TWI890701B - Skin topical agents - Google Patents
Skin topical agentsInfo
- Publication number
- TWI890701B TWI890701B TW109135638A TW109135638A TWI890701B TW I890701 B TWI890701 B TW I890701B TW 109135638 A TW109135638 A TW 109135638A TW 109135638 A TW109135638 A TW 109135638A TW I890701 B TWI890701 B TW I890701B
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- Prior art keywords
- skin
- cationic surfactant
- anionic polymer
- component
- topical
- Prior art date
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/67—Vitamins
- A61K8/673—Vitamin B group
- A61K8/675—Vitamin B3 or vitamin B3 active, e.g. nicotinamide, nicotinic acid, nicotinyl aldehyde
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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
- A61K8/11—Encapsulated compositions
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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
- A61K8/14—Liposomes; Vesicles
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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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
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/12—Face or body powders for grooming, adorning or absorbing
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/08—Anti-ageing preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
- A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
- A61K2800/5424—Polymers characterized by specific structures/properties characterized by the charge anionic
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Gerontology & Geriatric Medicine (AREA)
- Cosmetics (AREA)
Abstract
本發明係以獲得一種含有菸鹼醯胺、無黏膩感、滲透感優異且塗敷後肌膚之緊緻感優良的組成物為課題。解決該課題之皮膚外用劑係含有下列成分(A)~(D): (A)菸鹼醯胺1~10質量%、 (B)陽離子性界面活性劑、 (C)陰離子性高分子、 (D)水 的皮膚外用劑。This invention aims to produce a composition containing niacinamide that is non-sticky, has excellent penetrating properties, and leaves skin feeling firm and firm after application. The topical skin preparation that addresses this problem contains the following ingredients (A) to (D): (A) niacinamide (1-10% by weight), (B) a cationic surfactant, (C) an anionic polymer, (D) water.
Description
本發明係有關於一種含有菸鹼醯胺的皮膚外用劑,更詳而言之,係有關於一種含有陽離子性界面活性劑與陰離子性高分子,穩定性亦優良的皮膚外用劑。The present invention relates to a topical skin preparation containing niacinamide. More specifically, it relates to a topical skin preparation containing a cationic surfactant and an anionic polymer and having excellent stability.
皮膚會因年齡增長或壓力等內在因素,或者紫外線或空氣乾燥等外在因素而產生斑點、皺紋、鬆弛或色素沉著等。其中,由於皺紋、鬆弛等形態變化極影響外觀印象,而期望改善者眾。為了預防、改善此等皺紋、鬆弛,有人提出多種有效成分;其中,已知菸鹼醯胺的安全性高,且具有抗皮膚老化效果(例如參照專利文獻1、2)。然而,含有大量菸鹼醯胺時,已知黏膩感較強等有不理想的使用觸感,而有人已加以改善(例如參照專利文獻3)。Skin can develop spots, wrinkles, sagging, and hyperpigmentation due to internal factors like aging and stress, as well as external factors like UV rays and dry air. These changes significantly impact skin's appearance, leading to widespread desire for improvement. To prevent and improve these wrinkles and sagging, various active ingredients have been proposed. Among them, niacinamide is known to be highly safe and exhibits anti-aging effects (e.g., see Patents 1 and 2). However, high levels of niacinamide are known to cause undesirable tactile sensations, such as a sticky feel, which some researchers have attempted to improve (e.g., see Patent 3).
另外,對於局部塗佈於皮膚及毛髮而使用的化妝料或皮膚外用劑,有人致力研發提升有效成分對組織內部的滲透性。作為其手段之一,可舉出利用組成物中的電荷。咸認皮膚表面帶有負電荷,而帶有正電荷的陽離子性物質,已知對皮膚的吸附性或滲透性較高。因此,為了提高有效成分對生物體組織的吸附性及滲透性,有人提供含有陽離子化聚合物的化妝料(例如參照專利文獻4、5)。然而,併用陰離子性物質時,由於在組成物中會形成複合物,而有發生白濁,或者產生凝聚物或結塊等問題。又,作為供提升有效成分的滲透性的其他手段,可舉出利用囊泡粒子,亦已知有組合此2種手段之含有陽離子性界面活性劑的囊泡組成物(例如參照專利文獻6)。 [先前技術文獻] [專利文獻]Furthermore, efforts are underway to improve the penetration of active ingredients into tissues in cosmetics or topical preparations for topical application to the skin and hair. One approach involves utilizing the charge within the composition. While the skin surface is known to have a negative charge, positively charged cationic substances are known to have higher adsorption and permeability into the skin. Therefore, to enhance the adsorption and permeability of active ingredients into biological tissues, cosmetics containing cationic polymers have been proposed (e.g., see Patents 4 and 5). However, the combined use of anionic substances can lead to the formation of complexes within the composition, resulting in problems such as a cloudy appearance, aggregates, and clumping. Another approach for enhancing the permeability of active ingredients is the use of vesicle particles. Vesicle compositions containing cationic surfactants are also known, combining these two approaches (see, for example, Patent Document 6). [Prior Art Document] [Patent Document]
[專利文獻1]日本特開平10-130135號公報 [專利文獻2]日本特開平10-001414號公報 [專利文獻3]日本特表2003-502435號公報 [專利文獻4]日本特開2016-108344號公報 [專利文獻5]國際公開2019/111415號手冊 [專利文獻6]國際公開2014/069631號手冊[Patent Document 1] Japanese Patent Application Laid-Open No. 10-130135 [Patent Document 2] Japanese Patent Application Laid-Open No. 10-001414 [Patent Document 3] Japanese Patent Application Laid-Open No. 2003-502435 [Patent Document 4] Japanese Patent Application Laid-Open No. 2016-108344 [Patent Document 5] International Publication No. 2019/111415 [Patent Document 6] International Publication No. 2014/069631
[發明所欲解決之課題][The problem that the invention aims to solve]
從而,於本發明中,係以開發出一種雖含有皮膚滲透性優良的陽離子性界面活性劑,但可抑制、緩和電性交互作用所產生的凝聚物等而穩定性良好,且可與各種陰離子性物質併用之技術為課題。又,本發明係以提供一種大量摻混作為有效成分之菸鹼醯胺,使用時亦無黏膩感,對肌膚的滲透性優良,且塗敷後肌膚之緊緻感等的完妝真實感亦優異的皮膚外用劑為目的。 [解決課題之手段]Therefore, the present invention aims to develop a technology that, while containing a cationic surfactant with excellent skin penetration, can inhibit and mitigate the formation of aggregates resulting from electrical interactions, resulting in excellent stability and compatibility with various anionic substances. Furthermore, the present invention aims to provide a topical skin preparation that incorporates a large amount of niacinamide as an active ingredient, exhibits a non-sticky feel during use, has excellent skin penetration, and delivers a truly effective finish, such as a firming effect, upon application. [Means for Solving the Problem]
因此,本案發明人為解決上述課題而致力累積多次研究的結果發現,在含有陽離子性界面活性劑及陰離子性高分子的組成物中,透過共同使用菸鹼醯胺,可緩和陽離子性界面活性劑與陰離子性高分子之電性交互作用所引起的凝聚,而完成本發明。Therefore, the inventors of this case have devoted themselves to solving the above-mentioned problems and have accumulated many studies. As a result, they discovered that by using niacinamide in a composition containing a cationic surfactant and anionic polymer, the aggregation caused by the electrical interaction between the cationic surfactant and the anionic polymer can be alleviated, thus completing the present invention.
亦即,本發明係提供一種皮膚外用劑,其係含有下列成分(A)~(D): (A)菸鹼醯胺1~10質量%、 (B)陽離子性界面活性劑、 (C)陰離子性高分子、 (D)水。 [發明之效果]Specifically, the present invention provides a skin preparation containing the following ingredients (A) to (D): (A) 1-10% by weight of niacinamide, (B) a cationic surfactant, (C) an anionic polymer, and (D) water. [Effects of the Invention]
根據本發明,透過共同使用菸鹼醯胺,可抑制陽離子性界面活性劑與陰離子性高分子之電性交互作用所致之沉澱物的產生。又,本發明之皮膚外用劑,使用時無黏膩感,對肌膚的滲透感優良,且塗敷後肌膚之緊緻感等的完妝效果感優異。此外,該皮膚外用劑由於穩定性優良,可長時間使用,藉此,而有用於作為可提升肌膚的彈力,可預防或改善皺紋、肌膚鬆弛等老化形態變化之抗老化效果可期的化妝料。According to the present invention, the co-use of niacinamide inhibits the formation of deposits caused by the electrical interaction between cationic surfactants and anionic polymers. Furthermore, the skin topical preparation of the present invention is non-sticky upon application, penetrates the skin well, and provides a superior finish, such as a firming effect, after application. Furthermore, due to its excellent stability, the skin topical preparation can be used for extended periods of time, making it useful as an anti-aging cosmetic that can enhance skin elasticity and prevent or improve aging-related changes such as wrinkles and sagging.
[實施發明之形態][Form of implementing the invention]
以下就本發明詳細加以說明。此外,本說明書中,「~」係指包含其前後之數值的範圍。 本發明所使用之成分(A)菸鹼醯胺為菸鹼酸(維生素B3/菸酸)的醯胺化合物。菸鹼醯胺為水溶性維生素,係屬維生素B群之一的週知物質,可由天然物(米糠等)萃取而出,或者藉由週知方法來合成。具體而言,可使用第17次修訂日本藥典所記載者。The present invention is described below in detail. In this specification, "~" refers to a range inclusive of the numerical values before and after it. Ingredient (A) niacinamide used in the present invention is an amide compound of niacin (vitamin B3/niacin). Niacinamide is a water-soluble vitamin and a known substance belonging to the vitamin B complex. It can be extracted from natural sources (such as rice bran) or synthesized using known methods. Specifically, those listed in the 17th Revision of the Japanese Pharmacopoeia can be used.
本發明中之成分(A)的含量為1~10質量%(以下,將「質量%」簡稱為「%」),較佳為3~10%,特佳為4~9%。成分(A)的含量若未達1%,無法獲得緊緻感等;而超過10%時,則塗佈時的黏膩感較強,使用感較差。The content of component (A) in the present invention is 1-10% by mass (hereinafter referred to as "%"). It is preferably 3-10%, and particularly preferably 4-9%. If the content of component (A) is less than 1%, a firming effect, etc., cannot be achieved. If it exceeds 10%, the product will feel sticky during application, resulting in a poor feel during use.
本發明所使用之成分(B)陽離子性界面活性劑係供提升對肌膚的吸附性,以及作為皮膚外用劑之滲透感與肌膚親和性等者,只要是在一般的化妝料或皮膚外用劑等中使用者則不特別限制,可使用任意者。 成分(B)為烷基胺鹽、多胺及胺醇脂肪酸衍生物等胺鹽、烷基四級銨鹽、芳香族四級銨鹽、吡啶鎓鹽、咪唑鎓鹽等,可舉出例如氯化十六基三甲銨、溴化十六基三甲銨、氯化十八基三甲銨、溴化十八基三甲銨、氯化二十二基三甲銨、溴化二十二基三甲銨、甲基硫酸二十二基三甲銨、氯化二(十八基)二甲銨、溴化二油基二甲銨、甲基硫酸十六基二十二基二甲銨、氯化十八基二甲基苯甲銨、二棕櫚醯乙基羥乙基甲基銨甲基硫酸鹽、二椰油醯乙基羥乙基甲基銨甲基硫酸鹽、二硬脂醯乙基羥乙基甲基銨甲基硫酸鹽等四級銨鹽,可由此等當中選擇1種或2種以上。The cationic surfactant (Component (B) used in this invention is used to enhance skin adsorption, penetration, and skin compatibility of topical skin preparations. Any surfactant commonly used in cosmetics or topical skin preparations is not particularly limited and can be used. Component (B) is an alkylamine salt, an amine salt such as a polyamine or amino alcohol fatty acid derivative, an alkyl quaternary ammonium salt, an aromatic quaternary ammonium salt, a pyridinium salt, or an imidazolium salt. Examples include hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, behenyltrimethylammonium chloride, behenyltrimethylammonium bromide, and behenyltrimethylammonium methylsulfate. , dioctadecyldimethylammonium chloride, dioleyldimethylammonium bromide, hexadecyldimethylammonium methylsulfate, octadecyldimethylbenzylammonium chloride, disalamidoethyl hydroxyethyl methylammonium methylsulfate, dicocoylethyl hydroxyethyl methylammonium methylsulfate, distearylethyl hydroxyethyl methylammonium methylsulfate, and the like; one or more kinds thereof may be selected.
此外,就本發明之成分(B),只要是在組成物中具有陽離子性者,則亦可為兩性界面活性劑之骨架。作為此種界面活性劑,較佳為具有胺基酸殘基者,較佳的是該胺基酸殘基為鹼性胺基酸殘基。具體而言,可例示硬脂醯基離胺酸丁基酯・鹽酸鹽、N-椰油醯基-L-精胺酸乙基酯吡咯啶酮羧酸鹽、月桂醯基-鳥胺酸丙基酯・酢酸鹽等單-N-長鏈醯基鹼性胺基酸低級烷基酯鹽;癸基胍酢酸鹽、2-胍基乙基月桂基醯胺鹽酸鹽、2-胍基丁基硬脂醯胺・DL-吡咯啶酮羧酸鹽等胍衍生物等,可由此等當中選擇1種或2種以上。又,此等的鹽可舉出例如鹵素、甲基硫酸鹽、乙基硫酸鹽及甲基磷酸鹽等。Furthermore, component (B) of the present invention can also serve as the backbone of an amphoteric surfactant, as long as it is cationic in the composition. Such surfactants are preferably those having amino acid residues, and preferably, the amino acid residues are basic amino acid residues. Specific examples include mono-N-long-chain acyl basic amino acid lower alkyl ester salts such as butyl stearyl lysine hydrochloride, N-cocoyl-L-arginine ethyl ester pyrrolidone carboxylate, and lauryl-guanidine propyl ester anhydride; and guanidine derivatives such as decylguanidine anhydride, 2-guanidinoethyl laurylamide hydrochloride, and 2-guanidinobutylstearylamide DL-pyrrolidone carboxylate. One or more of these can be selected. Examples of these salts include halogens, methylsulfates, ethylsulfates, and methylphosphates.
此等當中,基於穩定性觀點,較佳為四級銨鹽及單-N-長鏈醯基鹼性胺基酸低級烷基酯鹽;四級銨鹽中,較佳為氯化烷基三甲銨、二長鏈醯基烷基羥烷基銨;單-N-長鏈醯基鹼性胺基酸低級烷基酯鹽中,較佳為N-椰油醯基-L-精胺酸乙基酯吡咯啶酮羧酸鹽。更具體而言,可使用與其他水性成分的混合物,而作為此種市售品,可舉出山嵛基三甲基氯化銨的混合物之GENAMIN KDMP(Clariant Japan公司製;純量81.5%)、二椰油醯乙基羥乙基甲基銨甲基硫酸鹽的混合物之DEHYQUART L80 T(BASF公司製:純分80%)、二棕櫚醯乙基羥乙基甲基銨甲基硫酸鹽的混合物之DEHYQUART AU56/G、DEHYQUART C4046(皆為BASF公司製)、N-椰油醯基-L-精胺酸乙基酯吡咯啶酮羧酸鹽之CAE(味之素公司製)等。其中,尤其若是二長鏈醯基烷基羥烷基銨這類雙鏈型界面活性劑,則可自行形成囊泡粒子,而進一步提升皮膚滲透性,且歷時穩定性亦優良而較佳。Among these, quaternary ammonium salts and mono-N-long-chain acyl basic amino acid lower alkyl ester salts are preferred from the perspective of stability; among quaternary ammonium salts, alkyltrimethylammonium chloride and di-long-chain acylalkylhydroxyalkylammonium are preferred; among mono-N-long-chain acyl basic amino acid lower alkyl ester salts, N-cocoyl-L-arginine ethyl ester pyrrolidone carboxylic acid salt is preferred. More specifically, a mixture with other aqueous components can be used. Examples of such commercially available products include GENAMIN KDMP (manufactured by Clariant Japan; pure content 81.5%), a mixture of behenyltrimethylammonium chloride; DEHYQUART L80 T (manufactured by BASF; pure content 80%), a mixture of dicocoylethyl hydroxyethyl methylammonium methylsulfate; DEHYQUART AU56/G and DEHYQUART C4046 (both manufactured by BASF), a mixture of disalcoholylethyl hydroxyethyl methylammonium methylsulfate; and CAE (manufactured by Ajinomoto Co., Ltd.), which is N-cocoyl-L-arginine ethyl ester pyrrolidone carboxylate. Among them, double-chain surfactants such as di-long-chain acylalkylhydroxyalkylammonium can form vesicle particles on their own, further enhancing skin permeability and providing excellent long-term stability.
本發明中之成分(B)的含量,基於對肌膚的滲透性或安全性觀點,約較佳為0.001~0.1%,更佳為0.002~0.05%,特佳為0.02~0.05%。The content of ingredient (B) in the present invention is preferably about 0.001-0.1%, more preferably 0.002-0.05%, and particularly preferably 0.02-0.05%, based on the viewpoint of skin permeability and safety.
於本發明中,成分(A)與成分(B)的含有質量比(A)/(B)不特別限定,基於作為皮膚外用劑的使用性觀點,係10~500,較佳為25~300,更佳為25~200。若為此範圍,使用時無黏膩感,且可良好地感到滲透感或塗敷後肌膚之緊緻感。In the present invention, the mass ratio (A)/(B) of component (A) to component (B) is not particularly limited, but from the perspective of usability as a skin external preparation, it is 10-500, preferably 25-300, and more preferably 25-200. Within this range, the product does not feel sticky during use, and a good penetration and firming feeling after application can be felt.
本發明所使用之成分(C)之陰離子性高分子係具有陰離子性的高分子,只要是一般作為化妝料使用者則不特別限定。具體而言,可舉出海藻酸、玻尿酸、阿拉伯膠、鹿角菜膠、硫酸軟骨素、明膠、羧甲基纖維素、羧基乙烯聚合物、聚丙烯酸等水溶性高分子及彼等之衍生物等,可使用此等當中的1種或2種以上。此外,此等可隨天然或合成等來源的不同而異,不特別限定。The anionic polymer used in component (C) of the present invention is an anionic polymer and is not particularly limited as long as it is commonly used in cosmetics. Specifically, examples include water-soluble polymers such as alginic acid, hyaluronic acid, gum arabic, carrageenan, chondroitin sulfate, gelatin, carboxymethyl cellulose, carboxyvinyl polymer, polyacrylic acid, and their derivatives. One or more of these polymers may be used. Furthermore, these polymers may vary depending on their source, whether natural or synthetic, and are not particularly limited.
其中,於本發明中,基於使用時無黏膩感及塗敷後肌膚之緊緻感優良之觀點,較佳為羧基乙烯聚合物及/或烷基改性羧基乙烯聚合物。此處所稱「羧基乙烯聚合物」,係指包含至少具有聚合性乙烯基與羧基或烷基改性羧基之聚合性單體作為構成單元之聚合物的總稱。此處所稱「烷基改性」,係指一部分或全部羧基經烷基酯化者,例如包含至少1種丙烯酸酯類或甲基丙烯酸酯類作為構成單體之聚合物係包含於經烷基改性之羧基乙烯聚合物的實例。烷基改性之烷基的碳數不予限定,較佳為10以上30以下,更佳為18以上24以下。烷基改性羧基乙烯聚合物之市售品可舉出CARBOPOL1342、CARBOPOL1382(以上為LUBRIZOL ADVANNCED MATERIALS公司製)、Pemulen TR-1、Pemulen TR-2(以上為NOVEON公司製)等;羧基乙烯聚合物之市售品可舉出CARBOPOL940、CARBOPOL941、CARBOPOL980、CARBOPOL934(以上為LUBRIZOL ADVANNCED MATERIALS公司製)、AQUPEC HV-501(住友精化公司製)等。Among them, in the present invention, carboxyvinyl polymers and/or alkyl-modified carboxyvinyl polymers are preferred from the viewpoint of having no sticky feeling during use and excellent skin tightening feeling after application. The "carboxyvinyl polymer" referred to herein is a general term for polymers containing polymerizable monomers having at least a polymerizable vinyl group and a carboxyl group or an alkyl-modified carboxyl group as constituent units. The "alkyl-modified" referred to herein refers to those in which a part or all of the carboxyl groups are esterified with an alkyl group. For example, a polymer containing at least one acrylic acid ester or methacrylic acid ester as a constituent monomer is included in the example of an alkyl-modified carboxyvinyl polymer. The number of carbon atoms in the alkyl-modified alkyl group is not limited, but is preferably 10 or more and 30 or less, and more preferably 18 or more and 24 or less. Commercially available products of alkyl-modified carboxyvinyl polymers include CARBOPOL 1342, CARBOPOL 1382 (all manufactured by LUBRIZOL Advanced Materials), Pemulen TR-1, and Pemulen TR-2 (all manufactured by NOVEON). Commercially available products of carboxyvinyl polymers include CARBOPOL 940, CARBOPOL 941, CARBOPOL 980, and CARBOPOL 934 (all manufactured by LUBRIZOL Advanced Materials), and AQUPEC HV-501 (manufactured by Sumitomo Seika Chemicals).
本發明中之成分(C)的摻混量,只要是一般使用於化妝料的摻混量則不特別限定,基於與成分(B)的交互作用之觀點,較佳處於0.001~10%,較佳為0.01~5%,且更佳為0.05~1%,特佳為0.05~0.2%的範圍。若為此範圍,則可提供穩定性優良或使用時無黏膩感、塗敷後肌膚之緊緻感優良的皮膚外用劑。The blending amount of ingredient (C) in the present invention is not particularly limited as long as it is a commonly used blending amount in cosmetics. However, from the perspective of interaction with ingredient (B), it is preferably in the range of 0.001-10%, more preferably 0.01-5%, more preferably 0.05-1%, and particularly preferably 0.05-0.2%. Within this range, a skin topical preparation with excellent stability, a non-sticky feel during use, and an excellent firming feel after application can be provided.
於本發明中,成分(A)與成分(C)的含有質量比(A)/(C)不特別限制,係5.0~150,較佳為5.0~125,更佳為10~100。若為此範圍,則無黏膩感,且塗敷後肌膚之緊緻感亦更優良。又,成分(B)與成分(C)的含有質量比(B)/(C)不特別限制,較佳為0.01~10,更佳為0.05~5,再更佳為0.1~1,特佳為0.2~0.6。若為此範圍,則凝聚抑制效果更優良。In the present invention, the mass ratio (A)/(C) of component (A) to component (C) is not particularly limited, but is 5.0-150, preferably 5.0-125, and more preferably 10-100. Within this range, a non-sticky feel is avoided, and the skin feels more firm after application. Furthermore, the mass ratio (B)/(C) of component (B) to component (C) is not particularly limited, but is preferably 0.01-10, more preferably 0.05-5, even more preferably 0.1-1, and particularly preferably 0.2-0.6. Within this range, the aggregation-inhibiting effect is even more enhanced.
本發明所使用之成分(D)水,只要是一般使用於化妝料等者則不特別限制。除純水外,在不損及本發明之效果的範圍,亦可為深層水,或者玫瑰水或薰衣草水等植物的水蒸氣蒸餾水,可視需求適宜選擇一種或二種以上來使用。 又,本發明中之成分(D)的摻混量,只要是一般使用於化妝料的摻混量則不特別限定,較佳為30~95%。The water component (D) used in this invention is not particularly limited, as long as it is commonly used in cosmetics. Besides pure water, deep water or plant-derived waters such as rose water and lavender water can also be used, as long as the effects of this invention are not compromised. One or more of these components can be selected as needed. The blending amount of component (D) in this invention is not particularly limited, as long as it is commonly used in cosmetics, but is preferably 30-95%.
再者,於本發明中,成分(E)若使用親水性之非離子性界面活性劑,則可抑制成分(B)與成分(C)的凝聚。作為成分(E),係HLB10~18的非離子性界面活性劑,更佳為HLB11~16者。此外,本發明中所使用之HLB(親水-親油平衡;Hydrophile-Lypophile Balance)值係根據格里芬法所得的值。具體而言,可舉出聚甘油脂肪酸酯、蔗糖脂肪酸酯、聚氧乙烯山梨醇酐脂肪酸酯、聚氧乙烯山梨醇脂肪酸酯、聚氧乙二醇脂肪酸酯、聚氧乙二醇脂肪酸酯、聚氧乙烯烷基醚、聚氧乙烯聚氧丙烯烷基醚、聚氧乙烯硬化蓖麻油、聚氧乙烯脂肪酸乙醇醯胺、聚氧乙烯膽固醇醚、聚氧乙烯二氫膽固醇醚、聚氧乙烯植物固醇醚、聚氧乙烯植物甾烷醇醚(polyoxyethylene phytostanol ether)、聚氧乙烯烷基醚、丙二醇脂肪酸酯、聚氧伸烷基改性聚矽氧、聚氧伸烷基烷基共改性聚矽氧等,可使用此等的1種或2種以上。其中,較佳為具有聚氧乙烯基之非離子性界面活性劑,較佳為環氧乙烷之平均加成莫耳數為5~100的非離子界面活性劑,更佳為10~80。Furthermore, in the present invention, using a hydrophilic nonionic surfactant as component (E) can inhibit aggregation of components (B) and (C). Component (E) is preferably a nonionic surfactant with an HLB of 10-18, more preferably 11-16. The HLB (Hydrophile-Lypophile Balance) value used in the present invention is the value obtained by the Griffin method. Specifically, polyglycerol fatty acid esters, sucrose fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycol fatty acid esters, polyoxyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid ethanolamides, polyoxyethylene cholesterol ethers, polyoxyethylene dihydrocholesterol ethers, polyoxyethylene phytosterol ethers, polyoxyethylene phytostanol ethers, polyoxyethylene alkyl ethers, propylene glycol fatty acid esters, polyoxyalkylene-modified polysilicone, polyoxyalkylene-alkyl co-modified polysilicone, and the like can be used alone or in combination. Among them, non-ionic surfactants having polyoxyethylene groups are preferred, and non-ionic surfactants having an average addition molar number of ethylene oxide of 5 to 100 are more preferred, and more preferably 10 to 80.
成分(E)可使用市售品,係例如單油酸聚氧乙烯山梨醇酐(20E.O.)之RHEODOL TW-O120V(花王公司製)、Nonion OT-221(日油公司製)、單硬脂酸聚氧乙烯山梨醇酐(20E.O.)之RHEODOL TW-S120V(花王公司製)、Nonion ST-221(日油公司製)、聚氧乙烯聚氧丙烯癸基十四基醚(20E.O.)之NIKKOL PEN-4620(Nikko Chemicals公司製)之EMALEX PS-30(NIHON EMULSION公司製)、NIKKOL BPS-30(Nikko Chemicals公司製)、聚氧乙烯硬化蓖麻油(60E.O.)之EMALEX HC-60(NIHON EMULSION公司製)、NIKKOL HCO-60(Nikko Chemicals公司製)、聚氧伸烷基改性有機聚矽氧烷,可例示KF-6011、KF-6011P、KF-6018、KF-6043(皆為信越化學工業公司製)、NUC Silicone SS-2802(Dow Corning Toray公司製)等。As component (E), commercially available products can be used, for example, RHEODOL TW-O120V (manufactured by Kao Corporation), Nonion OT-221 (manufactured by NOF Corporation) containing polyoxyethylene sorbitan monooleate (20 E.O.), RHEODOL TW-S120V (manufactured by Kao Corporation), Nonion ST-221 (manufactured by NOF Corporation) containing polyoxyethylene sorbitan monostearate (20 E.O.), NIKKOL PEN-4620 (manufactured by Nikko Chemicals) containing polyoxyethylene polyoxypropylene decyl tetradecyl ether (20 E.O.), EMALEX PS-30 (manufactured by NIHON EMULSION), NIKKOL BPS-30 (manufactured by Nikko Chemicals), EMALEX HC-60 (manufactured by NIHON EMULSION), NIKKOL HCO-60 (manufactured by Nikko Chemicals) containing polyoxyethylene hydrogenated castor oil (60 E.O.). Chemicals Co., Ltd.), polyoxyalkylene-modified organopolysiloxanes, such as KF-6011, KF-6011P, KF-6018, and KF-6043 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and NUC Silicone SS-2802 (manufactured by Dow Corning Toray Co., Ltd.).
本發明中之成分(E)的含量不特別限定,較佳為0.01~10%,更佳為0.05~8%,再更佳為0.1~6%,尤以0.5~6%為佳。若為此範圍,則可進一步抑制成分(B)與成分(C)的凝聚,而能夠獲得長期呈穩定的皮膚外用劑。The content of component (E) in the present invention is not particularly limited, but is preferably 0.01-10%, more preferably 0.05-8%, even more preferably 0.1-6%, and particularly preferably 0.5-6%. Within this range, the aggregation of components (B) and (C) can be further suppressed, resulting in a long-lasting, stable topical skin preparation.
於本發明中,成分(E)相對於成分(B)與成分(C)之總含有質量的比(E)/[(B)+(C)]不特別限定,基於成分(B)與成分(C)的凝聚抑制效果、使用時無黏膩感或滲透感良好,係0.1~150,較佳為0.5~100,更佳為1.0~80。In the present invention, the mass ratio of component (E) to the total mass of component (B) and component (C), (E)/[(B) + (C)], is not particularly limited. However, based on the aggregation-inhibiting effect of components (B) and (C) and the absence of a sticky feel or a good penetrating feel during use, it is preferably 0.1 to 150, preferably 0.5 to 100, and more preferably 1.0 to 80.
再者,於本發明中,透過成分(B)構成囊泡粒子,可提升電荷所產生的吸附性及作為皮膚外用劑的滲透性,且可進一步相乘性地發揮成分(A)及其他有效成分之效果。諸如前述,成分(B)之界面活性劑若為雙鏈型,則其單獨可形成囊泡,或者併用如磷脂質或二(月桂醯胺麩胺酸)離胺酸鈉之其他囊泡膜構成成分與成分(B),則亦可形成含有陽離子性界面活性劑的囊泡粒子。此等當中,基於安全性觀點,可較佳使用磷脂質。又,囊泡粒子的形成方法不特別限制,可根據習知方法來製造;囊泡粒子的確認方法,可使用偏光顯微鏡根據在正交偏光下有無馬耳他十字影像等來進行。使用磷脂質時,磷脂質的含量不特別限制,較佳為0.01~5%,更佳為0.05~1%,特佳為0.1~0.5%。Furthermore, in the present invention, by forming vesicle particles with component (B), the adsorption capacity generated by the charge and the permeability of the topical skin preparation can be enhanced, further synergistically promoting the effects of component (A) and other active ingredients. As mentioned above, if the surfactant component (B) is a bichain, it can form vesicles alone, or it can be combined with other vesicle membrane components such as phospholipids or sodium di(laurylaminoglutamic acid) lysine to form vesicle particles containing a cationic surfactant. Among these, phospholipids are preferred for safety reasons. The method for forming vesicle particles is not particularly limited and can be produced according to known methods. Vesicle particles can be confirmed using a polarizing microscope by observing the presence of a Maltese cross image under crossed polarized light. When phospholipids are used, the phospholipid content is not particularly limited, but is preferably 0.01-5%, more preferably 0.05-1%, and particularly preferably 0.1-0.5%.
又,本發明之皮膚外用劑的pH不特別限制,25℃的pH較佳為4.0~7.5的範圍內。The pH of the external skin preparation of the present invention is not particularly limited, but is preferably in the range of 4.0 to 7.5 at 25°C.
本發明之皮膚外用劑中,除上述成分(A)~(E)以外,亦可在不損及本發明之效果的範圍適宜含有一般使用於皮膚外用劑的成分。例如,可含有高級醇、烴油、酯油、蠟類、聚矽氧油等油劑、界面活性劑、水溶性高分子、多元醇、低級醇等水性成分、紫外線吸收劑、抗氧化劑、抗菌劑、防腐劑、保濕劑、pH調整劑、清涼劑、粉體、維生素類、美容成分、香料等。 如示出本發明皮膚外用劑之較佳組成的一樣態,則如以下所示: 成分 較佳 更佳 再更佳 特佳 (A) 1~10% 3~10% 4~9% 4~9% (B) 0.001~0.1% 0.002~0.05% 0.02~0.05% 0.02~0.05% (C) 0.001~10% 0.01~5% 0.05~1% 0.05~0.2% (D) 30~95% 30~95% 30~95% 30~95% (E) 0.01~10% 0.05~8% 0.1~6% 0.5~6%In addition to the aforementioned ingredients (A) to (E), the skin preparation of the present invention may also contain ingredients commonly used in skin preparations, as long as the effects of the present invention are not impaired. For example, it may contain oils such as higher alcohols, hydrocarbon oils, ester oils, waxes, silicone oils, surfactants, water-soluble polymers, polyols, aqueous components such as lower alcohols, UV absorbers, antioxidants, antibacterial agents, preservatives, moisturizers, pH adjusters, cooling agents, powders, vitamins, cosmetic ingredients, fragrances, etc. A preferred composition of the topical skin preparation of the present invention is as follows: Ingredients Preferred More Preferred Even More Preferred Particularly Preferred (A) 1-10% 3-10% 4-9% 4-9% (B) 0.001-0.1% 0.002-0.05% 0.02-0.05% 0.02-0.05% (C) 0.001-10% 0.01-5% 0.05-1% 0.05-0.2% (D) 30-95% 30-95% 30-95% 30-95% (E) 0.01~10% 0.05~8% 0.1~6% 0.5~6%
本發明之皮膚外用劑的製造方法不特別限定,可藉由常用方法來調製。可舉出例如將成分(B)與視需求而定的其他成分加熱溶解後,添加混合於經均勻地溶解混合之成分(A)、(C)~(E),進而視需求上述任意成分,並將其混合而調製的方法。The method for producing the skin external preparation of the present invention is not particularly limited and can be prepared by conventional methods. For example, component (B) and other components as needed are heated and dissolved, and then added and mixed to the uniformly dissolved and mixed components (A), (C) to (E), and then optionally any of the above components are added and mixed.
本發明之皮膚外用劑能以液狀、凝膠狀、乳膏狀等各種形態實施,且劑型為溶解型、水中油型、油中水型、油性型、水中油中水型、油中水中油型、多層型等,不特別限定。就穩定性觀點,在低黏度或者半透明之性質狀態下,可切身感受本發明之效果而較佳。The topical skin preparation of the present invention can be administered in various forms, including liquid, gel, and cream. The dosage forms include, but are not limited to, dissolving, oil-in-water, water-in-oil, oil-based, water-in-oil-in-water, oil-in-water, and multi-layer formulations. From a stability perspective, a low-viscosity or translucent formulation is preferred, as the effects of the present invention can be more readily felt.
此外,本發明之皮膚外用劑可作成皮膚用化妝料而利用,可例示例如化妝水、乳液、乳霜、美容液、按摩料、面膜料、護手霜、美體水(body lotion)、美體霜、防曬劑、粉底、眼影、眼線、遮瑕膏、頭皮用修補素(treatment)等。由可切身感受其效果而言,較佳為護膚化妝料;就其使用方法,可舉出以手、手指或化妝棉使用之方法、含浸於不織布等而使用之方法、直接噴霧而使用之方法等。於本發明之皮膚外用劑的較佳樣態中,可排除例如洗髮精、潤絲精、護髮素、髮蠟等專用於毛髮的毛髮化妝料。 [實施例]Furthermore, the skin topical preparation of the present invention can be used as a skin cosmetic. Examples include toners, emulsions, creams, serums, massage preparations, facial masks, hand creams, body lotions, body creams, sunscreens, foundations, eye shadows, eyeliners, concealers, and scalp treatments. Skin cosmetics are preferred because they offer a more tangible effect. Application methods include using hands, fingers, or cotton pads, impregnating nonwoven fabrics, and applying directly by spraying. Preferred forms of the skin topical preparation of the present invention exclude hair cosmetics specifically for hair, such as shampoos, conditioners, conditioners, and hair waxes. [Example]
以下,為了具體說明本發明而舉出實施例,惟本發明非限定於此等實施例等。又,除非特別明記,否則含量係以相對於含有該成分之組成物的質量%表示。In order to specifically illustrate the present invention, examples are given below, but the present invention is not limited to these examples, etc. In addition, unless otherwise specified, the content is expressed as a mass % relative to the composition containing the component.
實施例1~11及比較例1~4:美容液 根據下述製造方法製造表1所示組成之美容液,並針對A:凝聚抑制效果、B:滲透感、C:有無黏膩感、D:塗敷後肌膚之緊緻感,根據以下所示方法進行評定判定。將結果一併示於表1。Examples 1-11 and Comparative Examples 1-4: Beauty Essences The beauty essences with the compositions shown in Table 1 were prepared according to the following production method. The serums were evaluated using the following methods for: A: Aggregation-Inhibiting Effect; B: Penetration; C: Presence of Stickiness; and D: Skin Tightening Effect after Application. The results are summarized in Table 1.
(製造方法) A:將成分(1)、(2)、(5)~(11)及(16)以75℃均勻地加熱溶解。 B:將成分(3)、(4)、(12)~(15)以75℃均勻地加熱溶解。 C:於75℃下對B添加A,並加以攪拌而得到美容液。(Manufacturing method) A: Heat and dissolve ingredients (1), (2), (5) to (11), and (16) uniformly at 75°C. B: Heat and dissolve ingredients (3), (4), (12) to (15) uniformly at 75°C. C: Add A to B at 75°C and stir to obtain a beauty serum.
(評定方法1) (A.凝聚抑制效果) 就凝聚抑制效果,係以將實施例1~11及比較例1~4之美容液用水稀釋10倍時的透明性來評定。經確認該透明性可確保長期穩定性。 分別在玻璃製燒杯中量取1.0g的組成物,使用純水稀釋10倍並攪拌至獲得均勻的溶液。此時係使用金屬製軟膏刮鏟用手混合來攪拌。將所得試樣填充於光徑長10mm×光徑寬5mm的玻璃樣品槽,以分光光度計(UV-2500PC SHIMADZU公司製)測定波長700nm的穿透率。 <判定基準> (判定):(評定) ◎:穿透率為55%以上(室溫保存1個月後,無凝聚、沉澱) △:穿透率為45~55%(室溫保存1個月後,約略可看出凝聚、沉澱、濁度變化) ×:穿透率未達45%(室溫保存1個月後,可見凝聚、沉澱、濁度變化)(Evaluation Method 1) (A. Aggregation Inhibition Effect) The aggregation inhibition effect was evaluated based on the transparency of the serums from Examples 1-11 and Comparative Examples 1-4 when diluted 10-fold with water. This transparency was confirmed to ensure long-term stability. 1.0 g of each composition was weighed into a glass beaker, diluted 10-fold with pure water, and stirred until a uniform solution was obtained. The solution was stirred manually using a metal spatula. The resulting sample was placed in a glass sample cell with an optical diameter of 10 mm long and an optical diameter of 5 mm wide. The transmittance at a wavelength of 700 nm was measured using a spectrophotometer (UV-2500PC, manufactured by Shimadzu Corporation). <Evaluation Criteria> (Evaluation): (Evaluation) ◎: Transmission 55% or higher (no aggregation or sedimentation after one month at room temperature) △: Transmission 45-55% (slight aggregation, sedimentation, and turbidity changes are visible after one month at room temperature) ×: Transmission less than 45% (aggregation, sedimentation, and turbidity changes are visible after one month at room temperature)
(評定方法2) 由20多歲~40多歲的女性接受官能評定訓練,選出10位可根據既定基準進行評定的專業官能檢查員。請該專業官能檢查員於前腕使用各試料,並針對各者,將使用時所感受到的滲透感、有無黏膩感及塗敷後肌膚之緊緻感,依下述絕對評定按5等級進行評定並評分。依各試料,由全體官能檢查員的評分合計算出其平均值,根據下述4等級判定基準進行判定。(Evaluation Method 2) Ten professional sensory examiners, trained in sensory assessment and capable of performing evaluations based on established criteria, were selected from women in their 20s to 40s. Each tester applied each sample to their forearm and rated the sensation of penetration, stickiness, and post-application firmness on a 5-point scale using the absolute rating system described below. For each sample, the average score from all sensory examiners was calculated and evaluated using the 4-point rating system described below.
(B:滲透感) <絕對評定基準> (評分):(評定) 5分:感覺有化妝水對肌膚的滲透感 4分:略感覺有化妝水對肌膚的滲透感 3分:普通 2分:幾乎未感覺有化妝水對肌膚的滲透感 1分:未感覺有化妝水對肌膚的滲透感 <4等級判定基準> (就以下的評定項目亦同) (判定):(評分的平均分數) ◎:4.5分以上 :極為良好 ○:3.5分以上且未達4.5分 :良好 △:1.5分以上且未達3.5分 :略為不良 ×:未達1.5分 :不良(B: Penetration) <Absolute Rating Criteria> (Rating): (Rating) 5 points: The toner penetrates the skin 4 points: The toner slightly penetrates the skin 3 points: Average 2 points: The toner barely penetrates the skin 1 point: The toner does not penetrate the skin <4-Level Rating Criteria> (The same applies to the following rating items) (Rating): (Average of ratings) ◎: 4.5 points or higher: Very good ○: 3.5 points or higher but less than 4.5 points: Good △: 1.5 points or higher but less than 3.5 points: Slightly poor ×: Less than 1.5 points: Poor
(C:有無黏膩感) <絕對評定基準> (評分):(評定) 5分:無黏膩感 4分:幾無黏膩感 3分:略有黏膩感 2分:有黏膩感 1分:黏膩感極強(C: Stickiness) <Absolute Rating Criteria> (Rating): (Rating) 5 points: No stickiness 4 points: Almost no stickiness 3 points: Slightly sticky 2 points: Some stickiness 1 point: Extremely sticky
(D:塗敷後肌膚之緊緻感) <絕對評定基準> (評分):(評定) 5分:感覺有肌膚之緊緻感 4分:略感覺有肌膚之緊緻感 3分:普通 2分:幾乎未感覺有肌膚之緊緻感 1分:未感覺有肌膚之緊緻感(D: Skin tightening sensation after application) <Absolute Rating Criteria> (Rating): (Rating) 5 points: Skin tightening sensation 4 points: Slightly tightening sensation 3 points: Average 2 points: Almost no tightening sensation 1 point: No tightening sensation
由表1之結果可知,實施例1~11之美容液,相較於比較例1~4之美容液,凝聚抑制效果、滲透感、無黏膩感、塗敷後肌膚之緊緻感較優良。 另一方面,不含成分(A)的比較例1,塗敷後肌膚之緊緻感較差。將成分(A)變更為其他對皮膚有益之用劑(甘草酸二鉀)的比較例2,凝聚抑制效果、無黏膩感、塗敷後肌膚之緊緻感較差。成分(A)為0.5%的比較例3,亦同樣地無法感到塗敷後肌膚之緊緻感,而成分(A)為15%的比較例4,由於菸鹼醯胺過多,不易感到滲透感,且產生了黏膩感。As shown in Table 1, the serums of Examples 1-11 exhibited superior aggregation-inhibiting effects, penetration, a non-sticky feel, and a firming feel after application compared to the serums of Comparative Examples 1-4. On the other hand, Comparative Example 1, which did not contain ingredient (A), exhibited a poorer firming feel after application. Comparative Example 2, which replaced ingredient (A) with another skin-friendly agent (dipotassium glycyrrhizate), exhibited poor aggregation-inhibiting effects, a non-sticky feel, and a less firming feel after application. Comparative Example 3, with a 0.5% concentration of Ingredient (A), also failed to provide a firming sensation after application. In Comparative Example 4, with a 15% concentration of Ingredient (A), due to the excessive amount of niacinamide, the product did not penetrate the skin and had a sticky feel.
實施例12:化妝水 (成分) (%) (1)氯化烷基三甲銨 (註2) 0.1 (2)氫化大豆磷脂質 (註7) 0.5 (3)1,3-丁二醇 5.0 (4)單油酸聚氧乙烯山梨醇酐(20E.O.) 1.0 (5)香料 適量 (6)乙醇 10.0 (7)防腐劑 適量 (8)菸鹼醯胺 5.0 (9)傳明酸 2.0 (10)聚氧乙烯甘油(26E.O.) 2.0 (11)聚氧乙烯甲基葡萄糖苷 (註8) 2.0 (12)(丙烯酸酯/丙烯酸烷基酯(C10-C30))交聯共聚物(註3) 0.1 (13)羧基乙烯聚合物 0.1 (14)氫氧化鈉 0.05 (15)純水 餘量 (註8)Macbiobride MG-10E(日油公司製)Example 12: Toner (Ingredients) (%) (1) Alkyl trimethylammonium chloride (Note 2) 0.1 (2) Hydrogenated soybean lecithin (Note 7) 0.5 (3) 1,3-Butanediol 5.0 (4) Monooleate polyoxyethylene sorbitan (20 E.O.) 1.0 (5) Fragrance q. q. (6) Ethanol 10.0 (7) Preservative q. q. (8) Niacinamide 5.0 (9) Tranexamic acid 2.0 (10) Polyoxyethylene glycerol (26E.O.) 2.0 (11) Polyoxyethylene methyl glucoside (Note 8) 2.0 (12) (Acrylates/alkyl acrylate (C10-C30)) crosslinked copolymer (Note 3) 0.1 (13) Carboxyethylene polymer 0.1 (14) Sodium hydroxide 0.05 (15) Purified water Residue (Note 8) Macbiobride MG-10E (manufactured by NOF Corporation)
(製造方法) A:將成分(1)~(3)以75℃均勻地溶解混合。 B:一邊將前述A保持於75℃一邊添加一部分的成分(15),並以Disper mixer攪拌而得到囊泡分散液。 C:將成分(4)~(15)以室溫均勻地溶解混合。 D:對前述C添加混合冷卻至35℃的前述B而得到化妝水。 如以上所得之化妝水,其凝聚抑制效果、滲透感、無黏膩感、塗敷後肌膚之緊緻感優良。(Manufacturing method) A: Dissolve and mix components (1) to (3) uniformly at 75°C. B: While maintaining the temperature of the aforementioned A at 75°C, add a portion of the component (15) and stir with a disper mixer to obtain a vesicle dispersion. C: Dissolve and mix components (4) to (15) uniformly at room temperature. D: Add the aforementioned component B cooled to 35°C to the aforementioned component C to obtain a toner. The toner obtained above has excellent aggregation inhibition effect, penetrating feel, no stickiness, and a firming feel on the skin after application.
實施例13:透明化妝水 (成分) (%) (1)異硬脂酸聚氧乙烯(50)硬化蓖麻油 0.2 (2)PEG-10甲基醚聚二甲基矽氧烷 (註4) 0.1 (3)二椰油醯乙基羥乙基甲基銨甲基硫酸鹽 0.01 (4)氯化烷基三甲銨 0.01 (5)油酸乙酯 0.05 (6)2-乙基己酸十六酯 0.05 (7)香料 適量 (8)乙醇 1.0 (9)1,3-丁二醇 5.0 (10)甘油 5.0 (11)二甘油 2.0 (12)聚氧丁烯聚氧乙烯聚氧丙烯甘油醚 (3E.O.) (註9) 3.0 (13)菸鹼醯胺 5.0 (14)羧基乙烯聚合物 0.1 (15)氫氧化鈉 0.05 (16)傳明酸 1.0 (17)氫氧化鈉 0.05 (18)防腐劑 適量 (19)香料 適量 (20)純水 餘量 (註9)WILBRIDE S-753D(日油公司製)Example 13: Transparent toner (Ingredients) (%) (1) Polyoxyethylene Isostearate (50) Hardened Castor Oil 0.2 (2) PEG-10 Methyl Ether Dimethicone (Note 4) 0.1 (3) Dicocoyl Ethyl Hydroxyethyl Methylammonium Methyl Sulfate 0.01 (4) Alkyl Trimethylammonium Chloride 0.01 (5) Ethyl Oleate 0.05 (6) Hexadecyl 2-Ethylhexanoate 0.05 (7) Fragrance q.s. (8) Ethanol 1.0 (9) 1,3-Butanediol 5.0 (10) Glycerol 5.0 (11) Diglycerol 2.0 (12) Polyoxybutylene polyoxyethylene polyoxypropylene glycerol ether (3E.O.) (Note 9) 3.0 (13) Niacinamide 5.0 (14) Carboxyvinyl polymer 0.1 (15) Sodium hydroxide 0.05 (16) Tranexamic acid 1.0 (17) Sodium hydroxide 0.05 (18) Preservatives As needed (19) Flavorings As needed (20) Pure water Balance (Note 9) WILBRIDE S-753D (manufactured by NOF)
(製造方法) A:將成分(1)~(10)以70℃均勻地溶解混合。 B:將成分(11)~(20)以室溫均勻地溶解混合。 C:將前述A添加於B,於室溫下使其溶化而得到透明化妝水。 如以上所得之透明化妝水,其凝聚抑制效果、滲透感、無黏膩感、塗敷後肌膚之緊緻感優良。(Manufacturing method) A: Dissolve and mix ingredients (1) to (10) uniformly at 70°C. B: Dissolve and mix ingredients (11) to (20) uniformly at room temperature. C: Add ingredient A to ingredient B and dissolve them at room temperature to obtain a transparent toner. The transparent toner obtained above has excellent aggregation inhibition effect, good penetrating feeling, no stickiness, and a firming feeling on the skin after application.
實施例14:水中油乳化型美容液 (成分) (%) (1)聚甘油-10 (二十烷二酸/十四烷二酸)酯 1.5 (2)三丙二醇 15.0 (3)菸鹼醯胺 6.0 (4)L-茶胺酸 0.05 (5)1,3-丁二醇 3.5 (6)二丙二醇 0.5 (7)純水 餘量 (8)甘油 2.0 (9)聚乙二醇 2.0 (10)傳明酸 2.0 (11)磷酸氫鈉 0.3 (12)磷酸二氫鈉 0.6 (13)乙二胺四乙酸二鈉 0.02 (14)對羥基苯甲酸甲酯 0.1 (15)異硬脂酸聚氧乙烯(50)硬化蓖麻油 0.2 (16)聚氧乙烯(60)硬化蓖麻油 0.2 (17)二椰油醯乙基羥乙基甲基銨甲基硫酸鹽 0.01 (18)乙醇 5.0 (19)L-薄荷醇 0.02 (20)肉豆蔻酸異丙酯 0.3 (21)二聚物二亞麻油酸(植物固醇酯/異十八酯/十六酯/十八酯/二十二酯 (註10) 0.2 (22)油酸山梨醇酐 0.2 (23)生育三烯酚 0.02 (24)羧基乙烯聚合物 0.02 (25)(丙烯酸酯/丙烯酸烷基酯(C10-30))交聯共聚物 (註3) 0.02 (26)黃原膠 0.01 (27)氫氧化鈉 0.01 (28)水解玻尿酸 0.01 (註10)PLANDOOL-S(日本精化公司製)Example 14: Water-in-oil emulsion beauty serum (Ingredients) (%) (1) Polyglyceryl-10 (eicosanedioic acid/tetradecandioic acid) ester 1.5 (2) Tripropylene glycol 15.0 (3) Niacinamide 6.0 (4) L-theanine 0.05 (5) 1,3-Butanediol 3.5 (6) Dipropylene glycol 0.5 (7) Pure water Balance (8) Glycerin 2.0 (9) Polyethylene glycol 2.0 (10) Tranexamic acid 2.0 (11) Sodium hydrogen phosphate 0.3 (12) Sodium dihydrogen phosphate 0.6 (13) Disodium ethylenediaminetetraacetic acid 0.02 (14) Methyl p-hydroxybenzoate 0.1 (15) Polyoxyethylene (50) isostearate, hydrogenated castor oil 0.2 (16) Polyoxyethylene (60) hydrogenated castor oil 0.2 (17) Dicocoylethyl hydroxyethyl methylammonium methyl sulfate 0.01 (18) Ethanol 5.0 (19) L-Menthol 0.02 (20) Isopropyl myristate 0.3 (21) Dimer dilinoleic acid (phytosteryl esters/isostearyl/cetyl ester/octadecyl ester/behenyl ester (Note 10)) 0.2 (22) Sorbitan oleate 0.2 (23) Tocotrienols 0.02 (24) Carboxyvinyl polymer 0.02 (25) (Acrylates/alkyl acrylate (C10-30)) crosslinked copolymer (Note 3) 0.02 (26) Xanthan gum 0.01 (27) Sodium hydroxide 0.01 (28) Hydrolyzed hyaluronic acid 0.01 (Note 10) PLANDOOL-S (made by Seika Co., Ltd.)
(製造方法) A:將成分(1)~(14)以室溫均勻地混合。 B:將成分(15)~(23)以70℃均勻地溶解混合。 C:對前述A添加B並於70℃予以乳化。 D:將前述C冷卻至40℃後,添加成分(24)~(28)並予以均勻混合而得到美容液。 如以上所得之水中油乳化型美容液,其凝聚抑制效果、滲透感、無黏膩感、塗敷後肌膚之緊緻感優良。(Manufacturing method) A: Mix ingredients (1) to (14) uniformly at room temperature. B: Dissolve and mix ingredients (15) to (23) uniformly at 70°C. C: Add ingredient B to ingredient A and emulsify at 70°C. D: Cool ingredient C to 40°C, then add ingredients (24) to (28) and mix uniformly to obtain a beauty serum. The oil-in-water emulsion beauty serum obtained above has excellent aggregation inhibition effect, penetrating feeling, non-sticky feeling, and a firming feeling on the skin after application.
實施例15:防曬劑(水中油型) (成分) (%) (1)1,3-丁二醇 5.0 (2)二丙二醇 5.0 (3)山嵛基三甲基氯化銨 0.1 (4)氫化卵磷脂 (註11) 0.5 (5)膽固醇 (註12) 0.6 (6)植物固醇 0.1 (7)純水 餘量 (8)菸鹼醯胺 3.0 (9)傳明酸 2.0 (10)(丙烯酸/丙烯酸烷基酯(C10-30))共聚物 (註13) 0.4 (11)三乙醇胺 0.4 (12)聚矽氧烷-15 1.2 (13)4-第三丁基-4’-甲氧基-二苯甲醯基甲烷 2.0 (14)對甲氧基肉桂酸2-乙基己酯 7.0 (15)二乙胺基羥基苯甲醯基苯甲酸己酯 2.5 (16)硬脂酸硬化蓖麻油 (註14) 1.0 (17)丙二醇二癸酸酯 5.0 (18)油酸乙酯 0.3 (19)天然維生素E 0.1 (20)迷迭香油 0.01 (21)1,2-戊二醇 0.1 (22)氧化鋅 2.0 (23)水溶性膠原蛋白 0.01 (24)德國洋甘菊花萃取物 0.05 (25)金盞花萃取物 0.05 (26)甘油 1.0 (27)乙醇 7.0 (28)香料 0.1 (註11)NIKKOL RETINOL S-10(Nikko Chemicals公司製) (註12)海麗海洋膽固醇(日本水產公司製) (註13)Pemulen TR-2(NOVEON公司製) (註14)Castride MS(National Mimatsu公司製)Example 15: Sunscreen (Oil-in-Water Type) (Ingredients) (%) (1) 1,3-Butanediol 5.0 (2) Dipropylene glycol 5.0 (3) Behenyltrimethylammonium chloride 0.1 (4) Hydrogenated lecithin (Note 11) 0.5 (5) Cholesterol (Note 12) 0.6 (6) Phytosterols 0.1 (7) Purified water Remainder (8) Niacinamide 3.0 (9) Tranexamic acid 2.0 (10) (Acrylic acid/alkyl acrylate (C10-30)) copolymer (Note 13) 0.4 (11) Triethanolamine 0.4 (12) Polysilicone-15 1.2 (13) 4-tert-butyl-4'-methoxy-diphenylmethane 2.0 (14) 2-Ethylhexyl p-methoxycinnamate 7.0 (15) Diethylaminohydroxybenzoyl hexyl benzoate 2.5 (16) Stearic acid, hydrogenated castor oil (Note 14) 1.0 (17) Propylene glycol dicaprate 5.0 (18) Ethyl Oleate 0.3 (19) Natural Vitamin E 0.1 (20) Rosemary Oil 0.01 (21) 1,2-Pentanediol 0.1 (22) Zinc Oxide 2.0 (23) Water-soluble Collagen 0.01 (24) German Chamomile Flower Extract 0.05 (25) Calendula Flower Extract 0.05 (26) Glycerin 1.0 (27) Ethanol 7.0 (28) Fragrance 0.1 (Note 11) NIKKOL RETINOL S-10 (Nikko Chemicals) (Note 12) Haili Marine Cholesterol (Nihon Suisan Co., Ltd.) (Note 13) Pemulen TR-2 (Noveon) (Note 14) Castride MS (National Mimatsu)
(製造方法) A:將成分(1)~(6)以75℃均勻地溶解混合。 B:將成分(7)~(11)以70℃均勻地溶解混合。 C:將成分(12)~(19)以80℃均勻地溶解混合。 D:對前述A添加B及C並於70℃予以乳化。 E:對前述D添加混合成分(20)~(28)後,冷卻至40℃而得到防曬劑(水中油型)。 如以上所得之防曬劑(水中油型),其凝聚抑制效果、滲透感、無黏膩感、塗敷後肌膚之緊緻感優良。(Manufacturing method) A: Dissolve and mix components (1) to (6) uniformly at 75°C. B: Dissolve and mix components (7) to (11) uniformly at 70°C. C: Dissolve and mix components (12) to (19) uniformly at 80°C. D: Add components B and C to the above-mentioned A and emulsify at 70°C. E: Add and mix components (20) to (28) to the above-mentioned D, and cool to 40°C to obtain a sunscreen (oil-in-water type). The sunscreen (oil-in-water type) obtained as described above has excellent aggregation inhibition effect, penetrating feeling, non-sticky feeling, and a firming feeling on the skin after application.
實施例16:水中油型乳液 (成分) (%) (1)1,3-丁二醇 5.0 (2)二丙二醇 5.0 (3)氯化烷基三甲銨 (註2) 0.03 (4)氫化大豆磷脂質 (註7) 0.2 (5)膽固醇 (註12) 0.7 (6)純水 餘量 (7)菸鹼醯胺 8.0 (8)氫氧化鈉2%水溶液 0.2 (9)N-肉豆蔻醯基-L-麩胺酸 0.2 (10)聚氧乙烯(10)硬化蓖麻油 0.2 (11)澳洲堅果油脂肪酸植物固醇酯 (註15) 1.0 (12)三(辛酸/辛酸)甘油酯 0.2 (13)生育酚菸鹼酸酯 0.01 (14)天然維生素E 0.1 (15)米胚芽油 0.01 (16)生育酚乙酸酯 0.01 (17)單油酸聚氧乙烯山梨醇酐(20E.O.) 1.5 (18)十八醇 0.5 (19)二十二醇 1.0 (20)1,2-戊二醇 0.1 (21)十八醇 0.5 (22)羧基乙烯聚合物 0.2 (23)(丙烯酸鈉/丙烯醯基二甲基牛磺酸鈉)共聚物 (註16) 0.5 (24)傳明酸 1.0 (25)二甘油 0.5 (26)延命草萃取物 0.05 (27)鈍叉珊藻萃取物 0.05 (28)黑大豆萃取物 0.05 (29)芝麻發芽物萃取物 0.05 (30)甘油 1.0 (31)乙醇 5.0 (32)香料 0.1 (註15)PLANDOOL-MAS(日本精化公司製) (註16)SIMULGEL EG QD(SEPPIC公司製)Example 16: Oil-in-water emulsion (Ingredients) (%) (1) 1,3-Butanediol 5.0 (2) Dipropylene glycol 5.0 (3) Alkyltrimethylammonium chloride (Note 2) 0.03 (4) Hydrogenated soybean lecithin (Note 7) 0.2 (5) Cholesterol (Note 12) 0.7 (6) Pure water Residue (7) Niacinamide 8.0 (8) Sodium hydroxide 2% aqueous solution 0.2 (9) N-Myristyl-L-glutamine 0.2 (10) Polyoxyethylene (10) hydrogenated castor oil 0.2 (11) Macadamia nut oil fatty acid sterol esters (Note 15) 1.0 (12) Tri(caprylic/octanoic) glyceride 0.2 (13) Tocopheryl nicotinate 0.01 (14) Natural vitamin E 0.1 (15) Rice germ oil 0.01 (16) Tocopheryl acetate 0.01 (17) Polyoxyethylene sorbitan monooleate (20E.O.) 1.5 (18) Octadecanol 0.5 (19) Docosanol 1.0 (20) 1,2-Pentanediol 0.1 (21) Octadecanol 0.5 (22) Carboxyvinyl polymer 0.2 (23) (Sodium acrylate/sodium acryloyldimethyltaurate) copolymer (Note 16) 0.5 (24) Tranexamic acid 1.0 (25) Diglycerol 0.5 (26) Herba Lycopersicifoliae extract 0.05 (27) Coriander extract 0.05 (28) Black soybean extract 0.05 (29) Sesame sprout extract 0.05 (30) Glycerin 1.0 (31) Ethanol 5.0 (32) Fragrance 0.1 (Note 15) PLANDOOL-MAS (made by Nippon Seika Co., Ltd.) (Note 16) SIMULGEL EG QD (made by SEPPIC Co., Ltd.)
(製造方法) A:將成分(1)~(5)以75℃均勻地溶解混合。 B:一邊將前述A保持於75℃一邊添加一部分的成分(6),並以Disper mixer攪拌而得到囊泡分散液。 C:將其餘成分(6)~(8)以室溫均勻地溶解混合。 D:將成分(9)~(19)以80℃均勻地溶解混合。 E:一邊將前述D保持於75℃一邊添加經加熱之前述C而予以乳化。 F:對前述E添加混合成分(20)~(32)後,冷卻至40℃而得到水中油型乳液。 如以上所得之水中油型乳液,其凝聚抑制效果、滲透感、無黏膩感、塗敷後肌膚之緊緻感優良。(Manufacturing method) A: Dissolve and mix components (1) to (5) uniformly at 75°C. B: While maintaining the temperature of the aforementioned A at 75°C, add a portion of the component (6) and stir with a disper mixer to obtain a vesicle dispersion. C: Dissolve and mix the remaining components (6) to (8) uniformly at room temperature. D: Dissolve and mix components (9) to (19) uniformly at 80°C. E: While maintaining the temperature of the aforementioned D at 75°C, add the heated aforementioned C and emulsify. F: Add the mixed components (20) to (32) to the aforementioned E, and cool to 40°C to obtain an oil-in-water emulsion. The oil-in-water emulsion obtained above has excellent aggregation inhibition effect, penetrating feeling, non-sticky feeling, and a firming feeling on the skin after application.
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| JP2004203803A (en) * | 2002-12-26 | 2004-07-22 | Sunstar Inc | Cleanser composition |
| CN106265392A (en) * | 2016-11-07 | 2017-01-04 | 北京痘博士痤疮医学研究院 | A kind of health skin purifies essence |
| CN107823025A (en) * | 2017-12-24 | 2018-03-23 | 姚佑灿 | A kind of Whelk-eliminating paste |
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| JPH101414A (en) | 1996-06-12 | 1998-01-06 | Kanebo Ltd | Skin cosmetic |
| JP3922311B2 (en) | 1996-10-29 | 2007-05-30 | 花王株式会社 | Skin aging prevention cosmetics |
| BR0010930A (en) | 1999-05-25 | 2002-04-16 | Procter & Gamble | Topical composition of skin treatment, leave-on and use of polydecene and oil to reduce the glutinosity of this composition |
| DE19961256A1 (en) * | 1999-12-18 | 2001-06-21 | Clariant Gmbh | Cosmetic preparations |
| WO2014069631A1 (en) * | 2012-11-05 | 2014-05-08 | 株式会社コーセー | Vesicle composition, and external preparation for skin and cosmetic preparation each of which contains same |
| JP6715592B2 (en) | 2014-12-08 | 2020-07-01 | ワミレスコスメティックス株式会社 | Cosmetics containing low molecular weight cationized hyaluronic acid |
| CN106806297A (en) * | 2015-11-30 | 2017-06-09 | 朱延升 | A kind of environmentally friendly oil resistant handguard film |
| CN106619149A (en) * | 2017-01-23 | 2017-05-10 | 上海应用技术大学 | Method for preparing nicotinamide-coated multivesicular liposomes |
| JP2019014709A (en) * | 2017-07-07 | 2019-01-31 | ポーラ化成工業株式会社 | Skin care composition |
| CN111683650B (en) * | 2017-12-08 | 2021-11-05 | 和美令须化妆品株式会社 | Cationized vesicles and compositions thereof |
| JP7356228B2 (en) * | 2018-01-31 | 2023-10-04 | 株式会社コーセー | Composition |
| CN109700754B (en) * | 2019-02-27 | 2020-08-04 | 广东柏俐臣生物科技有限公司 | Preparation method of face protection spray |
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| JP2004203803A (en) * | 2002-12-26 | 2004-07-22 | Sunstar Inc | Cleanser composition |
| CN106265392A (en) * | 2016-11-07 | 2017-01-04 | 北京痘博士痤疮医学研究院 | A kind of health skin purifies essence |
| CN107823025A (en) * | 2017-12-24 | 2018-03-23 | 姚佑灿 | A kind of Whelk-eliminating paste |
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