.To tie
Fruit is shown in table 1.In table 1, the "-" in value column represents that not carrying out it evaluates.
(evaluation of isolation ultraviolet function)
According to ISO24443:2012, with 2mg/ on PMMA substrate (HELIOPLATE HD6, HelioScreen company)
cm2Coating weight coating Examples 1 water-in-oil type skin external preparation, make isolation ultraviolet functional evaluation sample.Use
This isolation ultraviolet functional evaluation sample, by SPF (Sun Protection Factor) analyzer (UV-2000S,
Labsphere society) measure UVAPF (UVA Protection Factor) value.Outside its result, the water-in-oil type skin of embodiment 1
It is 18.0 with the UVAPF value of agent.
Equally measure UVAPF value using the water-in-oil type skin external preparation of embodiment 2~10 and comparative example 1~3.
The relative value that the UVAPF value of the water-in-oil type skin external preparation of embodiment 1 is set to when 100 is shown in table 1.If relatively
It is worth for more than 75, then allow in practicality.
(evaluation of water-resistance)
After soaking 10 minutes above-mentioned UV resistance merit rating samples in the flowing water (1L/ second), and it is made to be dried, and above-mentioned
Measure UVAPF value in the same manner.Then, the UVAPF value of the sample before stream treatment is set to 100, calculates the sample after stream treatment
The relative value of the UVAPF value of product.Show the result in table 1.If relative value is more than 70, practicality allows.
(evaluation of smoothness)
10 panels of expert with finger, the water-in-oil type skin external preparation of embodiment 1~10 and comparative example 1~3 please be coated with
In on the face, and by the metewand in following 5 stages, smoothness during coating is evaluated.Then, will be little by 10 experts
The mean value of the evaluation of estimate that group is carried out is rounded to the value till 1.0 to 5.0 in units of 0.5, thus as smoothness
Evaluation result.Show the result in table 1.In view of merchantability, using more than 3.0 as allowed band.
In addition, " smoothness " refers to that water-in-oil type skin external preparation does not produce conflict and is put on touching on skin to finger
Sense.
- metewand-
5:Smoothness is very excellent
4:Excellent smoothness
3:There is smoothness
2:Smoothness is poor
1:Smoothness is excessively poor
(evaluation of salubrious sense)
10 panels of expert the water-in-oil type skin external preparation of embodiment 1~10 and comparative example 1~3 please be coated face
On, and by the metewand in following 5 stages, the salubrious sense after coating is evaluated.Then, will be entered by 10 panels of expert
The mean value of the evaluation of estimate of row is rounded to the value in units of 0.5 till 1.0 to 5.0, thus the evaluation as salubrious sense
Result.Show the result in table 1.In view of merchantability, using more than 3.0 as allowed band.
In addition, " salubrious sense " refers to do not have touching of sticky sense during the skin after touching coating water-in-oil type skin preparations for extenal use
Sense.
- metewand-
5:Salubrious sense is very excellent
4:Salubrious sense is excellent
3:There is salubrious sense
2:Salubrious sense is poor
1:Salubrious sense is excessively poor
(evaluation of the photostability of whitening compound)
By HPLC (High Performance Liquid Chromatography) to embodiment 1~10 and comparative example
The amount of the whitening compound in 1~3 water-in-oil type skin external preparation carries out quantitation.
Then, embodiment 1~10 and comparative example 1~3 are sandwiched between 2 glass sheets of the silicon spacer across thickness 1mm
Water-in-oil type skin external preparation, to make light stability evaluating sample.Away from the light stability evaluating height of sample 15cm
Upper setting day commonly uses LED illumination (1000lm), to 28 days LED light (being equivalent to 4000lx) of light stability evaluating sample irradiation.
Then, quantitation is carried out to the amount of the whitening compound in water-in-oil type skin external preparation by HPLC.
And, the amount of the whitening compound before irradiation LED light is set to 100, calculates the whitening compound after irradiation
Amount relative value.Show the result in table 1.If relative value is more than 75, practicality allows.
(evaluation of whitening effect)
With water by modulate embodiment 1~10 and comparative example 1~3 water-in-oil type skin external preparation when aqueous phase composition dilute
Release to 100 times, thus modulating evaluation sample.
Using the MEM culture medium (Minimum Essential Medium) containing hyclone for 10 volumes %, (GIBCO is public
Department), to become 2.5 × 10 on 12 well culture plates5The mode in individual/hole sows B16 MC, and carries out 24 hours
Front culture.
After front culture, it is substituted for and is added with the test medium evaluating sample, carry out 72 little cultures.As test
Culture medium, using becoming 0.25mmol/L with theophylline, dimethyl sulfoxide (DMSO) (DMSO) becomes 1 volume %, evaluate sample becomes
The mode of 0.1mmol/L makes an addition to the culture medium of above-mentioned front culture culture medium.
After terminating culture, after cleaning B16 MC with phosphate buffer normal saline, add and contain 10 volumes
The 1mol/L sodium hydrate aqueous solution of DMSO, carries out the ultrasonication of 30 minutes at 50 DEG C, is derived from lysate.So
Afterwards, measure the absorbance of lysate under wavelength 400nm, and calculate the melanin amount in B16 MC.
To be not added with the situation evaluating sample as comparison, calculate melanin and inhibiting rate (%) occurs, comment by following
Valency benchmark is evaluated.Show the result in table 1.In addition, the aqueous phase composition when modulating water-in-oil type skin external preparation shows
During whitening effect, water-in-oil type skin external preparation displays that whitening effect.
- metewand-
A:It is more than 30% that melanin occurs inhibiting rate
B:It is less than 30% that melanin occurs inhibiting rate
[table 1]
As known from Table 1, the composite granule containing titanium oxide and Parsol 1789 and whitening
Water-in-oil type skin external preparation display whitening effect (melanin generation inhibition) of the embodiment 1~10 of compound, and,
The photostability of whitening compound is significantly excellent.Therefore, the water-in-oil type skin external preparation of embodiment 1~10 can manifest for a long time
The effect of whitening compound.
And, the UV resistance ability of the water-in-oil type skin external preparation of embodiment 1~10, water-resistance and use feeling are all good
Good.
Comparative example 1~5 and embodiment 6~9 understand, water-in-oil type skin external preparation contains hydrophilic thickeners, by
This improves the use feeling (smoothness) of water-in-oil type skin external preparation and the photostability of whitening compound.
And, comparative example 1~5 and embodiment 10 understand, water-in-oil type skin external preparation is removing composite granule
Containing silicone oil more than 50 mass % in oil phase, the water-resistance and the use feeling that thus improve water-in-oil type skin external preparation are (salubrious
Sense).
On the other hand, surface treatment titanium oxide and the 4- tert-butyl group -4 '-methoxyl group containing whitening compound and are respectively contained
Although the water-in-oil type skin external preparation of the comparative example 3 of dibenzoyl methane shows that (melanin suppression effect to whitening effect occurs
Really), but compared with the water-in-oil type skin external preparation of embodiment 1~10, the photostability of whitening compound is substantially poor.
And, the UV resistance ability of the water-in-oil type skin external preparation of comparative example 3, water-resistance and use feeling are than embodiment 1
~10 water-in-oil type skin external preparation is worse.
In addition, though the composite granule containing titanium oxide and Parsol 1789, but do not contain
There is the water-in-oil type skin external preparation of the comparative example 1 of whitening compound although UV resistance ability is excellent, but do not show that whitening is imitated
Really (melanin generation inhibition).
And although contain whitening compound and contain surface treatment titanium oxide and the 4- tert-butyl group -4 '-methoxyl group two respectively
Benzoyl methane, but do not contain the 4- tert-butyl group -4 '-methoxyl group hexichol of the water-in-oil type skin external preparation of the comparative example 2 of ester oil
Formyl methane is not allowed to solve, and the UV resistance ability of water-in-oil type skin external preparation and the photostability of whitening compound are substantially poor.
[embodiment 11]
At room temperature, using disperser, cyclopentasiloxane and dimethyl silicone polymer 10CS are fully stirred mixing.
Then, add KF-6028 (KF-6028, SHIN-ETSU CHEMICAL further
CO., LTD.), oleic acid (LUNAC O-V, Kao Corporation), (dimethyl silicone polymer/vinylpolydimethyl silica
Alkane) cross-linked polymer (KSG-16,5 μm of volume average particle size, SHIN-ETSU CHEMICAL CO., LTD.) and (poly dimethyl
Siloxanes/(PEG-10/15) cross-linked polymer (KSG-210, SHIN-ETSU CHEMICAL CO., LTD.), and be stirred
Mix and so that it is homogenized, thus obtaining oil phase composition.
Then, at room temperature, by ethanol, 1,3-BDO, composite granule (HXMT-100ZA, TAYCA
CORPORATION), ursin and water (part for use level) are stirred mixing and so that it is homogenized, thus obtaining aqueous phase
Composition.
Then, using mixer for well-distribution, oil phase composition is stirred, marginally adds aqueous phase composition on one side
To be emulsified.Then add Phenoxyethanol, add remaining water to make it homogenize, be derived from the Water-In-Oil of embodiment 11
Type skin preparations for extenal use.
The composition of the water-in-oil type skin external preparation of embodiment 11 is shown in table 2.In table 2, the "-" in subfield is become to represent not
Containing its composition.
[embodiment 12]
In addition to adding cyclopentasiloxane and different tridecanol isononoate and replacing adding cyclopentasiloxane, with embodiment
11 are carried out in the same manner, thus obtaining the water-in-oil type skin external preparation of embodiment 12.By outside the water-in-oil type skin of embodiment 12
It is shown in table 2 with the composition of agent.
[evaluation]
For the water-in-oil type skin external preparation of embodiment 11 and embodiment 12, carry out UV resistance energy in the same manner as described above
Power, water-resistance, each evaluation of the photostability of smoothness, salubrious sense and whitening compound.Show the result in table 2.
[table 2]
From table 2 it can be seen that the composite granule containing titanium oxide and Parsol 1789 and
The photostability of the whitening compound of the water-in-oil type skin external preparation of the embodiment 11 of whitening compound and embodiment 12 is good.
And, the UV resistance ability of the water-in-oil type skin external preparation of embodiment 1~10, water-resistance and use feeling are all good
Good.
In addition, the embodiment 11 of the embodiment 6 of contrast table 1 and table 2 understand, compared to aqueous phase composite granule preferably with oil phase
Cooperation.
Claims (10)
1. a kind of water-in-oil type skin external preparation,
Described water-in-oil type skin external preparation contains composite granule and the whitening compound of titanium oxide and ultra-violet absorber.
2. water-in-oil type skin external preparation according to claim 1, wherein,
Described ultra-violet absorber comprises Parsol 1789.
3. water-in-oil type skin external preparation according to claim 1, wherein,
Described whitening compound comprises selected from ursin, ascorbic acid or ascorbic acid derivates or their salt and blood coagulation
At least one in acid or blood coagulation acid derivative or their salt.
4. water-in-oil type skin external preparation according to claim 2, wherein,
Described whitening compound comprises selected from ursin, ascorbic acid or ascorbic acid derivates or their salt and blood coagulation
At least one in acid or blood coagulation acid derivative or their salt.
5. water-in-oil type skin external preparation according to claim 1,
Described water-in-oil type skin external preparation with respect to remove described composite granule oil phase gross mass, comprise 50 mass % with
On silicone oil.
6. water-in-oil type skin external preparation according to claim 4,
Described water-in-oil type skin external preparation with respect to remove described composite granule oil phase gross mass, comprise 50 mass % with
On silicone oil.
7. water-in-oil type skin external preparation according to claim 1, wherein,
Described composite granule is contained in oil phase.
8. water-in-oil type skin external preparation according to claim 6, wherein,
Described composite granule is contained in oil phase
9. the water-in-oil type skin external preparation according to any one of claim 1~8,
Described water-in-oil type skin external preparation also contains hydrophilic thickeners.
10. water-in-oil type skin external preparation according to claim 9, wherein,
Described hydrophilic thickeners comprise at least one in hyaluronic acid or its salt, xanthans and curdlan.
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CN114599342A (en) * | 2019-10-23 | 2022-06-07 | 株式会社资生堂 | Water-in-oil type emulsified sunscreen cosmetic |
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JP2021080226A (en) * | 2019-11-22 | 2021-05-27 | 株式会社 資生堂 | Emulsion cosmetic |
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JP2003252718A (en) * | 2002-03-01 | 2003-09-10 | Shiseido Co Ltd | In vivo dihydroxyindole compound polymerization inhibitor |
JP2004307415A (en) * | 2003-04-08 | 2004-11-04 | Takeda Shiki Kk | Dermatologic preparation for external use |
JP2005041809A (en) * | 2003-07-28 | 2005-02-17 | Nonogawa Shoji Kk | Water-in-oil emulsified cosmetic |
JP2006282632A (en) * | 2005-04-04 | 2006-10-19 | Iwase Cosfa Kk | Solid state water-in-oil type emulsion cosmetic |
JP5053805B2 (en) * | 2007-11-12 | 2012-10-24 | 株式会社コーセー | Water-in-oil emulsified cosmetic |
JP2013075850A (en) * | 2011-09-30 | 2013-04-25 | Fujifilm Corp | Composition |
JP6754166B2 (en) * | 2013-05-14 | 2020-09-09 | 共栄化学工業株式会社 | Cosmetics |
JP6016728B2 (en) * | 2013-08-02 | 2016-10-26 | 富士フイルム株式会社 | Ceramide dispersion composition |
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WO2014185316A1 (en) * | 2013-05-15 | 2014-11-20 | 富士フイルム株式会社 | Water-in-oil cosmetic |
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