TWI672152B - Oil-in-water emulsion composition - Google Patents

Oil-in-water emulsion composition Download PDF

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TWI672152B
TWI672152B TW104109595A TW104109595A TWI672152B TW I672152 B TWI672152 B TW I672152B TW 104109595 A TW104109595 A TW 104109595A TW 104109595 A TW104109595 A TW 104109595A TW I672152 B TWI672152 B TW I672152B
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oil
acid
poe
allantoin
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TW104109595A
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TW201620484A (en
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五十嵐啟二
田中章博
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日商高絲股份有限公司
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/466Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/007Preparations for dry skin

Abstract

本發明之課題在於提供一種化妝料或皮膚外用劑,其係含有尿囊素之pH值3~6之水中油型乳化組合物,且其無低溫下之尿囊素之結晶析出之問題而乳化穩定性優異。本發明之水中油型乳化組合物係用以用作化妝料或皮膚外用劑者,其含有成分(a)尿囊素、成分(b)長鏈醯基甲基牛磺酸鹽、及成分(c)多元醇,較佳為成分(a)相對於成分(c)之含有質量比率為0.002~0.05,進而較佳為(b)之含量為0.2~3%,更佳為含有聚氧伸烷基加成甘油、聚氧伸烷基加成二甘油作為成分(d),且於25℃下pH值為3~6。 An object of the present invention is to provide a cosmetic or skin external preparation comprising an oil-in-water emulsion composition having a pH of 3 to 6 of allantoin, which is emulsified without the problem of crystal precipitation of allantoin at a low temperature. Excellent stability. The oil-in-water emulsion composition of the present invention is used as a cosmetic or external preparation for skin, which comprises the component (a) allantoin, the component (b) long-chain mercaptomethyltaurate, and the component ( c) the polyol, preferably having a mass ratio of the component (a) to the component (c) of 0.002 to 0.05, more preferably (b) of 0.2 to 3%, more preferably containing polyoxyalkylene The base is added to glycerin, polyoxyalkylene alkyl diglyceride as component (d), and has a pH of 3-6 at 25 °C.

Description

水中油型乳化組合物 Oil-in-water emulsion composition

本發明係關於一種包含尿囊素、長鏈醯基甲基牛磺酸鹽及多元醇、用以用作化妝料或皮膚外用劑之水中油型乳化組合物,更詳細而言,係關於防止尿囊素之結晶析出、且兼具製劑之穩定性之水中油型乳化化妝料或皮膚外用劑。 The present invention relates to an oil-in-water emulsion composition comprising allantoin, long-chain mercaptomethyltaurate and a polyhydric alcohol for use as a cosmetic or external preparation for skin, and more particularly, to prevent An oil-in-water emulsion cosmetic or an external preparation for skin which precipitates crystals of allantoin and which has the stability of the preparation.

尿囊素具有細胞增生作用或消炎作用,於化妝料領域以皮膚粗糙改善等為目的而被廣泛使用。然而,已知尿囊素若pH值超過6則會發生水解(參照專利文獻1),為了確保穩定性,必須在pH值6以下含有尿囊素。又,亦存在如下問題:尿囊素自身對水之溶解性較低,尤其是於低溫下容易析出結晶。 Allantoin has a cell proliferative action or an anti-inflammatory action, and is widely used for the purpose of improving skin roughness in the field of cosmetic materials. However, it is known that allantoin is hydrolyzed when the pH exceeds 6 (refer to Patent Document 1), and in order to ensure stability, it is necessary to contain allantoin at a pH of 6 or less. Further, there is also a problem that allantoin itself has low solubility in water, and is particularly likely to precipitate crystals at a low temperature.

另一方面,作為水中油型乳化組合物而研究有使用各種界面活性劑之乳化物,但於pH值6以下之酸性區域中,乳化滴容易凝聚,而難以確保良好之乳化狀態或經時穩定性。 On the other hand, as an oil-in-water emulsion composition, an emulsion using various surfactants has been studied, but in an acidic region having a pH of 6 or less, the emulsified droplets tend to aggregate, and it is difficult to ensure a good emulsified state or stabilized over time. Sex.

作為含尿囊素之組合物,已知有:調配有長鏈醯基烷基牛磺酸鹽型陰離子性界面活性劑之三乙醇胺鹽、或醚羧酸型陰離子性界面活性劑之三乙醇胺鹽、尿素、尿囊素等而高溫下或光照射下之長期保存穩定性良好之清潔劑(參照專利文獻2);將包含尿囊素、蜂蠟及月桂基硫酸鈉等陰離子界面活性劑之乳化系調整為pH值3~6之水中油型乳化組合物(參照專利文獻3);及調配有甘草次酸、單脂肪酸聚乙二醇酯、月桂醯甲基牛磺酸鈉、尿囊素等而抗炎症效果提高之外用組合 物(參照專利文獻4)。此外,已知有含有高級醇、長鏈醯基磺酸鹽型陰離子性界面活性劑及傳明酸、且pH值3~6之皮膚外用劑(參照專利文獻5)。 As a composition containing allantoin, a triethanolamine salt prepared with a long-chain mercaptoalkyl taurate type anionic surfactant or a triethanolamine salt of an ether carboxylic acid type anionic surfactant is known. A cleaning agent having good long-term storage stability under high temperature or light irradiation, such as urea or allantoin (refer to Patent Document 2); an emulsifying system containing an anionic surfactant such as allantoin, beeswax, and sodium lauryl sulfate The oil-type emulsified composition adjusted to a pH of 3 to 6 (refer to Patent Document 3); and the glycyrrhetinic acid, the mono-fatty acid polyethylene glycol ester, the lauryl methyl taurate, the allantoin, etc. Anti-inflammatory effect (refer to Patent Document 4). Further, an external preparation for skin containing a higher alcohol, a long-chain mercaptosulfonate-type anionic surfactant, and a tranexamic acid and having a pH of 3 to 6 is known (see Patent Document 5).

[專利文獻1]日本專利特開2013-1651號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-1651

[專利文獻2]日本專利特開平10-36886號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 10-36886

[專利文獻3]日本專利特表2003-505404號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2003-505404

[專利文獻4]日本專利特開2012-144490號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2012-144490

[專利文獻5]日本專利特開2011-84551號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-84551

本發明之課題在於提供一種含有尿囊素、並且尤其是無低溫下之結晶析出、尿囊素可穩定地存在且即便於pH值6以下之條件下經時穩定性亦良好的作為水中油型乳化組合物的化妝料或皮膚外用劑。 An object of the present invention is to provide an oil-in-water type which contains allantoin and, in particular, crystal precipitation without low temperature, and allantoin can be stably present and has good stability over time even under a pH of 6 or less. A cosmetic or skin external preparation for emulsifying the composition.

本發明者等人為了抑制尿囊素於低溫下之結晶析出、且確保pH值6以下之乳化穩定性而進行了努力研究,結果發現,藉由將尿囊素與多元醇組合,而尿囊素與多元醇之相互作用較尿囊素彼此之相互作用優先起作用,藉此容易維持尿囊素之水合,故而可顯著地降低結晶析出。又,亦獲得了如下見解:關於該效果,藉由將聚氧伸烷基加成甘油與聚氧伸烷基加成二甘油組合而效果進一步提高。進而發現,若使用長鏈醯基甲基牛磺酸鹽作為界面活性劑,則即便於pH值3~6之低pH值區域亦可獲得穩定性良好之水中油型乳化物,不僅如此,藉由與尿囊素之離子性相互作用,亦可協同地抑制結晶析出;基於該等見解以至完成本發明。 The inventors of the present invention have diligently studied to suppress the precipitation of allantoin at a low temperature and to ensure the emulsion stability of pH 6 or less, and as a result, it has been found that the allantoin is combined with the polyol and the allantoin The interaction between the element and the polyol preferentially acts on the interaction of the allantoin with each other, whereby the hydration of the allantoin is easily maintained, so that the crystallization is remarkably lowered. Further, the following findings have been obtained: With regard to this effect, the effect is further improved by combining a polyoxyalkylene group-added glycerin and a polyoxyalkylene group-added diglycerin. Further, it has been found that when a long-chain mercaptomethyltaurate is used as a surfactant, an oil-in-water emulsion having good stability can be obtained even in a low pH region of pH 3 to 6, and not only The ionic interaction with allantoin can also synergistically inhibit crystallization; based on these findings, the present invention has been completed.

即,本發明提供[1]一種用以用作化妝料或皮膚外用劑之水中油型乳化組合物,其含有成分(a)尿囊素、成分(b)長鏈醯基甲基牛磺酸 鹽、及成分(c)多元醇,且於25℃下pH值為3~6。進而,本發明提供[2]如上述[1]之水中油型乳化組合物,其特徵在於成分(a)相對於成分(c)之含有質量比率為0.002~0.05。進而,本發明提供[3]如上述[1]及[2]中任一項之水中油型乳化組合物,其特徵在於成分(b)之含量為0.2~3質量%。又,本發明提供[4]如上述[1]至[3]中任一項之水中油型乳化組合物,其特徵在於成分(c)係選自丙二醇、1,3-丁二醇、甘油、二丙二醇、二甘油、聚乙二醇、山梨糖醇、麥芽糖醇中之1種或2種以上;且提供[5]水中油型乳化組合物,其含有聚氧伸烷基加成甘油、聚氧伸烷基加成二甘油作為成分(d)。 That is, the present invention provides [1] an oil-in-water emulsion composition for use as a cosmetic or an external preparation for skin, which comprises the component (a) allantoin, component (b) long-chain mercaptomethyl taurine Salt, and component (c) polyol, and the pH is 3-6 at 25 °C. Further, the present invention provides [2] the oil-in-water emulsion composition according to [1] above, characterized in that the content ratio of the component (a) to the component (c) is 0.002 to 0.05. Further, the present invention provides the oil-in-water emulsion composition according to any one of the above [1], wherein the content of the component (b) is 0.2 to 3% by mass. The present invention provides the oil-in-water emulsion composition according to any one of the above [1] to [3] wherein the component (c) is selected from the group consisting of propylene glycol, 1,3-butylene glycol, and glycerin. And one or more of dipropylene glycol, diglycerin, polyethylene glycol, sorbitol, and maltitol; and provide [5] an oily emulsion type composition containing polyoxyalkylene alkyl addition glycerin, Polyoxyalkylene addition diglycerin is used as component (d).

本發明可提供一種尿囊素之經時穩定性良好、尤其無低溫下之結晶析出的水中油型乳化組合物。進而,本發明可提供一種即便於尿囊素不會發生水解之pH值6以下之低pH值區域,亦無分離或乳化滴之凝聚、合併等劣化而乳化狀態或經時穩定性良好的作為水中油型乳化組合物的化妝料或皮膚外用劑。 The present invention can provide an oil-in-water emulsion composition having good stability over time, particularly no precipitation of crystals at low temperatures. Further, according to the present invention, it is possible to provide a low pH region having a pH value of 6 or less which does not cause hydrolysis of allantoin, and there is no deterioration such as aggregation or aggregation of separation or emulsified droplets, and the emulsified state or the stability with time is good. A cosmetic or skin external preparation of an oily emulsified composition in water.

以下,對本發明進行詳細敍述。再者,於本說明書中,於使用~表示數值範圍時,其範圍設為包含兩端之數值。 Hereinafter, the present invention will be described in detail. Furthermore, in the present specification, when the range of values is used, the range is set to include the values of both ends.

本發明所使用之成分(a)之尿囊素之化學名為5-脲基乙內醯脲,已知其使細胞之功能活化而有細胞增生促進、抗炎症、止血、殺菌等作用效果。本發明中之尿囊素並未特別限定,可任意地選擇並使用通常化妝料或皮膚外用劑所使用者。 The chemical name of the allantoin of the component (a) used in the present invention is 5-ureido-sodium carbazide, which is known to activate the function of cells and has an effect of promoting cell proliferation, anti-inflammatory, hemostasis, sterilization, and the like. The allantoin in the present invention is not particularly limited, and a user of a usual cosmetic or external preparation for skin can be arbitrarily selected and used.

本發明之成分(a)尿囊素之含量並未特別限定,就皮膚粗糙改善效果及結晶析出抑制之觀點而言,於水中油型乳化組合物總量中較佳 為0.05~0.5質量%(以下,簡稱為「%」),進而較佳為0.05~0.3%。 The content of the component (a) allantoin of the present invention is not particularly limited, and is preferably in the total amount of the oily emulsified composition in water from the viewpoint of the skin roughness improving effect and the inhibition of crystal precipitation. It is 0.05 to 0.5% by mass (hereinafter referred to as "%"), and more preferably 0.05 to 0.3%.

本發明所使用之成分(b)之長鏈醯基甲基牛磺酸鹽為陰離子性界面活性劑,其於低pH值區域中之乳化穩定性優異,並且藉由與尿囊素之離子性相互作用而發揮結晶化抑制效果。於化妝品領域中,已知有各種化學結構之陰離子性界面活性劑,但不適合低pH值區域中之乳化或尿囊素之結晶化抑制效果不充分,於本發明中,選擇長鏈醯基甲基牛磺酸鹽作為滿足該兩種效果者。 The long-chain mercaptomethyltaurine salt of the component (b) used in the present invention is an anionic surfactant, which is excellent in emulsion stability in a low pH region, and is ionic with allantoin. The crystallization effect is exerted by interaction. In the field of cosmetics, anionic surfactants of various chemical structures are known, but they are not suitable for emulsification in low pH regions or insufficient crystallization inhibition effects of allantoin. In the present invention, long chain thiol groups are selected. Base taurates are used as those satisfying both effects.

作為本發明所使用之成分(b)之長鏈醯基甲基牛磺酸鹽,可任意使用通常化妝料或皮膚外用劑所使用之長鏈醯基甲基牛磺酸鹽。例如,可列舉N-硬脂醯基-N-甲基牛磺酸鈉、N-肉豆蔻醯基-N-甲基牛磺酸鈉、椰子油脂肪酸甲基牛磺酸鈉、月桂基甲基牛磺酸鈉等,可使用1種或2種以上。 As the long-chain mercaptomethyltaurate salt of the component (b) used in the present invention, a long-chain mercaptomethyltaurine salt which is usually used for a cosmetic or an external preparation for skin can be used arbitrarily. For example, sodium N-stearyl-N-methyltaurate, sodium N-myristyl-N-methyltaurate, sodium coconut oil fatty acid methyl taurate, lauryl methyl One or two or more kinds of sodium taurate or the like can be used.

本發明之成分(b)長鏈醯基甲基牛磺酸鹽之含量並未特別限定,就尿囊素之結晶析出抑制及乳化穩定性之觀點而言,於水中油型乳化組合物總量中,較佳為0.2~3.0%,進而較佳為0.3~2.0%。 The content of the component (b) long-chain mercaptomethyltaurate salt of the present invention is not particularly limited, and the total amount of the oil-type emulsified composition in water is from the viewpoint of inhibition of crystallization of the allantoin and emulsion stability. Preferably, it is 0.2 to 3.0%, and more preferably 0.3 to 2.0%.

本發明所使用之成分(c)之多元醇維持尿囊素之水合,尤其顯著地抑制低溫下之尿囊素之結晶化。作為本發明所使用之成分(c)之多元醇,可任意使用通常化妝料所使用之多元醇。例如可列舉:二元醇(例如乙二醇、丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、2-丁烯-1,4-二醇、己二醇、辛二醇等);三元醇(例如甘油、三羥甲基丙烷等);四元醇(例如1,2,6-己三醇等季戊四醇等);五元醇(例如木糖醇等);六元醇(例如山梨糖醇、甘露醇等);多元醇聚合物(例如二乙二醇、二丙二醇、三乙二醇、聚丙二醇、四乙二醇、二甘油、聚乙二醇、三甘油、四甘油、聚甘油等);及糖醇(例如山梨糖醇、麥芽糖醇、麥芽三糖、甘露醇、蔗糖、赤蘚醇、葡萄糖、果糖、澱粉分解糖、麥芽糖、木糖、澱粉分解糖還 原醇等),可使用1種或2種以上。 The polyol of the component (c) used in the present invention maintains the hydration of allantoin, and particularly inhibits the crystallization of allantoin at a low temperature. As the polyol of the component (c) used in the present invention, a polyol which is usually used for a cosmetic can be used arbitrarily. For example, a glycol (for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2, 3-butyl) Glycol, 1,5-pentanediol, 2-butene-1,4-diol, hexanediol, octanediol, etc.); triol (eg glycerol, trimethylolpropane, etc.); quaternary Alcohol (e.g., pentaerythritol such as 1,2,6-hexanetriol, etc.); pentavalent alcohol (e.g., xylitol, etc.); hexahydric alcohol (e.g., sorbitol, mannitol, etc.); polyol polymer (e.g., diethyl Glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerol, etc.; and sugar alcohols (eg sorbitol, maltitol, Maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch-decomposing sugar, maltose, xylose, starch-decomposing sugar As the raw alcohol or the like, one type or two or more types can be used.

上述多元醇之中,就水合能力與使用感之觀點而言,較佳為丙二醇、1,3-丁二醇、甘油、二丙二醇、二甘油、聚乙二醇、山梨糖醇、麥芽糖醇,進而較佳為1,3-丁二醇、丙二醇、甘油、聚乙二醇。 Among the above polyols, from the viewpoints of hydration ability and feeling of use, propylene glycol, 1,3-butylene glycol, glycerin, dipropylene glycol, diglycerin, polyethylene glycol, sorbitol, and maltitol are preferable. Further, preferred are 1,3-butanediol, propylene glycol, glycerin, and polyethylene glycol.

本發明之成分(c)多元醇之含量並未特別限定,於水中油型乳化組合物總量中較佳為4~36%,進而較佳為10~30%,進而較佳為12~25%。又,就尿囊素之結晶析出抑制效果及乳化穩定性之觀點而言,成分(a)相對於成分(c)之含有質量比率較佳為0.002~0.05,進而較佳為0.004~0.04。 The content of the component (c) of the present invention is not particularly limited, and is preferably from 4 to 36%, more preferably from 10 to 30%, still more preferably from 12 to 25, based on the total amount of the oily emulsion composition in water. %. In addition, the mass ratio of the component (a) to the component (c) is preferably from 0.002 to 0.05, and more preferably from 0.004 to 0.04, from the viewpoint of the effect of suppressing the crystal precipitation of allantoin and the emulsion stability.

本發明之水中油型乳化組合物於25℃下之pH值為3~6。pH值係以最終之水中油型乳化組合物之pH值成為上述範圍之方式適當添加pH值調整劑進行調整。作為pH值調整劑,例如可列舉:乳酸、檸檬酸、乙醇酸、琥珀酸、酒石酸、dl-蘋果酸、碳酸鉀、碳酸氫鈉、碳酸氫銨等,可使用1種或2種以上。又,調整方法亦並未特別限定,可溶解於製造水中油型乳化組合物之步驟之乳化水相或後添加水中,亦可不溶解而添加。又,亦可於製造水中油型乳化組合物後,一面確認pH值一面添加。 The oil-in-water emulsion composition of the present invention has a pH of 3 to 6 at 25 °C. The pH value is adjusted by appropriately adding a pH adjuster so that the pH of the final oil-based emulsified composition becomes the above range. Examples of the pH adjusting agent include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogencarbonate, and ammonium hydrogencarbonate. One type or two or more types may be used. Further, the adjustment method is not particularly limited, and it can be dissolved in the emulsified aqueous phase in the step of producing the oil-based emulsified composition in water or added to the water, or added without being dissolved. Further, after the oily emulsified composition in water is produced, it can be added while confirming the pH.

於本發明中,若pH值未達3,則有乳化穩定性與對皮膚之安全性之顧慮,若pH值超過6,則發生尿囊素之水解,而難以長期且穩定地獲得該成分之皮膚粗糙改善效果或抗炎症效果。 In the present invention, if the pH value is less than 3, there is a concern of emulsion stability and safety to the skin. If the pH exceeds 6, hydrolysis of allantoin occurs, and it is difficult to obtain the component in a long-term and stable manner. Rough skin improvement or anti-inflammatory effect.

於本發明中,為了製成水中油型乳化組合物,除上述各成分以外,必須含有水及油性成分。 In the present invention, in order to prepare the oil-in-water emulsion composition, water and oily components are required in addition to the above components.

作為水,只要為普通化妝料製造所使用之水,則並未特別限定,可列舉:普通水、純化水、溫泉水、深層水或熏衣草水、玫瑰水、橙花水等源自植物之水蒸氣蒸餾水等,可使用1種或2種以上。 The water is not particularly limited as long as it is used for the manufacture of ordinary cosmetic materials, and examples thereof include ordinary water, purified water, hot spring water, deep water or lavender water, rose water, orange blossom water, and the like. One type or two or more types may be used for the steam distilled water or the like.

本發明所使用之油性成分只要為普通化妝料或皮膚外用劑所使 用之油劑,則並未特別限定,可不論動物油、植物油、合成油等起源或固形油、半固形油、液體油、揮發性油等性狀而任意地選擇並使用1種或2種以上。作為油性成分,可列舉:烴類、油脂類、蠟類、氫化油類、酯油類、脂肪酸類、高級醇類、聚矽氧油類、氟系油類、羊毛脂衍生物類等油劑。若具體地例示,則可列舉:液態石蠟、角鯊烷、凡士林、聚異丁烯、聚丁烯、石蠟、地蠟、微晶蠟、費托(Fischer-Tropsch)蠟等烴類;木蠟、橄欖油、蓖麻油、貂油、夏威夷果油等油脂類;褐煤蠟、蜂蠟、巴西棕櫚蠟、堪地里拉蠟、鯨蠟等蠟類;異辛酸鯨蠟酯、肉豆蔻酸異丙酯、棕櫚酸異丙酯、肉豆蔻酸辛基十二烷基酯、三辛酸甘油酯、二異硬脂酸二甘油酯、三異硬脂酸二甘油酯、三山萮酸甘油酯、季戊四醇松脂酸酯、新戊二醇二辛酸酯、膽固醇脂肪酸酯、N-月桂醯-L-麩胺酸二(膽固醇基、山萮基、辛基十二烷基)酯等酯類;硬脂酸、月桂酸、肉豆蔻酸、山萮酸、異硬脂酸、油酸、松脂酸、12-羥基硬脂酸等脂肪酸類;硬酯醇、鯨蠟醇、鯨蠟硬脂醇、肉豆蓋醇、月桂醇、油醇、異硬脂醇、山萮醇等高級醇類;低聚合度二甲基聚矽氧烷、高聚合度二甲基聚矽氧烷、甲基苯基聚矽氧烷、十甲基環五矽氧烷、八甲基環四矽氧烷、氟改性聚矽氧等聚矽氧類;全氟聚醚、全氟癸烷、全氟辛烷等氟系油劑類;及羊毛脂、乙酸羊毛脂、羊毛脂脂肪酸異丙酯、羊毛醇等羊毛脂衍生物類等,可將該等使用1種或2種以上。又,本發明所使用之油性成分之量於水中油型乳化組合物總量中,較佳為0.1~10%,進而較佳為0.5~8%,尤佳為1.5~6%。 The oily component used in the present invention may be any ordinary cosmetic or external preparation for skin. The oil agent to be used is not particularly limited, and may be arbitrarily selected and used in one or two or more types depending on the nature of the animal oil, the vegetable oil, the synthetic oil, or the like, the solid oil, the semi-solid oil, the liquid oil, and the volatile oil. Examples of the oil component include oils such as hydrocarbons, oils and fats, waxes, hydrogenated oils, ester oils, fatty acids, higher alcohols, polyoxyxides, fluorine-based oils, and lanolin derivatives. . Specific examples thereof include hydrocarbons such as liquid paraffin, squalane, petrolatum, polyisobutylene, polybutene, paraffin wax, ceresin wax, microcrystalline wax, and Fischer-Tropsch wax; wood wax and olive oil; Oils such as oil, castor oil, eucalyptus oil, macadamia oil; waxes such as montan wax, beeswax, carnauba wax, canary wax, and cetyl wax; cetyl isooctanoate, isopropyl myristate, palmitic acid Isopropyl ester, octyl dodecyl myristate, tricaprylin, diisostearic acid diglyceride, triisostearic acid diglyceride, tribehenic acid glyceride, pentaerythritol rosinate, neopentyl Esters such as diol dicaprylate, cholesterol fatty acid ester, N-lauroside-L-glutamic acid bis(cholesteryl, behenyl, octyldodecyl) ester; stearic acid, lauric acid, Fatty acids such as myristic acid, behenic acid, isostearic acid, oleic acid, rosin acid, 12-hydroxystearic acid; stearyl alcohol, cetyl alcohol, cetearyl alcohol, myristyl alcohol, lauryl alcohol Higher alcohols such as oleyl alcohol, isostearyl alcohol, behenyl alcohol; low polymerization degree dimethyl polyoxane, high polymerization degree dimethyl polyoxyl , methylphenyl polyoxyalkylene, decamethylcyclopentaoxane, octamethylcyclotetraoxane, fluorine-modified polyfluorene oxide, etc.; perfluoropolyether, perfluorodecane, Fluorine-based oils such as perfluorooctane; and lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl ester, and lanolin, etc., may be used alone or in combination of two or more. Further, the amount of the oil component used in the present invention is preferably from 0.1 to 10%, more preferably from 0.5 to 8%, even more preferably from 1.5 to 6%, based on the total amount of the oily emulsion composition in water.

進而,於本發明中,若含有聚氧伸烷基加成甘油、聚氧伸烷基加成二甘油作為成分(d),則成分(a)之結晶析出抑制效果進而增高,較理想。所謂聚氧伸烷基加成甘油、聚氧伸烷基加成二甘油,係對甘油或二甘油加成聚合環氧烷而成者。環氧烷之碳數並未特別限定,較 佳為2~4,進而較佳為2~3。又,環氧烷之聚合度並未特別限定,較佳為3~30,進而較佳為9~26。環氧烷可使用2種以上,於此情形時,可使用嵌段狀、無規狀等任意地聚合而成者。 Furthermore, in the present invention, when the polyoxyalkylene group-added glycerin and the polyoxyalkylene group-added diglycerin are contained as the component (d), the effect of suppressing the crystallization of the component (a) is further increased, which is preferable. The polyoxyalkylene group-added glycerin and the polyoxyalkylene group-added diglycerin are obtained by adding propylene oxide or diglycerin to form an alkylene oxide. The carbon number of the alkylene oxide is not particularly limited, Preferably, it is 2 to 4, and more preferably 2 to 3. Further, the degree of polymerization of the alkylene oxide is not particularly limited, but is preferably 3 to 30, and more preferably 9 to 26. Two or more types of alkylene oxides can be used, and in this case, a block form, a random form, or the like can be arbitrarily polymerized.

作為成分(d),具體而言,例如可列舉:聚氧乙烯(26)甘油(銷售名:LIPONIC EG-1,LIPO CHEMICALS INC公司製造)、聚氧丙烯(9)二甘油(銷售名:SY-DP9,阪本藥品工業公司製造)、聚氧乙烯(24)聚氧丙烯(24)甘油醚(銷售名:Unilube 50TG-32,日油股份有限公司製造)、聚氧丁烯(3)聚氧乙烯(8)聚氧丙烯(5)甘油醚(銷售名:WILBRIDE S-753,日油股份有限公司製造)等,可較佳地使用。 Specific examples of the component (d) include polyoxyethylene (26) glycerin (sale name: LIPONIC EG-1, manufactured by LIPO CHEMICALS INC), and polyoxypropylene (9) diglycerin (sales name: SY) -DP9, manufactured by Sakamoto Pharmaceutical Co., Ltd.), polyoxyethylene (24) polyoxypropylene (24) glyceryl ether (sale name: Unilube 50TG-32, manufactured by Nippon Oil Co., Ltd.), polyoxybutylene (3) polyoxygen Ethylene (8) polyoxypropylene (5) glyceryl ether (trade name: WILBRIDE S-753, manufactured by Nippon Oil Co., Ltd.) or the like can be preferably used.

除上述必須成分以外,亦可於不損害本發明之效果之範圍內,作為通常化妝料所含有之成分,以不妨礙本發明之效果之範圍任意含有成分(b)以外之界面活性劑、水溶性高分子、保濕成分、紫外線吸收劑、pH值調整劑、抗氧化劑、金屬螯合劑、防腐劑、粉體、色素、香料、各種藥劑等。作為該成分,可列舉下述者。 In addition to the above-mentioned essential components, it may be a component contained in a general cosmetic, and may contain a surfactant other than the component (b) and water-soluble in a range that does not impair the effects of the present invention, within a range that does not impair the effects of the present invention. A polymer, a moisturizing component, a UV absorber, a pH adjuster, an antioxidant, a metal chelating agent, a preservative, a powder, a color, a fragrance, various chemicals, and the like. The following may be mentioned as this component.

作為成分(b)以外之陰離子性界面活性劑,例如可列舉:皂用生坯、月桂酸鈉、棕櫚酸鈉等脂肪酸皂;POE(聚氧乙烯,以下同樣)月桂基硫酸鈉等烷基醚硫酸酯鹽;月桂醯肌胺酸鈉等N-醯基肌胺酸鹽;POE油醚磷酸鈉、POE硬脂基醚磷酸鈉等磷酸酯鹽;二-2-乙基己基磺基琥珀酸鈉、單月桂醯單乙醇醯胺聚氧乙烯磺基琥珀酸鈉、月桂基聚丙二醇磺基琥珀酸鈉等磺基琥珀酸鹽;線性十二烷基苯磺酸鈉、線性十二烷基苯磺酸鉀等烷基苯磺酸鹽;N-月桂醯麩胺酸單鈉、N-硬脂醯麩胺酸二鈉、N-肉豆蔻醯-L-麩胺酸單鈉等N-醯基麩胺酸鹽;氫化椰子油脂肪酸甘油硫酸鈉等高級脂肪酸酯硫酸酯鹽;土耳其紅油等硫氧化物;及POE烷基醚羧酸鹽、POE烷基烯丙基醚羧酸鹽、α-烯烴磺酸鹽、高級脂肪酸酯磺酸鹽、二級醇硫酸酯鹽、高級脂肪酸烷醇醯胺硫酸酯鹽、月桂醯單乙醇醯胺琥珀酸鹽、N-棕櫚醯天冬胺酸鹽、酪蛋白 鈉等,可使用1種或2種以上。 Examples of the anionic surfactant other than the component (b) include a fatty acid soap such as a green body for soap, sodium laurate or sodium palmitate, and an alkyl ether such as sodium lauryl sulfate as POE (polyoxyethylene, the same applies hereinafter). Sulfate salt; N-mercapto sarcosinate such as sodium laurate; sodium phosphate such as POE oil ether sodium phosphate, POE stearyl ether sodium phosphate; sodium di-2-ethylhexyl sulfosuccinate , succinic acid monoethanolamine polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, sulfosuccinate; linear sodium dodecyl benzene sulfonate, linear dodecyl benzene sulfonate Alkylbenzenesulfonate such as potassium acid; N-lauric acid glutamic acid monosodium, N-stearyl glutamate disodium, N-myristyl-L-glutamic acid monosodium, etc. Amino acid salt; higher fatty acid ester sulfate salt such as hydrogenated coconut oil fatty acid sodium glycerate; sulfur oxide such as Turkish red oil; and POE alkyl ether carboxylate, POE alkyl allyl ether carboxylate, α- Olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate, higher fatty acid alkanolamine sulfate, lauryl monoethanol amide amber Salts, N- palmitoyl acyl aspartic acid salt, casein One type or two or more types can be used for sodium or the like.

作為親油性非離子界面活性劑,例如可列舉:山梨糖醇酐單油酸酯、山梨糖醇酐單異硬脂酸酯、山梨糖醇酐單月桂酸酯、山梨糖醇酐單棕櫚酸酯、山梨糖醇酐單硬脂酸酯、山梨糖醇酐倍半油酸酯、山梨糖醇酐三油酸酯、二甘油山梨糖醇酐五-2-乙基己酸酯、二甘油山梨糖醇酐四-2-乙基己酸酯等山梨糖醇酐脂肪酸酯類;甘油單棉籽油脂肪酸酯、甘油單芥酸酯、甘油倍半油酸酯、甘油單硬脂酸酯、甘油α,α'-油酸焦麩胺酸酯、單硬脂酸甘油蘋果酸等甘油聚甘油脂肪酸類;丙二醇單硬脂酸酯等丙二醇脂肪酸酯類;及氫化蓖麻油衍生物等,可使用1種或2種以上。 Examples of the lipophilic nonionic surfactant include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, and sorbitan monopalmitate. , sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycol sorbitan penta-2-ethylhexanoate, diglycerin sorbose Sorbitol fatty acid esters such as alcoholic anhydride tetra-2-ethylhexanoate; glycerol monocotton seed oil fatty acid ester, glycerol monoerucate, glycerol sesquioleate, glyceryl monostearate, glycerol alpha , glycerol polyglycerol fatty acid such as α'-oleic acid glutamate, monostearic acid glyceryl malic acid; propylene glycol fatty acid ester such as propylene glycol monostearate; and hydrogenated castor oil derivative, etc. Or two or more.

作為親水性非離子界面活性劑,例如可列舉:POE山梨糖醇酐單油酸酯(oleate)、POE山梨糖醇酐單硬脂酸酯、POE山梨糖醇酐單油酸酯(olete)、POE山梨糖醇酐四油酸酯等POE山梨糖醇酐脂肪酸酯類;POE山梨糖醇單月桂酸酯、POE山梨糖醇單油酸酯、POE山梨糖醇五油酸酯、POE山梨糖醇單硬脂酸酯等POE山梨糖醇脂肪酸酯類;POE甘油單硬脂酸酯、POE甘油單異硬脂酸酯、POE甘油三異硬脂酸酯等POE甘油脂肪酸酯類;POE單油酸酯、POE二硬脂酸酯、POE單二油酸酯、二硬脂酸乙二醇等POE脂肪酸酯類;POE月桂基醚、POE油基醚、POE硬脂基醚、POE山萮基醚、POE2-辛基十二烷基醚、POE二氫膽固醇醚等POE烷基醚類;POE辛基苯基醚、POE壬基苯基醚、POE二壬基苯基醚等POE烷基苯醚類;POE‧POP鯨蠟基醚、POE‧POP2-癸基十四烷基醚、POE‧POP單丁基醚、POE‧POP氫化羊毛脂、POE‧POP甘油醚等POE‧POP烷基醚類;Tetronic等四POE‧四POP乙二胺縮合物類;POE蓖麻油、POE氫化蓖麻油、POE氫化蓖麻油單異硬脂酸酯、POE氫化蓖麻油三異硬脂酸酯、POE氫化蓖麻油單焦麩胺酸單異硬脂酸二酯、POE氫化蓖麻油馬來酸等POE蓖麻油氫化 蓖麻油衍生物;POE山梨糖醇蜂蠟等POE蜂蠟、羊毛脂衍生物;椰子油脂肪酸二乙醇醯胺、月桂酸單乙醇醯胺、脂肪酸異丙醇醯胺等烷醇醯胺;及POE丙二醇脂肪酸酯、POE烷基胺、POE脂肪醯胺、蔗糖脂肪酸酯、POE壬基苯基甲醛縮合物、烷基乙氧基二甲基氧化胺、三油基磷酸等,可使用1種或2種以上。 Examples of the hydrophilic nonionic surfactant include POE sorbitan monooleate (oleate), POE sorbitan monostearate, and POE sorbitan monooleate (olete). POE sorbitan fatty acid esters such as POE sorbitan tetraoleate; POE sorbitol monolaurate, POE sorbitol monooleate, POE sorbitol pentoxide, POE sorbitol POE sorbitan fatty acid esters such as monostearate; POE glycerol monostearate, POE glycerol monoisostearate, POE glyceryl triisostearate, etc. POE glycerol fatty acid ester; POE monooleic acid POE fatty acid esters such as ester, POE distearate, POE mono-dioleate, ethylene glycol distearate; POE lauryl ether, POE oleyl ether, POE stearyl ether, POE behenyl ether POE alkyl ethers such as POE2-octyl lauryl ether and POE dihydrocholesterol ether; POE alkyl phenyl ethers such as POE octyl phenyl ether, POE nonyl phenyl ether, POE dinonyl phenyl ether POE‧POP alkyl ether, POE‧POP cetyl ether, POE‧POP2-decyltetradecyl ether, POE‧POP monobutyl ether, POE‧POP hydrogenated lanolin, POE‧POP glyceryl ether Class; Tetronic and other four POE‧ four POP ethylene diamine condensates; POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil triisostearate, POE hydrogenated hydrazine Sesame oil monopoly glutamic acid monoisostearic acid diester, POE hydrogenated castor oil maleic acid and other POE castor oil hydrogenation Castor oil derivatives; POE beeswax, lanolin derivatives such as POE sorbitol beeswax; coconut oil fatty acid diethanolamine, lauric acid monoethanolamine, fatty acid isopropanolamine and the like, and POE propylene glycol fat Acid ester, POE alkylamine, POE fatty decylamine, sucrose fatty acid ester, POE nonylphenyl formaldehyde condensate, alkyl ethoxy dimethyl amine oxide, trioleyl phosphate, etc., can be used in one or two More than one species.

作為兩性界面活性劑,例如可列舉:2-烷基-N-羧基甲基-N-羥基乙基咪唑啉鎓甜菜鹼、月桂基二甲基胺基乙酸甜菜鹼、烷基甜菜鹼、醯胺甜菜鹼、磺基甜菜鹼等甜菜鹼系界面活性劑;及卵磷脂等,可使用1種或2種以上。 Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl dimethylaminoacetate betaine, alkyl betaines, and decylamine. A betaine-based surfactant such as betaine or sulphobetaine; and lecithin or the like may be used alone or in combination of two or more.

作為陽離子性界面活性劑,例如可列舉:氯化硬脂基三甲基銨、氯化月桂基三甲基銨等烷基三甲基銨鹽;氯化二硬脂基二甲基銨等二烷基二甲基銨鹽;氯化聚(N,N'-二甲基-3,5-亞甲基哌啶鎓)、氯化鯨蠟基吡啶鎓等烷基吡啶鎓鹽;及烷基四級銨鹽、烷基二甲基苄基銨鹽、烷基異喹啉鎓鹽、二烷基嗎啉鎓鹽、POE烷基胺、烷基胺鹽、聚胺脂肪酸衍生物、戊醇脂肪酸衍生物、氯化苄烷銨、苄索氯銨等,可使用1種或2種以上。 Examples of the cationic surfactant include an alkyltrimethylammonium salt such as stearyltrimethylammonium chloride or lauryltrimethylammonium chloride; and distearyldimethylammonium chloride; Alkyldimethylammonium salt; alkyl (pyridinium salt) such as poly(N,N'-dimethyl-3,5-methylenepiperidinium) chloride; cetylpyridinium chloride; and alkyl group Quaternary ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl isoquinolinium salt, dialkyl morpholinium salt, POE alkyl amine, alkyl amine salt, polyamine fatty acid derivative, pentanol fatty acid The derivative, the benzalkonium chloride, the benzethonium chloride, etc. may be used alone or in combination of two or more.

作為水溶性高分子,可列舉:阿拉伯膠、黃芪膠、聚半乳糖、刺槐豆膠、古亞膠、陽離子化古亞膠、刺梧桐樹膠、角叉菜膠、果膠、瓊脂、榅桲籽(榅桲)、澱粉(大米、玉米、馬鈴薯、小麥)、海藻膠(褐藻萃取物)等植物系高分子;葡聚糖、琥珀醯聚糖、普魯蘭多糖等微生物系高分子;膠原蛋白、酪蛋白、白蛋白、明膠等動物系高分子;羧基甲基澱粉、甲基羥基丙基澱粉等澱粉系高分子;甲基纖維素、硝基纖維素、乙基纖維素、甲基羥基丙基纖維素、羥基乙基纖維素、纖維素硫酸鈉、羥基丙基纖維素、陽離子化羥基乙基纖維素、羧基甲基纖維素鈉、結晶纖維素、纖維素粉末等纖維素系高分子;海藻酸鈉、丙二醇海藻酸酯等海藻酸系高分子;聚乙烯甲基醚、羧基乙烯 聚合物(CARBOPOL(銷售名)等)、烷基改性羧基乙烯聚合物(PEMULEN(銷售名)等)等乙烯系高分子;聚氧乙烯系高分子、聚氧乙烯聚氧丙烯共聚物系高分子、聚丙烯酸鈉、聚丙烯酸乙酯、聚丙烯醯胺等丙烯酸系高分子;聚伸乙亞胺、陽離子性聚合物等有機系水溶性高分子;及膨潤土、矽酸鋁鎂、合成鋰皂石、鋰膨潤石、矽酸酐等無機系水溶性高分子等,可使用1種或2種以上。 Examples of the water-soluble polymer include gum arabic, tragacanth, polygalactose, locust bean gum, guar gum, cationized guar gum, karaya gum, carrageenan, pectin, agar, and alfalfa seeds. (榅桲), plant-based polymers such as starch (rice, corn, potato, wheat), seaweed gum (hay algae extract); microbial polymers such as dextran, amber turmeric, and pullulan; collagen , animal products such as casein, albumin, gelatin; starch-based polymers such as carboxymethyl starch and methyl hydroxypropyl starch; methyl cellulose, nitrocellulose, ethyl cellulose, methyl hydroxypropyl a cellulose-based polymer such as cellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, cationized hydroxyethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, or cellulose powder; Alginic acid polymer such as sodium alginate or propylene glycol alginate; polyvinyl methyl ether, carboxyvinyl Ethylene polymer such as polymer (CARBOPOL (sale name), etc.), alkyl-modified carboxyvinyl polymer (PEMULEN (sales name), etc.); polyoxyethylene polymer, polyoxyethylene polyoxypropylene copolymer Acrylic polymers such as molecules, sodium polyacrylate, polyethyl acrylate, and polyacrylamide; organic water-soluble polymers such as polyethylenimine and cationic polymers; and bentonite, aluminum magnesium silicate, and lithium silicate soap One or two or more kinds of inorganic water-soluble polymers such as stone, lithium bentonite, and phthalic anhydride can be used.

作為保濕成分,可列舉糖類、胺基酸及其衍生物、肽類、植物萃取液等,可使用1種或2種以上。 Examples of the hydrating component include a saccharide, an amino acid and a derivative thereof, a peptide, and a plant extract, and one type or two or more types can be used.

作為糖類,可列舉:山梨糖醇、赤蘚醇、麥芽糖、麥芽糖醇、木糖醇、木糖、海藻糖、肌醇、葡萄糖、甘露醇、季戊四醇、果糖、蔗糖及其酯、糊精及其衍生物、蜂蜜、黑砂糖萃取物等。作為胺基酸類,例如可列舉:甘胺酸、丙胺酸、纈胺酸、異白胺酸、絲胺酸、蘇胺酸、天冬胺酸、麩胺酸、天冬醯胺、麩醯胺、離胺酸、羥基離胺酸、精胺酸、胱胺酸、半胱胺酸、乙醯基半胱胺酸、甲硫胺酸、苯丙胺酸、酪胺酸、脯胺酸、羥基脯胺酸、鳥胺酸、瓜胺酸、茶胺酸、肌酸、肌酸酐等。作為胺基酸衍生物,可列舉:麩胱甘肽、吡咯啶酮羧酸、N-月桂醯-L-麩胺酸二(植物固醇、2-辛基十二烷基)酯、N-月桂醯-L-麩胺酸二(膽固醇基、山萮基、辛基十二烷基)酯、N-月桂醯-L-麩胺酸二(膽固醇基、辛基十二烷基)酯、N-月桂醯-L-麩胺酸二(植物固醇、山萮基、2-辛基十二烷基)酯、N-月桂醯-L-麩胺酸二(2-辛基十二烷基)酯、N-醯基麩胺酸離胺酸縮合物等。作為肽類,可為源自動物、魚、貝、植物之任一種,具體而言,可列舉:膠原蛋白及其衍生物或其等之水解物、彈力蛋白及其衍生物或其等之水解物、角蛋白及其衍生物或其等之分解物、小麥蛋白及其衍生物或其等之水解物、大豆蛋白及其衍生物或其等之水解物等。作為植物萃取物,例如可列舉使用黃柏、黃連、紫根、芍藥、當藥、樺木、鼠尾草、枇杷、人蔘、 蘆薈、錦葵、鳶尾、葡萄、薏仁、絲瓜、百合、番紅花、川芎、生薑、小連翹、花柄花、大蒜、辣椒、陳皮、當歸、海藻等並利用水或有機溶劑適當萃取而得者。 Examples of the saccharide include sorbitol, erythritol, maltose, maltitol, xylitol, xylose, trehalose, inositol, glucose, mannitol, pentaerythritol, fructose, sucrose and esters thereof, and dextrin and the like. Derivatives, honey, black granulated sugar extracts, etc. Examples of the amino acid include glycine, alanine, lysine, isoleucine, serine, threonine, aspartic acid, glutamic acid, aspartame, and glutamine. , aminic acid, hydroxy lysine, arginine, cystine, cysteine, acetylcysteine, methionine, phenylalanine, tyrosine, valine, hydroxyguanamine Acid, ornithine, citrulline, theanine, creatine, creatinine, and the like. Examples of the amino acid derivative include glutathione, pyrrolidone carboxylic acid, N-lauroside-L-glutamic acid bis (phytosterol, 2-octyldodecyl) ester, and N- Laurel-L-glutamic acid bis(cholesteryl, behenyl, octyldodecyl) ester, N-lauroside-L-glutamic acid bis(cholesteryl, octyldodecyl) ester, N-laurel-L-glutamic acid bis (phytosterol, behenyl, 2-octyldodecyl) ester, N-lauroside-L-glutamic acid bis(2-octyldodecane Ester), N-methyl glutamic acid lysine condensate, and the like. The peptide may be derived from any one of animals, fish, shellfish, and plants, and specific examples thereof include hydrolysis of collagen, a derivative thereof, or the like thereof, hydrolyzate, a derivative thereof, or the like. a substance, a keratin and a derivative thereof or a decomposition product thereof, a wheat protein and a derivative thereof or a hydrolyzate thereof, a soy protein and a derivative thereof or a hydrolyzate thereof or the like. Examples of the plant extract include the use of cork, berberine, purple root, peony, medicine, birch, sage, scorpion, human scorpion, Aloe, mallow, iris, grape, coix seed, loofah, lily, saffron, Chuanxiong, ginger, small forsythia, stalk flower, garlic, pepper, dried tangerine peel, angelica, seaweed, etc. and extracted with water or organic solvent By.

作為紫外線吸收劑,可列舉:2-羥基-4-甲氧基二苯甲酮、2,4,6-三苯胺基-對-(羰-2'-乙基己基-1'-氧基)-1,3,5-三嗪、水楊酸-2-乙基己酯、對二羥基丙基苯甲酸乙酯、對甲氧基桂皮酸-2-乙基己酯、4-第三-4'-甲氧基二苯甲醯甲烷、2-[4-(二乙基胺基)-2-羥基苯甲醯基]苯甲酸己酯、二甲氧基亞苄基二氧雜咪唑啶丙酸2-乙基己酯、2,2'-亞甲基雙[6-(2H-苯并三唑-2基)-4-(1,1,3,3-四甲基丁基)苯酚]、(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、二甲聚矽氧烷二乙基亞苄基丙二酸酯、2-羥基-4-甲氧基二苯甲酮-5-磺酸及其鈉鹽等。 Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone and 2,4,6-triphenylamino-p-(carbonyl-2'-ethylhexyl-1'-oxy). -1,3,5-triazine, 2-ethylhexyl salicylate, ethyl p-dihydroxypropyl benzoate, 2-ethylhexyl p-methoxycinnamate, 4-third- 4'-Methoxydibenzofuranium methane, 2-[4-(diethylamino)-2-hydroxybenzimidyl]benzoic acid hexyl ester, dimethoxybenzylidene dioxazimidazole 2-ethylhexyl propionate, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl) Phenol], (1,3,5)-triazine-2,4-bis[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxy Phenyl)-1,3,5-triazine, dimethoxane diethylbenzylidene malonate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and Sodium salt, etc.

作為抗氧化劑,可列舉抗壞血酸、α-生育酚、二丁基羥基甲苯、丁基羥基大茴香醚等。 Examples of the antioxidant include ascorbic acid, α-tocopherol, dibutylhydroxytoluene, and butylhydroxyanisole.

作為金屬螯合劑,例如可列舉:1-羥基乙烷-1,1-二膦酸、1-羥基乙烷-1,1-二膦酸四鈉鹽、乙二胺四乙酸二鈉、乙二胺四乙酸三鈉、乙二胺四乙酸四鈉、檸檬酸鈉、多磷酸鈉、偏磷酸鈉、葡萄糖酸、磷酸、檸檬酸、抗壞血酸、琥珀酸、乙二胺四乙酸、乙二胺羥基乙基三乙酸三鈉等。 Examples of the metal chelating agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium ethylenediaminetetraacetate, and ethylene. Trisodium aminotetraacetate, tetrasodium ethylenediaminetetraacetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, ethylenediaminetetraacetic acid, ethylenediamine hydroxyethyl Trisodium triacetate and the like.

作為防腐劑,可列舉:苯甲酸、水楊酸、苯酚、山梨酸、對羥基苯甲酸酯、氯化苄烷銨、氯化雙氯苯雙胍己啶、三氯對稱二苯脲、感光素、苯氧基乙醇等。 Examples of the preservative include benzoic acid, salicylic acid, phenol, sorbic acid, paraben, benzalkonium chloride, chlorhexidine dichloride, trichloro symmetrical diphenylurea, and photoreceptor. , phenoxyethanol, and the like.

作為粉體以及色素,例如可列舉:滑石、高嶺土、雲母、絹雲母(sericite)、白雲母、金雲母、合成雲母、紅雲母、黑雲母、蛭石、碳酸鎂、碳酸鈣、矽酸鋁、矽酸鋇、矽酸鈣、矽酸鎂、矽酸鍶、鎢酸金屬鹽、鎂、二氧化矽、沸石、硫酸鋇、焙燒硫酸鈣(燒石膏)、磷酸 鈣、氟磷灰石、羥基磷灰石、陶瓷粉末、肉豆蔻酸鋅等金屬皂、氮化硼等無機粉末;聚醯胺樹脂粉末(尼龍粉末)、聚乙烯粉末、聚甲基丙烯酸甲酯粉末、聚苯乙烯粉末、苯乙烯與丙烯酸之共聚物樹脂粉末、苯胍樹脂粉末、聚四氟乙烯粉末、纖維素粉末等有機粉末;二氧化鈦、氧化鋅等無機白色顏料;鐵丹、γ-氧化鐵、氧化鐵黃、氧化鐵黑、氧化鉻、群青、鐵藍等無機著色顏料;及珍珠顏料、金屬粉末顏料、有機顏料、天然色素等。 Examples of the powder and the coloring matter include talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, red mica, biotite, vermiculite, magnesium carbonate, calcium carbonate, and aluminum citrate. Barium citrate, calcium citrate, magnesium citrate, barium strontium citrate, metal tungstate, magnesium, cerium oxide, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), phosphoric acid Metal soap such as calcium, fluoroapatite, hydroxyapatite, ceramic powder, zinc myristic acid, inorganic powder such as boron nitride; polyamidamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate Powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, organic powder such as benzoquinone resin powder, polytetrafluoroethylene powder, cellulose powder; inorganic white pigment such as titanium dioxide and zinc oxide; iron oxide, γ-oxidation Inorganic coloring pigments such as iron, iron oxide yellow, iron oxide black, chromium oxide, ultramarine blue, iron blue; and pearl pigments, metal powder pigments, organic pigments, natural pigments, and the like.

作為各種藥劑,例如可以保濕、消炎、血流促進、細胞活化、抗菌、鎮痛等目的而含有,例如可列舉:消炎劑(例如甘草酸衍生物、甘草次酸衍生物、水楊酸衍生物、檜木醇、氧化鋅等);美白劑(例如維生素C衍生物、胎盤萃取物、虎耳草萃取物、熊果苷等);活化劑(例如蜂王漿、感光素、膽固醇衍生物等);血流促進劑(例如壬酸十一碳醯胺、煙鹼酸苄酯、煙鹼酸β-丁氧基乙酯、辣椒素、薑油酮、斑蝥酊、魚石脂、丹寧酸、α-龍腦、生育酚煙鹼酸酯、肌醇六煙鹼酸酯、環扁桃酯、肉桂苯哌嗪、托拉佐林、乙醯膽鹼、維拉帕米、頭花千金藤鹼、γ-穀維素等);抗脂漏劑(例如硫、二甲硫蒽等);及抗炎症劑(例如傳明酸、硫代牛磺酸、次牛膽精等)等,可使用1種或2種以上。 Examples of the various agents include, for example, moisturizing, anti-inflammatory, blood flow promoting, cell activation, antibacterial, analgesic, and the like, and examples thereof include anti-inflammatory agents (for example, glycyrrhizic acid derivatives, glycyrrhetic acid derivatives, salicylic acid derivatives, and the like). Alkali, zinc oxide, etc.; whitening agents (such as vitamin C derivatives, placenta extract, saxifrage extract, arbutin, etc.); activators (such as royal jelly, photoreceptors, cholesterol derivatives, etc.); blood flow Promoters (such as undecylamine decanoate, benzyl nicotinic acid, β-butoxyethyl nicotinic acid, capsaicin, zingerone, canthax, fish fat, tannic acid, α-borneol, Tocopherol nicotinic acid ester, phytallyl nicotinic acid ester, cyclomandelic acid ester, cinnamyl piperazine, torazoline, acetylcholine, verapamil, cephalosporin, γ-oryzanol Etc.); anti-lipid leakage agents (such as sulfur, dimethyl sulfonium, etc.); and anti-inflammatory agents (such as tranexamic acid, thiotaurine, secondary bovine cholesterol, etc.), one or more types may be used. .

本發明之水中油型乳化組合物之製造方法並未特別限制,可利用常法製備。例如可藉由如下方式而製備:將對油性成分進行加溫而得者添加混合至將成分(a)~(c)加溫溶解於水中而成者中並進行乳化,其後冷卻至室溫附近。 The method for producing the oil-in-water emulsion composition of the present invention is not particularly limited and can be produced by a usual method. For example, it can be prepared by heating and mixing the oily component until the components (a) to (c) are dissolved in water and emulsified, and then cooled to room temperature. nearby.

本發明之水中油型乳化組合物作為化妝料,可應用於乳液、乳霜、美容液、護髮素、整髮料、妝底、粉底液等,作為皮膚外用劑,可應用於外用液劑、外用凝膠劑、乳膏劑、軟膏劑、塗敷劑、洗劑、貼膏劑等。又,關於用以用作本發明之化妝料或皮膚外用劑之水中油 型乳化組合物之性狀,其可以固體狀、凝膠狀、乳膏狀、液狀等各種性狀之化妝料之方式實施。 The oil-in-water emulsion composition of the present invention can be used as a cosmetic, and can be applied to an emulsion, a cream, a beauty liquid, a conditioner, a hair styling, a makeup foundation, a liquid foundation, etc., and can be applied to an external liquid agent as an external preparation for skin. , topical gel, cream, ointment, coating agent, lotion, plaster, and the like. Further, regarding the oil used in the cosmetic or skin external preparation of the present invention The properties of the emulsified composition can be carried out in the form of a cosmetic such as a solid, a gel, a cream or a liquid.

[實施例] [Examples]

繼而,列舉實施例對本發明進一步進行說明。再者,該等絲毫不對本發明作任何限定。 The invention will now be further illustrated by the examples. Furthermore, these are not intended to limit the invention in any way.

實施例1~16及比較例1~6:水中油型乳液 Examples 1 to 16 and Comparative Examples 1 to 6: Oil-in-water emulsion

根據表1及表2所示之組成及下述製法製備水中油型乳液,並利用以下所示之方法進行<1>低溫下之結晶抑制效果、<2>高溫下之乳化穩定性之評價。將結果一併記載於表1及表2。 The oil-in-water emulsion was prepared according to the compositions shown in Tables 1 and 2 and the following production method, and the crystallization inhibition effect at <1> low temperature and the emulsion stability at high temperature were evaluated by the method shown below. The results are shown together in Tables 1 and 2.

<1>低溫下之結晶抑制效果 <1> Crystallization inhibition effect at low temperature

將各試樣加入至玻璃瓶中,並於-10℃之恆溫槽內保存24小時。其後,目視觀察剛自恆溫槽取出後(-10℃)及該試樣恢復至室溫時之結晶之狀態,並根據以下之基準進行判定。 Each sample was placed in a glass bottle and stored in a thermostat at -10 ° C for 24 hours. Thereafter, the state of the crystal immediately after the removal from the constant temperature bath (-10 ° C) and the sample was returned to room temperature was visually observed, and the judgment was made based on the following criteria.

[評價基準] [evaluation benchmark]

◎:於-10℃、室溫下均完全未觀察到結晶 ◎: No crystals were observed at -10 ° C at room temperature.

○:於-10℃下確認到少許結晶析出,但恢復至室溫則消失 ○: A little crystal precipitation was observed at -10 ° C, but disappeared when it returned to room temperature.

△:於-10℃下確認到少許結晶析出,且即便恢復至室溫結晶亦未消失 △: A slight crystal precipitation was observed at -10 ° C, and the crystal did not disappear even after returning to room temperature.

×:於-10℃下確認到結晶析出,且即便恢復至室溫結晶亦未消失 ×: Crystallization was confirmed at -10 ° C, and the crystal did not disappear even after returning to room temperature.

<2>高溫下之乳化穩定性 <2>Emulsification stability at high temperature

將各試樣加入至玻璃瓶中,並於50℃之恆溫槽內進行保存,一面將一個月後之乳化穩定性與5℃下之保存品進行比較一面利用目視及顯微鏡進行觀察,並根據以下之基準進行判定。 Each sample was placed in a glass bottle and stored in a thermostat at 50 ° C, and the emulsion stability after one month was compared with the stored product at 5 ° C, and observed by visual observation and microscope, and according to the following The basis is judged.

[評價基準] [evaluation benchmark]

◎:完全未變化 ◎: Not changed at all

○:確認到粒徑略微增大,但未確認到排液 ○: It was confirmed that the particle size slightly increased, but the liquid discharge was not confirmed.

△:確認到粒徑增大,且確認到少許排液 △: It was confirmed that the particle size was increased, and a little drainage was confirmed.

×:確認到粒徑增大,且確認到明顯之排液 ×: It was confirmed that the particle size was increased, and it was confirmed that the discharge was remarkable.

(製法) (method of law)

A.將成分(1)~(19)加溫至70℃而使其等均勻地溶解。 A. The components (1) to (19) were heated to 70 ° C to be uniformly dissolved.

B.將成分(20)~(23)加溫至70℃而使其等均勻地溶解,一面攪拌一面將其等添加至A中。 B. The components (20) to (23) were heated to 70 ° C to be uniformly dissolved, and the mixture was added to A while stirring.

C.一面對B進行攪拌一面使其冷卻,而獲得乳液。 C. An emulsion is obtained by cooling while facing B.

如根據表1及表2之結果明確可知,實施例1~16之乳液係結晶析出抑制效果優異,乳化穩定性亦良好。成分(a)相對於成分(c)之含有質量比率較小者更難以析出結晶,成分(b)之長鏈醯基甲基牛磺酸鹽 較多者獲得更好之結晶析出抑制效果。又,於含有成分(d)之「聚氧伸烷基加成甘油」之實施例16中,獲得更高之結晶析出抑制效果。 As is clear from the results of Tables 1 and 2, the emulsions of Examples 1 to 16 were excellent in crystal precipitation suppressing effect and excellent in emulsion stability. It is more difficult to precipitate crystals when the component (a) has a smaller mass ratio than the component (c), and the long chain mercaptomethyltaurate of the component (b) More people get better crystallization precipitation inhibition effect. Further, in Example 16 containing "polyoxyalkylene group-added glycerol" of the component (d), a higher crystal precipitation suppressing effect was obtained.

另一方面,不含有成分(b)之長鏈醯基甲基牛磺酸鹽而使用不同種類之界面活性劑的比較例1~4會發生尿囊素之結晶析出,乳化穩定性亦較差。不含有成分(c)之多元醇之比較例5無法抑制結晶析出,於室溫下亦觀察到結晶。進而比較例6不含成分(c)之多元醇而代替含有一元醇,於室溫下亦觀察到結晶,無法抑制析出。 On the other hand, in Comparative Examples 1 to 4 which did not contain the long-chain mercaptomethyltaurate of the component (b) and different types of surfactants, crystallinity of allantoin was observed, and the emulsion stability was also inferior. In Comparative Example 5, which did not contain the polyol of the component (c), crystal precipitation was not inhibited, and crystallization was observed also at room temperature. Further, in Comparative Example 6, the polyol of the component (c) was not contained, and instead of containing a monohydric alcohol, crystals were observed at room temperature, and precipitation was not inhibited.

實施例17 水中油型乳霜 Example 17 Oil-in-water cream

根據下述所示之組成及製法而製備水中油型乳霜。 An oil-in-water cream was prepared according to the composition and method described below.

(製法) (method of law)

A.將成分(1)~(9)加溫至80℃而使其等均勻地溶解。 A. The components (1) to (9) were heated to 80 ° C to be uniformly dissolved.

B.將成分(10)~(13)加溫至80℃而使其等均勻地溶解,一面攪拌一面將其等添加至A中。 B. The components (10) to (13) were heated to 80 ° C to be uniformly dissolved, and added to A while stirring.

C.於一面對B進行攪拌一面使其冷卻後,添加成分(14)~(16)。 C. Add the ingredients (14) to (16) after stirring in the face of B.

D.再次攪拌C,而獲得乳霜。 D. Stir C again to obtain a cream.

如上述般獲得之實施例17之乳霜係pH值為5,結晶析出抑制效果及乳化穩定性極其良好。 The cream of Example 17 obtained as described above had a pH of 5, and the crystallization precipitation inhibiting effect and the emulsion stability were extremely excellent.

實施例18 水中油型整髮料 Example 18 Oil-in-water type hair styling material

根據下述所示之組成及製法而製備整髮料。 The hair styling material was prepared according to the composition and preparation method shown below.

(16)乙烯吡咯啶酮-乙酸乙烯酯共聚物 0.3 (16) vinylpyrrolidone-vinyl acetate copolymer 0.3

(製法) (method of law)

A.將成分(1)~(9)加溫至70℃而使其等均勻地溶解。 A. The components (1) to (9) were heated to 70 ° C to be uniformly dissolved.

B.將成分(10)~(13)加溫至70℃而使其等均勻地溶解,一面攪拌一面將其等添加至A中。 B. The components (10) to (13) are heated to 70 ° C to be uniformly dissolved, and these are added to A while stirring.

C.於一面對B進行攪拌一面使其冷卻後,添加成分(14)~(16)。 C. Add the ingredients (14) to (16) after stirring in the face of B.

D.再次攪拌C,而獲得整髮料。 D. Stir C again to obtain a whole hair.

如上述般獲得之實施例18之整髮料係pH值為6,結晶析出防止及乳化穩定性極其良好。 The whole hair powder of Example 18 obtained as described above had a pH of 6, and the crystallization prevention and emulsion stability were extremely excellent.

實施例19 水中油型粉底液 Example 19 Oily liquid foundation in water

根據下述所示之組成及製法而製備水中油型粉底液。 An oily liquid foundation was prepared according to the composition and method described below.

(製法) (method of law)

A.將成分(1)~(8)加溫至90℃而使其等均勻地溶解。 A. The components (1) to (8) are heated to 90 ° C to be uniformly dissolved.

B.將成分(9)~(12)加溫至70℃而使其等均勻地溶解,一面攪拌一面將其等添加至A中。 B. The components (9) to (12) are heated to 70 ° C to be uniformly dissolved, and these are added to A while stirring.

C.於一面對B進行攪拌一面冷卻後,添加事前經滾筒處理之成分(13)~(18)。 C. After cooling with agitation in the face of B, add the components (13) to (18) which have been subjected to the drum treatment beforehand.

D.再次攪拌C,而獲得粉底液。 D. Stir C again to obtain a liquid foundation.

如上述般獲得之實施例19之粉底液係pH值為5.5,結晶析出防止及乳化穩定性極其良好。 The liquid foundation of Example 19 obtained as described above had a pH of 5.5, and the crystallization prevention and the emulsion stability were extremely excellent.

Claims (4)

一種用以用作化妝料或皮膚外用劑之水中油型乳化組合物,其含有如下成分(a)~(d):成分(a)尿囊素、成分(b)長鏈醯基甲基牛磺酸鹽、成分(c)多元醇、及成分(d)聚氧伸烷基加成甘油及/或聚氧伸烷基加成二甘油,且於25℃下pH值為3~6。 An oil-in-water emulsion composition for use as a cosmetic or external preparation for skin, which comprises the following components (a) to (d): component (a) allantoin, component (b) long-chain mercaptomethyl bovine The sulfonate, component (c) polyol, and component (d) polyoxyalkylene addition glycerol and/or polyoxyalkylene addition diglycerin, and having a pH of 3-6 at 25 °C. 如請求項1之水中油型乳化組合物,其中成分(a)相對於成分(c)之含有質量比率為0.002~0.05。 The oil-in-water emulsion composition of claim 1, wherein the content ratio of the component (a) to the component (c) is 0.002 to 0.05. 如請求項1及2中任一項之水中油型乳化組合物,其中成分(b)之含量為0.2~3質量%。 The oil-in-water emulsion composition according to any one of claims 1 to 2, wherein the content of the component (b) is 0.2 to 3% by mass. 如請求項1及2中任一項之水中油型乳化組合物,其中成分(c)係選自丙二醇、1,3-丁二醇、甘油、二丙二醇、二甘油、聚乙二醇、山梨糖醇、麥芽糖醇中之1種或2種以上。 The oil-in-water emulsion composition according to any one of claims 1 to 2, wherein the component (c) is selected from the group consisting of propylene glycol, 1,3-butylene glycol, glycerin, dipropylene glycol, diglycerin, polyethylene glycol, and sorbus One or two or more of a sugar alcohol and a maltitol.
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