CN106389135A

CN106389135A - O/W skin external-use agent

Info

Publication number: CN106389135A
Application number: CN201610453011.4A
Authority: CN
Inventors: 久保利昭; 铃木真由子
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2015-07-30
Filing date: 2016-06-21
Publication date: 2017-02-15
Also published as: JP2017031081A

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

Water-in-oil type skin external preparation

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 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.

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.

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

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,

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,

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.