TW200817040A - Emulsion composition with good feeling of use - Google Patents
Emulsion composition with good feeling of use Download PDFInfo
- Publication number
- TW200817040A TW200817040A TW96130182A TW96130182A TW200817040A TW 200817040 A TW200817040 A TW 200817040A TW 96130182 A TW96130182 A TW 96130182A TW 96130182 A TW96130182 A TW 96130182A TW 200817040 A TW200817040 A TW 200817040A
- Authority
- TW
- Taiwan
- Prior art keywords
- extract
- hyaluronic acid
- oil
- emulsified composition
- acid
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 239000000839 emulsion Substances 0.000 title abstract description 17
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims abstract description 52
- 229920002674 hyaluronan Polymers 0.000 claims abstract description 48
- 229960003160 hyaluronic acid Drugs 0.000 claims abstract description 48
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000000284 extract Substances 0.000 claims description 61
- 241000199919 Phaeophyceae Species 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 229960005489 paracetamol Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000000084 colloidal system Substances 0.000 abstract description 3
- 241000195493 Cryptophyta Species 0.000 abstract 2
- 229920002385 Sodium hyaluronate Polymers 0.000 description 29
- 229940010747 sodium hyaluronate Drugs 0.000 description 29
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 27
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- 239000003921 oil Substances 0.000 description 23
- 235000019198 oils Nutrition 0.000 description 23
- 229920002125 Sokalan® Polymers 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- -1 polyoxyethylene Polymers 0.000 description 14
- 239000006071 cream Substances 0.000 description 13
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 12
- 229940014041 hyaluronate Drugs 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- WCDDVEOXEIYWFB-VXORFPGASA-N (2s,3s,4r,5r,6r)-3-[(2s,3r,5s,6r)-3-acetamido-5-hydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-4,5,6-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@@H]1C[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](C(O)=O)O[C@@H](O)[C@H](O)[C@H]1O WCDDVEOXEIYWFB-VXORFPGASA-N 0.000 description 7
- 239000002537 cosmetic Substances 0.000 description 7
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- YYGNTYWPHWGJRM-UHFFFAOYSA-N (6E,10E,14E,18E)-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene Chemical compound CC(C)=CCCC(C)=CCCC(C)=CCCC=C(C)CCC=C(C)CCC=C(C)C YYGNTYWPHWGJRM-UHFFFAOYSA-N 0.000 description 5
- BHEOSNUKNHRBNM-UHFFFAOYSA-N Tetramethylsqualene Natural products CC(=C)C(C)CCC(=C)C(C)CCC(C)=CCCC=C(C)CCC(C)C(=C)CCC(C)C(C)=C BHEOSNUKNHRBNM-UHFFFAOYSA-N 0.000 description 5
- 239000010495 camellia oil Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
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- 229940119170 jojoba wax Drugs 0.000 description 5
- 230000003020 moisturizing effect Effects 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 229940031439 squalene Drugs 0.000 description 5
- TUHBEKDERLKLEC-UHFFFAOYSA-N squalene Natural products CC(=CCCC(=CCCC(=CCCC=C(/C)CCC=C(/C)CC=C(C)C)C)C)C TUHBEKDERLKLEC-UHFFFAOYSA-N 0.000 description 5
- 241000283153 Cetacea Species 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 4
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical class CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229930182558 Sterol Natural products 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 150000001241 acetals Chemical class 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
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- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
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- 239000002585 base Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- LPLVUJXQOOQHMX-UHFFFAOYSA-N glycyrrhetinic acid glycoside Natural products C1CC(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2=O)C(O)=O)C)(C)CC2)(C)C2C(C)(C)C1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O LPLVUJXQOOQHMX-UHFFFAOYSA-N 0.000 description 3
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- UYRUBYNTXSDKQT-UHFFFAOYSA-N glycyrrhizic acid Natural products CC1(C)C(CCC2(C)C1CCC3(C)C2C(=O)C=C4C5CC(C)(CCC5(C)CCC34C)C(=O)O)OC6OC(C(O)C(O)C6OC7OC(O)C(O)C(O)C7C(=O)O)C(=O)O UYRUBYNTXSDKQT-UHFFFAOYSA-N 0.000 description 3
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- BBZAGOMQOSEWBH-UHFFFAOYSA-N octyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCCCCCC BBZAGOMQOSEWBH-UHFFFAOYSA-N 0.000 description 3
- 150000003432 sterols Chemical class 0.000 description 3
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- 230000002087 whitening effect Effects 0.000 description 3
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
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- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
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- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 1
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- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 229940071127 thioglycolate Drugs 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/735—Mucopolysaccharides, e.g. hyaluronic acid; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/965—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution of inanimate origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Dermatology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Cosmetics (AREA)
- Botany (AREA)
- Microbiology (AREA)
- Mycology (AREA)
Abstract
Description
200817040 九、發明說明 【發明所屬之技術領域】 本發明係關於含有褐藻萃取膠以及玻尿酸,且具滑潤 的使用感之乳化組成物,特別適合皮膚外用劑之乳化組成 - 物。 【先前技術】 已知褐藻萃取膠及玻尿酸二者皆爲具優異保濕作用, 及促進血流作用之成分,且爲廣泛使用於化妝品等之成分 。褐藻萃取膠係自褐藻所萃取之天然成分,係由点-D-甘 露糖醛酸與a -L-葛羅酸以/3 -1,4-鍵而形成的多醣類,且 以藻酸爲主成分。已知褐藻萃取膠除具優異保濕作用外, 亦具美膚效果。至於玻尿酸,係具有由D -葡萄糖醒酸與 D-N-乙醯葡糖胺以沒-配醣體鍵而形成之重複雙糖構造之 物質,爲分子量高達數百萬之高分子化合物。且因玻尿酸 具有相當長的酸性糖鏈,而具有高含水能力。 含有褐藻萃取膠及玻尿酸二者之化妝品,可舉出例如 含有(A)千屈菜科(Lythraceae)紫薇屬(Lagerstroemia L.) 之植物萃取物,與一種以上選自(B)褐藻萃取物(褐藻萃取 膠)等之美白劑、抗氧化劑、抗發炎劑、紫外線防止劑、 玻尿酸等的保濕劑、細胞賦活劑、血流促進劑所成群之生 理活性成分爲特徵之皮膚化妝料(專利文件1)。然而,該 含有褐藻萃取膠以及玻尿酸之乳化組成物有於使用時欠缺 滑潤度,使用感不佳之缺點。 -5- 200817040 專利文件1 ··特開2005- 1 3 9070號公報 乙醯化玻尿酸係將玻尿酸之羥基乙醯化後之衍生物, 詳細係具有下述之構造式。[Technical Field] The present invention relates to an emulsified composition containing a brown algae extracting gel and hyaluronic acid and having a smooth feeling of use, and is particularly suitable for an emulsified composition of a skin external preparation. [Prior Art] It is known that both brown algae extract gel and hyaluronic acid are components having excellent moisturizing action and promoting blood flow, and are widely used in cosmetics and the like. The brown algae extract is a natural component extracted from brown algae, which is a polysaccharide formed by a point-D-mannuronic acid and a-L-groic acid with a /3 -1,4-bond, and is alginate. Main ingredient. It is known that the brown algae extracting gel has an excellent moisturizing effect as well as a skin-beautifying effect. As for hyaluronic acid, it is a substance having a repeating disaccharide structure formed by D-glucosinated acid and D-N-acetylglucosamine as a no-glycosidic bond, and is a polymer compound having a molecular weight of several millions. And because hyaluronic acid has a relatively long acid sugar chain, it has a high water content. The cosmetic containing both the brown algae extract gel and hyaluronic acid may, for example, be a plant extract containing (A) Lythraceae Lagerstroemia L., and one or more selected from (B) brown algae extract ( A skin-based cosmetic characterized by a group of physiologically active ingredients such as a whitening agent, an antioxidant, an anti-inflammatory agent, an ultraviolet ray preventive agent, a hyaluronic agent such as hyaluronic acid, a cell stimulating agent, and a blood flow promoting agent (patent document) 1). However, the emulsified composition containing brown algae extract gel and hyaluronic acid has a drawback of lack of smoothness and poor feeling in use. -5-200817040 Patent Document 1 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。
已知乙醯化後之玻尿酸具有較玻尿酸更好的保濕性。 另外,由於被導入乙醯基使疏水性變高,而具有對角質的 親和性變高、牽絲性變低、對醇類的溶解性佳等適於用作 皮膚外用劑之搭配成分之特徵。 【發明內容】 6 - 200817040 本發明係以提供對含褐藻萃取膠及玻尿酸之化妝料等 乳化組成物,賦予其滑潤的使用感之技術爲課題。 本發明之發明者們,爲解決上述課題進行專心硏究後 ,發現於含有褐藻萃取膠以及玻尿酸之乳化組成物,藉由 搭配乙醯化玻尿酸,而可提升於使用時之滑潤度,遂完成 下述之本發明。 (1) 一種乳化組成物,其係含有褐藻萃取膠、玻尿酸 以及乙醯化玻尿酸。 (2) 如(1)項之乳化組成物,其中乳化組成物係水中油 型乳化組成物。 (3) 如(1)或(2)項之乳化組成物,其係皮膚外用劑。 於含有褐藻萃取膠以及玻尿酸之乳化組成物中,藉由 搭配乙醯化玻尿酸可提升滑潤度,而可減低塗佈於皮膚時 之摩擦感。且於本說明書中,「滑潤度」係用以表示將乳 化組成物塗佈於皮膚時,塗佈用之手指或塗佈部位之皮膚 感覺摩擦感之程度。滑潤度一般除根據受試者之官能評價 外,亦可使用黏度等流變學特性而加以評價。 本發明乳化.組成物含有褐藻萃取膠、玻尿酸及乙醯化 玻尿酸。 於本發明中,褐藻萃取膠係自褐藻所萃取之天然成分 ,且以藻酸爲主成分。藻酸係由/3 -D-甘露糖醛酸與a -L-葛羅酸以/5-1,4-鍵而形成的多醣類。褐藻萃取膠可使用自 褐藻所萃取者。亦可使用市售品,該類市售品可舉出例如 褐藻萃取膠(BOTTGER公司製)。 200817040 並未特別限定褐藻萃取膠之含量,以相對於乳化組成 物之全量爲0.001〜5重量%爲佳,0.005〜2重量%更佳, 0·01〜1重量%最佳。 於本發明中,玻尿酸係具有由D-葡萄糖醛酸與D-N-乙醯葡糖胺以/3 -配醣體鍵而形成之重複雙糖構造之物質 ’爲分子量高達數百萬之高分子化合物及其鹽。於本發明 所使用之玻尿酸並未特別限定其分子量,但以1萬〜5 00萬 爲佳’ 10萬〜2 0 0萬特佳。玻尿酸之鹽類可舉出鈉鹽、鉀 鹽、鋰鹽、鎂鹽、鈣鹽等金屬鹽類、離胺酸鹽、精胺酸鹽 、組胺酸鹽等鹽基性胺基酸、銨鹽、三乙醇胺鹽、二異丙 醇胺鹽等有機鹽類。於本發明中,特別係以使用玻尿酸鈉 爲佳。玻尿酸可由培養微生物而生產,或自含有玻尿酸之 組織中萃取而得。亦可使用市售品,該類市售品可舉出例 如Bio玻尿酸鈉ΗΑ12(資生堂公司製)。 並未特別限定玻尿酸之含量,以相對於乳化組成物之 全量爲 0.001〜5重量%爲佳,0.005〜2重量%更佳, 0.01〜1重量%最佳。 於本發明中,乙醯化玻尿酸係指將至少一部分玻尿酸 之羥基乙醯化後之衍生物及其鹽。本發明中並未特別限定 所使用之乙醯化玻尿酸之分子量,但以1萬〜5 00萬爲佳, 1 0萬〜2 0 0萬特佳。另外,亦無特別限定對羥基之乙醢化 率,但於前述之一般式(I )所示之重複構造單位中,乙醯 基之取代數平均以2〜4個爲佳。乙醯化之玻尿酸鹽可舉出 鈉鹽、鉀鹽、鋰鹽、鎂鹽、鈣鹽等金屬鹽類、離胺酸鹽、 -8 - 200817040 精胺酸鹽、組胺酸鹽等鹽基性胺基酸、銨鹽、三乙醇胺鹽 、二異丙醇胺鹽等有機鹽類。可以相關業者周知之方法製 造乙醯化玻尿酸,該方法揭示於例如特開平6-6707號公 報及特開平8-5 3 5 0 1號公報。亦可使用市售品,該類市售 品可舉出例如乙醯化玻尿酸鈉(資生堂公司製)。 並未特別限定乙醯化玻尿酸之搭配量,但以相對於乳 化組成物全量爲0.0001〜1重量%爲佳,0.0002〜0.1重量 %更佳,0.0005〜0.01重量%最佳。 於本發明之乳化組成物中,並未特別限定褐藻萃取膠 與乙醯化玻尿酸之搭配量的相對比例。自提升滑潤度之觀 點而言,將乙醯化玻尿酸之搭配量設定爲1時,褐藻萃取 膠以0.01〜50000爲佳,0.1〜100 00更佳,10〜1000特佳。 另外,並未特別限定玻尿酸與乙醯化玻尿酸之搭配量的相 對比例。而自滑潤度等使用感之觀點而言,將乙醯化玻尿 酸之搭配量設定爲1時,玻尿酸以0.01〜1 0000爲佳, 0.1〜1000更佳,1〜100特佳° 本發明之乳化組成物之乳化形態,無論水中油型乳化 組成物及油中水型乳化組成物,或水中油中水型乳化組成 物,油中水中油型乳化組成物等多層乳化組成物均適用, 而自獲得清爽感等較佳的使用感之觀點而言,以水中油型 乳化組成物爲佳。於本發明之乳化組成物中,並未特別限 定水分與油分之相對比例,但自獲得清爽感等較佳的使用 感之觀點而言,水分:油分(質量比)=2 : 1〜100 : 1爲佳 ,水分:油分(質量比)=4 : 1〜50 : 1更佳。 -9- 200817040 於本發明之乳化組成物中所含之油分,可舉出以酪梨 油、夏威夷果核油、玉蜀黍油、橄欖油、菜籽油、月見草 油、蓖麻油、向日葵油、茶籽油、山茶花油、米糠胚芽油 、荷荷芭油、可可脂、椰子油、硬酯酸、鯨蠟醇、1,3-丁 基二醇、鯊烯、牛脂、木蠟、蜜躐、勘地里拉躐、棕櫚蠛 、鯨躐、羊脂油、流動石臘、聚氧乙烯(8莫耳)油基醇醚 、單油酸甘油酯、肉萱蔻酸辛基十二酯、環甲矽脂、二甲 基聚矽氧烷、二苯基聚矽氧烷等爲佳,特別以山茶花油、 荷荷芭油、鯊烯、硬酯酸、鯨鱲醇、肉宣蔻酸辛基十二酯 、1,3-丁基二醇爲佳。另外,油分之搭配量以相對於乳化 組成物全量爲 0.5〜4 0重量%爲佳’ 2〜30重量%更佳, 3〜20重量%特佳。藉由使乳化組成物中油分之搭配量限於 前述之範圍,可抑制於使用組成物時之黏腻感,而可提升 使用感。 於本發明之乳化組成物中可再進而使其含有增加乳化 安定性之乳化劑。該乳化劑若爲可使用於皮膚外用劑者則 無特別限制,例如可舉出烷基硫酸鹽、醯基胺基酸鹽、脂 肪酸鹽等陰離子界面活性劑、聚氧亞烷烯烷基醚、聚氧亞 烷烯脂肪酸酯、聚氧亞烷烯多元醇脂肪酸酯、多元醇脂肪 酸酯、蔗糖脂肪酸酯等非離子性界面活性劑、四烷基氨鹽 等陽離子界面活性劑、甜菜鹼型、硫甜菜鹼型、硫胺基酸 型、咪唑鎰型、卵磷脂、脫脂酸卵磷脂等兩性界面活性劑 ,特別以單硬酯酸甘油酯、加氫大豆磷脂質爲佳。 於本發明之乳化組成物中可再進而搭配美白成分、抗 -10- 200817040 發炎成分、抗氧化成分、增黏劑、保存劑、安定化劑、濕 潤劑、pH調整劑、香料等。 美白成分可舉出抗壞血酸及其衍生物以及其鹽、維他 命A或其衍生物、泛酸或其衍生物、熊果素等對苯二酚及 其衍生物、鞣花酸、麴酸、苔黑酚等之樹脂酚及其衍生物 、洋甘菊、組胺酸及其衍生物以及其鹽、甘草黃酮、甘草 雙酮、甘草苷、異甘草苷、阿魏酸及其衍生物以及其鹽、 咖啡酸及其衍生物以及其鹽。萃取物則可舉出含蟬殼萃取 物、胎盤萃取物、肝臟萃取物、洋甘菊萃取物、類胡蘿蔔 素萃取物等動植物萃取物、蘆筍萃取物、豌豆萃取物、小 金櫻萃取物、黃芩萃取物、芒柄花萃取物、海藻萃取物、 懸鉤子萃取物、苦參萃取物、雞血藤萃取物、五加皮萃取 物、咖啡萃取物、米糠萃取物、小麥胚芽萃取物、細辛萃 取物、山查子萃取物、山扁豆萃取物、白百合萃取物、芍 藥萃取物、懸覆花萃取物、大豆萃取物、茶萃取物、糖蜜 萃取物、番茄萃取物、白蔹萃取物、白木櫸苗萃取物、葡 萄萃取物、啤酒花萃取物、玫瑰萃取物、虎耳草萃取物、 尤加利萃取物、薏仁萃取物、及羅漢果萃取物等。 抗發炎成分則可舉出尿嚢素、菱鋅礦、甘草酸或其衍 生物、甘草次酸或其衍生物、氧化鋅、揚汝諾爾、醋酸生 育酚、維他命B6、薄荷腦、樟腦、松節油、美洒辛、水 楊酸或其衍生物等。 抗氧化成分可舉出生育酚及其衍生物、羥基茴香二丁 酯、二丁基羥基甲苯、亞硫酸氫鈉、異抗壞血酸及其鹽、 -11 - 200817040 類黃酮、麩胺基硫、麩胺基硫過氧化酶、麩胺基硫-S -移 轉酶、過氧化氫酶、超氧化物歧化酶、硫氧還蛋白、牛磺 酸、硫牛磺酸、亞牛磺酸等。 增黏劑可舉出羧基甲基纖維素鈉、羧基乙烯聚合物以 及/或其鹽、羥基乙基纖維素、鹿角膠、蟻酸鈉、三叉膠 、聚丙烯酸鈉、聚乙烯醇、刺槐豆膠、瓜耳豆膠、明膠、 羥丙基甲基纖維素等。 其中,可使用羧基乙烯聚合物以及/或其鹽爲合適。 羧基乙烯聚合物係具羧基之水溶性聚合物,爲丙烯酸之聚 合體。羧基乙烯聚合物以及/或其鹽係藉由鹼液將其水溶 液中和而增加黏性。並未特別限定本發明中所使用之羧基 乙烯聚合物,但0.2%之水溶液黏度爲1 000〜50000mPa· s 之範圍爲佳,特別以 5000〜30000mPa· s之範圍更佳。可 依據一般常用之方法聚合丙烯酸而製造羧基乙烯聚合物。 於本發明中,使用市售品亦可,此類之市售品可舉出例如 Carbopol 980、Carbopol 981、Carbopol 2984、Carbοροί 5 984、Carbopol ETD2050、Carbopol ultrez 1 0 ( Noveon 公 司製)、Haibesewako-103、Haibesewako-104、 Haibesewako-105、Shitaren K、Shitaren L(和光純藥工業 公司製)、氨基甲酸酯軟管(日本純藥公司製)等。 羧基乙烯聚合物因具有乳化安定性及隨溫度變化而提 高黏度安定性之作用’可特別適合使用於將乳化組成物製 作爲凝膠及乳霜之型態。進而,因羧基乙烯聚合物具黏流 性而具有保濕作用,且不易受微生物污染,與天然橡膠類 -12- 200817040 相比具有優異的品質均一性等優點。 並未特別限定羧基乙烯聚合物之含有量,但以相對於 乳化組成物全量爲0·01〜5重量%爲佳,〇·〇2〜2重量%更 佳,0.05〜1重量%最佳。 保存劑可舉出對羥苯甲酸酯類,氯化苯二甲烴銨等。 安定化劑可舉出亞硫酸鈉、亞硫酸氫鈉、二丁基羥基 甲苯、丁基經基茴香醚、乙二胺四乙酸或其鹽類等。It is known that hyaluronic acid after acetylation has better moisturizing properties than hyaluronic acid. In addition, since the hydrophobicity is increased by the introduction of the acetyl group, the affinity for the keratin is high, the stringiness is lowered, and the solubility to alcohol is good, and the like is suitable for use as a collateral component of the external preparation for skin. . [Explanation] 6 - 200817040 The present invention provides a technique for providing an emulsified composition such as a cosmetic material containing brown algae extract gel and hyaluronic acid, and imparting a smooth feeling of use. In order to solve the above problems, the inventors of the present invention have found that the emulsified composition containing brown algae extract gel and hyaluronic acid can be improved in the degree of smoothness during use by using acetaminophen hyaluronic acid. The invention described below. (1) An emulsified composition comprising brown algae extract gel, hyaluronic acid, and acetylated hyaluronic acid. (2) The emulsified composition of (1), wherein the emulsified composition is an oily emulsified composition in water. (3) The emulsified composition according to (1) or (2), which is an external preparation for skin. In the emulsified composition containing brown algae extract and hyaluronic acid, the hyaluronic acid can be improved by blending with acetylated hyaluronic acid, thereby reducing the friction when applied to the skin. In the present specification, "slipness" is used to indicate the degree of feeling of friction of the skin of the finger or the applied portion of the coating when the emulsified composition is applied to the skin. The degree of smoothness is generally evaluated in addition to the subject's functional evaluation, and can also be evaluated using rheological properties such as viscosity. The present invention is emulsified. The composition contains brown algae extract gel, hyaluronic acid and acetylated hyaluronic acid. In the present invention, the brown algae extraction gel is a natural component extracted from brown algae and is mainly composed of alginic acid. Alginic acid is a polysaccharide formed by /3 -D-mannuronic acid and a-L-groic acid with a /5-1,4-bond. The brown algae extract can be extracted from brown algae. Commercially available products can also be used, and such commercially available products include, for example, brown algae extract rubber (manufactured by BOTTGER Co., Ltd.). 200817040 The content of the brown algae extracting gel is not particularly limited, and is preferably 0.001 to 5% by weight based on the total amount of the emulsified composition, more preferably 0.005 to 2% by weight, most preferably 0. 01 to 1% by weight. In the present invention, hyaluronic acid has a repeating disaccharide structure formed by D-glucuronic acid and DN-acetylglucosamine as a /3-glycosidic bond, and is a polymer compound having a molecular weight of up to several million. And its salt. The hyaluronic acid used in the present invention is not particularly limited in its molecular weight, but is preferably from 10,000 to 50,000, and is preferably from 100,000 to 2,000,000. Examples of the salts of hyaluronic acid include metal salts such as sodium salts, potassium salts, lithium salts, magnesium salts, and calcium salts, and basic amino acids such as ammonium salts, arginine salts, and histamine salts, and ammonium salts. Organic salts such as triethanolamine salt and diisopropanolamine salt. In the present invention, it is particularly preferred to use sodium hyaluronate. Hyaluronic acid can be produced by culturing a microorganism or by extracting it from a tissue containing hyaluronic acid. Commercially available products can also be used, and such commercially available products include, for example, Bio Hyaluronate ΗΑ12 (manufactured by Shiseido Co., Ltd.). The content of hyaluronic acid is not particularly limited, and is preferably 0.001 to 5% by weight based on the total amount of the emulsified composition, more preferably 0.005 to 2% by weight, most preferably 0.01 to 1% by weight. In the present invention, acetylated hyaluronic acid refers to a derivative obtained by hydroxyethylating at least a part of hyaluronic acid and a salt thereof. In the present invention, the molecular weight of the acetylated hyaluronic acid used is not particularly limited, but it is preferably from 10,000 to 50,000 and more preferably from 100,000 to 20,000. Further, the oxime conversion ratio of the hydroxy group is not particularly limited. However, in the above-mentioned repeating structural unit represented by the general formula (I), the number of substitutions of the ethane group is preferably 2 to 4 on average. Examples of the hyaluronic acid hyaluronate include metal salts such as sodium salts, potassium salts, lithium salts, magnesium salts, and calcium salts, and the base salts such as the persalt, -8 - 200817040 arginine, and histidine. An organic salt such as an amino acid, an ammonium salt, a triethanolamine salt or a diisopropanolamine salt. The acetylated hyaluronic acid can be produced by a method known to a person skilled in the art, and the method is disclosed in, for example, JP-A-6-6707 and JP-A-8-5 3 0 1 . Commercially available products can also be used, and such commercially available products include, for example, sodium acetal hyaluronate (manufactured by Shiseido Co., Ltd.). The amount of the ethoxylated hyaluronic acid is not particularly limited, but it is preferably 0.0001 to 1% by weight based on the total amount of the emulsified composition, more preferably 0.0002 to 0.1% by weight, and most preferably 0.0005 to 0.01% by weight. In the emulsified composition of the present invention, the relative proportion of the amount of the brown algae extracting gel and the acetylated hyaluronic acid is not particularly limited. From the viewpoint of improving the degree of smoothness, when the amount of acetylated hyaluronic acid is set to 1, the brown algae extracting gel is preferably 0.01 to 50000, more preferably 0.1 to 100 00, and particularly preferably 10 to 1000. Further, the relative ratio of hyaluronic acid to acetylated hyaluronic acid is not particularly limited. From the viewpoint of the feeling of use such as the degree of smoothness, when the amount of the acetylated hyaluronic acid is set to 1, the hyaluronic acid is preferably 0.01 to 10,000, more preferably 0.1 to 1,000, and more preferably 1 to 100. The emulsified form of the composition is applicable to both the oil-type emulsified composition in the oil and the water-based emulsified composition in the oil, or the water-based emulsified composition in the oil, and the oil-based emulsified composition in the oil, and the like. From the viewpoint of obtaining a good feeling of use such as a refreshing feeling, it is preferred to use an oily emulsified composition in water. In the emulsified composition of the present invention, the relative ratio of the water content to the oil content is not particularly limited. However, from the viewpoint of obtaining a good feeling of use such as a refreshing feeling, the moisture: oil content (mass ratio) = 2: 1 to 100: 1 is better, moisture: oil (mass ratio) = 4: 1 to 50: 1 is better. -9- 200817040 The oil component contained in the emulsified composition of the present invention may, for example, be avocado oil, macadamia nut oil, maize oil, olive oil, rapeseed oil, evening primrose oil, castor oil, sunflower oil, tea. Seed oil, camellia oil, rice bran germ oil, jojoba oil, cocoa butter, coconut oil, stearic acid, cetyl alcohol, 1,3-butylene glycol, squalene, tallow, wood wax, candied fruit, survey Deli, palmetto, whale, sheep fat, mobile paraffin, polyoxyethylene (8 mol) oleyl alcohol ether, glycerol monooleate, octyl dodecanoate, cyclomethicone, Dimethyl polyoxyalkylene, diphenyl polyoxyalkylene, etc., especially camellia oil, jojoba oil, squalene, stearic acid, whale sterol, octyl dodecyl citrate, 1 3-butyl diol is preferred. Further, the amount of the oil is preferably from 0.5 to 40% by weight based on the total amount of the emulsified composition, more preferably from 2 to 30% by weight, particularly preferably from 3 to 20% by weight. By limiting the amount of the oil component in the emulsified composition to the above range, the feeling of stickiness when the composition is used can be suppressed, and the feeling of use can be improved. The emulsified composition of the present invention may further contain an emulsifier which increases the emulsion stability. The emulsifier is not particularly limited as long as it can be used for external use on the skin, and examples thereof include an anionic surfactant such as an alkyl sulfate, a decylamino acid salt or a fatty acid salt, and a polyoxyalkylene alkyl ether. Nonionic surfactants such as polyoxyalkylene fatty acid esters, polyoxyalkylene polyol fatty acid esters, polyhydric alcohol fatty acid esters, sucrose fatty acid esters, cationic surfactants such as tetraalkylammonium salts, and beets An amphoteric surfactant such as a base type, a thiobetaine type, a thiomethic acid type, an imidazolium type, a lecithin, or a defatted acid lecithin is particularly preferably a monostearic acid glyceride or a hydrogenated soybean phospholipid. The emulsified composition of the present invention can be further blended with a whitening component, an anti--10-200817040 inflammatory component, an antioxidant component, a tackifier, a preservative, a stabilizer, a moisturizer, a pH adjuster, a perfume, and the like. Examples of the whitening component include ascorbic acid and derivatives thereof, salts thereof, vitamin A or derivatives thereof, pantothenic acid or derivatives thereof, hydroquinone and its derivatives such as arbutin, ellagic acid, citric acid, and orcinol. Resin phenol and its derivatives, chamomile, histidine and its derivatives and its salts, licorice flavonoids, glycyrrhizin, glycyrrhizin, isoliquiritin, ferulic acid and its derivatives, and its salts, caffeic acid and its derivatives And its salt. Examples of the extract include animal extracts such as clam shell extract, placenta extract, liver extract, chamomile extract, carotenoid extract, asparagus extract, pea extract, sassafras extract, and astragalus extract. , stalk flower extract, seaweed extract, raspberry extract, Sophora flavescens extract, spatholobus extract, schisandra extract, coffee extract, rice bran extract, wheat germ extract, asarum extract , Mountain Chass Extract, Mountain Lentil Extract, White Lily Extract, Paeonia Extract, Overhang Flower Extract, Soy Extract, Tea Extract, Molasses Extract, Tomato Extract, Angelica Extract, White Wood Seedling Extracts, grape extract, hop extract, rose extract, saxifrage extract, eucalyptus extract, hazelnut extract, and mangosteen extract. Examples of anti-inflammatory ingredients include urinary strontium, smithite, glycyrrhizic acid or its derivatives, glycyrrhetinic acid or its derivatives, zinc oxide, yanoxiol, tocopherol acetate, vitamin B6, menthol, camphor, and turpentine. , sesame, salicylic acid or its derivatives. Antioxidant components include tocopherol and its derivatives, hydroxyanisuccinate, dibutylhydroxytoluene, sodium hydrogen sulfite, isoascorbic acid and its salts, -11 - 200817040 flavonoids, glutamine sulfur, glutamine Thiol peroxidase, glutamine-sulfur-S-transferase, catalase, superoxide dismutase, thioredoxin, taurine, sulfur taurine, hypotaurine, and the like. Examples of the tackifier include sodium carboxymethylcellulose, a carboxyvinyl polymer and/or a salt thereof, hydroxyethylcellulose, staghorn gum, sodium formate, tridentate, sodium polyacrylate, polyvinyl alcohol, locust bean gum, Guar gum, gelatin, hydroxypropyl methylcellulose, and the like. Among them, a carboxyvinyl polymer and/or a salt thereof can be used as appropriate. The carboxyvinyl polymer is a water-soluble polymer having a carboxyl group and is a polymer of acrylic acid. The carboxyvinyl polymer and/or its salt is viscous by neutralizing its aqueous solution with an alkali solution. The carboxyvinyl polymer used in the present invention is not particularly limited, but a 0.2% aqueous solution viscosity is preferably in the range of from 1 000 to 50,000 mPa·s, particularly preferably in the range of from 5,000 to 30,000 mPa·s. The carboxyvinyl polymer can be produced by polymerizing acrylic acid according to a commonly used method. In the present invention, a commercially available product may be used. Examples of such commercially available products include Carbopol 980, Carbopol 981, Carbopol 2984, Carbοροί 5 984, Carbopol ETD 2050, Carbopol ultrez 10 (manufactured by Noveon Corporation), and Haibesewako- 103, Haibesewako-104, Haibesewako-105, Shitaren K, Shitaren L (manufactured by Wako Pure Chemical Industries, Ltd.), and a urethane hose (manufactured by Nippon Pure Chemical Co., Ltd.). The carboxyvinyl polymer has an effect of improving the viscosity stability due to emulsification stability and temperature change, and is particularly suitable for use in the form of a gel composition and a cream composition. Further, the carboxyvinyl polymer has a moisturizing action and is less susceptible to microbial contamination, and has an excellent quality uniformity compared with the natural rubber type -12-200817040. The content of the carboxyvinyl polymer is not particularly limited, but it is preferably 0. 01 to 5% by weight based on the total amount of the emulsified composition, more preferably 2 to 2% by weight, and most preferably 0.05 to 1% by weight. The preservative may, for example, be a paraben or a benzyldimethylammonium chloride. Examples of the stabilizer include sodium sulfite, sodium hydrogen sulfite, dibutylhydroxytoluene, butyl thioanisole, ethylenediaminetetraacetic acid or a salt thereof.
濕潤劑可舉出甘油、乙二醇、丙二醇、1 , 3 - 丁二醇、 異丙二醇、聚乙二醇等多元醇等。 pH調整劑可舉出鹽酸等無機酸、檸檬酸等有機酸、 氫氧化鉀、氫氧化鈉等氫氧化鹼、三乙醇胺、二乙醇胺、 香料可舉出綠薄荷油、胡椒油、芳樟醇、冬青油、洋 擦木油、丁香油、薄荷油、百里香油、鼠尾草油、藍桉油 、薰衣草油、花薄荷油、肉桂油、萊姆油、檸檬油及柑橘 油等天然香料及1-薄荷醇,dl-樟腦等。 並未特別限制本發明之乳化組成物之劑型,可舉出乳 霜劑、乳液劑、乳劑、乳劑性軟膏等,其中特別以乳霜劑 、乳液劑及乳劑爲佳。 本發明之乳化組成物,可將乳化劑等必須成分分別混 合於水相、油相中,依據必要性加熱溶解後,進行混合並 乳化水相、油相而加以製造。本發明所使用之乳化方法, 可採用一般的乳化方法,或可使用膠體硏磨機、均質機、 高壓均質基、超音波乳化機等而進行乳化。 -13- 200817040 本發明之乳化組成物,藉由其於使用時之滑潤度及保 濕效果,可適用爲例如皮膚外用化妝料及對於乾燥性皮膚 疾病之治療劑等之皮膚外用劑,但本發明並未限定於此。 亦未特別限定本發明之乳化組成物之使用量及使用頻度, 可因應使用目的而適宜地選擇。 【實施方式】 實施例 以下藉由實施例具體詳述本發明,但本發明並非限定 於此。 〔實施例1〕 將o.lg之褐藻萃取膠(褐藻萃取膠:BOTTGER公司製 )、〇.〇5g之玻尿酸鈉(Bio玻尿酸鈉 HA12 :資生堂公司製 ,分子量110萬〜160萬)、0·005 g之乙醯化玻尿酸鈉(乙 醯化玻尿酸鈉:資生堂公司製,分子量約1 〇萬,乙醯化 率 2.8〜3.8)、lg之濃甘油、0.3g之羧基乙烯聚合物 (Carbopol Ultrez 10 : Noveon 公司製,黏度 16,000〜 28,000mPa· s(0.2%))以及0.25g之氫氧化鉀加入86.7g之 純化水中,使其成爲加熱至80 °C之水相者。另外,將3g 之硬酯酸,4g之山茶花油,〇.4g之荷荷芭油,〇.2g之鯨 蠟醇,3 g之角鯊烯,以及1 g之單硬酯酸甘油酯(曰光 MGS-BMV :日光化學公司製),使力卩其熱混合至80°C而做 爲油相者。再將油相加入水相中,於80°C下進行攪拌•混 合並乳化後,將其冷卻至3 0 °C以下,而製成乳霜劑。 -14- 200817040 〔比較例1〜3〕 製造將於實施例1中之乙醯化玻尿酸鈉以水取代而搭 配者做爲比較例1,將玻尿酸鈉以水取代而搭配者做爲比 較例2 ’將褐藻萃取膠以水取代而搭配者做爲比較例3之 乳霜劑。 〔比較例4〜6〕 將於實施例1中之褐藻萃取膠,玻尿酸鈉,乙醯化玻 尿酸鈉中之2成分以水取代而搭配者做爲比較例4,比較 例5,比較例6,將上述3成分以水取代而搭配者做爲對 照,而製造乳霜劑。 〔試驗例〕 針對實施例1及比較例1〜6所製造之乳霜劑,進行使 用感之評價。使用感係由1〇名受試者進行使用試驗,針 對滑潤度以下述之基準進行評價,再以其平均點進行判定 。另外,如前所述之滑潤度係與於塗佈時,用以塗佈之手 指或塗佈部位之皮膚所感受之摩擦感有關’認爲係與將本 發明之乳化組成物薄薄地推勻,並使其乾燥後之黏度有關 。因而藉由測定乾燥時之黏度,評價本發明之乳化組成物 於使用時之潤滑度。具體而言針對於實施例1及比較例 1〜6所製造之乳霜劑,藉由使用RHEO METER (AR- 1 000N ),將1 g之試樣均勻地推展於直徑4cm之圓形平板及試 -15- 200817040 樣台上,以乾燥機乾燥5分鐘後,於測定溫度2 5 °C,剪力 爲5 0 OPa下測定黏度而加以評價,另外,針對對照之乳霜 劑亦進行相同試驗。 〔判斷基準〕 滑潤度:將本外用劑組成物塗佈於手指部皮膚並充分 推展開後,以將塗佈部與其他手指摩擦時之摩擦感進行評 價。 〔評價基準〕 5點:非常良好(未感覺摩擦感,手指可滑順地移動) 4點:良好(幾乎未感覺摩擦感) 3點:普通(稍感覺摩擦感) 2點:不良(感覺有摩擦感) 1點:非常不良好(感覺強烈的摩擦感,手指打結) 〔判定〕 〇:平均點4.7以上 A :平均點3.5以上未達4.7 X :平均點未達3.5 試驗結果示於表1。 -16- 200817040Examples of the humectant include polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, 1,3-butanediol, isopropyl glycol, and polyethylene glycol. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, organic acids such as citric acid, alkali hydroxides such as potassium hydroxide and sodium hydroxide, triethanolamine, diethanolamine, and perfumes, which include spearmint oil, pepper oil, and linalool. Natural spices such as wintergreen oil, foreign rub oil, clove oil, peppermint oil, thyme oil, sage oil, blue eucalyptus oil, lavender oil, peppermint oil, cinnamon oil, lime oil, lemon oil and citrus oil - menthol, dl-camphor, etc. The dosage form of the emulsified composition of the present invention is not particularly limited, and examples thereof include a cream, an emulsion, an emulsion, an emulsion ointment, and the like, and particularly, a cream, an emulsion, and an emulsion are preferred. The emulsified composition of the present invention can be produced by mixing an essential component such as an emulsifier in an aqueous phase or an oil phase, heating and dissolving as necessary, and then mixing and emulsifying the aqueous phase and the oil phase. The emulsification method used in the present invention may be carried out by a general emulsification method, or may be carried out by using a colloid honing machine, a homogenizer, a high pressure homogenization base, an ultrasonic emulsifier or the like. -13- 200817040 The emulsified composition of the present invention can be applied to skin external preparations such as skin external cosmetics and therapeutic agents for dry skin diseases, for example, by the degree of smoothness and moisturizing effect at the time of use, but the present invention is Not limited to this. The amount and frequency of use of the emulsified composition of the present invention are not particularly limited, and may be appropriately selected depending on the purpose of use. [Embodiment] EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. [Example 1] O.lg's brown algae extract (brown algae extract: BOTTGER), 〇.〇5g of sodium hyaluronate (Bio sodium hyaluronate HA12: manufactured by Shiseido Co., Ltd., molecular weight 1.1 million to 1.6 million), 0· 005 g of acetaminophen sodium hyaluronate (sodium ethoxylated sodium hyaluronate: manufactured by Shiseido Co., Ltd., molecular weight of about 10,000, acetylation rate of 2.8 to 3.8), concentrated glycerol of lg, 0.3 g of carboxyvinyl polymer (Carbopol Ultrez 10 : Noveon Corporation, viscosity 16,000 to 28,000 mPa·s (0.2%)) and 0.25 g of potassium hydroxide were added to 86.7 g of purified water to make it an aqueous phase heated to 80 °C. In addition, 3 g of stearic acid, 4 g of camellia oil, 4 g of jojoba oil, 2 g of cetyl alcohol, 3 g of squalene, and 1 g of monostearic acid ester (曰) Light MGS-BMV: manufactured by Nikko Chemical Co., Ltd., which is used as an oil phase by mixing it with heat to 80 °C. The oil phase was added to the aqueous phase, stirred at 80 ° C, mixed and emulsified, and then cooled to below 30 ° C to prepare a cream. -14- 200817040 [Comparative Examples 1 to 3] The acetylated sodium hyaluronate in Example 1 was replaced with water as a comparative example 1, and the sodium hyaluronate was replaced with water as a comparative example 2 'The brown algae extract was replaced with water and used as the cream of Comparative Example 3. [Comparative Examples 4 to 6] The components of the brown algae extract gel, sodium hyaluronate, and sodium acetal hyaluronate in Example 1 were replaced with water, and the results were as Comparative Example 4, Comparative Example 5, and Comparative Example 6, The above-mentioned three components were replaced with water and used as a control to prepare a cream. [Test Example] The creams produced in Example 1 and Comparative Examples 1 to 6 were evaluated for their feeling of use. The use of the sensory system was tested by one subject, and the degree of smoothness was evaluated on the basis of the following criteria, and the average point was used for the determination. Further, the degree of smoothness as described above is related to the feeling of friction felt by the skin applied to the finger or the applied portion at the time of application, and it is considered that the emulsion composition of the present invention is thinly spread. And related to the viscosity after drying. Thus, the degree of lubrication of the emulsified composition of the present invention at the time of use was evaluated by measuring the viscosity at the time of drying. Specifically, for the creams produced in Example 1 and Comparative Examples 1 to 6, 1 g of the sample was uniformly spread on a circular plate having a diameter of 4 cm by using RHEO METER (AR-1 000 N ). Test -15- 200817040 On the sample stand, after drying for 5 minutes in a dryer, the viscosity was measured at a measurement temperature of 25 ° C and a shear force of 50 A, and the same test was performed on the control cream. . [Criteria for Judgment] Lubricity: After applying the composition of the external preparation to the skin of the finger and fully pushing it out, the friction feeling when the coated portion is rubbed against other fingers is evaluated. [Evaluation Criteria] 5 points: Very good (no feeling of friction, fingers can move smoothly) 4 points: Good (nearly feel no friction) 3 points: Normal (slightly felt friction) 2 points: Bad (feeling Friction) 1 point: Very bad (feeling strong friction, finger knotting) [Judgement] 〇: Average point 4.7 or more A: Average point 3.5 or more is less than 4.7 X: Average point is less than 3.5 Test results are shown in the table 1. -16- 200817040
t—Η撇 搭配量(g) 對照 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 全量l〇〇g X 6.377 比較例6 0.1 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 全量l〇〇g Δ 2.421 比較例5 0.05 1.0 0.3 0.25 3.0 4.0 0.4 0,2 3.0 1.0 全量l〇〇g △ 1.115 比較例4 0.005 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 全量100g X 12.910 比較例3 0.05 0.005 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 全量100g ! △ 0.985 比較例2 0.1 0.005 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 全量100g 1 1 △ 2.546 比較例1 1 0.1 0.05 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 全量l〇〇g X 3.085 --------------—| 實施例1 i 0.1 0.05 0.005 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 全量100g 〇 0.510 成分 擊 _ 啦 S 择勝駿 扭 躲霾澎 叢截 爱垣 瀣 踩暖蠢扭稍祕餾採靼藝酲与 颦澎K)纏澎_龌彐靼_€:酹駕 GO ·_ ^ ρμ m w 鲣鹋鍚 -17- 200817040 相對於含褐藻萃取膠與玻尿酸鈉之比較例1,含褐藻 萃取膠與乙醯化玻尿酸鈉之比較例2,含玻尿酸鈉與乙醯 化玻尿酸鈉之比較例3,僅含乙醯化玻尿酸鈉之比較例4 ,僅含玻尿酸鈉之比較例5,僅含褐藻萃取膠之比較例6 之乳霜劑,於使用時之滑潤感爲△(普通)至x(不良),含褐 藻萃取膠,玻尿酸鈉及乙醯化玻尿酸鈉之實施例1之乳霜 劑,於使用時之滑潤感爲〇(良好)。 另外,相對於含褐藻萃取膠與玻尿酸鈉之比較例1, 含褐藻萃取膠與乙醯化玻尿酸鈉之比較例2,含玻尿酸鈉 與乙醯化玻尿酸鈉之比較例3,僅含乙醯化玻尿酸鈉之比 較例4,僅含玻尿酸鈉之比較例5,僅含褐藻萃取膠之比 較例6之乳霜劑,於乾燥時之黏度分別爲3.0 8 5、2.5 46、 0.9 8 5、12.910、1.115、2.421之高値,含褐藻萃取膠,玻 尿酸鈉及乙醯化玻尿酸鈉之實施例1之乳霜劑,於乾燥時 之黏度爲0.510之低値。明顯可知於塗佈後之黏度變低。 由這些結果可明確得知,褐藻萃取膠,玻尿酸鈉及乙 醯化玻尿酸鈉均含有的乳化劑組成物係於使用時具極優異 之滑潤度。 〔實施例2〕 將O.lg之褐藻萃取膠(褐藻萃取膠:BOTTGER公司製 )、〇.〇5g之玻尿酸鈉(Bio玻尿酸鈉 HA12 :資生堂公司製 )、0.001 g之乙醯化玻尿酸鈉(乙醯化玻尿酸鈉:資生堂公 司製)、lg之濃甘油、2g之1,3-丁二醇、0.15 g之羧基乙 -18- 200817040 燒聚合物(Carbopol ETD2050 : Noveon公司製,黏度 4,000〜7,500mPa · s(0_2% ))及 〇.27g 之氫氧化鉀,加入 87.4g之純化水中,使其成爲加熱至8〇°C之水相者。另外 ,將2 g之硬酯酸,2 g之山茶花油,〇 . 4 g之荷荷芭油, 〇.3g之鯨鱲醇,2g之肉萱蔻酸辛基十二酯,2g之角鯊烯 ’及〇.3g之單硬酯酸甘油酯(日光MGS-BMV:日光化學 公司製),使加其熱混合至8 0 °C而做爲油相者。再將油相 加入水相中,於80 °C下進行攪拌•混合並乳化後,將其冷 卻至3〇°C以下,而製成乳液。根據10位受試者與上述之 實驗例同樣的進行使用試驗。結果示於表2。t-Η撇 collocation amount (g) Control 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 Total amount l〇〇g X 6.377 Comparative Example 6 0.1 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 Total amount l〇〇g Δ 2.421 Comparative Example 5 0.05 1.0 0.3 0.25 3.0 4.0 0.4 0,2 3.0 1.0 Total amount l〇〇g △ 1.115 Comparative Example 4 0.005 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 Total amount 100g X 12.910 Comparative example 3 0.05 0.005 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 Full amount 100g ! △ 0.985 Comparative Example 2 0.1 0.005 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 Total 100g 1 1 △ 2.546 Comparative Example 1 1 0.1 0.05 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 Full amount l〇〇g X 3.085 ---- ----------—| Example 1 i 0.1 0.05 0.005 1.0 0.3 0.25 3.0 4.0 0.4 0.2 3.0 1.0 Total 100g 〇0.510 Ingredients _ 啦 S 胜 胜 扭 扭 霾澎 霾澎 霾澎 霾澎 截 截 垣瀣 垣瀣Warm and stupid slightly distilled 靼 靼 酲 ) ) ) 澎 澎 澎 € € € € GO GO GO GO GO - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Example 1, Comparative Example 2, containing brown algae extraction gel and sodium acetylated hyaluronic acid, containing sodium hyaluronate and acetamidine Comparative Example 3 of sodium hyaluronate, Comparative Example 4 containing only acetaminophen sodium hyaluronate, Comparative Example 5 containing only sodium hyaluronate, and the cream of Comparative Example 6 containing only brown algae extraction gel, the smoothness at the time of use was △ (ordinary) to x (poor), the cream of Example 1 containing brown algae extract gel, sodium hyaluronate and sodium sulfonate hyaluronic acid, the slipperiness when used was 〇 (good). In addition, in Comparative Example 1 containing brown algae extract gel and sodium hyaluronate, Comparative Example 2 containing brown algae extract gel and sodium hyaluronate hyaluronic acid, Comparative Example 3 containing sodium hyaluronate and sodium hyaluronate, only containing acetamidine Comparative Example 4 of sodium hyaluronate, Comparative Example 5 containing only sodium hyaluronate, and the cream of Comparative Example 6 containing only brown algae extraction gel, the viscosity at the time of drying was 3.0 8 5, 2.5 46, 0.9 8 5, 12.910, respectively. The sorghum of 1.115 and 2.421, the cream of the first embodiment containing brown algae extracting gel, sodium hyaluronate and sodium acetylated hyaluronate, has a viscosity of 0.510 at the time of drying. It is apparent that the viscosity after coating becomes low. From these results, it is clear that the emulsifier composition contained in the brown algae extract gel, sodium hyaluronate and sodium hyaluronate has an excellent degree of smoothness when used. [Example 2] O.lg brown algae extract (brown algae extract: manufactured by BOTTGER), 〇.〇5g of sodium hyaluronate (Bio sodium hyaluronate HA12: manufactured by Shiseido Co., Ltd.), 0.001 g of sodium acetal hyaluronate ( Acetyl hyaluronate: manufactured by Shiseido Co., Ltd., lg concentrated glycerin, 2 g of 1,3-butanediol, 0.15 g of carboxyethyl-18-200817040 burned polymer (Carbopol ETD2050: manufactured by Noveon, viscosity 4,000~7,500 mPa · s (0_2%)) and 27.27 g of potassium hydroxide were added to 87.4 g of purified water to make it an aqueous phase heated to 8 °C. In addition, 2 g of stearic acid, 2 g of camellia oil, 4 g of jojoba oil, 3 g of whale sterol, 2 g of octyl dodecanoate, 2 g of squalene 'and 〇. 3g of monostearic acid glyceride (Daylight MGS-BMV: manufactured by Nikko Chemical Co., Ltd.), which was mixed with heat to 80 ° C as an oil phase. The oil phase was added to the aqueous phase, stirred at 80 ° C, mixed and emulsified, and then cooled to below 3 ° C to prepare an emulsion. Ten subjects were tested in the same manner as the above-mentioned experimental examples. The results are shown in Table 2.
-19- 200817040-19- 200817040
成分 實施例2(g) 褐藻萃取膠 0.1 玻尿酸鈉 0.0 5 乙醯化玻尿酸鈉 0.00 1 濃甘油 1.0 1,3-丁二醇 2.0 羧基乙烯聚合物 0.15 氫氧化鉀 0.2 7 硬酯酸 2.0 山茶花油 2.0 荷荷芭油 0.4 鯨鱲醇 0.3 肉萱蔻酸辛基十二酯 2.0 角鯊烯 2.0 單硬酯酸甘油酯 0.3 純化水 全量1 00g 評價項目 滑潤感 〇 由這些結果可明確得知,褐藻萃取膠,玻尿酸鈉及乙 醯化玻尿酸鈉均含有的實施例2之乳液,具有滑潤的使用 〔實施例3〕 將0.5g之加氫大豆磷脂質(PHOSPHOLIPON90H: H· Holstein· AND·公司製)加入 5g 之 1,3-丁二醇,於 65°C 下溶解後再冷卻至3 0 °C,並將其做爲油相。另外,將 O.lg之褐藻萃取膠(褊藻萃取膠:^〇丁丁0£以公司製)、 -20- 200817040 〇.〇5g之玻尿酸鈉(Bio玻尿酸鈉 HA12:資生堂公司製)、 0.001乙醯化玻尿酸鈉(乙醯化玻尿酸鈉··資生堂公司製) 、〇·1 g之竣基乙綺聚合物(ShitarenL:和光純藥工業公司 製,黏度 7,000 〜14,000mPa· s(0.2%) )、3g 之濃甘油、及 〇 · 〇 4 4 g之氫氧化鉀,加入9 1.2 g之純化水中,於室溫下攪 拌,將其做爲水相。再將水相加入油相中,於3 0。(:下進行 攪拌•混合’而製成乳液。所得乳液之使用感評價係根據 1 0位受試者與上述之實驗例同樣的進行使用試驗。結果示 於表3。Ingredient Example 2 (g) Brown algae extract 0.1 Sodium hyaluronate 0.0 5 Acetyl hyaluronate 0.00 1 Concentrated glycerol 1.0 1,3-butanediol 2.0 Carboxyvinyl polymer 0.15 Potassium hydroxide 0.2 7 Stearate 2.0 Camellia oil 2.0 Jojoba oil 0.4 whale sterol 0.3 octyl dodecanoate 2.0 squalene 2.0 glyceryl monostearate 0.3 purified water total amount 00g Evaluation of the project smoothness 〇 From these results, it is clear that brown algae extract The emulsion of Example 2 contained in both sodium hyaluronic acid and sodium acetylated hyaluronate was used for smoothing. [Example 3] 0.5 g of hydrogenated soybean phospholipid (PHOSPHOLIPON 90H: manufactured by H. Holstein·AND) was added to 5 g. The 1,3-butanediol was dissolved at 65 ° C and then cooled to 30 ° C and used as an oil phase. In addition, O.lg's brown algae extracting gel (褊藻提取胶: ^〇丁丁0£用制制制制), -20- 200817040 〇.〇5g of sodium hyaluronate (Bio sodium hyaluronate HA12: manufactured by Shiseido Co., Ltd.), 0.001 B Sodium hyaluronate (sodium sulphate hyaluronic acid · Shiseido Co., Ltd.), 〇·1 g of thioglycolate polymer (Shitaren L: Wako Pure Chemical Industries, Ltd., viscosity 7,000 ~ 14,000 mPa · s (0.2%)) 3 g of concentrated glycerin, and 〇· 4 4 g of potassium hydroxide were added to 9 1.2 g of purified water, and stirred at room temperature to make it an aqueous phase. The aqueous phase is then added to the oil phase at 30. (: stirring and mixing were carried out to prepare an emulsion. The evaluation of the feeling of use of the obtained emulsion was carried out in the same manner as in the above-mentioned experimental examples, and the results are shown in Table 3.
成分 實施例32(g) 褐藻萃取膠 0.1 玻尿酸鈉 0.05 乙醯化玻尿酸鈉 0.001 加氫大豆磷脂質 0.5 1,3-丁二醇 5.0 羧基乙烯聚合物 0.10 濃甘油 3.0 氬氧化鉀 0.044 純化水 全量1 0 0 g 評價項目 滑潤感 〇 由這些結果可明確得知,褐藻萃取膠,玻尿酸鈉及乙 醯化玻尿酸鈉均含有的實施例3之乳液,具有滑潤的使用 感。 -21 - 200817040 本發明係提供含有褐藻萃取膠以及玻尿酸,具滑潤的 使用感之乳化組成物。本發明之乳化組成物,可做爲皮膚 外用化妝料等利用於化妝品產業之外,亦可做爲對乾燥性 皮膚疾病之治療劑而利用於醫藥品產業,具產業上之可利 用性。Ingredient Example 32 (g) Brown algae extract 0.1 Sodium hyaluronate 0.05 Ethyl hyaluronate 0.001 Hydrogenated soybean phospholipid 0.5 1,3-butanediol 5.0 Carboxyvinyl polymer 0.10 Concentrated glycerol 3.0 Potassium argon oxide 0.044 Purified water total amount 1 0 0 g Evaluation of the smoothness of the evaluation of the item It is clear from these results that the emulsion of Example 3 contained in the brown algae extract gel, sodium hyaluronate and sodium ethionate hyaluronic acid has a smooth feeling of use. -21 - 200817040 The present invention provides an emulsified composition containing a brown algae extractant and hyaluronic acid, which has a smooth feeling of use. The emulsified composition of the present invention can be used in the cosmetics industry as a skin external cosmetic or the like, and can be used as a therapeutic agent for dry skin diseases in the pharmaceutical industry, and has industrial applicability.
•22-•twenty two-
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| CN102872482A (en) * | 2012-10-22 | 2013-01-16 | 温志仁 | Human body lubricating liquid |
| JP6092582B2 (en) * | 2012-11-08 | 2017-03-08 | 株式会社ミルボン | Scalp and hair cosmetics |
| CN104224853A (en) * | 2013-06-24 | 2014-12-24 | 李明贞 | Cream composition with glucosamine absorption enhancing effect |
| EP2835130A1 (en) * | 2013-08-05 | 2015-02-11 | Polichem SA | Composition for skin anti-ageing treatment |
| CN106913495A (en) * | 2015-12-24 | 2017-07-04 | 上海珍萃生物科技有限公司 | Profit maintenance skin essence dew and preparation method thereof |
| CN106176286B (en) * | 2016-08-30 | 2019-05-28 | 华熙生物科技股份有限公司 | Hyaluronic acid skin nursing film and preparation method and application |
| JP7543611B2 (en) * | 2019-11-18 | 2024-09-03 | 株式会社ファンケル | Skin care sheets |
| JP7699914B2 (en) * | 2020-08-19 | 2025-06-30 | クラシエ株式会社 | Emulsified cosmetics for the whole body |
| CN114939191B (en) * | 2022-04-20 | 2023-09-08 | 华熙生物科技股份有限公司 | Water-soluble lubricating liquid and preparation method and application thereof |
| CN118766787A (en) * | 2024-06-12 | 2024-10-15 | 广州兴美化妆品科技有限公司 | A composition for moisturizing and improving dry skin and a preparation method thereof |
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| JPS61204109A (en) * | 1985-03-07 | 1986-09-10 | Eisai Co Ltd | Emulsion-type composition for external use |
| JP2729304B2 (en) * | 1988-09-26 | 1998-03-18 | 株式会社コーセー | Oil-in-water emulsion composition |
| JP3557044B2 (en) * | 1995-06-29 | 2004-08-25 | 株式会社資生堂 | Emollient |
| JP3340310B2 (en) * | 1996-03-28 | 2002-11-05 | 株式会社資生堂 | Composite emulsion and method for producing the same |
| JPH10265332A (en) * | 1997-03-26 | 1998-10-06 | Shiseido Co Ltd | Oil-in-water type emulsion composition |
| JPH10279425A (en) * | 1997-03-31 | 1998-10-20 | Shiseido Co Ltd | Preparation for external use for skin |
| JP2001048769A (en) * | 1999-08-05 | 2001-02-20 | Shiseido Co Ltd | Skin lotion |
| JP2001233755A (en) * | 2000-02-25 | 2001-08-28 | Yakult Honsha Co Ltd | Skin external preparation composition |
| JP2005139070A (en) * | 2003-11-04 | 2005-06-02 | Kanebo Cosmetics Inc | Skin cosmetics |
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