TW202033177A - Water-in-oil composition - Google Patents

Abstract

The present invention addresses the problem of providing a water-in-oil composition that has a good usability, e.g., lacks stickiness, and imparts an excellent uniformity, water resistance, and stability over time to a coating film. The water-in-oil composition that has solved the problem comprises the following components (A) to (D): component (A) 5 to 30 mass% of zinc oxide surface-treated with a hydrophobing agent and silica; component (B) a polar oil; component (C) a silicone oil; and component (D) water, wherein component (A), when mixed at 0.25 mass% in a water/ethanol solvent (mass ratio of water : ethanol = 3 : 1), exhibits a transmittance for light at a wavelength of 700 nm of 0.8 to 20. The water-in-oil composition is characterized by having a surfactant content of not more than 1 mass%.

Description

油中水型組成物Oil-in-water composition

本發明有關油中水型組成物，詳言之，有關塗膜均一性、耐水性、經時安定性、使用性優異之油中水型組成物。The present invention relates to a water-in-oil type composition, specifically, it relates to a water-in-oil type composition having excellent coating film uniformity, water resistance, stability over time, and usability.

近幾年來，對於皮膚外用劑或化妝料有強烈要求能阻斷太陽光中之紫外線，賦予肌膚免於因紫外線之不良影響之效果之情況，雖已開發藉由含有氧化鋅或氧化鈦等之金屬氧化物粉體等，而具有紫外線防禦效果等之皮膚外用劑或化妝料，但大多要求於運動時或海水浴時等之高耐水性。 作為具有紫外線防禦效果之皮膚外用劑或化妝料，揭示有油中水型組成物之技術(例如參考專利文獻1、2)。In recent years, there has been a strong demand for skin external preparations or cosmetics that can block the ultraviolet rays in the sun and give the skin the effect of preventing the adverse effects of ultraviolet rays. Although it has been developed to contain zinc oxide or titanium oxide, etc. Metal oxide powder, etc., as well as external skin preparations or cosmetics with ultraviolet protection effects, etc., but most of them require high water resistance during exercise or bathing in the sea. As an external preparation or cosmetic for skin with ultraviolet protection effect, technology of water-in-oil composition is disclosed (for example, refer to Patent Documents 1 and 2).

專利文獻1揭示一種防曬化妝料，其係水相比為50質量%以上之高內相油中水防曬化妝料，且包含(A)交聯型聚甘油・烷基改質性矽氧0.1~10質量%，及(B)紫外線吸收劑。Patent Document 1 discloses a sunscreen cosmetic that is a high internal phase oil-in-water sunscreen cosmetic with a water ratio of 50% by mass or more, and contains (A) cross-linked polyglycerol and alkyl modified silica 0.1~ 10% by mass, and (B) ultraviolet absorber.

專利文獻2揭示一種油中水型乳化防曬化妝料，其特徵係含有(a)疏水化處理氧化鋅及疏水化處理氧化鈦：10~30質量%，(b)親油性非離子界面活性劑：0.5~5質量%，(c)選自N-月桂醯基L-麩醯胺酸(植物固醇基、2-辛基十二烷基)、澳洲胡桃仁脂肪酸植物固醇酯、澳洲胡桃仁脂肪酸膽固醇酯所成之群之1種或2種以上之油分：1~5質量%，(d)揮發性矽氧油及/或烴油：10~40質量%，(e)水：5~30質量%。 [先前技術文獻] [專利文獻]Patent Document 2 discloses a water-in-oil type emulsified sunscreen cosmetic, which is characterized by containing (a) hydrophobized zinc oxide and hydrophobized titanium oxide: 10-30% by mass, (b) lipophilic nonionic surfactant: 0.5~5% by mass, (c) selected from N-laurel L-glutamic acid (phytosterol, 2-octyldodecyl), Australian walnut fatty acid phytosterol ester, Australian walnut kernel One or more than two types of fatty acid cholesterol ester: 1~5 mass%, (d) volatile silicone oil and/or hydrocarbon oil: 10~40 mass%, (e) water: 5~ 30% by mass. [Prior Technical Literature] [Patent Literature]

[專利文獻1] 日本特開2016-145157號公報 [專利文獻2] 日本特開2013-43875號公報 [專利文獻3] 日本特表2001-518111號公報 [專利文獻4] 日本特開2008-208045號公報 [專利文獻5] 日本專利第6334167號公報 [非專利文獻1] B. Binks et. al., Advances in Colloid and Interface Science 100-102, 503-546(2003)[Patent Document 1] JP 2016-145157 A [Patent Document 2] JP 2013-43875 A [Patent Document 3] Japanese Special Publication No. 2001-518111 [Patent Document 4] JP 2008-208045 A [Patent Document 5] Japanese Patent No. 6334167 [Non-Patent Document 1] B. Binks et. al., Advances in Colloid and Interface Science 100-102, 503-546 (2003)

[發明欲解決之課題][The problem to be solved by the invention]

專利文獻1之技術於具有紫外線防禦效果之皮膚外用劑或化妝料中，由於油中水型組成物外相為油，故不易與水融合，雖可期待高的耐水性，但由於必須含有特定量之包含交聯型聚甘油・烷基共改質矽氧，故其塗膜與水接觸時，由於產生乳化，因此塗膜之耐水性降低。其結果，有金屬氧化物等剝落，紫外線防禦效果差的情況。The technology of Patent Document 1 is used in skin external preparations or cosmetics with ultraviolet protection effect. Since the outer phase of the water-in-oil composition is oil, it is difficult to blend with water. Although high water resistance can be expected, it must contain a specific amount It contains cross-linked polyglycerin and alkyl co-modified silica, so when the coating film comes into contact with water, it emulsifies and reduces the water resistance of the coating film. As a result, metal oxides and the like may be peeled off, and the ultraviolet protection effect may be poor.

專利文獻2之技術，特定量界面活性劑為必要，其結果，有黏膩感較強而使用性惡化之情況。又，其塗膜與水接觸時，由於產生乳化，因此有使耐水性降低之情況。The technique of Patent Document 2 requires a specific amount of surfactant, and as a result, the sticky feeling is strong and the usability may deteriorate. In addition, when the coating film comes into contact with water, emulsification occurs, which may reduce the water resistance.

因此，本發明人等為了穩定地含有氧化鋅或氧化鈦等之金屬氧化物粉末，嘗試藉由活用使用粉末進行乳化之皮克林(Pickering)乳液(例如參考專利文獻3~5、非專利文獻1)，而開發耐水性提高之油中水型組成物。Therefore, in order to stably contain metal oxide powders such as zinc oxide or titanium oxide, the present inventors tried to use Pickering emulsions that are emulsified using powders (for example, refer to Patent Documents 3 to 5, Non-Patent Documents). 1) To develop a water-in-oil composition with improved water resistance.

專利文獻3之技術係揭示表示水中油型之微細分散系且不含乳化劑之化妝品或皮膚科學之調製物，其含有1)油相、2)水相及3)含有a)具有未達200nm之平均粒度、其粒子具有b)親水性及親油性兩者之特性，因此具有兩親媒性之特徵，而且沿水/油界面排列，且選自c)金屬氧化物之群、d)依情況具有表面被膜之1種以上之微細化無機顏料，而且依情況含有作為輔助添加劑及/或活性劑之其他化妝品或製藥學上之物質。The technology of Patent Document 3 discloses a cosmetic or dermatological preparation that represents an oil-in-water type fine dispersion system and does not contain emulsifiers, which contains 1) an oil phase, 2) an aqueous phase, and 3) contains a) with a diameter of less than 200nm The average particle size of its particles has both b) hydrophilic and lipophilic characteristics, so it has the characteristics of amphiphilicity, and is arranged along the water/oil interface, and is selected from the group of c) metal oxides, d) according to In some cases, there are more than one kind of micronized inorganic pigments with a surface coating, and other cosmetic or pharmaceutical substances as auxiliary additives and/or active agents are included as appropriate.

專利文獻4之技術係揭示油中水型乳化組成物，其特徵係含有(a)未分散於水中之粉末成分1~40質量%，(b)親水性界面活性劑0.001~1質量%，(c)油相成分，(d)水相成分。The technology of Patent Document 4 discloses a water-in-oil emulsion composition, which is characterized by containing (a) 1-40% by mass of powder components not dispersed in water, (b) 0.001-1% by mass of hydrophilic surfactant, ( c) Oil phase components, (d) Water phase components.

專利文獻5之技術係揭示化妝品組成物，其係包含下述成分之油中水乳液形態之化妝品組成物： a)油性相之連續相， b)水相之分散相，及 c)數平均粒徑為200nm以上1μm以下且經至少1種N-醯基麩胺酸鹽表面處理之粒子， 前述N-醯基麩胺酸鹽係以選自Mg、Al、Ca、Zn之金屬的氫氧化物與前述粒子離子鍵結， 前述粒子存在於前述連續相與前述分散相之間的界面，且 相對於前述組成物總重量含有1重量%以下之至少1種乳化劑。The technology of Patent Document 5 discloses a cosmetic composition, which is a cosmetic composition in the form of an oil-in-water emulsion containing the following ingredients: a) Continuous phase of oily phase, b) The dispersed phase of the water phase, and c) Particles with a number average particle size of 200 nm or more and 1 μm or less and have been surface-treated with at least one N-glycoglutamate, The aforementioned N-aminoglutamate is ionically bonded to the aforementioned particles by a hydroxide of a metal selected from Mg, Al, Ca, and Zn, The aforementioned particles exist at the interface between the aforementioned continuous phase and the aforementioned dispersed phase, and At least one emulsifier is contained at 1% by weight or less with respect to the total weight of the aforementioned composition.

然而，使用專利文獻3~5之技術，因油性使用感，黏膩感較強，不僅欠缺使用性，依然存在有塗膜均一性、耐水性差的情況。且，依據含有的油劑種類而定，而有經時安定性差的情況。 亦即，具有塗膜均一性、耐水性、經時安定性優異，無黏膩等之良好使用性之油中水型組成物迄今尚未知。 [用以解決課題之手段]However, using the techniques of Patent Documents 3 to 5, due to the oily use feeling, the sticky feeling is strong, not only lacks usability, but also has poor coating uniformity and water resistance. Moreover, it depends on the type of oil agent contained, and may have poor stability over time. That is, a water-in-oil type composition having good usability such as coating uniformity, water resistance, stability over time, and non-stickiness has not yet been known. [Means to solve the problem]

本發明人等著眼於粉體，進而於其等中，使用經氧化矽及疏水化處理劑表面處理之氧化鋅，欲獲得解決上述課題之油中水型組成物進行積極檢討之結果，發現含有藉由氧化矽及疏水化處理劑表面處理之氧化鋅，且於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時之波長700nm之光的透過率為0.8~20者，進而將其以特定含量且含有極性油、矽氧油，界面活性劑含量為1質量%以下之油中水型組成物，其塗膜均一性、耐水性優異，經時安定性良好，使用性優異。The inventors of the present invention focused on powders, and used zinc oxide surface-treated with silicon oxide and a hydrophobizing treatment agent among them. The result of an active review in order to obtain a water-in-oil type composition that solves the above-mentioned problems has found that it contains Zinc oxide surface-treated with silicon oxide and hydrophobizing treatment agent, and the transmittance of light with a wavelength of 700nm when mixed in a water/ethanol solvent (mass ratio water: ethanol=3:1) at 0.25% by mass is 0.8~ 20, furthermore, it is a water-in-oil type composition containing polar oil, silicone oil, and surfactant content of less than 1% by mass in a specific content. The coating film has excellent uniformity, water resistance, and good stability over time , Excellent usability.

亦即，本發明提供 一種油中水型組成物，其含有以下成分(A)~(D)； 成分(A)藉由氧化矽及疏水化處理劑進行表面處理之氧化鋅5~30質量% 成分(B)極性油 成分(C)矽氧油 成分(D)水， 成分(A)係於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率為0.8~20者， 界面活性劑之含量為1質量%以下。That is, the present invention provides An oil-in-water composition, which contains the following components (A) ~ (D); Component (A) 5-30% by mass of zinc oxide surface-treated with silica and hydrophobizing treatment agent Ingredient (B) Polar oil Ingredient (C) Silicone oil Ingredient (D) water, Component (A) is a mixture of 0.25% by mass in water/ethanol solvent (mass ratio water:ethanol=3:1) with a light transmittance of 0.8-20 at 700nm wavelength, The content of the surfactant is 1% by mass or less.

提供前述油中水型組成物係皮克林(Pickering) 乳液之油中水型組成物。The aforementioned water-in-oil composition is a Pickering emulsion of the water-in-oil composition.

提供前述成分(B)之含量為5~30質量%之油中水型組成物。Provide a water-in-oil type composition with the content of the aforementioned component (B) of 5-30% by mass.

提供前述成分(B)及前述成分(C)之含有質量比例(B)/(C)為0.1~8之油中水型組成物。Provide a water-in-oil type composition with a mass ratio (B)/(C) of the aforementioned component (B) and the aforementioned component (C) of 0.1-8.

提供前述油中水型組成物之乳化滴的平均粒徑為10~500μm之油中水型組成物。It provides a water-in-oil composition with an average particle diameter of 10~500μm in emulsified droplets of the aforementioned water-in-oil composition.

提供作為前述成分(B)，含有於25℃下之液狀極性油與於25℃下之固形極性油之油中水型組成物。As the aforementioned component (B), an oil-in-water type composition containing liquid polar oil at 25°C and solid polar oil at 25°C is provided.

提供水相與油相之含有質量比例(水相)/(油相)為0.3~5之油中水型組成物。Provide a water-in-oil composition with a mass ratio of water phase to oil phase (water phase)/(oil phase) of 0.3~5.

提供水相與前述成分(A)之含有質量比例(水相)/(A)為0.75~10之油中水型組成物。 [發明效果]Provide a water-in-oil composition with a mass ratio (aqueous phase)/(A) of 0.75 to 10 between the water phase and the aforementioned component (A). [Invention Effect]

依據本發明，可提供塗膜均一性、耐水性、經時安定性、使用性優異之油中水型組成物。According to the present invention, it is possible to provide a water-in-oil type composition having excellent coating film uniformity, water resistance, stability over time, and usability.

針對本發明之細節說明如下。又，本說明書中，「~」意指包含其前後數值之範圍者。The details of the present invention are described below. In addition, in this specification, "~" means the range including the numerical value before and after it.

本發明中之成分(A)係藉由氧化矽及疏水化處理劑進行表面處理之氧化鋅，且於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率(以下有時簡稱為「透過率」)為0.8~20者。The component (A) in the present invention is zinc oxide surface-treated with silica and hydrophobizing treatment agent, and is mixed in water/ethanol solvent (mass ratio water: ethanol=3:1) at 0.25% by mass. The light transmittance of 700nm (hereinafter sometimes referred to as "transmittance") is 0.8-20.

本發明之成分(A)中之氧化鋅係藉由吸收、散射、反射、消光紫外線等而可阻斷紫外線之粉體，粒徑或形狀並未特別限定。The zinc oxide in the component (A) of the present invention is a powder that can block ultraviolet rays by absorbing, scattering, reflecting, extinction ultraviolet rays, etc., and the particle size or shape is not particularly limited.

本發明之成分(A)之氧化鋅之平均粒徑並未特別限定，但基於調配於香水化妝品時之處理容易性或經時安定性之觀點，平均粒徑較佳為1~200nm，更佳為10~100nm。The average particle size of the zinc oxide of the component (A) of the present invention is not particularly limited, but from the viewpoint of ease of handling or stability over time when formulated in perfume cosmetics, the average particle size is preferably 1 to 200 nm, more preferably It is 10~100nm.

本發明之成分(A)之氧化鋅之平均粒徑之測定方法係使用掃描型電子顯微鏡，針對任意視野之粒子100個測定粒徑之結果而算出。The method for measuring the average particle size of the zinc oxide of the component (A) of the present invention is calculated by using a scanning electron microscope to measure the particle size of 100 particles in an arbitrary field of view.

作為本發明之成分(A)之氧化鋅之形狀並未特別限定，但由經時安定性、使用性之觀點，較佳為無定形，更佳為長寬比(長軸徑/短軸徑)為1.2~1.6。The shape of zinc oxide as the component (A) of the present invention is not particularly limited, but from the viewpoint of stability and usability over time, it is preferably amorphous, and more preferably the aspect ratio (major axis diameter/minor axis diameter) ) Is 1.2~1.6.

本發明之成分(A)中之氧化矽並未特別限定，可使用通常化妝料或皮膚外用劑中使用者。本發明之成分(A)中，使用聚乙二醇或親水性界面活性劑之親水化處理劑替代氧化矽之情況，由於該等親水程度不足，故成分(A)對油水界面之選擇配向差，有經時安定性不優之情況。The silicon oxide in the component (A) of the present invention is not particularly limited, and ordinary cosmetics or external skin preparations can be used. In the component (A) of the present invention, the hydrophilization treatment agent of polyethylene glycol or hydrophilic surfactant is used instead of silica. Due to the insufficient degree of hydrophilicity, the component (A) has poor selection and alignment to the oil-water interface , There are situations where stability is not good over time.

本發明之成分(A)中之疏水化處理劑可使用習知表面處理方法所用者。可為例如以氟化合物處理、矽氧處理、矽氧樹脂處理、懸掛處理、矽烷偶合劑處理、鈦偶合劑處理、脂肪酸處理、矽烷處理、油劑處理、N-醯基化樹脂處理、糊精處理、神經醯胺處理、金屬皂處理、金屬氧化物粉體處理等之方法予以表面處理，亦可以該等之1種或2種以上予以表面處理。該等疏水化處理劑中，基於成分(A)對油水界面之配向與分散性、經時安定性之觀點，較佳為自矽氧處理、矽烷偶合劑處理、鈦偶合劑處理、脂肪酸處理中選擇之一種或兩種以上，更佳為自矽氧處理、矽烷偶合劑處理、脂肪酸處理中選擇之一種或兩種以上。The hydrophobization treatment agent in the component (A) of the present invention can be those used in conventional surface treatment methods. It can be, for example, fluorine compound treatment, silicone treatment, silicone resin treatment, suspension treatment, silane coupling agent treatment, titanium coupling agent treatment, fatty acid treatment, silane treatment, oil treatment, N-acid resin treatment, dextrin Surface treatment can be performed by methods such as treatment, ceramide treatment, metal soap treatment, metal oxide powder treatment, etc., and one or more of these can also be surface treated. Among the hydrophobization treatment agents, based on the orientation and dispersibility of component (A) to the oil-water interface, and the stability over time, it is preferably selected from silica treatment, silane coupling agent treatment, titanium coupling agent treatment, and fatty acid treatment. One or two or more selected, more preferably one or two or more selected from silica treatment, silane coupling agent treatment, and fatty acid treatment.

本發明中，於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率可如下般測定。 對於水/乙醇混合溶劑(質量比 水：乙醇=3：1) 40g，以成為0.25質量%之方式秤量0.1g之成分(A)，於其剛秤量後，以振盪器YS-8D (YAYOI公司製)以250次/分鐘、30秒之條件進行混合。混合後，於光路長10mm×光路寬10mm之塑膠槽中放入3.5g，使用分光光度計UV-2500PC(島津製作所公司製)，以波長：700nm測定混合後經過3分鐘之時點的溶液。且，參考組可使用水/乙醇混合溶劑(質量比 水：乙醇=3：1)。In the present invention, the light transmittance at a wavelength of 700 nm when mixed in a water/ethanol solvent (mass ratio water: ethanol = 3:1) at 0.25% by mass can be measured as follows. For 40g of water/ethanol mixed solvent (mass ratio water: ethanol=3:1), weigh 0.1g of component (A) so that it becomes 0.25% by mass. Just after weighing it, use the oscillator YS-8D (YAYOI) (System) Mix at 250 times/minute for 30 seconds. After mixing, put 3.5 g in a plastic tank with an optical path length of 10 mm × an optical path width of 10 mm, and use a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation) to measure the solution at the time of 3 minutes after mixing at a wavelength of 700 nm. In addition, the reference group can use a water/ethanol mixed solvent (mass ratio water:ethanol=3:1).

本發明中，於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率認為可表示分散於該溶劑中之粉體表面之親水疏水性程度。其理由於以下說明。水/乙醇溶劑(質量比 水：乙醇=3：1)可說是親水性高的溶劑。分散於該溶劑中之粉體表面之疏水性若高，則對粉體表面之濡濕性低，故粉體朝氣液界面移動，透過率變高。另一方面，分散於該溶劑中之粉體表面之親水性若高，則對粉體表面之濡濕性變高，故粉體不朝氣液界面移動，透過率變低。由以上，認為於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率與分散於該溶劑之粉體表面之親水疏水性具有相關性。In the present invention, the light transmittance at a wavelength of 700nm when mixed in a water/ethanol solvent (mass ratio water:ethanol=3:1) at 0.25% by mass is considered to indicate the degree of hydrophilicity and hydrophobicity of the powder surface dispersed in the solvent . The reason is explained below. The water/ethanol solvent (mass ratio water:ethanol=3:1) can be said to be a highly hydrophilic solvent. If the hydrophobicity of the surface of the powder dispersed in the solvent is high, the wettability to the surface of the powder is low, so the powder moves toward the gas-liquid interface and the transmittance becomes higher. On the other hand, if the hydrophilicity of the surface of the powder dispersed in the solvent is high, the wettability to the surface of the powder becomes high, so the powder does not move toward the gas-liquid interface and the transmittance becomes low. From the above, it is considered that the light transmittance of 700nm wavelength when mixed in water/ethanol solvent (mass ratio water:ethanol=3:1) at 0.25% by mass is related to the hydrophilicity and hydrophobicity of the powder surface dispersed in the solvent.

本發明中，成分(A)於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率若為0.8~20之範圍內，則未特別限定，但基於經時安定性之觀點，該透過率較佳為1~18，更佳為1~16，又更佳為3~12。In the present invention, when the component (A) is mixed at 0.25% by mass in a water/ethanol solvent (mass ratio water: ethanol=3:1), the light transmittance at a wavelength of 700 nm is not particularly limited if it is in the range of 0.8-20 , But from the viewpoint of stability over time, the transmittance is preferably 1-18, more preferably 1-16, and still more preferably 3-12.

用以調整本發明中之成分(A)於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率之方法，並未特別限定，可為習知表面處理方法，例如使氧化矽、疏水化處理劑之表面處理量適當變化，或使氧化矽之粒徑等適當變化等。具體而言，具有藉由使氧化矽之表面處理量增加等而透過率變高之傾向，或具有藉由使疏水化處理劑表面處理量增加等而透過率變低之傾向。The method for adjusting the light transmittance at a wavelength of 700 nm when the component (A) of the present invention is mixed in a water/ethanol solvent (mass ratio water: ethanol=3:1) at 0.25% by mass is not particularly limited and can be Conventional surface treatment methods, such as appropriately changing the surface treatment amount of silica and hydrophobizing treatment agent, or changing the particle size of silica. Specifically, the transmittance tends to increase by increasing the amount of surface treatment of silicon oxide, or the transmittance tends to decrease by increasing the amount of surface treatment of the hydrophobizing agent.

本發明之成分(A)之氧化矽、疏水化處理劑之個別處理劑量並未特別限定。就經時安定性之觀點，氧化矽處理量，相對於成分(A)之氧化鋅質量，較佳為0.5~10質量%，更佳為1~4質量%。就經時安定性之觀點，疏水化處理劑處理量，相對於成分(A)之氧化鋅質量，較佳為0.5~20質量%，更佳為1~10質量%。The individual treatment doses of the silicon oxide and the hydrophobizing treatment agent of the component (A) of the present invention are not particularly limited. From the viewpoint of stability over time, the amount of silicon oxide treated is preferably 0.5-10% by mass, and more preferably 1-4% by mass relative to the mass of zinc oxide of component (A). From the viewpoint of stability over time, the treatment amount of the hydrophobizing treatment agent is preferably 0.5-20% by mass, and more preferably 1-10% by mass relative to the mass of zinc oxide of component (A).

不含有本發明之(A)成分，而僅含有藉由氧化矽及疏水化處理劑進行表面處理之氧化鋅且於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率未達2者之情況，有經時安定性不優，進而耐水性、使用性亦差之情況。又，不含有本發明之成分(A)，而僅含有藉由氧化矽及疏水化處理劑進行表面處理之氧化鋅且於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率超過20者之情況，有經時安定性不優，進而耐水性、使用性亦差之情況。It does not contain the component (A) of the present invention, but only contains zinc oxide surface-treated with silica and a hydrophobizing treatment agent, and is 0.25% by mass in a water/ethanol solvent (mass ratio water: ethanol=3:1) When the light transmittance of 700nm wavelength is less than 2 during mixing, the stability over time may not be good, and the water resistance and usability may also be poor. In addition, it does not contain the component (A) of the present invention, but only contains zinc oxide surface-treated with silicon oxide and a hydrophobizing treatment agent, and is 0.25 in a water/ethanol solvent (mass ratio water: ethanol=3:1) When the light transmittance of 700nm wavelength exceeds 20 when the mass% is mixed, the stability over time may not be good, and the water resistance and usability may also be poor.

本發明中，作為成分(A)之市售品舉例為例如MZY-500SHE (TAYCA公司製)等。In the present invention, examples of commercially available products as component (A) include MZY-500SHE (manufactured by TAYCA).

圖2分別係表1~3之成分(1)的MZY-500SHE (TAYCA公司製)、成分(2)的FINEX-52W-LP2(堺化學工業公司製)、成分(4)的MZ-500(TAYCA公司製)之透過型電子顯微鏡(H-7650，日立高科技公司製)觀察之圖像(測定條件：加速電壓80KV)。如由圖2所可掌握，成分(4)中不僅粒子的輪廓，其粒子全體的對比亦不明瞭，故與氧化鋅比較，具有於氧化鋅表面緻密地被覆電子密度相對低的氧化矽之特徵。且，成分(2)具有粒子輪廓及粒子全體之對比度清楚，僅以氧化鋅構成之特徵。另一方面，成分(1)具有粒子輪廓稍不清楚，但粒子全體之對比度清楚，與氧化鋅比較，具有於氧化鋅表面斑狀被覆電子密度相對低的氧化矽之特徵，認為可辨識該等表面狀態之差異。Figure 2 shows the components (1) of MZY-500SHE (manufactured by TAYCA), component (2) of FINEX-52W-LP2 (manufactured by Sakai Chemical Industry Co., Ltd.), and component (4) of MZ-500 ( An image observed by a transmission electron microscope (H-7650, manufactured by Hitachi High-Technologies) manufactured by TAYCA Corporation (measurement condition: acceleration voltage 80KV). As can be understood from Fig. 2, in component (4), not only the outline of the particles, but also the overall contrast of the particles is not clear. Therefore, compared with zinc oxide, it has the characteristic of densely covering the surface of zinc oxide with silicon oxide with a relatively low electron density. . In addition, component (2) has the characteristics of clear particle outline and overall contrast of the particles, and is composed of only zinc oxide. On the other hand, component (1) has a slightly unclear particle outline, but the overall contrast of the particles is clear. Compared with zinc oxide, it has the characteristics of silicon oxide with a relatively low electron density on the surface of zinc oxide. The difference in surface condition.

本發明中成分(A)之含量，相對於油中水型組成物總量，為5~30質量%。成分(A)之含量未達5質量%時，有耐水性、經時安定性差的情況，超過30質量%時，有使用性差的情況。成分(A)含量若為5~30質量%，則未特別限定，但基於耐水性、經時安定性之觀點，較佳為8~30質量%，特佳為10~25質量%。The content of the component (A) in the present invention is 5-30% by mass relative to the total amount of the water-in-oil composition. When the content of the component (A) is less than 5 mass%, water resistance and stability over time may be poor, and when it exceeds 30 mass%, the usability may be poor. The content of the component (A) is not particularly limited if it is 5 to 30% by mass, but from the viewpoint of water resistance and stability over time, it is preferably 8 to 30% by mass, and particularly preferably 10 to 25% by mass.

本發明中成分(B)極性油係具有極性之油，可使用通常化妝料或皮膚外用劑所用者。In the present invention, the component (B) polar oil is an oil having polarity, and those commonly used in cosmetics or external skin preparations can be used.

作為成分(B)極性油並未特別限定，但可舉例為例如三(辛酸・癸酸)甘油酯、三2-乙基己酸甘油酯、三異硬脂酸甘油酯、三異硬脂酸二甘油酯、三異棕櫚酸甘油酯、三辛酸甘油酯、鯨蠟基異辛酸酯、肉豆蔻酸異丙酯、棕櫚酸異丙酯、肉豆蔻酸辛基十二烷酯、三辛酸甘油酯、二異硬脂酸聚甘油酯、三異硬脂酸二甘油酯、三山萮酸甘油酯、松香酸季戊四醇酯、二辛酸新戊二醇酯、膽固醇脂肪酸酯、N-月桂醯基-L-麩胺酸二(膽固醇基・山萮基・辛基十二烷基)酯、異辛酸鯨蠟酯、月桂酸己酯、異硬脂酸異丙酯、異棕櫚酸辛酯、己二酸二異丙酯、己二酸二2-乙基己酯、癸二酸二乙酯、癸二酸二異丙酯、癸二酸二辛酯、異壬酸異壬酯、異壬酸異十三烷酯、琥珀酸二酯、硬脂酸硬化蓖麻油、荷荷芭油、2-乙基己酸鯨蠟酯、植固醇脂肪酸酯、蘋果酸二異硬脂酯、苯偏三酸三-十三烷酯、苯偏三酸三(2-乙基己酯)、苯甲酸烷酯(C12-15)、癸二酸二異丙酯、二新戊酸二乙基戊二醇酯、二新戊酸甲基戊二醇酯等，或作為紫外線吸收劑使用之油劑，例如作為二苯甲酮系，舉例為2-羥基-4-甲氧基二苯甲酮、2-羥基-4-甲氧基二苯甲酮-5-磺酸、2-羥基-4-甲氧基二苯甲酮-5-磺酸鈉、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮-5-磺酸鈉、2,4-二羥基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2,4,6-三苯胺基-對-(碳-2’-乙基己基-1’-氧基)-1,3,5-三嗪、2,4-雙[{4-(2-乙基己氧基)-2-羥基}-苯基]-6-(4-甲氧基苯基)-(1,3,5)-三嗪、2,2’-亞甲基-雙-{6-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)酚}等，作為PABA系舉例為對-胺基苯甲酸、對-胺基苯甲酸乙酯、對-胺基苯甲酸甘油酯、對-二甲胺基苯甲酸胺基酯、對-二甲胺基苯甲酸-2-乙基己酯、對-二羥基丙基苯甲酸乙酯、2-{4-(二乙胺基)-2-羥基苯甲醯基}苯甲酸己酯等，作為桂皮酸系舉例為對-甲氧基桂皮酸-2-乙基己酯、4-甲氧基桂皮酸-2-乙氧基乙酯等，作為水楊酸系舉例為水楊酸-2-乙基己酯、水楊酸苯酯、水楊酸均薄荷酯等，作為二苯甲醯基甲烷系舉例為4-第三-4’-甲氧基二苯甲醯基甲烷等，又，舉例為2,2’-亞甲基-雙-{6-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)酚}等，該等可使用一種或組合兩種以上使用。The component (B) polar oil is not particularly limited, but can be exemplified by glyceryl tris(caprylic acid/capric acid), glyceryl tri-2-ethylhexanoate, glyceryl triisostearate, and triisostearic acid. Diglycerides, glyceryl tripalmitate, glyceryl tricaprylate, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyl dodecyl myristate, glyceryl tricaprylate , Polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, pentaerythritol rosinate, neopentyl glycol dicaprylate, cholesterol fatty acid ester, N-laurinyl-L -Glutamate (cholesteryl, behenyl, octyldodecyl) ester, cetyl isooctanoate, hexyl laurate, isopropyl isostearate, octyl isopalmitate, diadipate Isopropyl ester, di-2-ethylhexyl adipate, diethyl sebacate, diisopropyl sebacate, dioctyl sebacate, isononyl isononanoate, isononyl isononanoate Alkyl esters, succinic acid diesters, stearic acid hardened castor oil, jojoba oil, cetyl 2-ethylhexanoate, phytosterol fatty acid esters, diisostearyl malate, trimellitate -Tridecyl ester, tris(2-ethylhexyl trimellitate), alkyl benzoate (C12-15), diisopropyl sebacate, diethylpentanediol dipivalate, Methyl pentanediol dipivalate, etc., or oils used as ultraviolet absorbers, such as benzophenone series, for example 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- 4-Methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sodium sulfonate, 2,2'-dihydroxy-4,4'-dimethyl Oxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sodium sulfonate, 2,4-dihydroxybenzophenone, 2,2' ,4,4'-tetrahydroxybenzophenone, 2,4,6-triphenylamino-p-(carbon-2'-ethylhexyl-1'-oxy)-1,3,5-triazine , 2,4-bis[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-(1,3,5)-three Oxazine, 2,2'-methylene-bis-{6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol} etc., Examples of PABA systems include p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, p-dimethylaminobenzoic acid amino ester, and p-dimethylaminobenzoic acid 2-ethylhexyl ester, ethyl p-dihydroxypropyl benzoate, 2-{4-(diethylamino)-2-hydroxybenzyl}hexyl benzoate, etc., as examples of cinnamic acid series It is p-methoxycinnamic acid-2-ethylhexyl ester, 4-methoxycinnamic acid-2-ethoxyethyl ester, etc., as the salicylic acid series, exemplified by salicylic acid-2-ethylhexyl , Phenyl salicylate, homomenthyl salicylate, etc., as the dibenzylmethane series, exemplified by 4-third-4'-methoxydibenzylmethane, etc., and, for example, 2, 2'-methylene-bis-{6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol} etc. These can be used One Use one or a combination of two or more.

該等中，基於經時安定性、使用性之觀點，作為成分(B)，較好含有於25℃之液狀極性油，再者，作為於25℃之液狀極性油較佳為自三(辛酸・癸酸)甘油酯、三2-乙基己酸甘油酯、三異硬脂酸甘油酯、三異棕櫚酸甘油酯、三辛酸甘油酯等之三酸甘油酯，對-甲氧基桂皮酸-2-乙基己酯、肉豆蔻酸異丙酯、苯甲酸烷酯(C12-15)、己二酸二異丙酯、癸二酸二異丙酯、異壬酸異壬酯中選擇之一種或兩種以上，更佳為自肉豆蔻酸異丙酯、苯甲酸烷酯(C12-15)、己二酸二異丙酯、癸二酸二異丙酯中選擇之一種或兩種以上。又，本發明中所謂液狀係於常溫(25℃)常壓下具有流動性者。Among them, from the viewpoint of stability over time and usability, as component (B), a liquid polar oil at 25°C is preferably contained, and furthermore, a liquid polar oil at 25°C is preferably from three (Caprylic acid, capric acid) glycerides, triglycerides of 2-ethylhexanoic acid, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl tricaprylate and other triglycerides, p-methoxy 2-ethylhexyl cinnamic acid, isopropyl myristate, alkyl benzoate (C12-15), diisopropyl adipate, diisopropyl sebacate, isononyl isononanoate One or two or more selected, more preferably one or two selected from isopropyl myristate, alkyl benzoate (C12-15), diisopropyl adipate, and diisopropyl sebacate More than species. In addition, the term "liquid" in the present invention has fluidity at normal temperature (25°C) and normal pressure.

基於耐水性之觀點，作為成分(B)較佳含有於25℃之固形極性油，作為於25℃之固形極性油，較佳為自2-{4-(二乙胺基)-2-羥基苯甲醯基}苯甲酸己酯、2,4-雙[{4-(2-乙基己氧基)-2-羥基}-苯基]-6-(4-甲氧基苯基)-(1,3,5)-三嗪、2,4,6-三[{4-(2-乙基己氧基羰基)苯胺基]-1,3,5-三嗪、4-第三丁基-4’-甲氧基二苯甲醯基甲烷、三聯苯基三嗪、亞甲基雙苯并***基四甲基丁基酚中選擇之一種或兩種以上，更佳為自2-{4-(二乙胺基)-2-羥基苯甲醯基}苯甲酸己酯、2,4-雙[{4-(2-乙基己氧基)-2-羥基}-苯基]-6-(4-甲氧基苯基]-(1,3,5)-三嗪、2,4,6-三[{4-(2-乙基己氧基羰基)苯胺基}-1,3,5-三嗪、4-第三丁基-4’-甲氧基二苯甲醯基甲烷中選擇之一種或兩種以上。又，本發明中所謂固形係於常溫(25℃)常壓下顯示半固體~固體之性狀，熔點為40℃以上者。From the viewpoint of water resistance, as component (B), it is preferable to contain a solid polar oil at 25°C, and as a solid polar oil at 25°C, it is preferably from 2-{4-(diethylamino)-2-hydroxyl Benzyl}hexyl benzoate, 2,4-bis[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)- (1,3,5)-triazine, 2,4,6-tris[{4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, 4-tert-butyl One or two or more selected from the group consisting of 4'-methoxydibenzamethane, terphenyltriazine, and methylene bisbenzotriazolyl tetramethylbutyl phenol, more preferably from 2 -{4-(Diethylamino)-2-hydroxybenzyl}hexyl benzoate, 2,4-bis[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl ]-6-(4-methoxyphenyl)-(1,3,5)-triazine, 2,4,6-tris[{4-(2-ethylhexyloxycarbonyl)anilino}- One or two or more selected from 1,3,5-triazine and 4-tert-butyl-4'-methoxydibenzamethane. In addition, the so-called solid system in the present invention is at room temperature (25°C). ) It shows semi-solid to solid properties under normal pressure, and the melting point is above 40℃.

作為成分(B)極性油之市售品舉例為例如M Fine Oil CCT-1 (MIYOSHI油脂公司製)、T.I.O(NISSHIN OILLIO GROUP公司製)、TISG(高級醇工業公司製)、ISO ESTERIDE G-NP(國際美松公司製)、UVINUL MC 80、UVINUL MC 80N(日本BASF公司製)、IPM(日本精化公司製)、FINSOLV TN(Innospec Active Chemicals LLC製)、FineNeo-DIA、FineNeo-iPSE(日本精化公司製)、SALACOS 99 (NISSHIN OILLIO GROUP公司製)等。Examples of commercially available products of polar oil as component (B) are, for example, M Fine Oil CCT-1 (manufactured by MIYOSHI Oil & Fat Co., Ltd.), TIO (manufactured by Nisshin OILLIO GROUP), TISG (manufactured by Advanced Alcohol Industry Co., Ltd.), ISO ESTERIDE G-NP (Manufactured by International Misson Corporation), UVINUL MC 80, UVINUL MC 80N (manufactured by BASF Japan), IPM (manufactured by Nippon Seiki Co., Ltd.), FINSOLV TN (manufactured by Innospec Active Chemicals LLC), FineNeo-DIA, FineNeo-iPSE (Japan) Fine Chemicals Corporation), SALACOS 99 (NISSHIN OILLIO GROUP Corporation), etc.

本發明中使用之成分(B)極性油之含量並未特別限定，但就均一塗佈膜、使用性優異之觀點，相對於油中水型組成物總量，較佳為5~30質量%，更佳為10~25質量%。The content of the component (B) polar oil used in the present invention is not particularly limited, but from the viewpoint of uniform coating film and excellent usability, it is preferably 5-30% by mass relative to the total amount of the water-in-oil composition , More preferably 10-25% by mass.

本發明中，作為成分(B)，若含有於25℃之液狀極性油與於25℃之固形極性油，則塗佈之際之塗膜形成時之油相流動性變適當，進而成為耐水性良好之塗膜故而較佳。 又，合併含有於25℃之液狀極性油與於25℃之固形極性油之情形，基於耐水性之觀點，於25℃之液狀極性油與於25℃之固形極性油之含有質量比例(於25℃之液狀極性油)/(於25℃之固形極性油)較佳為1~250，更佳為2.5~150，特佳為3~15。In the present invention, if the component (B) contains a liquid polar oil at 25°C and a solid polar oil at 25°C, the fluidity of the oil phase at the time of coating film formation at the time of coating becomes appropriate, and it becomes water resistant. A good coating film is therefore better. Furthermore, in the case of combining the liquid polar oil at 25°C and the solid polar oil at 25°C, based on the water resistance point of view, the content ratio of the liquid polar oil at 25°C to the solid polar oil at 25°C ( Liquid polar oil at 25°C)/(solid polar oil at 25°C) is preferably 1 to 250, more preferably 2.5 to 150, particularly preferably 3 to 15.

本發明之成分(C)矽氧油可使用通常化妝料或皮膚外用劑所用者。As the component (C) silicone oil of the present invention, those commonly used in cosmetics or skin external preparations can be used.

作為本發明之成分(C)矽氧油並未特別限定，但基於經時安定性、使用性優異之觀點，較佳於25℃為液狀。作為矽氧油舉例為例如二甲基聚矽氧烷、甲基苯基聚矽氧烷、八甲基環四矽氧烷、十甲基環五矽氧烷、甲基三甲矽氧烷、聚醚改質甲基聚矽氧烷、油基改質甲基聚矽氧烷、聚乙烯基吡咯啶酮改質甲基聚矽氧烷等，可自該等中適當選擇一種或兩種以上使用。該等中，基於經時安定性、使用性之觀點，較佳為自25℃下2cs之二甲基聚矽氧烷、25℃下6cs之二甲基聚矽氧烷、25℃下10cs之二甲基聚矽氧烷、三甲矽氧烷、環甲矽氧烷之中選擇之一種或兩種以上，基於經時安定性之觀點，更佳為環甲矽氧烷、25℃下2cs之二甲基聚矽氧烷、25℃下6cs之二甲基聚矽氧烷中選擇之一種或兩種以上。The silicone oil as the component (C) of the present invention is not particularly limited, but from the viewpoint of excellent stability over time and usability, it is preferably liquid at 25°C. Examples of silicone oils include, for example, dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, methyltrimethylsiloxane, and polysiloxane. Ether modified methyl polysiloxane, oil-based modified methyl polysiloxane, polyvinyl pyrrolidone modified methyl polysiloxane, etc., one or more of them can be appropriately selected for use . Among them, from the viewpoints of stability and usability over time, dimethylpolysiloxane of 2cs at 25°C, 6cs of dimethylpolysiloxane at 25°C, and 10cs at 25°C are preferred. Choose one or two or more of dimethylpolysiloxane, trimethicone, and cyclomethicone. Based on the viewpoint of stability over time, cyclomethicone is more preferred, 2cs at 25℃ One or two or more of dimethyl polysiloxane, 6cs dimethyl polysiloxane at 25°C.

作為成分(C)矽氧油之市售品舉例為例如KF-96A-1cs/1、5cs/2cs/5cs/6cs/10cs/20cs/30cs/50cs/100cs/200cs /300c/350cs/500cs/1000cs/3000cs/5000cs/6000cs、KF-96H-1萬cs/1、25萬cs/3萬cs/5萬cs/6萬cs/10萬cs/30萬cs/50萬cs/100萬cs、KF-995/994、TMF-1.5、KF-50-100cs/1000cs、KF-53、KF-54、KF-56A、KF-54HV(以上為信越化學工業公司製)、SH-200 C Fluid 5CS/6CS/10CS/20CS/30CS/50CS/ 100CS/200CS/350CS/500CS/1000CS/3000CS/5000CS/10000CS/12500CS/30000CS/60000CS/100000CS/1000000CS、BY11-040 /003/007/014/026/320、SH-556 Fluid、PH-1555 HRI Cosmetic Fluid、FZ-3156(以上為東麗道康寧公司製)等。Examples of commercially available products of silicone oil as component (C) are KF-96A-1cs/1, 5cs/2cs/5cs/6cs/10cs/20cs/30cs/50cs/100cs/200cs/300c/350cs/500cs/1000cs /3000cs/5000cs/6000cs, KF-96H-10,000cs/1, 250,000cs/310,000cs/50,000cs/610,000cs/100,000cs/300,000cs/500,000cs/1,000,000cs, KF -995/994, TMF-1.5, KF-50-100cs/1000cs, KF-53, KF-54, KF-56A, KF-54HV (the above are made by Shin-Etsu Chemical Co., Ltd.), SH-200 C Fluid 5CS/6CS /10CS/20CS/30CS/50CS/ 100CS/200CS/350CS/500CS/1000CS/3000CS/5000CS/10000CS/12500CS/30000CS/60000CS/100000CS/1000000CS, BY11-040 /003/007/014/026/320, SH -556 Fluid, PH-1555 HRI Cosmetic Fluid, FZ-3156 (the above are manufactured by Toray Dow Corning Corporation), etc.

本發明中使用之成分(C)矽氧油之含量並未特別限定，但就均一塗佈膜、經時安定性優異之觀點，相對於油中水型組成物總量，較佳為3~40質量%，更佳為5~30質量%，又更佳為7.5~20質量%，特佳為13~18質量%。The content of the component (C) silicone oil used in the present invention is not particularly limited, but from the viewpoint of a uniform coating film and excellent stability over time, it is preferably 3~ 40% by mass, more preferably 5-30% by mass, still more preferably 7.5-20% by mass, particularly preferably 13-18% by mass.

本發明中，雖未特別限定，但基於塗膜均一性、經時安定性、使用性之觀點，成分(B)與成分(C)之含有質量比例(B)/(C)較佳為0.1~8，更佳為0.4~3.3，又更佳為1~3.3，特佳為1~2。In the present invention, although not particularly limited, from the viewpoints of uniformity of the coating film, stability over time, and usability, the content mass ratio (B)/(C) of component (B) to component (C) is preferably 0.1 ~8, more preferably 0.4~3.3, still more preferably 1~3.3, particularly preferably 1~2.

本發明中之成分(D)水可使用通常化妝料或皮膚外用劑所用者，並未特別限定。作為成分(D)水，可使用自來水，亦可使用藉蒸餾等純化之純化水、溫泉水、深層水等。且，亦可使用費拉蘆薈、金縷梅、北美金縷梅、黃瓜、檸檬、薰衣草、玫瑰水等之植物萃取液。As the component (D) water in the present invention, those commonly used in cosmetics or external skin preparations can be used, and are not particularly limited. As the component (D) water, tap water can be used, and purified water purified by distillation or the like, hot spring water, deep-seated water, etc. can also be used. In addition, plant extracts such as aloe vera, witch hazel, witch hazel, cucumber, lemon, lavender, rose water, etc. can also be used.

本發明之油中水型組成物中之水相量並未特別限定，但基於經時安定性、使用性優異之觀點，較佳為10~60質量%，更佳為20~55質量%，又更佳為30~50質量%。本發明中，辛醇/水分配係數未達1之成分可構成水相。具體而言，成分(D)、多元醇、水溶性高分子、水溶性皮膜形成性樹脂、保濕劑等之水性成分可形成水相。The amount of the water phase in the water-in-oil composition of the present invention is not particularly limited, but from the viewpoint of excellent stability and usability over time, it is preferably 10-60% by mass, more preferably 20-55% by mass, It is more preferably 30-50% by mass. In the present invention, components whose octanol/water partition coefficient is less than 1 can constitute the water phase. Specifically, aqueous components such as component (D), polyols, water-soluble polymers, water-soluble film-forming resins, and humectants can form an aqueous phase.

本發明之油中水型組成物中之油相量並未特別限定，但基於經時安定性、使用性優異之觀點，較佳為20~60質量%，更佳為25~50質量%。本發明之油中水型組成物中之油相量係將成分(A)之量除外而算出。本發明中，辛醇/水分配係數為1以上之成分可構成油相。具體而言，成分(B)、成分(C)、其他油性成分可形成油相。The amount of the oil phase in the water-in-oil composition of the present invention is not particularly limited, but from the viewpoint of excellent stability over time and usability, it is preferably 20-60% by mass, more preferably 25-50% by mass. The amount of the oil phase in the water-in-oil composition of the present invention is calculated excluding the amount of component (A). In the present invention, components with an octanol/water partition coefficient of 1 or more can constitute the oil phase. Specifically, component (B), component (C), and other oily components may form an oil phase.

本發明中，雖未特別限定，但基於經時安定性、使用性優異之觀點，水相與油相之含有質量比例(水相)/(油相)較佳為0.3~5，更佳為0.7~2。Although not particularly limited in the present invention, based on the viewpoints of excellent stability over time and usability, the content ratio of the water phase to the oil phase (water phase)/(oil phase) is preferably 0.3 to 5, more preferably 0.7~2.

本發明中，雖未特別限定，但基於塗佈膜之均一性、經時安定性、使用性優異之觀點，水相與成分(A)之含有質量比例(水相)/(A)較佳為0.75~10，更佳為1~4。Although not particularly limited in the present invention, based on the viewpoint that the uniformity of the coating film, the stability over time, and the usability are excellent, the mass ratio (water phase)/(A) of the water phase and the component (A) is preferable It is 0.75~10, more preferably 1~4.

本發明之油中水型組成物，除上述成分(A)~(D)以外，在不妨礙本發明效果之範圍內可含有通常於化妝料或皮膚外用劑中使用之成分，例如成分(B)及成分(C)以外之油性成分、成分(A)以外之粉體、界面活性劑、纖維、多元醇、水溶性高分子、水溶性皮膜形成性樹脂、保濕劑等之水性成分、抗氧化劑、消泡劑、美容成分、防腐劑、香料等。The water-in-oil composition of the present invention, in addition to the above-mentioned components (A) to (D), may contain components commonly used in cosmetics or skin external preparations, such as component (B ) And oily ingredients other than ingredient (C), powders other than ingredient (A), surfactants, fibers, polyols, water-soluble polymers, water-soluble film-forming resins, humectants, and other water-based ingredients, antioxidants , Defoamers, beauty ingredients, preservatives, fragrances, etc.

成分(B)及成分(C)以外之油性成分若為通常於化妝料或皮膚外用劑中使用者，則未特別限定，不管是動物油、植物油、合成油等之起源或半固形油、液體油、揮發性油等之性狀，可使用烴類、油脂類、氟系油類等。具體可舉例為液體鏈烷、角鯊烷、凡士林、聚異丁烯之烴類、全氟癸烷、全氟辛烷、全氟聚醚等之氟系油劑類等。If the oily ingredients other than ingredient (B) and ingredient (C) are usually used in cosmetics or external skin preparations, they are not particularly limited, whether they are derived from animal oil, vegetable oil, synthetic oil, etc. or semi-solid oil, liquid oil For properties such as volatile oil, hydrocarbons, greases, fluorine-based oils, etc. can be used. Specific examples include liquid paraffins, squalane, petrolatum, polyisobutylene hydrocarbons, perfluorodecane, perfluorooctane, perfluoropolyether, and other fluorinated oils.

成分(A)以外之粉體若為通常於化妝料或皮膚外用劑中使用者，則未藉由板狀、針狀等之形狀、煙霧狀、微粒子、顏料等級之粒徑、多孔質、無孔質等之粒子構造等而特別限定，可舉例為無機粉體類、光亮性粉體類、有機粉體類、色素粉體類、金屬粉體類、複合粉體類等。若具體例示，則可舉例為氧化鐵、碳黑、氧化鉻、氫氧化鉻、紺青、群青等之有色無機顏料、滑石、白雲母、金雲母、紅雲母、黑雲母、合成雲母、絹雲母(sericite)、合成絹雲母、硫酸鋇、高嶺土、碳化矽、膨潤土、綠土、矽藻土、矽酸鋁、偏矽酸鋁鎂、矽酸鈣、矽酸鋇、矽酸鎂、碳酸鎂、羥基磷灰石、氮化硼等之白色體質粉體、氧化鈦被覆雲母、氧化鈦被覆氧氯化鉍、氧化鐵雲母鈦、紺青處理雲母鈦、胭脂紅處理雲母鈦、氧氯化鉍、魚鱗箔、聚對苯二甲酸乙二酯・鋁・環氧積層粉末、聚對苯二甲酸乙二酯・聚烯烴積層膜粉末、聚對苯二甲酸乙二酯・聚甲基丙烯酸甲酯積層膜粉末等的光輝性粉末、硬脂酸鋅、N-醯賴胺酸等有機低分子性粉體、滑石粉末、纖維素粉末、糊精粉末等之天然有機粉體、紅色201號、紅色202號、紅色205號、紅色226號、紅色228號、橙色203號、橙色204號、藍色404號、黃色401號等，或紅色3號、紅色104號、紅色106號、橙色205號、黃色4號、黃色5號、綠色3號、藍色1號等之鋯、鋇或鋁色澱等之有機顏料粉體或進而為鋁粉、金粉、銀粉等之金屬粉體、微粒子氧化鈦被覆雲母鈦、硫酸鋇被覆雲母鈦、含氧化鈦之二氧化矽等之複合粉體、尼龍、聚酯、縲縈、纖維素等之纖維等，該等粉體可使用一種或兩種以上，進而亦可使用經表面處理或複合化者。作為表面處理劑，舉例為例如氟化合物、矽氧油、粉體、油劑、凝膠化劑、界面活性劑等。If powders other than ingredient (A) are usually used in cosmetics or external skin preparations, they are not based on the shape of plate, needle, etc., smoke, fine particles, pigment grade particle size, porous, and The particle structure of pores and the like is particularly limited, and examples thereof include inorganic powders, bright powders, organic powders, pigment powders, metal powders, and composite powders. Specific examples include iron oxide, carbon black, chromium oxide, chromium hydroxide, cyanine, ultramarine and other colored inorganic pigments, talc, muscovite, phlogopite, red mica, biotite, synthetic mica, sericite ( sericite), synthetic sericite, barium sulfate, kaolin, silicon carbide, bentonite, smectite, diatomaceous earth, aluminum silicate, aluminum magnesium metasilicate, calcium silicate, barium silicate, magnesium silicate, magnesium carbonate, hydroxyl White body powder such as apatite, boron nitride, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, iron oxide mica titanium, cyan treatment mica titanium, carmine treated mica titanium, bismuth oxychloride, fish scale foil , Polyethylene terephthalate, aluminum, epoxy laminated powder, polyethylene terephthalate, polyolefin laminated film powder, polyethylene terephthalate, polymethyl methacrylate laminated film powder Bright powders such as zinc stearate, N-lysine and other organic low-molecular-weight powders, natural organic powders such as talc powder, cellulose powder, and dextrin powder, Red No. 201, Red No. 202, Red 205, red 226, red 228, orange 203, orange 204, blue 404, yellow 401, etc., or red 3, red 104, red 106, orange 205, yellow 4 , Yellow No. 5, Green No. 3, Blue No. 1 and other organic pigment powders such as zirconium, barium or aluminum lakes, or further metal powders such as aluminum powder, gold powder, silver powder, etc., fine particles of titanium oxide coated with mica titanium, Barium sulfate-coated mica titanium, titanium dioxide-containing silicon dioxide and other composite powders, nylon, polyester, rayon, cellulose and other fibers, etc., these powders can be used one or more than two, and can also be used After surface treatment or compounding. Examples of surface treatment agents include fluorine compounds, silicone oils, powders, oils, gelling agents, and surfactants.

界面活性劑若為通常於化妝料或皮膚外用劑中使用者，則未特別限定，可在不損及本發明效果之範圍內含有，但界面活性劑之含量，相對於油中水型組成物總量，為1質量%以下。界面活性劑之含量超過1質量%時，有塗膜之均一性、耐水性、使用性差的情況。界面活性劑之含量若為1質量%以下，則未特別限定，但基於耐水性、使用性之觀點，較佳為0.6質量%以下，更佳為0.3質量%以下，又更佳為0.1質量%以下。Surfactant is not particularly limited if it is usually used in cosmetics or external skin preparations, and it can be contained within a range that does not impair the effects of the present invention. However, the content of surfactant is relative to that of water-in-oil composition The total amount is 1% by mass or less. When the content of the surfactant exceeds 1% by mass, the uniformity, water resistance, and usability of the coating film may be poor. If the content of the surfactant is 1% by mass or less, it is not particularly limited, but from the viewpoint of water resistance and usability, it is preferably 0.6% by mass or less, more preferably 0.3% by mass or less, and still more preferably 0.1% by mass the following.

作為界面活性劑並未特別限定，但可舉例為非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑等。The surfactant is not particularly limited, but examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

作為界面活性劑並未特別限定，但若具體例示，則作為非離子性界面活性劑可舉例為山梨糖醇酐脂肪酸酯、甘油脂肪酸酯、聚甘油脂肪酸酯、丙二醇脂肪酸酯、聚乙二醇脂肪酸酯、蔗糖脂肪酸酯、聚氧乙烯烷基醚、聚氧丙烯烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、聚氧乙烯甘油脂肪酸酯、聚氧乙烯丙二醇脂肪酸酯、聚氧乙烯蓖麻油、聚氧乙烯硬化蓖麻油、聚氧乙烯植甾醇醚、聚氧乙烯植固醇醚、聚氧乙烯膽固醇醚、聚氧乙烯膽固醇基醚、聚氧乙烯改質有機聚矽氧烷、聚氧伸烷基・烷基共改質有機聚矽氧烷、月桂酸二乙醇醯胺、椰子油脂肪酸二乙醇醯胺、椰子油脂肪酸單乙醇醯胺、聚氧乙烯椰子油脂肪酸單乙醇醯胺、月桂酸單異丙醇醯胺、椰子油脂肪酸單異丙醇醯胺、聚氧丙烯椰子油脂肪酸單異丙醇醯胺、烷醇醯胺、糖醚、糖醯胺等。作為陰離子性界面活性劑可舉例為聚氧乙烯月桂醚硫酸鈉、聚氧乙烯月桂醚硫酸銨、聚氧乙烯月桂醚硫酸三乙醇胺等之聚氧乙烯月桂醚硫酸鹽；月桂硫酸鈉、月桂硫酸三乙醇胺等烷基硫酸鹽；十四碳烯磺酸鈉、十四碳烯磺酸鉀等之α-烯烴磺酸鹽；N-月桂醯基羥乙磺酸鈉、N-月桂醯基羥乙磺酸鉀等之醯基羥乙磺酸鹽；N-椰油脂肪酸甲基牛磺酸鈉、N-月桂醯基甲基牛磺酸鈉、N-椰油脂肪酸甲基牛磺酸鉀、月桂醯水解絲鈉等之N-醯基聚胜肽鹽；磺基琥珀酸鈉等之磺基琥珀酸等。作為陽離子性界面活性劑可舉例為烷基胺鹽、聚胺及胺基醇脂肪酸衍生物等之胺鹽、烷基四級銨鹽、芳香族四級銨鹽、吡啶鎓鹽、咪唑鎓鹽等，氯化硬脂基三甲基銨、氯化山萮基三甲基銨、氯化鯨蠟基三甲基銨、氯化二硬脂基二甲基銨、氯化二山萮基二甲基銨、氯化二鯨蠟基二甲基銨、氯化硬脂基二甲基苄基銨、氯化二月桂基二甲基銨、氯化二聚氧乙烯(15EO)椰油烷基甲基銨、氯化二聚氧乙烯(4EO)月桂醚二甲基銨、二可可基乙基羥基乙銨硫酸鹽、二硬脂醯基乙基羥基乙銨硫酸鹽、二硬脂醯基乙基羥基乙銨甲基硫酸鹽、二棕櫚醯基乙基羥基乙銨甲基硫酸鹽、棕櫚醯胺丙基三甲基氯化銨。作為兩性界面活性劑，作為乙酸甜菜鹼型界面活性劑舉例為辛基二甲胺基乙酸甜菜鹼、月桂基二甲胺基乙酸甜菜鹼、椰油脂肪酸醯胺丙基甜菜鹼、椰油脂肪酸烷基二甲胺基乙酸甜菜鹼、肉豆蔻積二甲胺基乙酸甜菜鹼、鯨蠟基二甲胺基乙酸甜菜鹼、椰油脂肪酸醯胺丙基二甲胺基乙酸甜菜鹼、月桂酸醯胺丙基二甲胺基乙酸甜菜鹼、月桂基二羥基乙胺基乙酸甜菜鹼、鯨蠟基二羥基乙胺基乙酸甜菜鹼等，又，作為咪唑啉型界面活性劑舉例為N-椰油脂肪酸醯基-N-羧基甲基-N-羥基乙基乙二胺鈉、N-椰油脂肪酸醯基-N-羧基甲氧基乙基-N-羧基甲基乙二胺二鈉等。The surfactant is not particularly limited, but if specifically exemplified, the nonionic surfactant can be exemplified by sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, and polyglycerin fatty acid ester. Ethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fat Acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerol fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene phytosterol ether, polyoxyethylene Oxyethylene phytosterol ether, polyoxyethylene cholesterol ether, polyoxyethylene cholesteryl ether, polyoxyethylene modified organopolysiloxane, polyoxyalkylene and alkyl co-modified organopolysiloxane, lauric acid Diethanolamide, coconut oil fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, polyoxyethylene coconut oil fatty acid monoethanolamide, lauric acid monoisopropanolamide, coconut oil fatty acid monoisopropanolamide , Polyoxypropylene coconut oil fatty acid monoisopropanol amide, alkanol amide, sugar ether, sugar amide, etc. Examples of anionic surfactants include polyoxyethylene lauryl ether sulfate, polyoxyethylene lauryl ether ammonium sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, etc.; polyoxyethylene lauryl ether sulfate; sodium lauryl sulfate, three laurel sulfate Alkyl sulfates such as ethanolamine; α-olefin sulfonates such as sodium tetradecene sulfonate and potassium tetradecene sulfonate; sodium N-laurel isethionate, N-lauric isethionate Sodium N-coconut oil fatty acid methyl taurate, sodium N-lauric acid methyl taurate, potassium N-coco fatty acid methyl taurate, laurel Hydrolyzed N-acyl polypeptide salts such as sodium sulphonate; sulfosuccinic acid such as sodium sulfosuccinate. Examples of cationic surfactants include amine salts such as alkyl amine salts, polyamines and amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridinium salts, imidazolium salts, etc. , Stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dimethyl ammonium chloride Base ammonium, dicetyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dilauryl dimethyl ammonium chloride, dipolyoxyethylene chloride (15EO) coco alkyl methane Base ammonium, dipolyoxyethylene chloride (4EO) lauryl ether dimethyl ammonium, dicocoethyl hydroxyethyl ammonium sulfate, distearyl ethyl hydroxyethyl ammonium sulfate, distearyl ethyl ammonium sulfate Hydroxyethylammonium methyl sulfate, dipalmitoylethylhydroxyethylammonium methylsulfate, palmitoylamine propyltrimethylammonium chloride. As amphoteric surfactants, betaine acetate-type surfactants are exemplified by octyl dimethyl amino betaine, lauryl dimethyl amino betaine, coconut fatty acid amide propyl betaine, and coconut fatty acid alkane. Betaine, Myristyl Dimethylamino Betaine, Cetyl Dimethylamino Betaine, Coconut Fatty Acid Amidopropyl Dimethylamino Betaine, Lauramide Propyl dimethylaminoacetic acid betaine, lauryl dihydroxyethylaminoacetic acid betaine, cetyl dihydroxyethylaminoacetic acid betaine, etc. In addition, examples of imidazoline-type surfactants include N-coco fatty acid Acetyl-N-carboxymethyl-N-hydroxyethyl ethylenediamine sodium, N-coconut oil fatty acid phenol-N-carboxymethoxyethyl-N-carboxymethyl ethylenediamine disodium and the like.

作為抗氧化劑若為通常於化妝料或皮膚外用劑所用者，則未特別限定，舉例為例如生育酚、抗壞血酸等，作為防腐劑舉例為例如對羥基苯甲酸酯、苯氧基乙醇、1,2-戊二醇等。The antioxidant is not particularly limited as long as it is usually used in cosmetics or external skin preparations. Examples include tocopherol, ascorbic acid, etc., and examples of preservatives include parabens, phenoxyethanol, 1, 2-Pentanediol and so on.

作為美容成分若為通常於化妝料或皮膚外用劑所用者，則未特別限定，舉例為例如蝦青素、維他命類、消炎劑、生藥等。The cosmetic ingredient is not particularly limited as long as it is usually used in cosmetics or external skin preparations, and examples include astaxanthin, vitamins, anti-inflammatory agents, crude drugs, and the like.

本發明之油中水型組成物之製造方法並未特別限制，但例如可藉由於成分(A)、(B)、(C)中添加其他任意成分等，於90℃加熱均一混合，添加水相，藉由分散混合機等予以乳化混合而獲得。再者，作為本發明之油中水型組成物之製造方法，基於提高油中水型組成物之收率之觀點，較佳不採取輥處理步驟。含有不為成分(A)以外之氧化鋅或氧化鈦等之際，為了提高油中水型組成物中之分散性，大多採取輥處理步驟，但本發明中之成分(A)，由於其本身於油中水型組成物中顯示高分散性，故可不經過輥處理步驟而含有。The production method of the water-in-oil composition of the present invention is not particularly limited, but for example, it can be heated at 90°C by adding other optional components to the components (A), (B), and (C), and adding water The phase is obtained by emulsifying and mixing with a dispersion mixer or the like. Furthermore, as the method for producing the water-in-oil composition of the present invention, from the viewpoint of increasing the yield of the water-in-oil composition, it is preferable not to take a roller treatment step. When zinc oxide or titanium oxide other than the component (A) is contained, in order to improve the dispersibility in the water-in-oil composition, roll treatment is often adopted. However, the component (A) in the present invention is due to its own Since it exhibits high dispersibility in an oil-in-water type composition, it can be contained without a roller treatment step.

本發明之油中水型組成物之性狀並未特別限定，可為液狀、凝膠狀、乳霜狀、半固形狀、固形狀、棒狀等之任一者。The properties of the water-in-oil type composition of the present invention are not particularly limited, and may be any of liquid, gel, cream, semi-solid, solid, rod-shaped, etc.

本發明中之油中水型組成物雖並未特別限定，但較佳為皮克林乳液。皮克林乳液係利用於界面吸附粉末而調製之乳液(例如參考非專利文獻1)。Although the water-in-oil composition in the present invention is not particularly limited, it is preferably Pickering emulsion. Pickering emulsion is an emulsion prepared by adsorbing powder at the interface (for example, refer to Non-Patent Document 1).

本發明之油中水型組成物之乳化滴的平均粒徑並未特別限定，但就經時安定性、使用性之觀點，平均粒徑較佳為10~500μm，更佳為20~300μm，又更佳為150~300μm。 又，本發明之油中水型組成物之乳化滴的平均粒徑之測定可使用光學顯微鏡(OLYMPUS公司製)，於室溫測定100個乳化滴之粒徑，算出該等之平均值而進行。 塗佈本發明之油中水型組成物之際，以目視觀察自乳化滴中釋出之水滴若越為大粒，越無黏膩感，進而具有水嫩之良好使用感，為此，如上述，平均粒徑較佳為10~500μm，更佳為20~300μm，又更佳為150~300μm。本發明之油中水型組成物之乳化粒徑為較佳值時，認為於塗佈之際自乳化滴中釋出之水滴大小成為適度。 再者，塗佈之際自乳化滴中釋出之水滴大小適度之際，由於塗膜形成時之水相與由相之局部化為適當，結果，塗膜之均一性亦良好，耐水性亦優異。The average particle size of the emulsified droplets of the water-in-oil composition of the present invention is not particularly limited, but from the viewpoints of stability over time and usability, the average particle size is preferably 10 to 500 μm, more preferably 20 to 300 μm. It is more preferably 150 to 300 μm. In addition, the average particle size of the emulsified droplets of the water-in-oil composition of the present invention can be measured by measuring the particle size of 100 emulsified droplets at room temperature using an optical microscope (manufactured by OLYMPUS), and calculating the average value. . When applying the water-in-oil composition of the present invention, visually observe that the larger the water droplets released from the emulsified droplets, the less greasy they are, and the smoother and good use feeling. For this reason, as described above , The average particle size is preferably 10 to 500 μm, more preferably 20 to 300 μm, and still more preferably 150 to 300 μm. When the emulsified particle size of the water-in-oil composition of the present invention is a preferable value, it is considered that the size of the water droplets released from the emulsified droplets at the time of coating becomes appropriate. Furthermore, when the size of the water droplets released from the emulsified droplets during coating is moderate, the water phase and the resulting phase are properly localized when the coating film is formed. As a result, the uniformity of the coating film is also good, and the water resistance is also good. Excellent.

意料外地，本發明之油中水型組成物之乳化滴的平均粒徑可藉由於乳化混合處理中之攪拌速度或攪拌時間等以外，亦可藉由調整成分(B)與成分(C)之含有質量比例(B)/(C)之值而調整，增大含有質量比例(B)/(C)時，有乳化滴之平均粒徑變大之傾向。例如，本發明之油中水型組成物之乳化滴的平均粒徑設為10~500μm時，含有質量比例(B)/(C)較佳為0.1~8，乳化滴的平均粒徑設為20~300μm時，含有質量比例(B)/(C)較佳為0.4~3.3，乳化滴的平均粒徑設為150~300μm時，含有質量比例(B)/(C)較佳為1~3.3，乳化滴的平均粒徑設為150~200μm時，含有質量比例(B)/(C)較佳為1~2。Unexpectedly, the average particle size of the emulsified droplets of the water-in-oil composition of the present invention can be determined by the stirring speed or the stirring time in the emulsification mixing process, or by adjusting the composition (B) and the component (C) Adjust the content ratio (B)/(C) to increase the content ratio (B)/(C), the average particle size of the emulsified droplets tends to increase. For example, when the average particle size of the emulsified droplets of the water-in-oil composition of the present invention is set to 10~500μm, the content mass ratio (B)/(C) is preferably 0.1~8, and the average particle size of the emulsified droplets is set to When 20~300μm, the content mass ratio (B)/(C) is preferably 0.4~3.3, when the average particle size of the emulsified droplets is set to 150~300μm, the content mass ratio (B)/(C) is preferably 1~ 3.3. When the average particle size of the emulsified droplets is set to 150-200 μm, the content mass ratio (B)/(C) is preferably 1-2.

本發明之油中水型組成物雖未特別限定，但可使用作為化妝料或皮膚外用劑等。作為化妝料，舉例為例如外用固形劑、外用液劑、噴霧劑、軟膏劑、乳霜劑、凝膠劑、貼附劑等，或乳液、化妝水、敷面化妝料、洗臉料、按摩用化妝料、保養用化妝料、防曬料、身體乳霜等之身體用化妝料、眼霜等之眼周用化妝料、唇精華液、唇霜等之***保養用化妝料、粉底、底霜、遮瑕膏、粉餅、眼影、腮紅、口紅、睫毛膏、眼線筆等之彩妝製劑等。作為皮膚外用劑可舉例為例如擦劑、洗劑、軟膏劑等。該等中，尤其基於耐水性之觀點，較佳為防曬料、眼周用化妝料、***用化妝料、彩妝製劑，更佳為防曬化妝料、彩妝製劑。 [實施例]Although the water-in-oil composition of the present invention is not particularly limited, it can be used as a cosmetic or an external preparation for skin. Examples of cosmetics include solid preparations for external use, liquids for external use, sprays, ointments, creams, gels, patches, etc., or emulsions, lotions, facial cosmetics, facial cleansers, and massage Cosmetics, cosmetics for maintenance, sunscreens, body creams and other body cosmetics, eye creams and other eye cosmetics, lip essences, lip creams and other lip care cosmetics, foundations, primers, concealers Make-up preparations such as cream, pressed powder, eye shadow, blush, lipstick, mascara, eyeliner, etc. Examples of the external preparation for skin include liniment, lotion, ointment and the like. Among these, particularly from the viewpoint of water resistance, sunscreen cosmetics, eye cosmetics, lip cosmetics, and color cosmetic preparations are preferable, and sunscreen cosmetics and color cosmetic preparations are more preferable. [Example]

以下列舉實施例詳細說明本發明。又，本發明不受該等之任何限制。The following examples illustrate the present invention in detail. In addition, the present invention is not subject to any such restrictions.

實施例1~21及比較例1~9：油中水型防曬料Examples 1-21 and Comparative Examples 1-9: Oil-in-water type sunscreen

1.針對粉體之透過率，關於成分(1)~(5)，藉由下述(評價方法)進行評價。 進而，調製表1~4中所示配方之油中水型防曬料，針對2.塗膜均一性、3.耐水性、4.經時安定性、5.使用性藉由下述(評價方法)進行評價。綜合評價5項目，將ABC作為合格分數，全部評價項目獲得合格分數者記為可，其以外記為不可。又針對實施例，使用光學顯微鏡(OLYMPUS公司製)，於室溫測定100個乳化滴之粒徑，算出該等之平均值而進行乳化滴之平均粒徑測定。該等評價結果一併示於表1~4。1. Regarding the transmittance of the powder, the components (1) to (5) are evaluated by the following (evaluation method). Furthermore, the water-in-oil type sunscreen formulations shown in Tables 1 to 4 were prepared, and the following (evaluation method) was used for 2. film uniformity, 3. water resistance, 4. stability with time, and 5. usability ) To evaluate. Comprehensive evaluation of 5 items, ABC as a passing score, all evaluation items with a passing score are recorded as acceptable, and the others are recorded as impossible. For the examples, the particle size of 100 emulsified droplets was measured at room temperature using an optical microscope (manufactured by OLYMPUS), and the average value was calculated to measure the average particle size of the emulsified droplets. The evaluation results are shown in Tables 1 to 4.

(評價項目) 1.粉體透過率 2.塗膜均一性 3.耐水性 4.經時安定性 5.使用性(Evaluation item) 1. Powder transmittance 2. Film uniformity 3. Water resistance 4. Stability over time 5. Usability

(評價方法) 1.粉體透過率 對於水/乙醇混合溶劑(質量比 水：乙醇=3：1) 40g，以成為0.25質量%之方式秤量0.1g成分(1)~(5)，於其剛秤量後，以振盪器YS-8D (YAYOI公司製)以250次/分鐘、30秒之條件進行混合。混合後，於光路長10mm×光路寬10mm之塑膠槽中放入3.5g，將混合後經3分鐘的時間點的溶液，使用分光光度計UV-2500PC(島津製作所公司製)，以波長：700nm進行測定，獲得測定值(%)。又參考組使用水/乙醇混合溶劑(質量比 水：乙醇=3：1)。(Evaluation method) 1. Powder transmittance For 40g of water/ethanol mixed solvent (mass ratio water:ethanol=3:1), weigh 0.1g of components (1)~(5) so that it becomes 0.25% by mass. Just after weighing, use the oscillator YS-8D (Manufactured by YAYOI Corporation) The mixing was performed under the conditions of 250 times/minute for 30 seconds. After mixing, put 3.5 g in a plastic tank with an optical path length of 10 mm × an optical path width of 10 mm, and use a spectrophotometer UV-2500PC (manufactured by Shimadzu Corporation) with a wavelength of 700 nm after mixing the solution at a time point of 3 minutes Perform the measurement to obtain the measured value (%). The reference group used a mixed solvent of water/ethanol (mass ratio water:ethanol=3:1).

2.塗膜均一性 將實施例1~21、比較例1~9之各試料以厚度50μm塗佈於聚甲基丙烯酸甲酯板上，於室溫乾燥15分鐘後，以SPF分析儀UV-2000S (Labsphere公司製)於10處測定SPF值，所得之標準偏差除以平均值而得之變動係數藉由下述＜判定基準1＞進行判定。2. Film uniformity The samples of Examples 1 to 21 and Comparative Examples 1 to 9 were coated on a polymethyl methacrylate board with a thickness of 50 μm, dried at room temperature for 15 minutes, and then SPF analyzer UV-2000S (manufactured by Labsphere) The SPF value is measured at 10 points, and the obtained standard deviation is divided by the average value to determine the variation coefficient by the following <Judgement Criteria 1>.

＜判定基準1＞ (判定)：(變動係數之值) A：0以上0.25以下 B：超過0.25且0.50以下 C：超過0.50且0.75以下 D：超過0.75且1.00以下 E：超過1.00<Judgment Criteria 1> (Judgment): (value of coefficient of variation) A: Above 0 and below 0.25 B: more than 0.25 and less than 0.50 C: more than 0.50 and less than 0.75 D: more than 0.75 and less than 1.00 E: more than 1.00

3.耐水性 將實施例1~21、比較例1~9之各試料以厚度50μm塗佈於聚甲基丙烯酸甲酯板上，於室溫乾燥15分鐘後，以SPF分析儀UV-2000S (Labsphere公司製)測定3次SPF值，將其平均值設為初期值。隨後，於直徑50cm、深度15cm之臉盆狀水槽容器中放入25℃水至11cm深度，將固定有聚甲基丙烯酸甲酯板之平板以距水槽容器之旋轉軸為21cm之距離，設置為浸漬至10cm之深度，以該狀態旋轉水槽容器，調整為平板前之水流流速為24~28cm/s，水槽容器之旋轉速度為45rpm。隨後，將塗佈有各試料之聚甲基丙烯酸甲酯板固定於平板，將該平板固定於水槽容器中距底面1cm之位置並浸漬，旋轉水槽容器開始水浴。經過80分鐘後，自水槽容器內取出固定有聚甲基丙烯酸甲酯板之平板，於室溫乾燥15分鐘，同樣測定3次SPF值，將其平均值設為殘存值。算出水浴處理前後之SPF值之殘存率(=(殘存值)/(初期值))，藉由下述＜判定基準2＞進行判定。 ＜判定基準2＞ (判定)：(殘存率之值) A：殘存率超過90% B：殘存率超過75%且90%以下 C：殘存率超過60%且75%以下 D：殘存率超過45%且60%以下 E：殘存率為45%以下3. Water resistance The samples of Examples 1 to 21 and Comparative Examples 1 to 9 were coated on a polymethyl methacrylate board with a thickness of 50 μm, dried at room temperature for 15 minutes, and then SPF analyzer UV-2000S (manufactured by Labsphere) The SPF value was measured 3 times, and the average value was set as the initial value. Then, put 25°C water in a basin-shaped sink container with a diameter of 50cm and a depth of 15cm to a depth of 11cm, and set the plate with the polymethyl methacrylate board at a distance of 21cm from the rotation axis of the sink container. Dip to a depth of 10cm, rotate the water tank container in this state, adjust the flow rate of the water before the plate to be 24~28cm/s, and the rotation speed of the water tank container is 45rpm. Subsequently, the polymethyl methacrylate plate coated with each sample was fixed to the flat plate, and the flat plate was fixed at a position 1 cm from the bottom surface in the water tank container and immersed, and the water tank container was rotated to start the water bath. After 80 minutes, the plate with the polymethyl methacrylate plate fixed was taken out from the water tank container and dried at room temperature for 15 minutes. The SPF value was also measured 3 times, and the average value was set as the residual value. Calculate the residual rate of SPF value before and after the water bath treatment (=(survival value)/(initial value)), and judge by the following <judgment criterion 2>. <Judgment Criteria 2> (Judgment): (Value of Survival Rate) A: Survival rate exceeds 90% B: Survival rate exceeds 75% and below 90% C: Survival rate is more than 60% and less than 75% D: Survival rate exceeds 45% and less than 60% E: Survival rate is below 45%

4.經時安定性 將實施例1~21、比較例1~9之各試料30g量入玻璃瓶(6號規格，PS-NO.6)中，於50℃恆溫槽中保存1個月，1個月後之各試料狀態以目視確認，藉由下述＜判定基準3＞進行判定。 ＜判定基準3＞ (判定)：(外觀狀態) A：未確認到水相分離 B：確認到水相分離層為0.5mm以下，將各試料上下振盪3次時，分離層消失 C：確認到水相分離層超過0.5mm且1.0mm以下，將各試料上下振盪3次時，分離層消失 D：確認到水相分離層超過1.0mm且1.5mm以下，將各試料上下振盪3次時，分離層消失 E：確認到水相分離層超過1.5mm且1.0mm以下，即使將各試料上下振盪3次時，分離層亦未消失4. Stability over time Put 30g of each sample of Examples 1-21 and Comparative Examples 1-9 into a glass bottle (No. 6 specification, PS-NO.6), and store in a 50℃ constant temperature bath for 1 month, and each after 1 month The state of the sample was visually confirmed and judged by the following <Judgment Criteria 3>. <Judgment Criteria 3> (Judgment): (Appearance state) A: Water phase separation is not confirmed B: It is confirmed that the water phase separation layer is 0.5 mm or less, and the separation layer disappears when each sample is shaken up and down 3 times C: It is confirmed that the water phase separation layer exceeds 0.5 mm and 1.0 mm or less. When each sample is shaken up and down 3 times, the separation layer disappears D: It is confirmed that the water phase separation layer exceeds 1.0 mm and 1.5 mm or less. When each sample is shaken up and down three times, the separation layer disappears E: It is confirmed that the water phase separation layer exceeds 1.5mm and 1.0mm or less, even when each sample is shaken up and down three times, the separation layer does not disappear

5.使用性 使20餘歲~40餘歲之女性接受官能評價訓練，以一定基準選定10位可評價之專門試驗員。使專門試驗員針對實施例1~21、比較例1~9之各試料5g塗佈於上腕部，再以另一手之中指及無名指溫和描繪圓而施用，藉由下述＜絕對評價基準＞以5階段評價此時感覺之使用性，賦予評分，對每各試料，由試驗員全體之評分合計，算出平均分數，藉由下述＜判定基準4＞進行判定。 ＜絕對評價基準＞ (評分)：(使用性) 5分：施用時，圓在5次循環以內，描繪時觀察到水滴，未感覺到黏膩感，非常水嫩 4分：施用時，圓在超過5次循環且10次循環以內，描繪時觀察到水滴，未感覺到黏膩感，而水嫩 3分：施用時，圓在超過10次循環，描繪時雖未觀察到水滴，但幾乎未感覺到黏膩感 2分：施用時，圓在超過10次循環，描繪時雖未觀察到水滴，但稍感覺到黏膩感，塗抹於超過15次循環且20次循環以內觀察到水滴 1分：施用時，圓在超過10次循環，描繪時雖未觀察到水滴，但強烈感覺到黏膩感 ＜判定基準4＞ (判定)：(評分之平均分數) A：4.2分以上                        ：非常良好 B：未達4.2分且3.4分以上        ：良好 C：未達3.4分且2.6分以上        ：稍良好 D：未達2.6分且1.8分以上        ：稍不良 E：未達1.8分                        ：不良5. Usability To enable women in their 20s to 40s to receive sensory evaluation training, and select 10 evaluable professional testers based on a certain standard. A specialist tester applied 5 g of each sample of Examples 1 to 21 and Comparative Examples 1 to 9 on the upper wrist, and then used the middle finger and ring finger of the other hand to gently draw a circle, using the following <Absolute Evaluation Criteria> to The usability of the feeling at this time was evaluated in five stages, and scores were assigned. For each sample, the scores of all testers were added together to calculate the average score, and the following <judgment criteria 4> were used to determine. ＜Absolute evaluation standard＞ (Score): (Usability) 5 points: when applied, the circle is within 5 cycles, water droplets are observed when drawing, no sticky feeling is felt, very tender 4 points: When applied, the circle is more than 5 cycles and within 10 cycles, water droplets are observed when drawing, no sticky feeling is felt, but tender 3 points: When applied, the circle circulates more than 10 times. Although no water droplets are observed when drawing, there is almost no stickiness 2 points: When applied, the circle has more than 10 cycles, although no water droplets are observed when drawing, but a little sticky feeling is felt, and water droplets are observed within 20 cycles after applying more than 15 cycles 1 point: When applied, the circle circulates more than 10 times. Although no water droplets are observed when drawing, a strong feeling of stickiness is felt <Judgment Criteria 4> (Judgment): (Average score of score) A: 4.2 points or more: Very good B: Less than 4.2 points and above 3.4 points: Good C: less than 3.4 points and more than 2.6 points: slightly better D: Less than 2.6 points and more than 1.8 points: Slightly bad E: less than 1.8 points: bad

※1：MZY-500SHE(TAYCA公司製)平均粒徑25nm，不定形 ※2：FINEX-52W-LP2(堺化學工業公司製)平均粒徑20nm，不定形 ※3：MZY-505S(TAYCA公司製)平均粒徑25nm，不定形 ※4：MZ-500(TAYCA公司製)平均粒徑25nm，不定形 ※5：NAI-鈦MP-1133(三好化成公司製)平均粒徑250nm ※6：D-400(根上工業公司製)平均粒徑15μm ※7：TOSPERAL2000B(Momentive Performance Material Japan公司製)平均粒徑6μm ※8：PEMULEN TR-1(LUBRIZOL ADVANCED MATERIALS 公司製)※1: MZY-500SHE (manufactured by TAYCA), with an average particle size of 25nm, indefinite shape ※2: FINEX-52W-LP2 (manufactured by Sakai Chemical Industry Co., Ltd.), with an average particle size of 20nm, indefinite shape ※3: MZY-505S (manufactured by TAYCA), with an average particle size of 25nm, irregular ※4: MZ-500 (manufactured by TAYCA), average particle size 25nm, irregular ※5: NAI-Titanium MP-1133 (manufactured by Miyoshi Chemical Co., Ltd.) with an average particle size of 250nm ※6: D-400 (manufactured by Nejo Kogyo Co., Ltd.) average particle size 15μm ※7: TOSPERAL2000B (manufactured by Momentive Performance Material Japan) average particle size 6μm ※8: PEMULEN TR-1 (made by LUBRIZOL ADVANCED MATERIALS)

(製造方法) A：將成分(6)~(13)於80℃均一混合溶解。 B：將成分(1)~(5)及成分(14)~(22)以輥磨機均一混合分散，並與A混合。 C：將成分(23)~(29)均一混合。 D：將C添加於B中，以分散混合機於2000rpm、室溫乳化5分鐘。 E：將D填充於容器中，獲得油中水型防曬料。(Production method) A: The components (6) to (13) are uniformly mixed and dissolved at 80°C. B: Ingredients (1) to (5) and ingredients (14) to (22) are uniformly mixed and dispersed with a roller mill, and mixed with A. C: The components (23) to (29) are uniformly mixed. D: C is added to B, and it is emulsified with a dispersing mixer at 2000 rpm and room temperature for 5 minutes. E: Fill D in the container to obtain a water-in-oil sunscreen.

如由表1之結果可了解，本發明之實施例1~5之油中水型防曬料係塗膜均一性、耐水性、經時安定性、使用性優異。 另一方面，不含成分(A)，而使用以氧化矽及疏水化處理劑表面處理之氧化鋅且於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率並為0.8~20者之比較例1，塗膜均一性、經時安定性、使用性差。理由認為係成分(2)未發揮兩親媒性，而無法引起良好乳化之故。 不含成分(A)，而使用以疏水化處理劑表面處理之氧化鋅且於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率並為0.8~20者之比較例2，塗膜均一性、經時安定性、使用性差。理由認為係成分(3)未發揮兩親媒性，而無法引起良好乳化之故。 不含成分(A)，而使用無處理氧化鋅且於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率並為0.8~20者之比較例3，塗膜均一性、耐水性、經時安定性、使用性差。理由認為係成分(4)未發揮兩親媒性，而無法引起良好乳化之故。 不含成分(A)，而使用硬脂醯基麩胺酸二鈉處理之氧化鈦且於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率並為0.8~20者之比較例4，塗膜均一性、經時安定性、使用性差。理由認為係成分(5)對油水界面之選擇配向差，而無法引起良好乳化之故。As can be understood from the results in Table 1, the water-in-oil sunscreen systems of Examples 1 to 5 of the present invention have excellent coating film uniformity, water resistance, stability over time, and usability. On the other hand, when the component (A) is not included, and zinc oxide surface-treated with silicon oxide and a hydrophobizing treatment agent is used and mixed in water/ethanol solvent (mass ratio water: ethanol=3:1) at 0.25% by mass In Comparative Example 1, where the light transmittance at a wavelength of 700 nm is 0.8 to 20, the uniformity of the coating film, the stability over time, and the usability are poor. The reason is that the component (2) does not exert amphiphilic properties and cannot cause good emulsification. It does not contain component (A), but uses zinc oxide surface-treated with a hydrophobizing treatment agent and mixes in a water/ethanol solvent (mass ratio water: ethanol=3:1) at a light transmittance of 700nm at a wavelength of 0.25 mass%. In Comparative Example 2, which is 0.8 to 20, the coating film uniformity, stability over time, and usability are poor. The reason is that the component (3) does not exert amphiphilic properties and cannot cause good emulsification. Does not contain component (A), but uses untreated zinc oxide and 0.25% by mass in a water/ethanol solvent (mass ratio water: ethanol=3:1) when the light transmittance at a wavelength of 700nm is 0.8-20 Comparative Example 3 has poor coating film uniformity, water resistance, stability over time, and usability. The reason is that the component (4) does not exert amphiphilic properties and cannot cause good emulsification. Does not contain ingredient (A), but uses titanium oxide treated with disodium stearyl glutamate and mixed in water/ethanol solvent (mass ratio water: ethanol=3:1) at a wavelength of 700nm when mixed at 0.25% by mass Comparative Example 4 with a transmittance of 0.8 to 20 has poor coating uniformity, stability over time, and usability. The reason is that the component (5) has poor selective alignment to the oil-water interface and cannot cause good emulsification.

如由表2可了解，成分(A)未達5質量%之比較例5，與實施例相比，塗膜均一性、耐水性、經時安定性、使用性較差。理由認為係吸附於界面之成分(A)的量不足，而無法引起良好乳化之故。 成分(A)超過30質量%之比較例6，塗膜均一性、使用性較差。理由認為係成分(A)未吸附於界面而過量分散於油相中，於塗佈時成分(A)本身觸感成為支配，無法獲得乾爽感，而強烈感到黏膩感，而欠缺使用性之故。 且界面活性劑含量超過1質量%之比較例7，與實施例相比，塗膜均一性、耐水性、經時安定性較差。As can be understood from Table 2, Comparative Example 5 in which the component (A) is less than 5% by mass has inferior coating film uniformity, water resistance, stability over time, and usability compared with the Examples. The reason is that the amount of component (A) adsorbed on the interface is insufficient to cause good emulsification. Comparative Example 6 in which the component (A) exceeds 30% by mass has poor coating uniformity and usability. The reason is that the component (A) is not adsorbed on the interface but is excessively dispersed in the oil phase, and the component (A) itself is dominated by the touch during coating, and the dry feeling cannot be obtained, and the sticky feeling is strongly felt, which lacks usability. Therefore. In addition, Comparative Example 7 in which the surfactant content exceeds 1% by mass has inferior coating film uniformity, water resistance, and stability over time as compared with the examples.

如由表3可了解，各實施例之防曬料之各項中成為評價較高者，尤其是乳化滴於150~300μm之範圍的實施例1、14、15於所有項目中均為A評價，係尤其具有水嫩之良好使用性者。且認為伴隨含有質量比例(B)/(C)變大，有乳化滴之平均粒徑變大之傾向，確認上述乳化滴設為150~300μm之範圍時，較佳含有質量比例(B)/(C)設為1~3.3之範圍。 另一方面，不含成分(B)之比較例8，塗膜均一性、使用性較差。 不含成分(C)之比較例9，塗膜均一性、耐水性、經時安定性較差。As can be understood from Table 3, the sunscreens of the various examples have a higher evaluation, especially the examples 1, 14, and 15 that are emulsified in the range of 150~300μm are evaluated as A in all items. It is especially soft and good for use. It is considered that as the content mass ratio (B)/(C) increases, the average particle size of the emulsified droplets tends to increase. When it is confirmed that the emulsified droplets are in the range of 150 to 300 μm, the content mass ratio (B)/ (C) Set the range from 1 to 3.3. On the other hand, Comparative Example 8 which does not contain the component (B) has poor coating film uniformity and usability. In Comparative Example 9, which does not contain the component (C), the coating film uniformity, water resistance, and stability over time are poor.

如由表4可了解，與不含成分(B)極性油之比較例8相比，藉由調配極性油，塗膜均一性或使用性等顯著被改善，尤其併用液狀極性油與固形液狀油，確認成為耐水性進而優異者。As can be understood from Table 4, compared with Comparative Example 8 which does not contain the component (B) polar oil, the uniformity and usability of the coating film are significantly improved by blending the polar oil, especially the combination of liquid polar oil and solid liquid It was confirmed that the oil was excellent in water resistance.

實施例16：油中水型液狀粉底 (成分)                                             (質量%) (1)由氧化矽及疏水處理劑表面處理之氧化鋅 ※9                                                       8 (2)由三異硬脂酸異丙基鈦處理之二氧化鈦 ※10                                                      8 (3)由甲基氫聚矽氧烷處理之二氧化鈦 ※11                                                      2 (4)對-甲氧基桂皮酸-2-乙基己酯                  5 (5)2-{4-(二乙胺基)-2-羥基苯甲醯基}苯甲酸己酯                                                                     1.5 (6)2,4-雙[{4-(2-乙基己氧基)-2-羥基}-苯基]-6-(4-甲氧基苯基)-(1,3,5)-三嗪                                      0.5 (7)三(辛酸・癸酸)甘油酯                           3 (8)月桂酸己酯                                         3 (9)氫化聚異丁烯※12                                3 (10)環甲矽氧                                          10 (11)甲基三甲矽氧                                    5 (12)苯基三甲矽氧※13                              2 (13)月桂基PEG-9聚二甲基矽氧基乙基二甲矽氧  0.2 (14)矽酸酐※14                                       1.5 (15)三乙氧基辛基矽烷處理絹雲母※15         2 (16)純化水                                             餘量 (17)乙醇                                                5 (18)丙二醇                                             5 (19)苯氧基乙醇                                       0.3 (20)水解玻尿酸                                       0.5 (21)水解膠原蛋白                                    0.5 (22)茶胺酸                                             0.5 (23)絲胺酸                                             0.2 (24)氯化鈉                                             0.2 (25)山梨糖醇                                          2 (26)銀耳多糖體                                       0.01 (27)牡丹皮萃取物                                    0.03 (28)抗壞血酸                                          0.001 ※9：(評價方法)依據1.粉體透過率中記載之方法測定之透過率為1.5%，平均粒徑25nm ※10：ITT-2 TiO2 CR-50(KOBO PRODUCTS公司製)平均粒徑250nm ※11：MT-05(TAYCA公司製)平均粒徑10nm ※12：PARLEAM 4(日油公司製) ※13：SH556 FLUID(東麗道康寧公司製) ※14：CHIFFONSIL P-3R(日揮觸媒化成公司製)平均粒徑5μm ※15：OTS-2絹雲母FSE(大東化成工業公司製)平均粒徑10μmExample 16: Water-in-oil liquid foundation (Ingredients) (Quality %) (1) Zinc oxide surface-treated with silicon oxide and hydrophobic treatment agent ※9 ​ (2) Titanium dioxide treated with isopropyl titanium triisostearate ※10 ▫ ▫ ▫ ▫ ▫ 8 (3) Titanium dioxide treated with methyl hydrogen polysiloxane ※11 ▫ ▫ ▫ ▫ ▫ ▫ 2 (4) p-Methoxycinnamic acid-2-ethylhexyl ester 5 (5) 2-(4-(Diethylamino)-2-hydroxybenzyl hexyl benzoate) Hexyl benzoate, 1.5 1.5 (6)2,4-Bis[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-(1,3,5) -Triazine 0.5 (7) Three (caprylic acid, capric acid) glycerides 3 (8) Hexyl lauric acid, hexyl lauric acid, 3 (9) Hydrogenated polyisobutylene※12 3 (10) Cyclomethicone 10 (11) Methyltrimethicone 5​ (12) Phenyltrimethicone*13 2 (13) Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 0.2 (14) Silicic anhydride※14 1.5 (15) Triethoxy octyl silane treated sericite*15 2 (16) Purified water, balance (17) Ethanol 5 (18) Propylene glycol 5 (19) Phenoxyethanol 0.3 (20) Hydrolyzed Hyaluronic Acid 0.5 (21)Hydrolyzed collagen 0.5 (22) Theanine acid 0.5 (23) Serine acid 0.2 (24) Sodium Chloride 0.2..................... .. 0.2 (25)Sorbitol,,,,,,, 2 (26) Tremella polysaccharides 0.01 (27) Moutan peel extract 0.03 (28) Ascorbic acid 0.001 ※9: (Evaluation method) The transmittance measured according to the method described in 1. Powder transmittance is 1.5%, and the average particle size is 25nm ※10: ITT-2 TiO2 CR-50 (manufactured by KOBO PRODUCTS) average particle size 250nm ※11: MT-05 (manufactured by TAYCA) with an average particle size of 10nm ※12: PARLEAM 4 (manufactured by NOF Corporation) ※13: SH556 FLUID (manufactured by Toray Dow Corning Corporation) ※14: CHIFONSIL P-3R (manufactured by Nikkei Catalytic Chemicals Co., Ltd.) average particle size 5μm ※15: OTS-2 Sericite FSE (manufactured by Dadong Chemical Industry Co., Ltd.) with an average particle size of 10μm

(製造方法) A：將成分(4)~(8)於80℃均一混合溶解。 B：將成分(1)~(3)及成分(9)~(15)以分散混合機於2000rpm、室溫均一混合分散5分鐘，並與A混合。 C：將成分(16)~(28)均一混合。 D：將C添加於B中，以分散混合機於2000rpm、室溫乳化5分鐘。 E：將D填充於容器中，獲得油中水型液狀粉底。(Production method) A: The components (4) to (8) are uniformly mixed and dissolved at 80°C. B: The ingredients (1) to (3) and the ingredients (9) to (15) are uniformly mixed and dispersed with a dispersing mixer at 2000 rpm and room temperature for 5 minutes, and mixed with A. C: The components (16) to (28) are uniformly mixed. D: C is added to B, and it is emulsified with a dispersing mixer at 2000 rpm and room temperature for 5 minutes. E: D is filled in a container to obtain a water-in-oil type liquid foundation.

實施例16之油中水型液狀粉底係塗膜均一性、耐水性、經時安定性、使用性優異者。The water-in-oil type liquid foundation of Example 16 has excellent coating film uniformity, water resistance, stability over time, and usability.

實施例17：油中水型白天使用美容液 (成分)                                                (質量%) (1)由氧化矽及疏水處理劑表面處理之氧化鋅※16  10 (2)由二甲基聚矽氧處理之二氧化鈦※17              1 (3)三乙氧基辛基矽烷處理之二氧化鈦※18           1 (4)對-甲氧基桂皮酸-2-乙基己酯                        5 (5)2,4,6-三[{4-(2-乙基己氧基羰基)苯胺基]-1,3,5-三嗪                                                                1.5 (6)己二酸二異丙酯                                         5 (7)異壬酸異壬酯                                            2 (8)三異硬脂酸甘油酯                                   0.1 (9)角鯊烷                                                     3 (10)蝦青素                                                       0.002 (11)異十二烷                                                3 (12)環甲矽氧                                                10 (13)二甲基聚矽氧烷※19                                 3 (14)二甲基聚矽氧烷※20                                 3 (15)倍半異硬脂酸山梨糖醇酐                        0.2 (16)交聯型矽氧・網狀型矽氧嵌段共聚物※21      2 (17)聚甲基丙烯酸甲酯※22                              2 (18)純化水                                             餘量 (19)乙醇                                                      5 (20)三丙二醇                                                5 (21)甘油                                                   2.5 (22)二甘油                                                0.5 (23)1,3-丁二醇                                              5 (24)苯氧基乙醇                                          0.2 (25)聚氧乙烯甲基葡萄糖苷                           0.5 (26)乙醯基化玻尿酸鈉                                 0.1 (27)玻尿酸丙二醇酯                                    0.2 (28)氯化鈉                                                0.2 (29)赤蘚醇                                                   3 (30)水前寺藍藻多糖體                                0.05 (31)桑白皮根皮萃取物                               0.05 (32)抗壞血酸葡萄糖苷                                 0.2 ※16：(評價方法)依據1.粉體透過率中記載之方法測定之透過率為18%，平均粒徑25nm ※17：SA-鈦MP-1133(三好化成公司製)平均粒徑250nm ※18：OTS-2 TiO2 MP-1133(大東化成工業公司製)平均粒徑250nm ※19：KF-96A-1.5cs(信越化學工業公司製) ※20：KF-96A-6cs(信越化學工業公司製) ※21：KSP-101(信越化學工業公司製)平均粒徑12μm ※22：MATSUMOTO MICROSPHERE M101(松本油脂製藥公司製)平均粒徑9μmExample 17: Water-in-oil type beauty lotion for daytime use (Ingredient) (Quality%) (Quality%) (1) Zinc oxide surface-treated with silicon oxide and hydrophobic treatment agent※16 10 (2) Titanium dioxide treated by dimethylpolysiloxane*17 1 (3) Titanium dioxide treated with triethoxy octyl silane*18 1 (4) p-methoxycinnamic acid-2-ethylhexyl ester 5 (5) 2,4,6-three[{4-(2-ethylhexyloxycarbonyl)anilinyl]-1,3,5-triazine 1.5 (6) Diisopropyl adipate 5 (7) Isononyl isononanoic acid and isononyl ester 2 (8) Glycerol triisostearate 0.1 (9) squalane squalane 3 (10) Astaxanthin 0.002 (11) Isododecane 3 (12) Cyclomethicone 10 (13)Dimethylpolysiloxane※19 3 (14)Dimethylpolysiloxane※20 3 (15) Sorbitan sesquiisostearate 0.2 (16)Cross-linked silicone and reticulated silicone block copolymer※21 2 (17) Polymethyl methacrylate※22 2 (18) Purified water Remaining balance (19) Ethanol 5 (20) Tripropylene glycol 5 (21) Glycerin 2.5 ​ (22) Diglycerol 0.5 (23)1,3-Butanediol 5​ (24) Phenoxyethanol 0.2 (25) Polyoxyethylene methyl glucoside 0.5 (26) Sodium Acetate Hyaluronate 0.1 (27) Hyaluronic Acid Propylene Glycol Ester 0.2 (28) Sodium Chloride 0.2...................... 0.2 (29) Erythritol 3 (30) Shuiqian Temple cyanobacteria polysaccharide 0.05 (31) Mulberry bark root bark extracts 0.05 (32) Ascorbyl glucoside 0.2 ※16: (Evaluation method) The transmittance measured according to the method described in 1. Powder transmittance is 18%, and the average particle size is 25nm ※17: SA-Titanium MP-1133 (manufactured by Miyoshi Chemical Co., Ltd.) with an average particle size of 250nm ※18: OTS-2 TiO2 MP-1133 (manufactured by Daito Chemical Industry Co., Ltd.) with an average particle size of 250nm ※19: KF-96A-1.5cs (manufactured by Shin-Etsu Chemical Co., Ltd.) ※20: KF-96A-6cs (manufactured by Shin-Etsu Chemical Co., Ltd.) ※21: KSP-101 (manufactured by Shin-Etsu Chemical Co., Ltd.) with an average particle size of 12μm ※22: MATSUMOTO MICROSPHERE M101 (manufactured by Matsumoto Oil Pharmaceutical Co., Ltd.) average particle size 9μm

(製造方法) A：將成分(4)~(8)於80℃均一混合溶解。 B：將成分(1)~(3)及成分(9)~(17)以輥磨機均一混合分散，並與A混合。 C：將成分(18)~(32)均一混合。 D：將C添加於B中，以分散混合機於2000rpm、室溫乳化5分鐘。 E：將D填充於容器中，獲得油中水型白天用美溶液。(Production method) A: The components (4) to (8) are uniformly mixed and dissolved at 80°C. B: Ingredients (1) to (3) and ingredients (9) to (17) are uniformly mixed and dispersed with a roll mill, and mixed with A. C: The components (18) to (32) are uniformly mixed. D: C is added to B, and it is emulsified with a dispersing mixer at 2000 rpm and room temperature for 5 minutes. E: Fill D in a container to obtain a water-in-oil type daytime beauty solution.

實施例17之油中水型白天用美溶液係塗膜均一性、耐水性、經時安定性、使用性優異者。The water-in-oil type daytime beauty solution of Example 17 has excellent film uniformity, water resistance, stability over time, and usability.

實施例18：油中水型化妝粉底 (成分)                                               (質量%) (1)由氧化矽及疏水處理劑表面處理之氧化鋅※23  12 (2)由月桂醯基天門冬胺酸鈉處理之二氧化鈦※24    2.5 (3)由月桂醯基麩胺酸鈉處理之二氧化鈦※25     2.5 (4)對-甲氧基桂皮酸-2-乙基己酯                        4 (5)2,4,6-三[{4-(2-乙基己氧基羰基)苯胺基]-1,3,5-三嗪                                                                    1 (6)2-{4-(二乙胺基)-2-羥基苯甲醯基}苯甲酸己酯   1 (7)2,4-雙[{4-(2-羥基己氧基)-2-羥基}-苯基]-6-(4-甲氧基苯基)-(1,3,5)-三嗪                                            1 (8)三異硬脂酸二甘油酯                               0.3 (9)苯甲酸烷酯(C12-15)                                    5 (10)苯偏三酸三2-乙基己酯                               2 (11)異十二烷                                            2.5 (12)環甲矽氧                                                14 (13)二甲基聚矽氧烷※26                                 2 (14)二甲基聚矽氧烷※27                                 2 (15)三甲基矽氧基矽酸                                    2 (16)月桂基聚甘油-3聚二甲基矽氧基乙基二甲矽氧  0.2 (17)尼龍-12※28                                            3 (18)月桂醯基離胺酸                                    0.1 (19)純化水                                               餘量 (20)乙醇                                                      3 (21)1,2-戊二醇                                           0.5 (22)苯氧基乙醇                                          0.2 (23)二丙二醇                                                3 (24)1,3-丁二醇                                              5 (25)聚乙二醇※29                                          2 (26)(二十烷二酸・十四烷二酸)聚甘油酯-10      0.1 (27)三聯苯基三嗪                                          1 (28)亞甲基雙苯并***基四甲基丁基酚               1 (29)玻尿酸羥基丙基三甲銨                           0.3 (30)琥珀醯基去端肽膠原(succinoyl atelocollagen) 0.5 (31)N-乙醯基-L-羥基脯胺酸                          0.5 (32)檸檬酸鈉                                            0.05 (33)氯化鉀                                                0.2 (34)依克多因(ectoine)                                     1 (35)(PEG-240・Decyltetradeceth-20・HDI)共聚物 0.05 (36)2-甲基丙烯醯氧基乙基磷酸膽鹼・甲基丙烯酸丁酯共聚物液                                                      0.5 (37)腐植土萃取物                                      0.05 (38)磷酸L-抗壞血酸鎂                                  0.2 ※23：(評價方法) 依據1.粉體透過率中記載之方法測定之透過率為5%，平均粒徑25nm ※24：ASI TiO2 CR-50(大東化成工業公司製)平均粒徑250nm ※25：ASL-1 TiO2 MP-1133(大東化成工業公司製) 平均粒徑250nm ※26：KF-96A-1cs(信越化學工業公司製) ※27：KF-96A-20cs(信越化學工業公司製) ※28：ORGASOL 2002D(ARKEMA公司製)平均粒徑20μm ※29：PEG-400(東邦化學工業公司製)Example 18: Oil-in-water cosmetic foundation (Ingredients) (Quality%) (1) Zinc oxide surface-treated with silicon oxide and hydrophobic treatment agent※23 12 (2) Titanium dioxide treated with sodium lauryl aspartate*24 2.5 (3) Titanium dioxide treated with sodium lauryl glutamate*25 2.5 (4) p-methoxycinnamic acid-2-ethylhexyl ester 4 (5) 2,4,6-three[{4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazine 1 1 (6) 2-{4-(Diethylamino)-2-hydroxybenzyl}hexyl benzoate 1 (7) 2,4-Bis[{4-(2-hydroxyhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-(1,3,5)- Triazines 1 (8) Triisostearate diglyceride 0.3 (9) Alkyl benzoate (C12-15) 5 (10) Tri-2-ethylhexyl trimellitate 2 (11) Iso-dodecane 2.5 (12) Cyclomethicone 14 (13)Dimethylpolysiloxane※26 2 (14)Dimethylpolysiloxane※27 2 (15) Trimethylsiloxy silicic acid 2 (16) Lauryl polyglycerol-3 polydimethylsiloxyethyl dimethicone 0.2 (17) Nylon-12※28 3 (18) Laurel-based lysine acid 0.1 (19) Purified water remaining balance (20) Ethanol,,, 3 (21) 1,2-pentanediol 0.5 (22) Phenoxyethanol 0.2 (23) Dipropylene glycol 3 (24) 1,3-Butanediol 5 (25)Polyethylene glycol※29 2 (26) (Eicosanedioic Acid, Tetradecanedioic Acid) Polyglycerol Ester-10 0.1 (27) Triple phenyl triazines 1 (28) Methylene dibenzotriazole tetramethyl butyl phenol 1 (29) Hyaluronic acid hydroxypropyl trimethylammonium 0.3 (30) succinoyl atelocollagen 0.5 (31)N-Acetyl-L-Hydroxyproline 0.5 (32) Sodium citrate 0.05 (33)Potassium Chloride 0.2 (34) ectoine (ectoine) 1 (35)(PEG-240・Decyltetradeceth-20・HDI) copolymer 0.05 (36) 2-Methyl propylene oxyethyl phosphate choline butyl methacrylate copolymer liquid 0.5 (37) Humus soil extracts 0.05 (38) Magnesium L-Ascorbate Phosphate 0.2 ※23: (Evaluation method) The transmittance measured according to the method described in 1. Powder transmittance is 5% and the average particle size is 25nm ※24: ASI TiO2 CR-50 (manufactured by Dadong Chemical Industry Co., Ltd.) with an average particle size of 250nm ※25: ASL-1 TiO2 MP-1133 (manufactured by Daito Chemical Co., Ltd.), average particle size 250nm ※26: KF-96A-1cs (manufactured by Shin-Etsu Chemical Co., Ltd.) ※27: KF-96A-20cs (manufactured by Shin-Etsu Chemical Co., Ltd.) ※28: ORGASOL 2002D (manufactured by ARKEMA) average particle size 20μm ※29: PEG-400 (manufactured by Toho Chemical Industry Co., Ltd.)

(製造方法) A：將成分(4)~(8)於80℃均一混合溶解。 B：將成分(1)~(3)及成分(9)~(16)以輥磨機均一混合分散，並與A混合。 C：將成分(17)~(38)均一混合。 D：將C添加於B中，以分散混合機於2000rpm、室溫乳化5分鐘。 E：將D填充於容器中，獲得油中水型化妝粉底。(Production method) A: The components (4) to (8) are uniformly mixed and dissolved at 80°C. B: Ingredients (1) to (3) and ingredients (9) to (16) are uniformly mixed and dispersed with a roller mill, and mixed with A. C: The components (17) to (38) are uniformly mixed. D: C is added to B, and it is emulsified with a dispersing mixer at 2000 rpm and room temperature for 5 minutes. E: D is filled in a container to obtain a water-in-oil cosmetic foundation.

實施例18之油中水型化妝粉底係塗膜均一性、耐水性、經時安定性、使用性優異者。The water-in-oil cosmetic foundation of Example 18 has excellent coating film uniformity, water resistance, stability over time, and usability.

實施例19：油中水型防曬棒 (成分)                                               (質量%) (1)由氧化矽及疏水處理劑表面處理之氧化鋅※30  8 (2)由羥丙基雙棕櫚醯胺MEA處理之二氧化鈦※31  2 (3)由全氟辛基三乙氧基矽烷處理之二氧化鈦※32  1 (4)硬脂酸鎂處理之二氧化鈦※33                       1 (5)對-甲氧基桂皮酸-2-乙基己酯                        6 (6)2-{4-(二乙胺基)-2-羥基苯甲醯基}苯甲酸己酯   1 (7)2,4-雙[{4-(2-羥基己氧基)-2-羥基}-苯基]-6-(4-甲氧基苯基)-(1,3,5)-三嗪                                            1 (8)2,4,6-三[{4-(2-乙基己氧基羰基)苯胺基]-1,3,5-三嗪                                                                    1 (9)癸二酸二乙酯                                            4 (10)琥珀酸二乙基己酯                                    4 (11)二新戊酸鉀基戊二醇酯                              4 (12)二聚亞油酸酯(植物甾基・異硬脂基・鯨蠟基・硬脂基・山萮基)                                                     2 (13)生育酚                                               0.02 (14)聚乙烯※34                                             5 (15)微晶蠟※35                                             4 (16)鏈烷※36                                                2 (17)二甲基聚矽氧烷※37                                 10 (18)凡士林                                                   2 (19)(二甲矽氧・聚甘油-3)交錯聚合物              0.1 (20)(PEG-15・月桂基二甲矽氧)交錯聚合物       0.1 (21)矽酸酐※38                                             3 (22)二甲矽氧・胺基丙基三乙氧基矽烷處理之滑石 ※39                                                                 2 (23)純化水                                             餘量 (24)1,3-丁二醇                                              2 (25)甘油                                                      2 (26)聚氧乙烯甘油(26.EO.)                                2 (27)聚氧丙烯二甘油醚                                    2 (28)環己烷-1,4-二羧酸雙乙氧基二甘醇酯         0.5 (29)苯氧基乙醇                                          0.2 (30)忍冬花萃取物                                       0.5 (31)赤蘚醇                                                   1 (32)海藻糖                                                   1 (33)三甲基甘胺酸                                          1 (34)薄荷醇                                                0.2 ※30：(評價方法) 依據1.粉體透過率中記載之方法測定之透過率為15%，平均粒徑25nm ※31：X-CERA TiO2 R250(大東化成工業公司製)平均粒徑250nm ※32：FHS-3 TiO2 MP-1133(大東化成工業公司製)平均粒徑250nm ※33：MST-1 TiO2 R250(大東化成工業公司製)平均粒徑250nm ※34：PERFORMALENE 500(New Phase Technologies公司製) ※35：MULTIWAX W445(Sonneborn公司製) ※36：PARACERA 256(Paramelt公司製) ※37：KF-96A-5cs(信越化學工業公司製) ※38：COSME SILICA CQ4(FUJI SILYSIA化學公司製)平均粒徑4μm ※39：SE-TA-EX(三好化成公司製)平均粒徑15μmExample 19: Water-in-oil sunscreen stick (Ingredients) (Quality%) (1) Zinc oxide surface-treated with silicon oxide and hydrophobic treatment agent*30 8 (2) Titanium dioxide treated with hydroxypropyl dipalmitamide MEA※31 2 (3) Titanium dioxide treated with perfluorooctyltriethoxysilane*32 1 (4) Titanium dioxide treated with magnesium stearate*33 1 (5) p-methoxycinnamic acid-2-ethylhexyl ester 6 (6) 2-{4-(Diethylamino)-2-hydroxybenzyl}hexyl benzoate 1 (7) 2,4-Bis[{4-(2-hydroxyhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-(1,3,5)- Triazines 1 (8)2,4,6-three[{4-(2-ethylhexoxycarbonyl)anilinyl]-1,3,5-triazine 1 (9) Diethyl sebacate 4 (10) Diethylhexyl succinate 4 (11) Potassium Dipivalate Pentylene Glycol Ester 4 (12) Di-linoleic acid ester (phytosteryl, isostearyl, cetyl, stearyl, behenyl) 2 (13) Tocopherols 0.02 (14) Polyethylene※34 5 (15) Microcrystalline wax※35 4 (16) Alkane※36 2 (17)Dimethylpolysiloxane※37 10 (18) Vaseline 2 (19) (Dimethicone・Polyglycerol-3) Interlaced polymer 0.1 (20) (PEG-15・Lauryl Dimethicone) Interlaced Polymer 0.1 (21) Silicic anhydride※38 3 (22) Talc for the treatment of methicone and aminopropyl triethoxysilane *39 2 2 (23) Purified water, balance (24) 1,3-Butanediol 2 (25) Glycerin 2 (26) Polyoxyethylene glycerin (26.EO.) 2 (27) Polyoxypropylene diglycerol ether 2 (28) Cyclohexane-1,4-dicarboxylic acid diethoxydiglycol ester 0.5 (29) Phenoxyethanol 0.2 (30) Honeysuckle flower extract 0.5 0.5 (31) Erythritol 1 (32) Trehalose 1 (33) Trimethylglycine acid 1 (34) Menthol 0.2 ※30: (Evaluation method) The transmittance measured according to the method described in 1. Powder transmittance is 15% and the average particle size is 25nm ※31: X-CERA TiO2 R250 (manufactured by Dadong Chemical Industry Co., Ltd.) with an average particle size of 250nm ※32: FHS-3 TiO2 MP-1133 (manufactured by Dadong Chemical Industry Co., Ltd.) with an average particle size of 250nm ※33: MST-1 TiO2 R250 (manufactured by Dadong Chemical Industry Co., Ltd.) with an average particle size of 250nm ※34: PERFORMALENE 500 (manufactured by New Phase Technologies) ※35: MULTIWAX W445 (manufactured by Sonneborn) ※36: Paracera 256 (manufactured by Paramelt) ※37: KF-96A-5cs (manufactured by Shin-Etsu Chemical Co., Ltd.) ※38: COSME SILICA CQ4 (manufactured by FUJI SILYSIA Chemical Co., Ltd.) with an average particle size of 4μm ※39: SE-TA-EX (manufactured by Miyoshi Chemical Co., Ltd.) with an average particle size of 15μm

(製造方法) A：將成分(5)~(16)於90℃均一混合溶解。 B：將成分(1)~(4)及成分(17)~(22)以輥磨機均一混合分散，並與A混合。 C：將成分(23)~(34)均一混合。 D：於90℃將C添加於B中，以分散混合機於2000rpm、90℃乳化5分鐘。 E：將D填充於容器中，冷卻固化，獲得油中水型防曬棒。(Production method) A: The components (5) to (16) are uniformly mixed and dissolved at 90°C. B: Ingredients (1) to (4) and ingredients (17) to (22) are uniformly mixed and dispersed with a roller mill, and mixed with A. C: The components (23) to (34) are uniformly mixed. D: Add C to B at 90°C, and emulsify with a dispersing mixer at 2000 rpm and 90°C for 5 minutes. E: Fill D in a container, cool and solidify to obtain a water-in-oil sunscreen stick.

實施例19之油中水型防曬棒係塗膜均一性、耐水性、經時安定性、使用性優異者。The water-in-oil sunscreen stick of Example 19 has excellent coating film uniformity, water resistance, stability over time, and usability.

[圖1]係對於水/乙醇混合溶劑(質量比 水：乙醇=  3：1) 40g，以成為0.25質量%之方式秤量0.1g之表1~4中之成分(1)~(5)，於其剛秤量後，以振盪器YS-8D(YAYOI公司製)以250次/分鐘、30秒之條件進行混合後，於光路長10mm×光路寬10mm之塑膠槽(cell)中放入3.5g，拍攝混合後經過3分鐘之時點的溶液外觀的照片，試料由左起依序為成分(1)、成分(2)、成分(3)、成分(4)、成分(5)之溶液。 [圖2]分別係表1~4之成分(1)的MZY-500SHE(TAYCA公司製)、成分(2)的FINEX-52W-LP2(堺化學工業公司製)、成分(4)的MZ-500(TAYCA公司製)之透過型電子顯微鏡(H-7650，日立高科技公司製)觀察之圖像(測定條件：加速電壓80KV)。[Figure 1] For 40g of water/ethanol mixed solvent (mass ratio water: ethanol = 3:1), 0.1g of components (1) to (5) in Tables 1 to 4 are weighed to become 0.25% by mass. Just after weighing it, mix it with an oscillator YS-8D (manufactured by YAYOI) at 250 times/min for 30 seconds, and put 3.5g in a plastic cell with a light path length of 10mm×a light path width of 10mm , Take a picture of the appearance of the solution at 3 minutes after mixing. The samples are the solutions of component (1), component (2), component (3), component (4), and component (5) from the left. [Figure 2] MZY-500SHE (manufactured by TAYCA) of component (1), FINEX-52W-LP2 (manufactured by Sakai Chemical Industry Co., Ltd.) of component (2), MZ- of component (4) 500 (manufactured by TAYCA) transmission electron microscope (H-7650, manufactured by Hitachi High-Technologies) observation image (measurement condition: acceleration voltage 80KV).

Claims (8)

一種油中水型組成物，其含有以下成分(A)~(D)； 成分(A)藉由氧化矽及疏水化處理劑進行表面處理之氧化鋅5~30質量% 成分(B)極性油 成分(C)矽氧油 成分(D)水， 成分(A)係於水/乙醇溶劑(質量比 水：乙醇=3：1)中以0.25質量%混合時波長700nm的光透過率為0.8~20者， 界面活性劑之含量為1質量%以下。An oil-in-water composition, which contains the following components (A) ~ (D); Component (A) 5-30% by mass of zinc oxide surface-treated with silica and hydrophobizing treatment agent Ingredient (B) Polar oil Ingredient (C) Silicone oil Ingredient (D) water, Component (A) is a mixture of 0.25% by mass in water/ethanol solvent (mass ratio water:ethanol=3:1) with a light transmittance of 0.8-20 at 700nm wavelength, The content of the surfactant is 1% by mass or less. 如請求項1之油中水型組成物，其中前述油中水型組成物係皮克林(Pickering)乳液。The water-in-oil composition according to claim 1, wherein the water-in-oil composition is Pickering emulsion. 如請求項1或2之油中水型組成物，其中前述成分(B)之含量為5~30質量%。Such as the water-in-oil composition of claim 1 or 2, wherein the content of the aforementioned component (B) is 5-30% by mass. 如請求項1至3中任一項之油中水型組成物，其中前述成分(B)及前述成分(C)之含有質量比例(B)/(C)為0.1~8。Such as the water-in-oil composition of any one of claims 1 to 3, wherein the content ratio (B)/(C) of the aforementioned component (B) and the aforementioned component (C) is 0.1-8. 如請求項1至4中任一項之油中水型組成物，其中前述油中水型組成物之乳化滴的平均粒徑為10~500μm。The water-in-oil composition according to any one of claims 1 to 4, wherein the average particle size of the emulsified droplets of the water-in-oil composition is 10 to 500 μm. 如請求項1至5中任一項之油中水型組成物，其中作為前述成分(B)，含有於25℃下之液狀極性油與於25℃下之固形極性油。The water-in-oil composition according to any one of claims 1 to 5, wherein as the aforementioned component (B), a liquid polar oil at 25°C and a solid polar oil at 25°C are contained. 如請求項1至6中任一項之油中水型組成物，其中水相與油相之含有質量比例(水相)/(油相)為0.3~5。Such as the water-in-oil composition of any one of claims 1 to 6, wherein the mass ratio of the water phase to the oil phase (water phase)/(oil phase) is 0.3-5. 如請求項1至7中任一項之油中水型組成物，其中水相與前述成分(A)之含有質量比例(水相)/(A)為0.75~10。Such as the water-in-oil composition of any one of claims 1 to 7, wherein the mass ratio (water phase)/(A) of the water phase to the aforementioned component (A) is 0.75-10.

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