JP2020109074A - Composition for forming liquid crystal, liquid crystal-containing emulsifier, and liquid crystal-containing cosmetic that is creamy or film-like - Google Patents
Composition for forming liquid crystal, liquid crystal-containing emulsifier, and liquid crystal-containing cosmetic that is creamy or film-like Download PDFInfo
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- JP2020109074A JP2020109074A JP2019218502A JP2019218502A JP2020109074A JP 2020109074 A JP2020109074 A JP 2020109074A JP 2019218502 A JP2019218502 A JP 2019218502A JP 2019218502 A JP2019218502 A JP 2019218502A JP 2020109074 A JP2020109074 A JP 2020109074A
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- Prior art keywords
- liquid crystal
- film
- cosmetic
- mass
- skin
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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Abstract
Description
本発明は、液晶を形成するために用いられる組成物及び該組成物を利用した液晶を含有する乳化剤並びにクリーム状及びフィルム状の化粧料に関する。 The present invention relates to a composition used for forming a liquid crystal, an emulsifier containing the liquid crystal using the composition, and a creamy or filmy cosmetic.
液晶(Liquid crystalline;LC)には、ラメラ相、ヘキサゴナル相、キュービック相などの構造があることが知られている。液晶構造を有する材料は、美容上の利点のために、化粧品及びパーソナルケア品において広く利用されている。 It is known that liquid crystal (LC) has a structure such as a lamella phase, a hexagonal phase, and a cubic phase. Materials with a liquid crystal structure are widely used in cosmetics and personal care products because of their cosmetic benefits.
ラメラ相を有する液晶及びゲル、特にケラチノサイト間のラメラ脂質と構造及び性質が類似した脂質を含むものは、それらの保湿及びバリア機能のために皮膚の水和状態を改善することが示されている。ラメラ層間の結合水分量並びにラメラ相に含まれる脂質の性質及び濃度は、保湿効果及びバリア効果の有効性に影響を与える。 Liquid crystals and gels with lamellar phases, especially those containing lipids similar in structure and properties to lamellar lipids between keratinocytes, have been shown to improve the hydration state of the skin due to their moisturizing and barrier functions. .. The amount of bound water between lamella layers and the nature and concentration of lipids contained in the lamella phase influence the effectiveness of moisturizing and barrier effects.
化粧品分野で応用されるラメラ液晶は、通常、ゲル、クリーム、ローションなどに含まれる液滴エマルションとしてもたらされる。しかし、これらの化粧料中に形成されるラメラ液晶は、溶媒の蒸発の際に濃縮して結晶化が起こる。さらに、化粧料の作製時又は皮膚適用時に機械的なせん断によって、容易に消失し得る。 Lamellar liquid crystals applied in the cosmetic field are usually provided as droplet emulsions contained in gels, creams, lotions and the like. However, the lamellar liquid crystals formed in these cosmetics are concentrated and crystallized when the solvent is evaporated. Furthermore, it can be easily eliminated by mechanical shearing during the preparation of the cosmetic or the application to the skin.
仮に、化粧料中のラメラ状液晶滴(ラメラ脂質)を皮膚表面に安定して高濃度に固定化することができれば、ラメラ脂質の連続シート、すなわち液晶フィルムを形成することができる。このような液晶フィルムを形成する濃縮されたラメラ脂質会合体の存在は、十分な保湿機能及び優れたフィルムバリア機能を同時的に皮膚にもたらし、非常に有用である。 If the lamellar liquid crystal droplets (lamellar lipids) in the cosmetic can be stably immobilized on the skin surface at a high concentration, a continuous sheet of lamellar lipids, that is, a liquid crystal film can be formed. The presence of the concentrated lamellar lipid aggregates forming such a liquid crystal film simultaneously brings sufficient moisturizing function and excellent film barrier function to the skin, which is very useful.
しかしながら、脂質及び水分がラメラ状の液晶微小滴として濃縮されたこのようなラメラ脂質の連続シートの実現は、皮膚に適用される間にラメラ脂質液滴が不安定化するためにこれまでに達成されていない。 However, the realization of such continuous sheets of lamellar lipids in which lipids and water are concentrated as lamellar liquid crystal microdroplets has been achieved so far due to destabilization of lamellar lipid droplets during application to the skin. It has not been.
ラメラ液晶を含有する化粧品の調製では、乳化剤、主として界面活性剤及び極性脂質を使用する。しかし、界面活性剤は皮膚の脂質バリアを破壊することによって間接的に皮膚刺激を引き起こす。また、極性脂質は、通常はセラミドやステロールなどの天然の膜脂質であり、これらは溶解性が低く、結晶化度が高いという問題がある。 In the preparation of cosmetics containing lamellar liquid crystals, emulsifiers, mainly surfactants and polar lipids are used. However, surfactants indirectly cause skin irritation by breaking the lipid barrier of the skin. In addition, polar lipids are usually natural membrane lipids such as ceramide and sterols, and these have the problems of low solubility and high crystallinity.
液晶形成用の乳化剤としては、例えば、特許文献1には、ステロール、ポリグリセリン脂肪酸エステル及びレシチンを必須成分として含有する液晶形成用乳化剤が記載されている。 As the liquid crystal forming emulsifier, for example, Patent Document 1 describes a liquid crystal forming emulsifier containing sterol, polyglycerin fatty acid ester and lecithin as essential components.
特許文献1には、特許文献1に記載の乳化剤を用いることにより、角質細胞間脂質に類似の液晶構造を形成し、皮膚に塗布されている間も液晶構造を安定に保持して、高いスキンケア効果を発揮するとともに製剤化が容易である化粧料を製造することができるという記載がある。 In Patent Document 1, by using the emulsifier described in Patent Document 1, a liquid crystal structure similar to inter-keratinocyte lipids is formed, and the liquid crystal structure is stably maintained even while being applied to the skin, and high skin care is achieved. There is a description that it is possible to produce a cosmetic that exerts an effect and is easily formulated.
しかし、本発明者らが調べたところによれば、特許文献1に記載の乳化剤の必須成分であるステロール、ポリグリセリン脂肪酸エステル及びレシチンの混合物を融解することは非常に困難であり、例えば、これらを水性溶媒又は油性溶媒で分散しようとしても、ステロールの残留物や結晶の析出物である凝集体が存在し続けるという問題がある。 However, according to a study conducted by the present inventors, it is extremely difficult to melt a mixture of sterol, polyglycerin fatty acid ester and lecithin, which are essential components of the emulsifier described in Patent Document 1, for example, However, there is a problem that even if an aqueous solution or an oily solvent is to be dispersed, a sterol residue or an agglomerate that is a precipitate of crystals continues to exist.
また、ステロール、ポリグリセリン脂肪酸エステル及びレシチンの混合物を溶解するためには、特許文献1の実施例に記載があるとおりに、多量の高級アルコールを使用しなければならない。その結果として、特許文献1に記載の乳化剤を利用して、液晶を含有する化粧料を得るためには、多量の油性成分を含有させなければならず、配合する水の量が限定されるという問題が生じる。 Further, in order to dissolve the mixture of sterol, polyglycerin fatty acid ester and lecithin, a large amount of higher alcohol must be used as described in the example of Patent Document 1. As a result, in order to obtain a cosmetic containing liquid crystal using the emulsifier described in Patent Document 1, a large amount of oily component must be contained, and the amount of water to be blended is limited. The problem arises.
液晶を含有する化粧料を皮膚上に塗布して液晶フィルムを形成する際に、形成したフィルムに接着性、弾力性及び展延性を付与するために、皮膜形成高分子を配合することが考えられる。このような化粧料に使用する皮膜形成高分子は水溶性のものが多く、配合する水の量が限定される特許文献1に記載の乳化剤を利用した化粧料では、このような水溶性の皮膜形成高分子を含有せしめることは困難である。 When a cosmetic containing a liquid crystal is applied on the skin to form a liquid crystal film, it may be possible to incorporate a film-forming polymer in order to impart adhesiveness, elasticity and spreadability to the formed film. .. Many of the film-forming polymers used in such cosmetics are water-soluble, and in the cosmetic using the emulsifier described in Patent Document 1 in which the amount of water to be mixed is limited, such a water-soluble film is used. It is difficult to incorporate the forming polymer.
特許文献1の実施例をみると、特許文献1に記載の乳化剤には必ず多量の高級アルコールなどの界面活性剤が使用されている。これはレシチンやフィトステロールなどの成分よりも過剰な量である。このような多量の界面活性剤は皮膚にとって刺激になり得る。また、高級アルコールなどの界面活性剤が多量に含まれる化粧料は皮膚上で塗布時にこすると石けんのように白く残るなどの問題が生じ得る。 Looking at the examples of Patent Document 1, a large amount of a surfactant such as a higher alcohol is always used in the emulsifier described in Patent Document 1. This is in excess of ingredients such as lecithin and phytosterols. Such high amounts of surfactant can be irritating to the skin. Further, a cosmetic material containing a large amount of a surfactant such as higher alcohol may cause a problem that it remains white like soap when rubbed on the skin during application.
また、後述する実施例に記載されているとおりに、多量の高級アルコールを水系の製剤に入れた場合、水和結晶となりゲルネットワーク構造が築かれるが、経時変化と共に溶媒の蒸散などが起こって結晶化が起こり、製剤が相分離するなどの問題が生じ得る。 Further, as described in Examples described later, when a large amount of higher alcohol is added to an aqueous preparation, a hydrated crystal is formed and a gel network structure is built up, but with evaporation over time of the solvent and the like, crystals are formed. This may cause problems such as degrading and phase separation of the preparation.
そこで、本発明は、溶媒中に分散することにより構成成分による残留物が観察できず、構成成分が均一に融解した状態で液晶を含有することができ、さらに種々の皮膜形成高分子とともに含有せしめることにより、容器中では液状で、及び皮膚上ではフィルム状で安定的に液晶構造を保持する化粧料を調製するために利用可能な組成物並びに該組成物を利用した乳化剤及び化粧料を提供することを、発明が解決しようとする課題とする。 Therefore, in the present invention, the residue due to the constituents cannot be observed by dispersing in the solvent, and the liquid crystal can be contained in a state where the constituents are uniformly melted, and further, it can be contained together with various film-forming polymers. The present invention provides a composition that can be used for preparing a cosmetic that stably holds a liquid crystal structure in a liquid state in a container and in a film shape on the skin, and an emulsifier and a cosmetic agent using the composition. This is the problem to be solved by the invention.
本発明者らは、上記の課題を解決しようとして、鋭意研究開発を進めた結果、両親媒性脂質、ステロール及び直鎖飽和脂肪酸の天然膜脂質の3成分の組み合わせに着眼するに至った。この3成分の組み合わせは、加温することにより融解することができ、そして、驚くべきことに、種々の水性溶媒及び油性溶媒を用いて膨潤することにより、上記3成分による残留物が観察できない状態で液晶を形成することができることを見出した。 As a result of intensive research and development in order to solve the above problems, the present inventors have come to focus on a combination of three components of an amphipathic lipid, a sterol, and a natural membrane lipid of a linear saturated fatty acid. This combination of the three components can be melted by warming and, surprisingly, swelled with various aqueous and oily solvents so that no residue from the three components can be observed. It was found that a liquid crystal can be formed by.
さらに驚くべきことに、上記3成分と溶媒とを含有する乳化剤を、種々の皮膜形成高分子と組み合わせることにより得られる化粧料は、容器中では液状で存在して安定的に液晶構造を保持するとともに、皮膚上に塗布した際にはフィルム状で存在して安定的に液晶構造を保持し得るものであった。 Even more surprisingly, a cosmetic obtained by combining an emulsifier containing the above-mentioned three components and a solvent with various film-forming polymers exists in a liquid state in a container and stably retains a liquid crystal structure. At the same time, when it was applied on the skin, it existed in the form of a film and could stably maintain the liquid crystal structure.
例えば、上記3成分を含有する組成物を用い、さらに乳化剤を調製する際に利用する溶媒として水性溶媒を用い、かつ、皮膜形成高分子として水溶性の皮膜形成高分子を用いることにより、乳化剤を被膜形成高分子によって覆うことにより、溶媒の蒸発及び濃縮によるラメラ液晶滴の凝集や塗布時のせん断、汗や皮脂の混入などによる液晶の破壊を防ぎ、細胞間脂質に類似した、ラメラ液晶滴が高濃度に固定化されたフィルムを形成する化粧料を調製することが可能である。 For example, an emulsifier is prepared by using a composition containing the above-mentioned three components, further using an aqueous solvent as a solvent used when preparing an emulsifier, and using a water-soluble film-forming polymer as the film-forming polymer. By covering with a film-forming polymer, aggregation of lamella liquid crystal droplets due to evaporation and concentration of the solvent, shearing during application, destruction of liquid crystal due to mixing of sweat and sebum, etc. are prevented, and lamellar liquid crystal droplets similar to intercellular lipids are formed. It is possible to prepare a cosmetic that forms a film that is immobilized at a high concentration.
結果として、本発明者らは、本発明の課題を解決するものとして、両親媒性脂質と、ステロールと、直鎖飽和脂肪酸とを含有する組成物並びに該組成物を利用した乳化剤及び化粧料を創作することに成功した。本発明は、上記の知見及び成功例に基づき完成された発明である。 As a result, as a solution to the problems of the present invention, the present inventors provide a composition containing an amphipathic lipid, a sterol, and a linear saturated fatty acid, and an emulsifier and a cosmetic using the composition. I succeeded in creating it. The present invention has been completed based on the above findings and successful examples.
したがって、本発明の一態様によれば、以下の[1]〜[11]の組成物、乳化剤及び化粧料が提供される。
[1]両親媒性脂質と、ステロールと、直鎖飽和脂肪酸とを含有する、液晶形成用組成物。
[2]前記液晶形成用組成物は、25℃で固体の状態である、[1]に記載の組成物。
[3]前記両親媒性脂質は、レシチン、水添レシチン、セラミド及びホスファチジルコリンからなる群から選ばれる少なくとも1種の両親媒性脂質である、[1]〜[2]のいずれか1項に記載の組成物。
[4]前記レシチン及び前記水添レシチンは、それぞれホスファチジルコリンの含有量が20質量%以上であるレシチン及び水添レシチンである、[1]〜[3]のいずれか1項に記載の組成物。
[5]前記両親媒性脂質の含有量は、前記ステロールの含有量よりも多い量である、又は前記直鎖飽和脂肪酸の含有量よりも多い量である、[1]〜[4]のいずれか1項に記載の組成物。
[6]両親媒性脂質 38質量%〜70質量%と、ステロール 5質量%〜40質量%と、直鎖飽和脂肪酸 10質量%〜45質量%とを含有し、かつ25℃で固体の状態である液晶形成用組成物。
[7][1]〜[6]のいずれか1項に記載の組成物と、溶媒とを含有する、液晶含有乳化剤。
[8]前記溶媒が、水、多価アルコール、アルコール、エステル油、シリコーン油、炭化水素油及び植物油からなる群から選ばれる少なくとも1種の溶媒である、[7]に記載の乳化剤。
[9]前記溶媒の含有量は50質量%〜90質量%である、[7]〜[8]のいずれか1項に記載の乳化剤。
[10][1]〜[6]のいずれか1項に記載の液晶形成用組成物と、多価アルコール、アルコール、エステル油、シリコーン油、炭化水素油及び植物油からなる群から選ばれる少なくとも1種の溶媒と、被膜形成高分子と、水とを含有する、液晶含有化粧料。
[11]前記化粧料は皮膚に塗布して含水量が50%以下になった場合にフィルム状を呈し、かつ、安定した液晶相を含有する、[10]に記載の化粧料。
また、本発明の一態様によれば、以下の[A1]〜[A9]の組成物、乳化剤及び化粧料が提供される。
[A1]両親媒性脂質と、ステロールと、直鎖飽和脂肪酸とを含有する、液晶形成用組成物。
[A2]前記両親媒性脂質は、レシチン、水添レシチン、セラミド及びホスファチジルコリンからなる群から選ばれる少なくとも1種の両親媒性脂質である、[A1]に記載の組成物。
[A3]前記レシチン及び前記水添レシチンは、それぞれホスファチジルコリンの含有量が20質量%以上であるレシチン及び水添レシチンである、[A1]〜[A2]のいずれか1項に記載の組成物。
[A4]前記両親媒性脂質の含有量は、前記ステロールの含有量よりも多い量である、又は前記直鎖飽和脂肪酸の含有量よりも多い量である、[A1]〜[A3]のいずれか1項に記載の組成物。
[A5][A1]〜[A4]のいずれか1項に記載に組成物と、溶媒とを含有する、液晶含有乳化剤。
[A6]前記溶媒が、多価アルコール又は水である、[A5]に記載の乳化剤。
[A7][A5]〜[A6]のいずれか1項に記載の乳化剤と、被膜形成高分子と、水とを含有する、液晶含有化粧料。
[A8]前記乳化剤の含有量は5質量%〜20質量%であり、前記被膜形成高分子の含有量は2質量%〜10質量%であり、かつ、前記水の含有量は80質量%〜90質量%である、[A7]に記載の化粧料。
[A9]前記化粧料は含水量が50%以上である場合にクリーム状を呈し、又は含水量が50%以下である場合にフィルム状を呈し、かつ、安定した液晶相を含有する、[A7]〜[A8]のいずれか1項に記載の化粧料。
Therefore, according to one aspect of the present invention, the following compositions [1] to [11], emulsifiers, and cosmetics are provided.
[1] A liquid crystal-forming composition containing an amphipathic lipid, a sterol, and a linear saturated fatty acid.
[2] The composition according to [1], wherein the liquid crystal forming composition is in a solid state at 25°C.
[3] The amphipathic lipid is at least one amphipathic lipid selected from the group consisting of lecithin, hydrogenated lecithin, ceramide and phosphatidylcholine, according to any one of [1] to [2]. Composition.
[4] The composition according to any one of [1] to [3], wherein the lecithin and the hydrogenated lecithin are lecithin and hydrogenated lecithin each having a phosphatidylcholine content of 20% by mass or more.
[5] Any of [1] to [4], in which the content of the amphipathic lipid is greater than the content of the sterol or the content of the linear saturated fatty acid. The composition according to item 1.
[6] Amphipathic lipid 38% by mass to 70% by mass, sterol 5% by mass to 40% by mass, linear saturated fatty acid 10% by mass to 45% by mass, and in a solid state at 25°C. A composition for forming a liquid crystal.
[7] A liquid crystal-containing emulsifier containing the composition according to any one of [1] to [6] and a solvent.
[8] The emulsifier according to [7], wherein the solvent is at least one solvent selected from the group consisting of water, polyhydric alcohols, alcohols, ester oils, silicone oils, hydrocarbon oils and vegetable oils.
[9] The emulsifier according to any one of [7] to [8], wherein the content of the solvent is 50% by mass to 90% by mass.
[10] At least one selected from the group consisting of the composition for liquid crystal formation according to any one of [1] to [6] and a polyhydric alcohol, alcohol, ester oil, silicone oil, hydrocarbon oil, and vegetable oil. A liquid crystal-containing cosmetic containing a seed solvent, a film-forming polymer, and water.
[11] The cosmetic according to [10], which has a film form when applied to the skin and has a water content of 50% or less and contains a stable liquid crystal phase.
According to one aspect of the present invention, the following compositions [A1] to [A9], emulsifiers and cosmetics are provided.
[A1] A liquid crystal-forming composition containing an amphipathic lipid, a sterol, and a linear saturated fatty acid.
[A2] The composition according to [A1], wherein the amphipathic lipid is at least one amphipathic lipid selected from the group consisting of lecithin, hydrogenated lecithin, ceramide and phosphatidylcholine.
[A3] The composition according to any one of [A1] to [A2], wherein the lecithin and the hydrogenated lecithin are lecithin and hydrogenated lecithin each having a phosphatidylcholine content of 20% by mass or more.
[A4] Any of [A1] to [A3], in which the content of the amphipathic lipid is greater than the content of the sterol, or is greater than the content of the linear saturated fatty acid. The composition according to item 1.
[A5] A liquid crystal-containing emulsifier containing the composition according to any one of [A1] to [A4] and a solvent.
[A6] The emulsifier according to [A5], wherein the solvent is a polyhydric alcohol or water.
[A7] A liquid crystal-containing cosmetic containing the emulsifier according to any one of [A5] to [A6], a film-forming polymer, and water.
[A8] The content of the emulsifier is 5% by mass to 20% by mass, the content of the film-forming polymer is 2% by mass to 10% by mass, and the content of the water is 80% by mass to. The cosmetic material according to [A7], which is 90% by mass.
[A9] The cosmetic has a cream-like form when the water content is 50% or more, or a film-like form when the water content is 50% or less, and contains a stable liquid crystal phase. ]-[A8] cosmetics of any one statement.
本発明の一態様の組成物、乳化剤及び化粧料によれば、改善された保湿能力を示し、生体適合性が高く、かつ、ヒトの皮膚に優れた感触を有する液晶材料と皮膜形成高分子との複合体フィルムが得られる。本発明の一態様の化粧料は広範囲の化粧品用溶媒において安定な液晶相を形成し、さらに角層の細胞間脂質に類似した構成及び構造の混合物を含み得る。本発明の一態様の化粧料により複合体フィルムを皮膚表面上に形成することで、その保湿性脂質複合体及び結合性層間水(bound interlamellar water)により実現する液晶成分の完全な湿潤性が保証され、それだけでなくフィルムの優れたバリア特性を同時に皮膚に付与することができる。該複合体フィルムの所望の保湿及びバリアの効果は、液晶成分及びフィルム成分によって相乗的に得られる。 According to the composition, the emulsifier, and the cosmetic of one embodiment of the present invention, a liquid crystal material and a film-forming polymer that exhibit improved moisturizing ability, are highly biocompatible, and have an excellent feel to human skin. A composite film of The cosmetic material of one embodiment of the present invention forms a stable liquid crystal phase in a wide range of cosmetic solvents, and may further contain a mixture of structures and structures similar to intercellular lipids of the stratum corneum. By forming the composite film on the skin surface with the cosmetic of one embodiment of the present invention, the complete wettability of the liquid crystal component realized by the moisturizing lipid composite and the bound interlamellar water is guaranteed. In addition, the excellent barrier properties of the film can be simultaneously imparted to the skin. The desired moisturizing and barrier effects of the composite film are obtained synergistically with the liquid crystal component and the film component.
本発明の一態様の化粧料は、皮膚に局所適用することにより、湿度に富むラメラ液晶相を微小液滴分散体として多量に含む液晶含有フィルムを形成する。本発明の一態様の化粧料によって得られる複合体フィルムは、保湿性、長時間着用性、透過性及び光沢を備えることができ、ケラチン物質の化粧用物理的遮蔽材としても使用することが期待できる。 The cosmetic of one embodiment of the present invention is topically applied to the skin to form a liquid crystal-containing film containing a large amount of a lamellar liquid crystal phase rich in humidity as a fine droplet dispersion. The composite film obtained by the cosmetic material of one embodiment of the present invention can have moisturizing properties, long-term wearability, permeability and luster, and is expected to be used as a cosmetic physical shielding material for keratin materials. it can.
以下、本発明の一態様である組成物、乳化剤及び化粧料の詳細について説明するが、本発明の技術的範囲は本項目の事項によってのみに限定されるものではなく、本発明はその目的を達成する限りにおいて種々の態様をとり得る。 Hereinafter, the details of the composition, the emulsifier, and the cosmetic, which are one aspect of the present invention, will be described, but the technical scope of the present invention is not limited only by the items of this item, and the present invention has the following objects. As long as it is achieved, various modes can be adopted.
本明細書における各用語は、別段の定めがない限り、当業者により通常用いられている意味で使用され、不当に限定的な意味を有するものとして解釈されるべきではない。また、本明細書においてなされている理論や推測は、本発明者らのこれまでの知見や経験によってなされたものであることから、本発明の技術的範囲はこのような理論や推測のみによって拘泥されるものではない。 Unless otherwise specified, each term used in the present specification has a meaning commonly used by those skilled in the art, and should not be interpreted as having an unreasonably limiting meaning. Further, the theories and speculations made in this specification are based on the knowledge and experience of the present inventors, and therefore the technical scope of the present invention is limited only by such theories and speculations. It is not something that will be done.
例えば、「及び/又は」との用語は、列記した複数の関連項目のいずれか1つ、又は2つ以上の任意の組み合わせ若しくは全ての組み合わせを意味する。 For example, the term "and/or" means any one of the listed related items, or any combination or all of two or more of the related items.
「含有量」は、濃度と同義であり、水中油型乳化化粧料の全体量に対する成分の量の割合を意味する。本明細書では、別段の定めがない限り、含有量の単位は「質量%(wt%)」を意味する。ただし、成分の含有量の総量は、100質量%を超えることはない。 The "content" is synonymous with the concentration and means the ratio of the amount of the component to the total amount of the oil-in-water emulsion cosmetic. In the present specification, unless otherwise specified, the unit of content means “mass% (wt %)”. However, the total content of the components does not exceed 100% by mass.
数値範囲の「〜」は、本明細書において、その前後の数値を含む範囲であり、例えば、「0質量%〜100質量%」は、0質量%以上であり、かつ、100質量%以下である範囲を意味する。 In the present specification, “to” in the numerical range is a range including numerical values before and after the numerical range, for example, “0 mass% to 100 mass%” is 0 mass% or more and 100 mass% or less. Means a range.
「(メタ)アクリル酸」は、アクリル酸及びメタクリル酸を包含する総称である。 “(Meth)acrylic acid” is a general term that includes acrylic acid and methacrylic acid.
「液晶形成性」は、溶媒で膨潤することにより、リオトロピック液晶を形成する機能である。
「液晶の安定性」は、容器中又は皮膚に塗布した際に形成されるフィルム中で液晶形成性が確認できる状態を生じせしめる機能である。
「保湿性」は、皮膚における角層水分量を保持する機能である。
「閉塞性」は、皮膚表面からの水分蒸発を抑制する機能である。
「接着性」は、皮膚上でフィルム状に展延した状態で皮膚に付着する機能である。
これらの特性は、それぞれ後述する実施例に記載の方法により評価及び確認できる。
“Liquid crystal forming property” is a function of forming a lyotropic liquid crystal by swelling with a solvent.
The "stability of liquid crystal" is a function of causing a state in which the liquid crystal forming property can be confirmed in a container or a film formed when applied to the skin.
“Moisturizing property” is a function of retaining the amount of water in the stratum corneum of the skin.
“Occlusion” is a function of suppressing evaporation of water from the skin surface.
"Adhesiveness" is a function of adhering to the skin in a state of being spread in a film shape on the skin.
These characteristics can be evaluated and confirmed by the methods described in Examples described later.
本発明の一態様の組成物は、液晶の構成成分を少なくとも含有する。本発明の一態様の乳化剤は、液晶の構成成分と溶媒とを少なくとも含有することにより、液晶構造を備える。本発明の一態様の化粧料は、液晶の構成成分を溶媒で膨潤させ、液晶構造を有する乳化剤と皮膜形成高分子と水とを含有することにより、皮膚に局所的に適用した場合に、剥離可能であり、保湿性及びバリア機能を有するラメラ液晶構造を有するフィルムを形成することができる。 The composition of one embodiment of the present invention contains at least a component of liquid crystal. The emulsifier of one embodiment of the present invention has a liquid crystal structure by containing at least a component of liquid crystal and a solvent. The cosmetic according to one aspect of the present invention is a composition that swells liquid crystal constituents with a solvent and contains an emulsifier having a liquid crystal structure, a film-forming polymer, and water, so that when applied topically to the skin, it exfoliates. It is possible to form a film having a lamellar liquid crystal structure having a moisture retaining property and a barrier function.
[1.組成物]
本発明の一態様の組成物は、液晶の構成成分(以下、液晶成分ともよぶ。)として、両親媒性脂質と、ステロールと、直鎖飽和脂肪酸とを少なくとも含有する。本発明の一態様の組成物は、液晶成分を含有すればよく、皮膚刺激性をもたらすような界面活性剤を含有しなくともよい。また、液晶成分は、それぞれ天然成分から選択することができるので、皮膚に適合し、角質層中の細胞間脂質に類似した構成及び構造を形成することが可能である。
[1. Composition]
The composition of one embodiment of the present invention contains at least an amphipathic lipid, a sterol, and a straight-chain saturated fatty acid as constituent components of liquid crystal (hereinafter, also referred to as liquid crystal component). The composition of one embodiment of the present invention only needs to contain a liquid crystal component, and need not contain a surfactant that causes skin irritation. In addition, since the liquid crystal component can be selected from natural components, it is possible to be compatible with the skin and form a structure and structure similar to the intercellular lipid in the stratum corneum.
両親媒性脂質は、分子内に親水基と親油基とを有する脂質であれば特に限定されないが、例えば、リン脂質、スフィンゴ脂質、糖脂質などが挙げられるが、角質細胞間脂質に類似した構造を形成するという観点では、レシチン、水素添加(水添)レシチン、セラミド及びホスファチジルコリンが好ましい。両親媒性脂質は、上記したものの1種を単独で、又は2種以上を組み合わせて使用できる。なお、両親媒性脂質には、上記列挙したものを酵素処理などによりモノアシル体としたリゾ体などであってもよい。ただし、両親媒性脂質には、ステロール及び直鎖飽和脂肪酸を含まない。 The amphipathic lipid is not particularly limited as long as it is a lipid having a hydrophilic group and a lipophilic group in the molecule, and examples thereof include phospholipids, sphingolipids, glycolipids, etc. From the viewpoint of forming a structure, lecithin, hydrogenated (hydrogenated) lecithin, ceramide and phosphatidylcholine are preferable. As the amphipathic lipid, one type of the above-mentioned ones can be used alone, or two or more types can be used in combination. In addition, the amphipathic lipid may be a lyso form or the like in which the above-listed products are converted into a monoacyl form by enzymatic treatment or the like. However, the amphipathic lipid does not include sterols and linear saturated fatty acids.
レシチン及び水添レシチンは、化粧品分野で通常用いられているものであれば特に限定されず、例えば、大豆レシチン、卵黄レシチン、水添大豆レシチン、水添卵黄レシチンなどを挙げることができる。ただし、本発明の一態様の組成物を用いて得られる乳化剤及び化粧料並びに該化粧料を皮膚に塗布して形成される液晶フィルムが安定した液晶構造を形成及び保持するためには、レシチン及び水添レシチンは、ホスファチジルコリン(PC)の含有量が20質量%以上であることが好ましく、35質量%以上であることがより好ましく、50質量%以上であることがさらに好ましい。レシチン及び水添レシチンのうち、水添レシチンがより好ましい。 The lecithin and hydrogenated lecithin are not particularly limited as long as they are commonly used in the cosmetics field, and examples thereof include soybean lecithin, egg yolk lecithin, hydrogenated soybean lecithin, hydrogenated egg yolk lecithin and the like. However, in order to form and maintain a stable liquid crystal structure of the emulsifier and the cosmetic obtained by using the composition of one embodiment of the present invention and the liquid crystal film formed by applying the cosmetic to the skin, lecithin and The hydrogenated lecithin has a phosphatidylcholine (PC) content of preferably 20% by mass or more, more preferably 35% by mass or more, and further preferably 50% by mass or more. Among lecithin and hydrogenated lecithin, hydrogenated lecithin is more preferable.
レシチン及び水添レシチンの市販品としては、例えば、「LIPOID P75」(エイチ・ホルスタイン社製)、「Basis LP−20H」(日清オイリオグループ社製)、「Basis LS−60HR」(日清オイリオグループ社製)、「NIKKOL Lecinol S−10」(日光ケミカルズ社製)、「NIKKOL Lecinol S−10EX」(日光ケミカルズ社製)、「NIKKOL Lecinol S−10E」(日光ケミカルズ社製)、「NIKKOL Lecinol S−10M」(日光ケミカルズ社製)、「Phospholipon(登録商標) 80H」(エイチ・ホルスタイン社製)、「COATSOME NC−21」(日油社製)、「COATSOME NC−61」(日油社製)などが挙げられるが、これらに限定されない。 Examples of commercial products of lecithin and hydrogenated lecithin include, for example, "LIPOID P75" (manufactured by H-Holstein), "Basis LP-20H" (manufactured by Nisshin Oillio Group), "Basis LS-60HR" (Nisshin Oilio). Group company), "NIKKOL Lecinol S-10" (manufactured by Nikko Chemicals), "NIKKOL Lecinol S-10EX" (manufactured by Nikko Chemicals), "NIKKOL Lecinol S-10E" (manufactured by Nikko Chemicals), "NIKKOL Lec". "S-10M" (manufactured by Nikko Chemicals), "Phospholipon (registered trademark) 80H" (manufactured by H-Holstein), "COATSOME NC-21" (manufactured by NOF CORPORATION), "COATSOME NC-61" (NOF CORPORATION) Manufactured) and the like, but are not limited thereto.
セラミドは、スフィンゴシン及び脂肪酸で構成されるスフィンゴ脂質であれば特に限定されないが、例えば、セラミド1、セラミド2、セラミド3、セラミド3B、セラミド4、セラミド5、セラミド6、セラミド6I、セラミド6II及びこれらの混合物などが挙げられ、皮膚の細胞の細胞膜を構成する主要脂質であるとの観点から、セラミド3、セラミド3B、セラミド4、セラミド6II及びこれらの混合物が好ましい。 Ceramide is not particularly limited as long as it is a sphingolipid composed of sphingosine and a fatty acid. For example, ceramide 1, ceramide 2, ceramide 3, ceramide 3B, ceramide 4, ceramide 5, ceramide 6, ceramide 6I, ceramide 6II and these And the like, and ceramide 3, ceramide 3B, ceramide 4, ceramide 6II, and mixtures thereof are preferable from the viewpoint of being the main lipid constituting the cell membrane of skin cells.
セラミドの市販品としては、例えば、「CERAMIDE 2」(クローダジャパン社製)、「CERAMIDE I」(Evonik Nutrition & Care GmbH社製)、「CERAMIDE III」(Evonik Nutrition & Care GmbH社製)、「CERAMIDE IIIB」(Evonik Nutrition & Care GmbH社製)、「CERAMIDE VI」(Evonik Nutrition & Care GmbH社製)、「CERAMIDE TIC−001」(高砂香料工業社製)などが挙げられるが、これらに限定されない。 Examples of commercially available ceramides include "CERAMIDE 2" (manufactured by Croda Japan), "CERAMIDE I" (manufactured by Evonik Nutrition & Care GmbH), "CERAMIDE III" (manufactured by Evonik Nutrition & Care GmbH EMBCRAM). IIIB" (manufactured by Evonik Nutrition & Care GmbH), "CERAMIDE VI" (manufactured by Evonik Nutrition & Care GmbH), "CERAMIDE TIC-001" (manufactured by Takasago International Corporation), but not limited to these.
ステロールは、ステロイド骨格(シクロペンタヒドロフェナントレン)のA環の3位にOH基を有する構造を基本骨格とする化合物であれば特に限定されず、例えば、β−シトステロール、スチグマステロール、カンペステロール、ブラシカステロール、エルゴステロールなどの植物ステロール(フィトステロール);コレステロール、コレスタノール、ラノステロール、デヒドロコレステロールなどの動物ステロール;ミコステロール、チモステロールなどの微生物由来のステロールなどが挙げられる。また、ステロールは、ラウロイルグルタミン酸ジ(オクチルドデシル/フィトステリル/ベヘニル)、オレイン酸コレステリル、マカデミアナッツ脂肪酸フィトステリルなどの、ステロールのOH基に任意のアミノ酸や脂肪酸などが結合したステロールエステルであってもよい。ステロールは、天然由来のものでも合成化合物でもどちらでもよく、これらを安定化のために水素添加などの処理に供したものであってもよいが、皮膚に対する安全性や液晶を安定的に形成するという観点では、天然由来のものが好ましく、フィトステロールがさらに好ましい。 The sterol is not particularly limited as long as it is a compound having a structure having an OH group at the 3-position of the A ring of the steroid skeleton (cyclopentahydrophenanthrene) as a basic skeleton, for example, β-sitosterol, stigmasterol, campesterol, Examples thereof include plant sterols (phytosterols) such as brassicasterol and ergosterol; animal sterols such as cholesterol, cholestanol, lanosterol and dehydrocholesterol; and sterols derived from microorganisms such as mycosterol and timosterol. The sterol may be a sterol ester in which any amino acid or fatty acid is bonded to the OH group of sterol such as di(octyldodecyl/phytosteryl/behenyl) lauroylglutamate, cholesteryl oleate, and macadamia nut fatty acid phytosteryl. The sterol may be a naturally occurring compound or a synthetic compound, and may be one that has been subjected to a treatment such as hydrogenation for stabilization, but it is safe for the skin and stably forms a liquid crystal. From this point of view, naturally-derived ones are preferable, and phytosterols are more preferable.
ステロールの市販品としては、例えば、「フィトステロール(QI)」(タマ生化学社製)、「フィトステロール(SKP)」(タマ生化学社製)、「フィトステロール」(エーザイフード・ケミカル社製)、「コレステロール JSQI」(日本精化社製)、「日本薬局方コレステロール」(日本精化社製)、「エルデュウPS−203」及び「エルデュウPS−306」(それぞれ味の素ヘルシーサプライ社製)、「海麗マリンコレステロールエステル」及び「マリンコレステロールエステルC」(それぞれ日本水産社製)、「PlandoolTM−MAS」(日本精化社製)などが挙げられるが、これらに限定されない。 Examples of commercially available sterols include, for example, "phytosterol (QI)" (manufactured by Tama Biochemical), "phytosterol (SKP)" (manufactured by Tama Biochemical), "phytosterol" (manufactured by Eisai Food Chemical Co., Ltd.), Cholesterol JSQI" (manufactured by Nippon Seika Co., Ltd.), "Japanese Pharmacopoeia Cholesterol" (manufactured by Nippon Seika Co., Ltd.), "Eldu PS-203" and "Eldu PS-306" (each manufactured by Ajinomoto Healthy Supply Co., Ltd.), "Kairei". Examples thereof include, but are not limited to, “Marine cholesterol ester” and “Marine cholesterol ester C” (each manufactured by Nippon Suisan Kaisha, Ltd.) and “Planool ™ -MAS” (manufactured by Nippon Seika Co., Ltd.).
直鎖飽和脂肪酸は、直鎖状のアルキル基を有するカルボン酸であれば特に限定されず、例えば、酢酸、酪酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキジン酸、ベヘン酸、リグノセリン酸などが挙げられ、液晶を安定的に形成するという観点では炭素数が6〜22の直鎖飽和脂肪酸が好ましい。 The linear saturated fatty acid is not particularly limited as long as it is a carboxylic acid having a linear alkyl group, and examples thereof include acetic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid. , Arachidic acid, behenic acid, lignoceric acid, etc., and a linear saturated fatty acid having 6 to 22 carbon atoms is preferable from the viewpoint of stably forming a liquid crystal.
本発明の一態様の組成物において、両親媒性脂質、ステロール及び直鎖飽和脂肪酸の含有量は特に限定されないが、両親媒性脂質の含有量は、ステロールの含有量よりも多く、又は直鎖飽和脂肪酸の含有量よりも多いことが好ましく;ステロールの含有量よりも多く、かつ、直鎖飽和脂肪酸の含有量よりも多いことがより好ましく;ステロールの含有量及び直鎖飽和脂肪酸の含有量の総量よりも多いことがさらに好ましい。両親媒性脂質の含有量がステロール及び/又は直鎖飽和脂肪酸の含有量よりも小さくなると、本発明の一態様の組成物を溶媒に溶解して得られる乳化剤は液晶を安定的に含有することができなくなるおそれがある。 In the composition of one embodiment of the present invention, the content of amphipathic lipid, sterol and linear saturated fatty acid is not particularly limited, the content of amphipathic lipid is more than the content of sterol, or linear It is preferably higher than the content of saturated fatty acids; more preferably higher than the content of sterols and higher than the content of straight chain saturated fatty acids; More preferably, it is greater than the total amount. When the content of the amphipathic lipid becomes smaller than the content of the sterol and/or the linear saturated fatty acid, the emulsifier obtained by dissolving the composition of one embodiment of the present invention in the solvent should contain the liquid crystal stably. May not be possible.
本発明の一態様の組成物における両親媒性脂質の含有量は、例えば、38質量%〜70質量%であり、好ましくは40質量%〜60質量%であり、より好ましくは約55質量%である。両親媒性脂質がレシチン及び/又は水添レシチンである場合は、これらのPC含有率が小さいときは、両親媒性脂質の含有量を大きくし、該PC含有率が大きいときは、両親媒性脂質の含有量を小さくしてもよい。 The content of the amphipathic lipid in the composition of one embodiment of the present invention is, for example, 38% by mass to 70% by mass, preferably 40% by mass to 60% by mass, and more preferably about 55% by mass. is there. When the amphipathic lipid is lecithin and/or hydrogenated lecithin, when the PC content of these is low, the content of the amphipathic lipid is increased, and when the PC content is high, the amphipathic lipid is The lipid content may be reduced.
本発明の一態様の組成物におけるステロールの含有量は、例えば、5質量%〜40質量%であり、好ましくは10質量%〜30質量%であり、より好ましくは約25質量%である。本発明の一態様の組成物における直鎖飽和脂肪酸の含有量は、例えば、10質量%〜45質量%であり、好ましくは10質量%〜30質量%であり、より好ましくは約20質量%である。ステロールの含有量と直鎖飽和脂肪酸の含有量との関係性は特に限定されないが、本発明の一態様の組成物を用いて安定的な液晶を形成するためには、ステロールの含有量と直鎖飽和脂肪酸の含有量とは同程度の量であることが好ましい。 The content of sterol in the composition of one embodiment of the present invention is, for example, 5% by mass to 40% by mass, preferably 10% by mass to 30% by mass, and more preferably about 25% by mass. The content of the linear saturated fatty acid in the composition of one embodiment of the present invention is, for example, 10% by mass to 45% by mass, preferably 10% by mass to 30% by mass, more preferably about 20% by mass. is there. The relationship between the sterol content and the linear saturated fatty acid content is not particularly limited, but in order to form a stable liquid crystal using the composition of one embodiment of the present invention, the sterol content is not directly related to the sterol content. It is preferable that the content of the chain saturated fatty acid is about the same.
本発明の一態様の組成物における両親媒性脂質、ステロール及び直鎖飽和脂肪酸の含有量は上記した量であれば特に限定されないが、本発明の一態様の組成物における両親媒性脂質、ステロール及び直鎖飽和脂肪酸の含有量の割合(両親媒性脂質:ステロール:直鎖飽和脂肪酸)は、角層の細胞間脂質の構成比に類似した配合比であることが好ましく、40〜60:20〜30:10〜25であることがさらに好ましく、55:25:20であることがより好ましいが、これらに限定されない。両親媒性脂質の含有量は、ステロールの含有量及び/又は直鎖飽和脂肪酸の含有量に対して、10質量%よりも多い量であることが好ましく、20質量%よりも多い量であることがより好ましく、30質量%よりも多い量であることがさらに好ましい。 The content of the amphipathic lipid, the sterol, and the linear saturated fatty acid in the composition of one embodiment of the present invention is not particularly limited as long as it is the above amount, but the amphipathic lipid, the sterol in the composition of one embodiment of the present invention And the ratio of the content of the linear saturated fatty acid (amphipathic lipid:sterol:linear saturated fatty acid) is preferably 40 to 60:20, which is similar to the composition ratio of the intercellular lipid in the stratum corneum. It is more preferably ˜30:10 to 25, more preferably 55:25:20, but not limited to these. The content of the amphipathic lipid is preferably more than 10% by mass, and more than 20% by mass with respect to the content of the sterol and/or the content of the linear saturated fatty acid. Is more preferable, and the amount is more preferably more than 30% by mass.
本発明の一態様の組成物は、本発明の課題の解決を妨げない限り、すなわち、液晶形成性を有し、さらに構成成分による残留物が生じない限り、両親媒性脂質、ステロール及び直鎖飽和脂肪酸に加えて、他の成分を含有し得る。他の成分としては、後述する本発明の一態様の化粧料に含有することができる他の成分などが挙げられる。ただし、本発明の一態様の組成物は、化粧料を調製するために用いられることから、天然成分からなることが好ましく、皮膚刺激性のあるような界面活性剤などを含有しないことがより好ましく、両親媒性脂質、ステロール及び直鎖飽和脂肪酸のみからなることがさらに好ましい。 The composition of one embodiment of the present invention is an amphipathic lipid, a sterol, and a straight chain, as long as they do not prevent the solution of the problems of the present invention, that is, as long as they have a liquid crystal forming property and do not generate a residue due to a constituent component. In addition to saturated fatty acids, other ingredients may be included. Examples of the other components include other components that can be contained in the cosmetic of one aspect of the present invention described below. However, since the composition of one aspect of the present invention is used for preparing cosmetics, it is preferable that the composition be made of a natural component, and it is more preferable not to include a skin-irritating surfactant or the like. More preferably, it consists only of amphipathic lipids, sterols and linear saturated fatty acids.
本発明の一態様の組成物は、両親媒性脂質、ステロール及び直鎖飽和脂肪酸、並びに任意に他の成分を加温しながら撹拌混合することなどにより調製できる。本発明の一態様の組成物は、加温した状態から25℃以下にまで冷却されると、通常は固体の状態になる。 The composition of one embodiment of the present invention can be prepared by stirring and mixing the amphipathic lipid, the sterol and the linear saturated fatty acid, and optionally other components while heating. When the composition of one embodiment of the present invention is cooled from a heated state to 25° C. or lower, it usually becomes a solid state.
[2.乳化剤]
溶液状又は固体状にある本発明の一態様の組成物を溶媒で膨潤又は溶媒に分散することにより、安定な液晶構造を含有する、本発明の一態様の乳化剤が得られる。
[2. emulsifier]
By swelling or dispersing the composition of one embodiment of the present invention in a solution or solid form with a solvent, the emulsifier of one embodiment of the present invention containing a stable liquid crystal structure can be obtained.
本発明の一態様の乳化剤を得るために使用される溶媒は、通常化粧料を調製するために使用される溶媒などであれば特に限定されないが、例えば、水、多価アルコール(グリセリン、BG、PGなど)、アルコール(エタノールなど)、エステル油、シリコーン油、炭化水素油(パラフィン、水添ポリイソブテン、スクアレン、スクワランなど)、植物油(ホホバ油、マカデミアナッツ種子油、ゴマ油、など)などが挙げられるが、本発明の一態様の乳化剤を用いて得られる化粧料を皮膚に塗布することによって得られるフィルムが、角質細胞間脂質に類似する液晶構造、すなわち、ラメラ液晶構造を安定的に形成するという観点では、多価アルコール又は水が好ましい。 The solvent used to obtain the emulsifier of one embodiment of the present invention is not particularly limited as long as it is a solvent usually used for preparing cosmetics, and examples thereof include water and polyhydric alcohols (glycerin, BG, PG), alcohol (ethanol etc.), ester oil, silicone oil, hydrocarbon oil (paraffin, hydrogenated polyisobutene, squalene, squalane, etc.), vegetable oil (jojoba oil, macadamia nut seed oil, sesame oil, etc.) and the like. From the viewpoint that a film obtained by applying a cosmetic obtained using the emulsifier of one embodiment of the present invention to the skin stably forms a liquid crystal structure similar to intercorneal lipids, that is, a lamellar liquid crystal structure. Then, polyhydric alcohol or water is preferable.
本発明の一態様の乳化剤における溶媒の含有量は、本発明の一態様の組成物に対して十分に多い量であれば特に限定されないが、例えば、50質量%〜90質量%であり、60質量%〜80質量%が好ましく、65質量%〜70質量%がより好ましく、約67質量%がさらに好ましい。溶媒の含有量が50質量%未満である場合は、本発明の一態様の組成物が均一に膨潤及び分散せずに、良好な液晶形成性が認められないおそれがある。 The content of the solvent in the emulsifier of one embodiment of the present invention is not particularly limited as long as it is a sufficiently large amount with respect to the composition of one embodiment of the present invention, and is, for example, 50% by mass to 90% by mass, 60 Mass% to 80 mass% is preferable, 65 mass% to 70 mass% is more preferable, and about 67 mass% is still more preferable. When the content of the solvent is less than 50% by mass, the composition of one embodiment of the present invention may not be uniformly swollen and dispersed, and good liquid crystal forming property may not be recognized.
本発明の一態様の乳化剤を調製する方法は特に限定されないが、例えば、含有する液晶構造を消失させない程度に、本発明の一態様の組成物と溶媒とを均一化するまで加温及び撹拌し、さらに室温まで冷却することで、溶媒中に液晶成分が均一に分散することにより、本発明の一態様の乳化剤が得られる。本発明の一態様の乳化剤の形態は特に限定されず、液晶成分の種類や含有比率などに基づく脂質構成及び使用溶媒によって変動があり得るが、例えば、粘性のあるピーナッツバターのようなクリーム状や流動性のあるペースト状などが挙げられる。 The method for preparing the emulsifier of one embodiment of the present invention is not particularly limited, and for example, heating and stirring until the composition of one embodiment of the present invention and the solvent are homogenized to the extent that the contained liquid crystal structure is not lost. By further cooling to room temperature, the liquid crystal component is uniformly dispersed in the solvent, whereby the emulsifier of one embodiment of the present invention can be obtained. The form of the emulsifier of one embodiment of the present invention is not particularly limited, and may vary depending on the lipid composition based on the type and content ratio of the liquid crystal component and the solvent used. For example, a creamy product such as viscous peanut butter or Examples include a fluid paste.
本発明の一態様の乳化剤における液晶は、後述する実施例に記載の偏光光学顕微鏡法(Polarizing Optical Microscopy;POM)を利用した液晶形成性を評価する方法などにより確認することができるが、示差走査熱量測定(Differential Scanning Calorimetry;DSC)やX線回折(X−Ray Diffraction;XRD)などの当業界において公知の技術によって確認してもよい。 The liquid crystal in the emulsifier of one embodiment of the present invention can be confirmed by a method for evaluating the liquid crystal forming property using Polarizing Optical Microscopy (POM) described in Examples described later, or the like. It may be confirmed by a technique known in the art such as calorimetry (Differential Scanning Calorimetry; DSC) and X-ray diffraction (X-Ray Diffraction; XRD).
本発明の一態様の乳化剤は、本発明の一態様の組成物における液晶成分を溶媒中に分散して液晶を形成してなるものであることから、該液晶はリオトロピック液晶であるといえる。リオトロピック液晶の定義及びその相挙動(安定性)の詳細は、「Cosmetic Science and Technology:Theoretical Principles and Applications」などの文献を参照することができる。 Since the emulsifier of one embodiment of the present invention is one in which the liquid crystal component in the composition of one embodiment of the present invention is dispersed in a solvent to form a liquid crystal, it can be said that the liquid crystal is a lyotropic liquid crystal. For details of the definition of lyotropic liquid crystal and its phase behavior (stability), reference can be made to documents such as “Cosmetic Science and Technology: Theoretical Principles and Applications”.
一般に、リオトロピック液晶相は、ある温度で溶媒系中の両親媒性分子によって形成される会合体を指す。界面活性剤及び膜脂質などの両親媒性分子は、1つ又は複数の非極性鎖に結合した極性頭部基からなることが多い。そのような両親媒性分子が水のような溶媒に溶解されると、それらは極性(親水性)頭部が非極性(疎水性)尾部を保護するような会合体を形成する。例えば、過剰溶媒中では、両親媒性分子はミセルとして知られている球状の会合体を形成し、(溶媒蒸発又はそれらの濃度の増加によって)濃縮すると、通常ミセルとは異なる形状、構造又は光学特性を有する会合体を形成する。これらの会合体は、六方晶系液晶相を含み、両親媒性分子は六角形配列中に充填される柱状構造を形成する。ラメラ液晶相はより高い両親媒性物質濃度で出現し、両親媒性分子は二分子膜構造を形成する。溶媒及び濃縮効果に加えて、温度はリオトロピック液晶相の形成及び安定性に劇的に影響し得る。例えば、リオトロピック液晶相がクラフト点(Kp)より低い一定の温度まで冷却されると、相転移が起こり、ゲル相が出現することが多い。液晶相又はゲル相の形成は化粧料においてもみられ、それらの相転移の制御は、流動性及び安定性を含む化粧料の物理的性質を維持するために機能する。 Generally, a lyotropic liquid crystal phase refers to an association formed by amphiphilic molecules in a solvent system at a certain temperature. Amphipathic molecules such as surfactants and membrane lipids often consist of polar head groups attached to one or more non-polar chains. When such amphipathic molecules are dissolved in a solvent such as water, they form an association in which the polar (hydrophilic) head protects the non-polar (hydrophobic) tail. For example, in excess solvent, amphipathic molecules form spherical aggregates known as micelles, which, upon concentration (by solvent evaporation or an increase in their concentration), usually result in a shape, structure or optical difference from the micelles. Form an aggregate with characteristics. These aggregates contain a hexagonal liquid crystal phase and the amphipathic molecules form a columnar structure that is packed in a hexagonal array. The lamellar liquid crystal phase appears at higher amphiphile concentrations and the amphipathic molecules form a bilayer structure. In addition to solvent and concentration effects, temperature can dramatically affect the formation and stability of lyotropic liquid crystal phases. For example, when a lyotropic liquid crystal phase is cooled to a certain temperature below the Kraft point (Kp), a phase transition often occurs and a gel phase appears. The formation of liquid crystal or gel phases is also found in cosmetics, and their control of phase transitions serves to maintain the physical properties of the cosmetic, including fluidity and stability.
本発明の一態様の乳化剤と化粧料の調製に通常使用される成分とを、高負荷をかけることなく撹拌混合などをすることによって、液晶を含有する化粧料が得られる。この際、本発明の一態様の乳化剤とともに、皮膜形成高分子及び水を含有せしめることにより、皮膚に塗布することによってラメラ液晶構造を有するフィルムを形成し得る化粧料を得ることができる。すなわち、本発明の一態様の化粧料は、本発明の一態様の乳化剤と、皮膜形成高分子と、水とを少なくとも含有する、液晶含有化粧料である。なお、溶媒として油性成分を用いて、油分の多い化粧料とすることにより、皮膚上にヘキサゴナル液晶構造を有するフィルムを形成し得る化粧料を得ることができる。 A cosmetic containing a liquid crystal is obtained by stirring and mixing the emulsifier of one embodiment of the present invention and the components usually used for preparation of cosmetics without a high load. At this time, by containing the film-forming polymer and water together with the emulsifier of one embodiment of the present invention, a cosmetic capable of forming a film having a lamellar liquid crystal structure by applying to the skin can be obtained. That is, the cosmetic of one aspect of the present invention is a liquid crystal-containing cosmetic containing at least the emulsifier of one aspect of the present invention, a film-forming polymer, and water. By using an oily component as a solvent to prepare a cosmetic with a large amount of oil, a cosmetic capable of forming a film having a hexagonal liquid crystal structure on the skin can be obtained.
[3.化粧料]
本発明の一態様の化粧料は、水中に約10μm〜30μmの液晶微小滴を安定的に分散したクリーム状の水中油型乳化物であり得るが、本発明の一態様の化粧料の形態はこれに限定されない。本発明の一態様の化粧料は、クリーム状態においては白く、高粘度であり得るが、皮膚上に塗布されて余剰な水分が蒸散するとフィルムを形成する。皮膚上で形成した複合体フィルムは、べたつかず、半透明で光沢が抑えられるので皮膚上で違和感がないものとすることができる。
[3. Cosmetics]
The cosmetic of one aspect of the present invention can be a creamy oil-in-water emulsion in which liquid crystal microdroplets of about 10 μm to 30 μm are stably dispersed in water, but the form of the cosmetic of one aspect of the present invention is It is not limited to this. The cosmetic of one embodiment of the present invention may be white in a cream state and have high viscosity, but forms a film when applied on the skin and excess water evaporates. The composite film formed on the skin does not become sticky, is semitransparent, and has a reduced gloss, so that the composite film does not feel uncomfortable on the skin.
本発明の一態様の化粧料は、皮膜形成高分子を含有することにより、液晶の安定化だけではなく、相乗的な保湿効果をもたらす。また、本発明の一態様の化粧料を皮膚表面上に塗布して形成されるフィルムによって、閉塞効果が付与される。本発明の一態様の化粧料における皮膜形成高分子と液晶との相互作用は、フィルム形成における自然蒸発過程での液晶の融合及び結晶化を防ぎ、さらにフィルムに抱え込むことのできる水分量が増加するのでフィルムの耐水性を改善し得る。液晶を高分子フィルムのフィラーとして配合することにより、皮膚への接着性が向上し、長時間の皮膚への接着と高い水分閉塞性とを実現し得る。 The cosmetic of one aspect of the present invention not only stabilizes the liquid crystal but also provides a synergistic moisturizing effect by containing the film-forming polymer. Further, the film formed by applying the cosmetic of one embodiment of the present invention on the surface of the skin imparts the blocking effect. The interaction between the film-forming polymer and the liquid crystal in the cosmetic of one embodiment of the present invention prevents fusion and crystallization of the liquid crystal during the natural evaporation process in film formation, and further increases the amount of water that can be held in the film. Therefore, the water resistance of the film can be improved. By blending liquid crystal as a filler for the polymer film, the adhesion to the skin is improved, and long-term adhesion to the skin and high water occluding property can be realized.
本発明の一態様の化粧料において、本発明の一態様の乳化剤の含有量は、化粧料中及び化粧料を皮膚に適用して得られるフィルム中において液晶形成性が確認できる量であれば特に限定されないが、例えば、2質量%〜30質量%であり、好ましくは5質量%〜20質量%である。本発明の一態様の化粧料において、本発明の一態様の組成物の含有量は、例えば、1質量%〜15質量%であり、好ましくは1質量%〜10質量%であり、より好ましくは2質量%〜5質量%である。本発明の一態様の組成物の含有量がこれらの範囲にない場合は、本発明の一態様の化粧料を皮膚に塗布して形成されるフィルムにおいて、安定的な液晶構造を維持することが困難になるおそれがある。 In the cosmetic according to one aspect of the present invention, the content of the emulsifier according to one aspect of the present invention is particularly preferably an amount in which the liquid crystal forming property can be confirmed in the cosmetic and in the film obtained by applying the cosmetic to the skin. Although not limited, it is, for example, 2% by mass to 30% by mass, preferably 5% by mass to 20% by mass. In the cosmetic of one aspect of the present invention, the content of the composition of one aspect of the present invention is, for example, 1% by mass to 15% by mass, preferably 1% by mass to 10% by mass, and more preferably It is 2% by mass to 5% by mass. When the content of the composition of one embodiment of the present invention is not within these ranges, it is possible to maintain a stable liquid crystal structure in the film formed by applying the cosmetic of one embodiment of the present invention to the skin. It can be difficult.
本発明の一態様の化粧料は、皮膜形成高分子を含有する。皮膜形成高分子は、皮膚に化粧料を塗布した際に、フィルム状の皮膜を皮膚上に形成及び保持し得る機能(皮膜形成機能)を有するものであれば特に限定されず、天然由来のものでも、合成して得られるものであっても、これらの混合物であってもいずれのものでもよい。ただし、液晶成分に天然由来成分を用いて、皮膚上に天然由来成分からなるラメラ相を形成するためには、皮膜形成高分子は天然由来の高分子であることが好ましく、生体高分子として知られているものであることがさらに好ましい。 The cosmetic of one aspect of the present invention contains a film-forming polymer. The film-forming polymer is not particularly limited as long as it has a function of forming and retaining a film-like film on the skin (a film-forming function) when a cosmetic is applied to the skin, and a naturally-occurring one However, it may be one obtained by synthesis, a mixture thereof, or any of them. However, in order to form a lamellar phase composed of a naturally-derived component on the skin by using the naturally-derived component as the liquid crystal component, the film-forming polymer is preferably a naturally-derived polymer, which is known as a biopolymer. It is more preferable that the
天然由来の皮膜形成高分子の具体例としては、ヒアルロン酸塩(アセチル化ヒアルロン酸ナトリウム、ヒアルロン酸ナトリウム、カルボキシメチルヒアルロン酸ナトリウムなど)、チューベロース多糖体、キトサン(ヒドロキシプロピルキトサン、キトフィルマーなど)、糖鎖ポリマー及びガラクタン(ガラクトマンナン、硫酸化ガラクタン)、スイゼンジノリ多糖体、セルロース(カルボキシメチルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロースなど)、アルギン酸塩(アルギン酸プロピレングリコール)、プルラン、カラギーナン、デンプン誘導体(グリコシルトレハロース、加水分解水添デンプンなど)、植物性ヘテロ多糖類(ホソバセンナ(cassia angustifolia)種子多糖体など)、コラーゲン(海洋コラーゲンなど)、タマリンドガムなどが挙げられるが、特に限定されない。天然由来の皮膜形成高分子は、上記したものなどの1種を単独で、又は2種以上を組み合わせて使用し得る。 Specific examples of naturally-occurring film-forming polymers include hyaluronate (acetylated sodium hyaluronate, sodium hyaluronate, sodium carboxymethyl hyaluronate, etc.), tuberose polysaccharide, chitosan (hydroxypropyl chitosan, chitofilmer, etc.), Sugar chain polymer and galactan (galactomannan, sulfated galactan), suisendinori polysaccharide, cellulose (carboxymethylcellulose, hydroxypropylmethylcellulose, methylcellulose, etc.), alginate (propylene glycol alginate), pullulan, carrageenan, starch derivative (glycosyltrehalose, hydrous) decomposition hydrogenated starch), etc. vegetable heteropolysaccharide (Hosobasen'na (cassia angustifolia) seed polysaccharides), such as collagen (marine collagen), but like tamarind gum and the like, are not particularly limited. The naturally-occurring film-forming polymers may be used alone or in combination of two or more.
合成品である皮膜形成高分子の具体例としては、例えば、シリコーン改質多糖類(トリメチルシロキシシリルカルバモイルプルラン、「TSPL−30−ID」(信越化学工業社製)など)、シリコーンゴム及び樹脂(トリメチルシロキシケイ酸、「KF−9021」、「KF−7312J」、「X−21−5250L」、「X−21−5616」(それぞれ信越化学工業社製)など)、シリコーンエラストマー(ポリシリコーン11など)、アクリレートコポリマー(アクリレート/VAコポリマーなど)、ポリ(メタ)アクリル酸((メタ)アクリル酸/(メタ)アクリル酸アルキル(C10−30)クロスポリマーなど)、ポリビニルアルコール(PVA)、ポリビニルピロリドン(PVP)、ポリエーテル(高重合ポリエチレングリコールなど)、2−メタクリロイルオキシエチルホスホリルコリンとn−ブチルメタクリレートとの共重合体(ポリクオタニウム−51など)、ポリオレフィン(エチレン/オクテン共重合体、エチレン/アクリル酸ナトリウム共重合体など)などが挙げられるが、これらに限定されない。合成品である皮膜形成高分子は、上記したものなどの1種を単独で、又は2種以上を組み合わせて使用し得る。 Specific examples of the film-forming polymer that is a synthetic product include, for example, silicone-modified polysaccharides (trimethylsiloxysilylcarbamoyl pullulan, "TSPL-30-ID" (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.), silicone rubber and resin ( Trimethylsiloxysilicic acid, "KF-9021", "KF-7312J", "X-21-5250L", "X-21-5616" (each manufactured by Shin-Etsu Chemical Co., Ltd.), silicone elastomer (polysilicone 11 etc.) ), acrylate copolymer (acrylate/VA copolymer, etc.), poly(meth)acrylic acid ((meth)acrylic acid/alkyl (meth)acrylate (C10-30) crosspolymer, etc.), polyvinyl alcohol (PVA), polyvinylpyrrolidone ( PVP, polyether (highly polymerized polyethylene glycol, etc.), copolymer of 2-methacryloyloxyethylphosphorylcholine and n-butyl methacrylate (polyquaternium-51, etc.), polyolefin (ethylene/octene copolymer, ethylene/sodium acrylate) But not limited thereto. The film-forming polymer that is a synthetic product may be used alone or in combination of two or more kinds such as those mentioned above.
本発明の一態様の化粧料における皮膜形成高分子の含有量は、皮膜形成機能を発揮し得る量であれば特に限定されないが、例えば、1質量%〜15質量%であり、好ましくは2質量%〜10質量%であり、より好ましくは3質量%〜8質量%である。皮膜形成高分子の含有量が1質量%未満である場合は、本発明の一態様の化粧料を皮膚に塗布しても皮膜状のフィルムを形成しなかったり、破れや剥がれなどの形状安定性に乏しいフィルムが形成したりするおそれがある。 The content of the film-forming polymer in the cosmetic of one aspect of the present invention is not particularly limited as long as it can exhibit the film-forming function, but is, for example, 1% by mass to 15% by mass, and preferably 2% by mass. % To 10% by mass, and more preferably 3% to 8% by mass. When the content of the film-forming polymer is less than 1% by mass, even if the cosmetic of one embodiment of the present invention is applied to the skin, a film-like film is not formed, or shape stability such as tearing or peeling is formed. The film may be poor.
天然由来の皮膜形成高分子に加えて、合成品である皮膜形成高分子を用いることもできる。しかしながら、液晶の安定性、フィルムの自立性、保湿性の向上のために生体高分子が優先的に配合されることが好ましい。 In addition to the naturally-occurring film-forming polymer, it is also possible to use a synthetic film-forming polymer. However, it is preferable that the biopolymer is preferentially blended in order to improve the stability of the liquid crystal, the self-sustaining property of the film, and the moisture retention property.
皮膜形成高分子とともに、ゲル化剤として機能する高分子を配合することにより、皮膚上に形成したフィルムにゲルの特性(増粘性)を付与する、又は湿度応答性などの刺激応答性を向上させるなどの機能を付与し得る。ゲル化剤として機能する高分子としてはキサンタンガム、ヒドロキシエチルセルロースなどが挙げられ、その含有量は0.1質量%〜0.5質量%程度である。また、フィルムの柔軟性及び皮膚表面の耐久性を改善するために、多価アルコールやポリオキシエチレンメチルグルコシドなどの可塑剤を含有してもよい。可塑剤の含有量は、2質量%〜10質量%程度であることが好ましい。 By adding a polymer that functions as a gelling agent together with a film-forming polymer, it imparts gel characteristics (thickening) to the film formed on the skin, or improves stimulus responsiveness such as humidity responsiveness. And the like. Examples of the polymer that functions as a gelling agent include xanthan gum and hydroxyethyl cellulose, and the content thereof is about 0.1% by mass to 0.5% by mass. Further, in order to improve the flexibility of the film and the durability of the skin surface, a plasticizer such as polyhydric alcohol or polyoxyethylene methyl glucoside may be contained. The content of the plasticizer is preferably about 2% by mass to 10% by mass.
本発明の一態様の化粧料における水の含有量は、水中油型化粧料が得られる程度の量であれば特に限定されないが、例えば、70質量%〜95質量%であり、好ましくは80質量%〜90質量%である。本発明の一態様の化粧料において、液晶成分は安定な微小液滴エマルションとして柱状の液晶相を形成して安定的に保持される(化粧料の水分量が50質量%以上)。また、本発明の一態様の化粧料を皮膚に塗布して水やその他の溶媒を蒸発させて高濃縮条件下(化粧料の水分量が50質量%以下)におくと、液晶成分は高分子フィルム(固体)マトリックス中に安定な微小液滴分散体としてラメラ液晶相を含有する液晶フィルムを形成する。 The content of water in the cosmetic of one aspect of the present invention is not particularly limited as long as an oil-in-water cosmetic is obtained, but is, for example, 70% by mass to 95% by mass, and preferably 80% by mass. % To 90 mass %. In the cosmetic according to one aspect of the present invention, the liquid crystal component forms a columnar liquid crystal phase as a stable microdroplet emulsion and is stably retained (water content of the cosmetic is 50% by mass or more). In addition, when the cosmetic of one embodiment of the present invention is applied to the skin and water or other solvent is evaporated under high-concentration conditions (the water content of the cosmetic is 50% by mass or less), the liquid crystal component becomes a polymer. A liquid crystal film containing a lamellar liquid crystal phase is formed as a stable microdroplet dispersion in a film (solid) matrix.
一般的に、角質層のラメラ構造を有する細胞間脂質は、液晶の特性のために変形可能であり、これにより、せん断時に互いに摺動し、ひいては皮膚に弾力性及び可撓性を付与する(Progress in Lipid Research 42、1−36(2003)を参照)。ラメラ構造をとる細胞間脂質は、第一には角質層を通る水の移動を制限することで過度の経表皮水分損失(TEWL)を防止し、そして水溶性化合物(NMF(Natural Moisturizing Factor;天然保湿因子))が角質細胞から浸出するのを効果的に防止する、重要なバリア機能を果たす(Dermatologic Therapy 17,6−15(2004)を参照)。また、細胞間脂質は、汚染物質及び有害な太陽放射線などの環境傷害に対する物理的障壁として作用する。 In general, intercellular lipids with a lamellar structure of the stratum corneum are deformable due to the properties of the liquid crystals, which allow them to slide on each other when sheared, thus imparting elasticity and flexibility to the skin ( Progress in Lipid Research 42, 1-36 (2003)). Intercellular lipids that adopt a lamellar structure prevent excessive transepidermal water loss (TEWL) by first limiting the movement of water through the stratum corneum, and water-soluble compounds (NMF (Natural Moisturizing Factor; (Moisturizing factor)) plays an important barrier function, effectively preventing the exudation of keratinocytes (see Dermatologic Therapy 17, 6-15 (2004)). In addition, intercellular lipids act as a physical barrier to environmental damage such as pollutants and harmful solar radiation.
本発明の一態様の化粧料によって皮膚上に形成される液晶フィルムは、成分に自然由来の膜脂質を用いた複数のラメラ液晶滴が凝縮されることで、連続したような構造となり、角質層の細胞間脂質に見出される構成又は構造に類似し得る。このことから、本発明の一態様の化粧料によって皮膚上に形成される液晶フィルムは細胞間脂質と同様の保湿機能及びバリア機能、さらに化粧料に許容可能な皮膚を保護する機能を発揮できる。 The liquid crystal film formed on the skin by the cosmetic according to one embodiment of the present invention has a continuous structure due to the condensation of a plurality of lamellar liquid crystal droplets using a naturally-occurring membrane lipid as a component, and forms a stratum corneum. Can resemble the structure or structure found in the intercellular lipids of. From this, the liquid crystal film formed on the skin by the cosmetic of one aspect of the present invention can exhibit the same moisturizing function and barrier function as the intercellular lipid, and further the function of protecting the skin that is acceptable to the cosmetic.
本発明の一態様の化粧料のpHは、通常知られているとおりの水中油型乳化化粧料のpHの範囲内であれば特に限定されないが、例えば、5〜9であり、好ましくは6〜8である。pHの値が5〜9の範囲外にある場合は、安定的に液晶を維持することが困難であり、さらに安定的な高分子フィルムの形成が困難になるおそれがある。 The pH of the cosmetic of one embodiment of the present invention is not particularly limited as long as it is within the range of the pH of the oil-in-water emulsion cosmetic as is generally known, but is, for example, 5 to 9, and preferably 6 to. 8 When the pH value is out of the range of 5 to 9, it is difficult to stably maintain the liquid crystal, and it may be difficult to form a stable polymer film.
本発明の一態様の化粧料は、化粧料として用いられる限りにおいて、その機能や効果については特に限定されない。本発明の一態様の化粧料は、液晶の安定性について、例えば、後述する実施例に記載の容器中及び/又は皮膚上における液晶の安定性を試験することにより、マルターゼクロスが観察でき、かつ、結晶の析出及びステロールの不溶解物を観察できないものであることが好ましい。 The cosmetics of one aspect of the present invention are not particularly limited in their functions and effects as long as they are used as cosmetics. The cosmetic of one aspect of the present invention has a stability of liquid crystal, for example, by testing the stability of the liquid crystal in the container and/or on the skin described in Examples described later, maltase cloth can be observed, and It is preferable that the precipitation of crystals and the insoluble matter of sterol cannot be observed.
本発明の一態様の化粧料のより具体的な態様は、両親媒性脂質を0.5質量%〜5.0質量%、ステロールを0.1質量%〜2.0質量%、直鎖飽和脂肪酸を0.1質量%〜2.25質量%、多価アルコールを2質量%〜15質量%、皮膜形成高分子を2質量%〜10質量%及び水を80質量%〜90質量%で含有し、かつ、容器中及び/又は皮膚上における液晶の安定性が優れた水中油型乳化化粧料であるが、これに限定されない。 A more specific aspect of the cosmetic of one aspect of the present invention is that the amphipathic lipid is 0.5% by mass to 5.0% by mass, the sterol is 0.1% by mass to 2.0% by mass, and the linear saturated Contains 0.1% by mass to 2.25% by mass of fatty acid, 2% by mass to 15% by mass of polyhydric alcohol, 2% by mass to 10% by mass of film-forming polymer, and 80% by mass to 90% by mass of water. However, the oil-in-water type emulsion cosmetic is excellent in stability of the liquid crystal in the container and/or on the skin, but is not limited thereto.
本発明の一態様の化粧料や本発明の一態様の化粧料によって皮膚表面上に形成される複合体液晶フィルムには、種々のメリットがある。これらによって享受されるメリットについて以下に列挙するが、これらのメリットの有無によってのみでは本発明の技術的範囲は限定されない。
(1)化粧料は、低溶解性脂質を多く含む場合さえ(例えば、脂質の総量に対して30質量%)、凝集(液滴融合)や結晶化が生じることなく、−10℃〜50℃の温度範囲内で約1ヶ月間は安定に保持し得る。
(2)化粧料は、周囲条件下(温度:25℃、相対湿度:50%)において、特別な脱水処理やその他のフィルム形成技術を適用することなく、溶媒及び他の揮発性物質の自然蒸発により、皮膚上に連続的なフィルムを容易に形成し得る。
(3)複合体液晶フィルムは、水分及び脂質に富み、複数の分散されたラメラ液晶滴を含む接着フィルムである。分散された液晶滴は、機械的摩擦による液晶相転移、液滴合体、脂質結晶化などの問題が生じ難い。
(4)複合体液晶フィルムは、含有する成分によっては、生体適合性及び通気性があり、さらに安全かつ皮膚表面を損傷することなく自立シートとして剥がすことができる。剥がれたシートに埋め込まれた液晶液滴(ラメラ脂質)を分解することなく、剥離した自立シートを周囲条件(温度:25℃、相対湿度:50%)で3ヶ月を超えて保存することが可能である。
(5)複合体液晶フィルムは、皮膜形成高分子が水溶性高分子である場合、過剰の水で洗浄することにより、除去することができる。
(6)複合体液晶フィルムは、しっとり感、冷たさ、及び軽い触感を有し、使用に際して不快感を生じさせないようにすることができる。
(7)複合体液晶フィルムは、分散されたラメラ液晶滴が、高分子フィルムの補強充填剤として機能し、その保湿性、皮膚への接着性及び閉塞性、さらに光沢度を相乗的に改善したものとなり得る。
(8)複合体液晶フィルムは、所望によって透明又は半透明にすることができ、その透明度は、例えば、液晶分散物の液滴サイズを変化させることによって制御可能である。透明性の他に、複合体液晶フィルムの光沢度は、脂質成分の濃度を変えることによって制御することが可能であり、分散された液晶滴は高分子フィルムの過度な光沢を抑え得る。
(9)複合体液晶フィルムは、耐久性のある長時間の接着が可能な保湿フィルムであり、後述する実施例に記載があるとおり、8時間以上安定して接着したままで皮膚を湿潤状態にし得る。
(10)複合体液晶フィルムは、悪化した皮膚の特性を改善するための皮膚矯正剤及びコンシーラーとしても使用することができる。
(11)複合体液晶フィルムは、化粧品に通常使用される粉末及び顔料により粉末化及び着色することができる。
(12)複合体液晶フィルムは、空気中の粉塵、灰、粒子状物質(PM)、破片、微生物、花粉などの汚染性物質及び他の有害な環境要因に対して、美容上許容可能な物理的遮蔽物として使用することが可能である。
(13)複合体液晶フィルムによって得られる種々の機能、作用及び効果は、液晶成分及び皮膜形成高分子の両方によって相乗的に得られ、個々の成分によって達成することが難しいものである。
(14)複合体液晶フィルムの厚さは特に限定されないが、例えば、100μm〜200μm程度である。本発明の一態様の化粧料の含水量が86質量%である場合、化粧料 約1.0gを健常な肌を有する者の皮膚上に塗布すると、約8×3cm2の面積になるように均一に広がり、次いで周囲条件(温度:25℃、相対湿度:50%)下で約10分間にて自然に乾燥することにより、該面積にてフィルムが形成される。
(15)複合体液晶フィルムに含まれる天然膜脂質は細胞間脂質と同様の構造を有するラメラ液晶滴中に担持される。
(16)複合体液晶フィルムの含水率はDSC測定により、及び液晶滴の含水率は(結合性層間水として)XRD測定により確認する。その結果、角層の含水率(約10〜20%)に比べて複合体液晶フィルムは含水率が高く(少なくとも40質量%)、さらに複合体液晶フィルムに比べて液晶滴の含水率が高い。よって、皮膚上に複合体液晶フィルムを塗布することで、皮膚へ水分を供給する水分勾配システムを実現し得る。
(17)複合体液晶フィルムによって被覆される皮膚領域の連続的な水和は、膜閉塞力とともに水勾配システムによって達成することができ、経皮水分蒸散などによって皮膚から失われた水分を再捕捉し、さらに複合体液晶フィルムに蓄積することができる。
(18)複合体液晶フィルムは、皮膚水和状態が複合体液晶フィルムによって良好に管理され、過水和も脱水も起こり難い。これは、複合体液晶フィルムの水分勾配システム及び水分応答性によるものであり、皮膚表面の統合性及び性能を損なうことなく、フィルムの含水量を調節するための可逆的膨潤挙動を可能にする。
(19)複合体液晶フィルムは、分散されたラメラ液晶相の所望の機能、例えば、清浄性、光学性、内包物徐放性又は保湿性が凝縮フィルム状態で増幅され得る。これは、フィルム内に安定して埋め込まれた、各液滴が所望の機能を付与する活性物質によりもたらされ、ラメラ液晶滴の多くの集合の存在に起因する。また、複合体液晶フィルムはラメラ液晶滴の多くの集合体を含むため、フィルムの均質性(固体フィルム中の活性物質の分布)は特に問題とならない。また、フィルムが皮膚の広い表面積に物理的に接触している、又は液晶滴の分散がより大きな表面積を有し得るので、化粧料又は液晶の効果は最大化され、等しく送達され得る。
The cosmetic material of one embodiment of the present invention and the composite liquid crystal film formed on the skin surface by the cosmetic material of one embodiment of the present invention have various advantages. The merits enjoyed by these are listed below, but the technical scope of the present invention is not limited only by the presence or absence of these merits.
(1) Even when the cosmetic contains a large amount of low-solubility lipid (for example, 30% by mass with respect to the total amount of lipid), -10°C to 50°C without aggregation (droplet fusion) or crystallization. It can be kept stable within the temperature range of about 1 month.
(2) Under the ambient conditions (temperature: 25° C., relative humidity: 50%), cosmetics are allowed to spontaneously evaporate the solvent and other volatile substances without applying special dehydration treatment or other film forming technology. Can easily form a continuous film on the skin.
(3) The composite liquid crystal film is an adhesive film that is rich in water and lipid and that contains a plurality of dispersed lamellar liquid crystal droplets. The dispersed liquid crystal droplets are unlikely to cause problems such as liquid crystal phase transition due to mechanical friction, droplet coalescence, and lipid crystallization.
(4) The composite liquid crystal film has biocompatibility and air permeability depending on the contained components, and is safe and can be peeled off as a self-supporting sheet without damaging the skin surface. It is possible to store the peeled free-standing sheet under ambient conditions (temperature: 25°C, relative humidity: 50%) for more than 3 months without decomposing liquid crystal droplets (lamellar lipids) embedded in the peeled sheet. Is.
(5) When the film-forming polymer is a water-soluble polymer, the composite liquid crystal film can be removed by washing with excess water.
(6) The composite liquid crystal film has a moist feeling, a cold feeling, and a light tactile sensation, and can prevent discomfort during use.
(7) In the composite liquid crystal film, the dispersed lamella liquid crystal droplets functioned as a reinforcing filler for the polymer film, and synergistically improved the moisturizing property, the adhesiveness to the skin and the blocking property, and the glossiness. Can be something.
(8) The composite liquid crystal film can be made transparent or semitransparent as desired, and its transparency can be controlled by, for example, changing the droplet size of the liquid crystal dispersion. Besides transparency, the glossiness of the composite liquid crystal film can be controlled by changing the concentration of the lipid component, and the dispersed liquid crystal droplets can suppress the excessive gloss of the polymer film.
(9) The composite liquid crystal film is a durable moisturizing film that can be adhered for a long time. As described in Examples below, the composite liquid crystal film keeps the skin in a moist state while being stably adhered for 8 hours or more. obtain.
(10) The composite liquid crystal film can also be used as a skin straightener and a concealer for improving deteriorated skin properties.
(11) The composite liquid crystal film can be powdered and colored with powders and pigments usually used in cosmetics.
(12) The composite liquid crystal film has a cosmetically acceptable physical property against airborne dust, ash, particulate matter (PM), debris, microorganisms, pollutants such as pollen, and other harmful environmental factors. It can be used as a mechanical shield.
(13) The various functions, actions and effects obtained by the composite liquid crystal film are synergistically obtained by both the liquid crystal component and the film-forming polymer, and are difficult to achieve by the individual components.
(14) The thickness of the composite liquid crystal film is not particularly limited, but is, for example, about 100 μm to 200 μm. When the water content of the cosmetic of one embodiment of the present invention is 86% by mass, when about 1.0 g of the cosmetic is applied onto the skin of a person having healthy skin, an area of about 8×3 cm 2 is obtained. A film is formed in the area by spreading evenly and then naturally drying under ambient conditions (temperature: 25° C., relative humidity: 50%) for about 10 minutes.
(15) The natural membrane lipid contained in the complex liquid crystal film is carried in the lamellar liquid crystal droplets having the same structure as the intercellular lipid.
(16) The water content of the composite liquid crystal film is confirmed by DSC measurement, and the water content of the liquid crystal droplets (as binding interlayer water) is confirmed by XRD measurement. As a result, the composite liquid crystal film has a higher water content (at least 40% by mass) than the water content of the stratum corneum (about 10 to 20%), and the water content of the liquid crystal droplets is higher than that of the composite liquid crystal film. Therefore, by applying the composite liquid crystal film on the skin, a water gradient system for supplying water to the skin can be realized.
(17) Continuous hydration of the skin area covered by the composite liquid crystal film can be achieved by a water gradient system together with the membrane occluding force to re-capture the water lost from the skin due to transepidermal water loss etc. And can be further stored in the composite liquid crystal film.
(18) In the complex liquid crystal film, the skin hydration state is well controlled by the complex liquid crystal film, and neither hyperhydration nor dehydration occurs easily. This is due to the water gradient system and water responsiveness of the composite liquid crystal film, allowing a reversible swelling behavior to control the water content of the film without compromising the integrity and performance of the skin surface.
(19) In the composite liquid crystal film, desired functions of the dispersed lamellar liquid crystal phase, such as cleanliness, optical properties, sustained release of inclusions, or moisturizing properties, can be amplified in a condensed film state. This is due to the presence of many aggregates of lamellar liquid crystal droplets, which are stably embedded in the film, each droplet being provided by an active substance that imparts the desired function. Further, since the composite liquid crystal film contains many aggregates of lamellar liquid crystal droplets, the homogeneity of the film (distribution of the active substance in the solid film) does not matter in particular. Also, because the film is in physical contact with a large surface area of the skin or the dispersion of liquid crystal droplets can have a larger surface area, the cosmetic or liquid crystal effect can be maximized and delivered equally.
本発明の一態様の化粧料は他の成分を含有してもよい。他の成分は、本発明の課題の解決を妨げない限り特に限定されないが、例えば、着色剤及び顔料、香料、粉末、抗老化剤、抗しわ剤、抗皮膚萎縮剤、細胞賦活剤、抗汚染剤、抗菌剤及び防腐剤、皮膚軟化剤、保湿剤及び質感向上剤、界面活性剤、乳化剤、油溶性コンディショニング剤、増粘ポリマー、抗酸化剤、ゲル化剤、ハリや弾力を与える成分、美白剤、抗炎症剤、冷却剤、加温剤、キレート剤、pH調整剤、無機塩及び無機物、紫外線吸収剤及び紫外線散乱剤、日焼け止め剤、創傷治癒剤、ビタミン及びビタミン誘導体、剥離剤及び研磨剤、吸収剤、抗生物質、凝固防止剤、生物学的添加剤、漂白活性化剤、化学添加物、クレンザー、脱臭剤、酵素、乳白剤、酸化剤、緩衝剤、可塑剤、ラジカル捕捉剤、皮膚浸透促進剤、安定剤、美容成分、植物抽出物、制汗剤、昆虫忌避剤、抗ざ瘡剤、消毒剤、皮膚鎮静剤、皮膚バリア修復補助剤、皮膚修復剤、脂質、皮脂抑制剤、痒み防止剤、毛髪の成長を阻害するための薬剤、抗糖化剤、湿潤剤、光散乱剤その他の光学成分などが挙げられる。他の成分は上記したものなどの1種を単独で、又は2種以上を組み合わせて使用し得る。他の成分の含有量は特に限定されないが、例えば、0質量%〜10質量%程度である。 The cosmetic of one aspect of the present invention may contain other components. Other components are not particularly limited as long as they do not prevent the solution of the problems of the present invention, and include, for example, colorants and pigments, fragrances, powders, anti-aging agents, anti-wrinkle agents, anti-skin atrophy agents, cell activating agents, and anti-staining agents. Agents, antibacterial agents and antiseptics, emollients, moisturizers and texture improvers, surfactants, emulsifiers, oil-soluble conditioning agents, thickening polymers, antioxidants, gelling agents, ingredients that give firmness and elasticity, whitening Agents, anti-inflammatory agents, cooling agents, warming agents, chelating agents, pH adjusting agents, inorganic salts and inorganic substances, UV absorbers and UV scattering agents, sunscreens, wound healing agents, vitamins and vitamin derivatives, peeling agents and polishing agents Agents, absorbents, antibiotics, anticoagulants, biological additives, bleach activators, chemical additives, cleansers, deodorants, enzymes, opacifiers, oxidants, buffers, plasticizers, radical scavengers, Skin penetration enhancer, stabilizer, cosmetic ingredient, plant extract, antiperspirant, insect repellent, anti-acne agent, disinfectant, skin sedative, skin barrier repair aid, skin repair agent, lipid, sebum suppressant , Antipruritic agents, agents for inhibiting hair growth, anti-glycation agents, wetting agents, light scattering agents and other optical components. The other components may be used alone or in combination of two or more as described above. The content of other components is not particularly limited, but is, for example, about 0% by mass to 10% by mass.
本発明の一態様の化粧料は、それ自体で保湿性や閉塞性をもたらし得るものであるが、活性成分を含有することにより、適用する皮膚に対して追加的な機能を付与し得る。追加的な機能は特に限定されないが、例えば、皮膚を水和させること、小じわ及びしわの平滑化、ざ瘡の美容的処置、皮膚の引き締め(ファーミング)、皮膚の軟化、皮膚への活性物質等の浸透性の促進、皮膚のクレンジング、古くなった角層の除去、メイクアップリムーバー、メーキャップベースフィルム、肌の色合い及び質感の改善又は滑らかにすること、皮膚のコンシーラーリングと着色、肌のコンディショニング、毛穴を目立たなくすること、分泌物の吸収及び制御、皮膚の保護、皮膚のリフレッシュと冷却、炎症緩和、衝撃を緩和すること、浄化すること、香り付け、細菌増殖を減少させること、不要な毛髪の除去、防虫、汚れ(汚染物質)とメイクアップ残りの除去などが挙げられる。本発明の一態様の化粧料によって皮膚上に形成された複合体液晶フィルムは、皮膚を水和させ、皮膚を環境損傷から保護し、かつ身体的風貌を美容的に改善するために使用され得る。 The cosmetic of one aspect of the present invention can provide moisturizing properties and occlusive properties by itself, but by containing an active ingredient, it can impart an additional function to the skin to which it is applied. Additional functions are not particularly limited, for example, hydrating the skin, smoothing fine lines and wrinkles, cosmetic treatment of acne, skin tightening (firming), skin softening, active substances to the skin, etc. Penetration of skin, cleansing the skin, removing old stratum corneum, makeup remover, makeup base film, improving or smoothing skin tone and texture, skin concealer ring and coloring, skin conditioning, Decrease pores, absorb and control secretions, protect skin, refresh and cool skin, reduce inflammation, reduce shock, cleanse, fragrance, reduce bacterial growth, unwanted hair Removal of insects, insect repellent, stains (pollutants) and makeup residue removal. The composite liquid crystal film formed on the skin by the cosmetic according to one aspect of the present invention can be used for hydrating the skin, protecting the skin from environmental damage, and cosmetically improving the physical appearance. ..
本発明の一態様の化粧料を適用する部位は特に限定されず、例えば、顔(額、目元、目じり、頬、口元など)、腕、肘、手の甲、指先、足、膝、かかと、首、脇、背中、頭皮、毛髪などが挙げられる。 The site to which the cosmetic material according to one embodiment of the present invention is applied is not particularly limited, and examples thereof include face (forehead, eye area, eyes, cheek, mouth area, etc.), arm, elbow, back of hand, fingertip, foot, knee, heel, neck, Armpits, back, scalp, hair, etc.
本発明の一態様の化粧料は、その使用態様や剤形については特に限定されず、例えば、スキンケア化粧品、メーキャップ化粧品、フレグランス化粧品、ボディケア化粧品などが挙げられ、より具体的にはクリーム、乳液、ファンデーション、化粧水、美容液、オールインワンジェル、サンスクリーンジェル、ローション、パック、マスク、ポイントマスク、パッチ、洗顔クリーム、ハンドクリーム、メーキャップクレンジング、化粧下地、コンシーラー、ほほ紅、アイシャドウ、アイライナー、アイブロウ、口紅、日焼け止めクリーム、脱毛・除毛クリームなどが挙げられる。ただし、本発明の一態様の化粧料について、他の化粧料を製造する際の原料(中間原料)として用いることを妨げない。 The use form and dosage form of the cosmetic of one aspect of the present invention are not particularly limited, and examples thereof include skin care cosmetics, makeup cosmetics, fragrance cosmetics, body care cosmetics, and the like, and more specifically creams and emulsions. , Foundation, lotion, beauty essence, all-in-one gel, sunscreen gel, lotion, pack, mask, point mask, patch, face cleansing cream, hand cream, makeup cleansing, makeup base, concealer, blusher, eye shadow, eyeliner, Examples include eyebrow, lipstick, sunscreen cream, hair removal and hair removal cream. However, the cosmetic of one embodiment of the present invention can be used as a raw material (intermediate raw material) when manufacturing other cosmetics.
本発明の一態様の化粧料を調製する方法は特に限定されないが、例えば、含有する液晶構造を消失させない程度に、加温し、本発明の一態様の乳化剤、皮膜形成高分子及び水、並びに任意にその他の成分を撹拌混合などによって均一に液晶成分を分散させることにより、本発明の一態様の化粧料が得られる。 The method for preparing the cosmetic of one embodiment of the present invention is not particularly limited, and for example, heating is performed to such an extent that the contained liquid crystal structure is not lost, the emulsifier of one embodiment of the present invention, a film-forming polymer and water, and The liquid crystal component is dispersed uniformly by optionally mixing other components with stirring and the like to obtain the cosmetic material of one embodiment of the present invention.
本発明の一態様の化粧料は、皮膚に塗布することにより液晶フィルムを形成し、これにより皮膚表面からの水分蒸発を防ぐことが可能になり、乾燥した皮膚を改善すること又はさらなる乾燥による悪化を抑制することが可能である。本発明の別の一態様として、本発明の一態様の化粧料を、皮膚に局所的に適用することにより、液晶フィルム、好ましくはラメラ液晶構造を有する液晶フィルムを形成する工程を少なくとも含む、皮膚上での液晶フィルムの形成方法が提供される。 The cosmetic material according to one embodiment of the present invention forms a liquid crystal film when applied to the skin, which makes it possible to prevent water evaporation from the skin surface, improve dry skin, or worsen by further drying. Can be suppressed. As another aspect of the present invention, the cosmetic of one aspect of the present invention is topically applied to the skin, thereby comprising at least a step of forming a liquid crystal film, preferably a liquid crystal film having a lamellar liquid crystal structure, the skin A method of forming a liquid crystal film above is provided.
以下、本発明を実施例によってさらに具体的に説明するが、本発明はこれら実施例に限定されるものではなく、本発明の課題を解決し得る限り、本発明は種々の態様をとることができる。 Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples, and the present invention can take various aspects as long as the problems of the present invention can be solved. it can.
[1.被験試料の調製]
(1−1)実施例1〜実施例12の乳化剤及び化粧料
表1に示した処方に従い、以下の手順により、実施例1〜実施例12の乳化剤及び化粧料を調製した。なお、表中の水添レシチンの含有量は、原料である「Basis LS−60HR」(日清オイリオグループ社製;ホスファチジルコリン(PC)含有率:65〜75%)の添加量を表わす。表中のレシチンの含有量は、原料である「LIPOID P75」(エイチ・ホルスタイン株式会社製)の添加量を表す。表中のセラミドの含有量は、原料である「Ceramide VI」(Evonik Nutrition&Care GmbH社製)の添加量を表す。
[1. Preparation of test sample]
(1-1) Emulsifiers and cosmetics of Examples 1 to 12 According to the formulations shown in Table 1, the emulsifiers and cosmetics of Examples 1 to 12 were prepared by the following procedure. In addition, the content of hydrogenated lecithin in the table represents the addition amount of "Basis LS-60HR" (manufactured by Nisshin Oillio Group; phosphatidylcholine (PC) content rate: 65 to 75%) as a raw material. The content of lecithin in the table represents the addition amount of "LIPOID P75" (manufactured by H-Holstein Co., Ltd.) as a raw material. The content of ceramide in the table represents the addition amount of "Ceramide VI" (manufactured by Evonik Nutrition & Care GmbH) as a raw material.
表中のA相について、各成分を加温及び手動撹拌により均一に融解するように混合して調製した。調製したA相に、B相を加えて、均一になるまで加温及び手動撹拌により混合して、クリーム状を呈した実施例1〜実施例12の乳化剤を調製した。 Phase A in the table was prepared by mixing each component by heating and manual stirring so as to uniformly melt. Phase B was added to the prepared phase A, and the mixture was heated and mixed until it became uniform to prepare creamy emulsifiers of Examples 1 to 12.
実施例1〜実施例12の乳化剤に、別途各成分を溶解したC相を加えて均一になるまで加温及び手動撹拌により混合した。得られた乳化剤及びC相の混合物を室温になるまで冷却して、実施例1〜実施例12の化粧料を調製した。 Phase C in which each component was separately dissolved was added to the emulsifiers of Examples 1 to 12 and mixed by warming and manual stirring until uniform. The obtained mixture of the emulsifier and the phase C was cooled to room temperature to prepare the cosmetics of Examples 1 to 12.
(1−2)比較例1及び比較例5の化粧料
表1に示した処方に従い、B相とC相の各成分とを加温及び手動撹拌により均一に溶解するように混合することにより、比較例1及び比較例5の化粧料を調製した。
(1-2) Cosmetics of Comparative Example 1 and Comparative Example 5 According to the formulations shown in Table 1, the components of phase B and phase C were mixed by heating and manual stirring so as to be uniformly dissolved, The cosmetics of Comparative Example 1 and Comparative Example 5 were prepared.
(1−3)比較例2〜比較例4の乳化剤及び化粧料
表1に示した処方に従い、上記(1−1)の手順に従って、比較例2〜比較例4の乳化剤及び化粧料を調製した。
(1-3) Emulsifiers and cosmetics of Comparative Examples 2 to 4 According to the formulations shown in Table 1, the emulsifiers and cosmetics of Comparative Examples 2 to 4 were prepared according to the procedure of (1-1). ..
(1−4)実施例13〜14の乳化剤及び比較例6の乳化剤
表1に示した処方に従い、上記(1−1)の手順に従って、クリーム状を呈した実施例13〜14の乳化剤及び比較例6の乳化剤を調製した。
(1-4) Emulsifiers of Examples 13 to 14 and Emulsifier of Comparative Example 6 According to the formulation shown in Table 1, according to the procedure of (1-1) above, creamy emulsifiers of Examples 13 to 14 and comparisons were made. The emulsifier of Example 6 was prepared.
表中の※印の原料について、以下のものを用いた:
モノステアリン酸デカグリセリル:「NIKKOLデカグリン1−SV」(日光ケミカルズ社製)
フィトステロール:「フィトステロール(QI)」(タマ生化学社製)
ラウロイルグルタミン酸ジ(オクチルドデシル/フィトステリル/ベヘニル):「エルデュウPS−306」(味の素ヘルシーサプライ社製)
オレイン酸コレステリル、コレステロール:「マリンコレステロールエステルC」(日本水産社製)
ヒアルロン酸Na:「ヒアルロンサン液HA−LQ1」(キューピー社製)
アセチル化ヒアルロン酸Na:「アセチル化ヒアルロン酸ナトリウム」(資生堂社製)
ヒプロメロースおよびメチルセルロース:「METOLOSE(登録商標) 90SH−4000」(信越化学工業社製)
ポリオキシエチレンメチルグルコシド:「Glucam E−10」(Lubrizol社製)
(アクリレーツ/アクリル酸アルキル(C10−30))クロスポリマー:「PemulenTM EZ−4U」(Lubrizol社製)
ポリビニルアルコール:「ゴーセノール EG−40C」(日本合成化学工業社製)
For the ingredients marked with * in the table, the following were used:
Decaglyceryl monostearate: "NIKKOL Decagrin 1-SV" (manufactured by Nikko Chemicals)
Phytosterol: "Phytosterol (QI)" (manufactured by Tama Seikagaku)
Lauroyl glutamate di (octyldodecyl/phytosteryl/behenyl): "Eldu PS-306" (manufactured by Ajinomoto Healthy Supply Co.)
Cholesteryl oleate, cholesterol: "Marine cholesterol ester C" (manufactured by Nippon Suisan)
Hyaluronic Acid Na: “Hyaluronic Sun Liquid HA-LQ1” (Kewpie)
Acetylated sodium hyaluronate: "Sodium acetylated hyaluronate" (made by Shiseido Co., Ltd.)
Hypromellose and methylcellulose: "METOLOSE (registered trademark) 90SH-4000" (manufactured by Shin-Etsu Chemical Co., Ltd.)
Polyoxyethylene methyl glucoside: "Glucam E-10" (manufactured by Lubrizol)
(Acrylates/alkyl acrylate (C10-30)) Crosspolymer: "Pemulen ™ EZ-4U" (manufactured by Lubrizol)
Polyvinyl alcohol: "Gothenol EG-40C" (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
[2.評価方法]
(2−1)液晶形成性
室温下で、スライドガラスに被験試料を薄く延ばし、カバーガラスで覆った後、偏光顕微鏡(「BX41−P」;倍率40倍;OLYMPUS製)を用いて、観察視野におけるマルターゼクロス、結晶の析出及びステロールの不溶解物を観察し、以下の基準により分類した上で、「◎」と評価したものを液晶形成性を有するものとして評価した。
[2. Evaluation method]
(2-1) Liquid Crystal Formability At room temperature, the test sample was thinly spread on a slide glass, covered with a cover glass, and then observed with a polarizing microscope (“BX41-P”; 40× magnification; manufactured by OLYMPUS). The maltase cloth, the precipitation of crystals, and the insoluble matter of sterol in Example 2 were observed and classified according to the following criteria, and those evaluated as “⊚” were evaluated as having a liquid crystal forming property.
「◎」:マルターゼクロスが観察でき、かつ、結晶の析出及びステロールの不溶解物を観察できなかったもの
「×」:マルターゼクロスを観察できなかったもの
「△」:結晶の析出が観察されたもの
「□」:フィトステロールの残留物が観察されたもの
"A": Maltase cross was observable, and crystal precipitation and sterol insoluble matter could not be observed "X": Maltase cross could not be observed "△": Crystal precipitation was observed Item "□": phytosterol residue was observed
(2−2)容器中での液晶の安定性
被験試料をスクリュー管に入れ、室温で1ヵ月保管後に、上記(2−1)の液晶形成性によって評価した。
(2-2) Liquid Crystal Stability in Container The test sample was put in a screw tube and stored at room temperature for 1 month, and then evaluated by the liquid crystal forming property of (2-1).
(2−3)皮膚上における液晶の安定性
被験試料を皮膚上に塗布することにより形成したフィルムを塗布8時間後に皮膚から剥がした。得られたフィルムを、スライドガラスに乗せ、カバーガラスで覆った後、上記(2−1)と同様にして液晶形成性を評価した。
(2-3) Stability of liquid crystal on skin A film formed by applying the test sample on the skin was peeled off from the skin 8 hours after the application. The obtained film was placed on a slide glass and covered with a cover glass, and then the liquid crystal formability was evaluated in the same manner as in (2-1) above.
(2−4)液晶構造
被験試料及び被験試料を皮膚上に塗布して形成したフィルムについて、次の手順によりX線回折装置(「NANO Viewer」;Rigaku社製)を用いてX線小角散乱解析を行い、液晶の構造を確認及び評価した。
(2-4) Liquid Crystal Structure Regarding a test sample and a film formed by applying the test sample on the skin, an X-ray small angle scattering analysis was performed by using the X-ray diffractometer (“NANO Viewer”; manufactured by Rigaku) according to the following procedure. Then, the structure of the liquid crystal was confirmed and evaluated.
皮膚に塗布する前のクリーム状の被験試料についてはガラスキャピラリー(φ=3mm)に直接充填し、被験試料を皮膚に適用し、室温環境下で約8時間自然乾燥させた後に得られるフィルムについては、皮膚から剥がして小片に切断した後、ガラスキャピラリー(φ=3mm)の中に充填した。いずれの被験試料も室温にてX線小角散乱(SAXS)を測定した。SAXS回折計をλ=1.541ÅのCu−Ka放射線で操作し、試料からの回折X線の強度を2θの関数として記録した。ここで、2θ及びλはそれぞれX線ビームの散乱角及び波長を示す。被験試料に含まれる液晶構造解析のために、ブラッグの法則(d =λ/2sinθ)を用いてd間隔を計算した。したがって、SAXSパターンの回折ピークはMiller−Bravais指数(hkl)を用いて指標付けした。 For the creamy test sample before applying to the skin, the glass capillary (φ=3 mm) was directly filled, the test sample was applied to the skin, and the film obtained after air-drying for about 8 hours in a room temperature environment was used. After peeling from the skin and cutting into small pieces, the pieces were filled in a glass capillary (φ=3 mm). Small-angle X-ray scattering (SAXS) was measured at room temperature for all test samples. The SAXS diffractometer was operated with Cu-Ka radiation at λ = 1.541Å and the intensity of the diffracted X-rays from the sample was recorded as a function of 2θ. Here, 2θ and λ represent the scattering angle and wavelength of the X-ray beam, respectively. For analysis of the liquid crystal structure contained in the test sample, d-spacing was calculated using Bragg's law (d 2 =λ/2 sin θ). Therefore, the diffraction peaks of the SAXS pattern were indexed using the Miller-Bravais index (hkl).
(2−5)in vivo保湿性
健常な肌を有する被験者の前腕内側に被験試料を48mg/cm2で塗布し、塗布後の角層水分量をコルネオメーター(「Corneometer CM825」;Courage+Khazaka社製 )を用いて、室温(22℃)、湿度50%の環境下にて測定した。塗布前の角層水分量に対し、塗布6時間後に形成したフィルムを剥がした後の角層水分量の変化量により保湿性を評価した。
(2-5) In Vivo Moisturizing Property A test sample is applied at 48 mg/cm 2 to the inside of the forearm of a subject having healthy skin, and the amount of water in the stratum corneum after application is a corneometer (“Corneometer CM825”; manufactured by Courage+Khazaka). Was measured in an environment of room temperature (22° C.) and humidity of 50%. Moisture retention was evaluated by the amount of change in the amount of water in the stratum corneum after peeling off the film formed 6 hours after the application, with respect to the amount of moisture in the stratum corneum before application.
(2−6)閉塞性
直径14.5cmのプラスチックディッシュに、被験試料を15.75gを塗布して50℃の恒温槽で1日静置することで0.3g/cm2のフィルムを形成させた。スクリュー管に精製水を加え、恒温槽(温度:39.6℃、湿度:7%)に24時間静置し、重量変化を測定した。被験試料のフィルムで蓋をしたスクリュー管の重量(サンプル変化量)と蓋をしていないスクリュー管の重量(コントロール変化量)で割ることにより水分蒸発率を算出した。
(2-6) Occlusion property A plastic dish with a diameter of 14.5 cm was coated with 15.75 g of the test sample and left standing in a constant temperature bath at 50°C for 1 day to form a film of 0.3 g/cm 2. It was Purified water was added to the screw tube, and it was left standing in a thermostat (temperature: 39.6°C, humidity: 7%) for 24 hours, and the weight change was measured. The water evaporation rate was calculated by dividing by the weight of the screw tube covered with the film of the test sample (sample change amount) and the weight of the uncovered screw tube (control change amount).
(2−7)接着性
被験者の前腕内側に、被験試料を48mg/cm2で塗布した。塗布直後、塗布5時間後及び塗布8時間後に皮膚上に形成したフィルムを観察することにより、目視によりフィルムの接着性を確認した。
(2-7) Adhesiveness The test sample was applied to the inside of the forearm of the test subject at 48 mg/cm 2 . Immediately after the application, 5 hours after the application and 8 hours after the application, the film formed on the skin was observed to visually confirm the adhesiveness of the film.
[3.評価結果]
(3−1)液晶形成
被験試料について評価した結果を表1に示す。
[3. Evaluation results]
(3-1) Table 1 shows the evaluation results of the liquid crystal formation test sample.
実施例1〜実施例12の乳化剤及び化粧料は、いずれも液晶の形成が認められた。また、実施例1〜実施例12の化粧料は、塗布8時間後においても、機械的な負荷、水分蒸発、汗や皮脂などの接触などによってさえ、液晶が破壊することなく皮膚上で液晶フィルム状を維持した。さらに、実施例1〜実施例12の化粧料は、1ヵ月の保管後においても液晶の形成が認められ、液晶の安定性に優れたものであった。実施例1、実施例2、実施例6及び実施例11の化粧料を皮膚に塗布することにより形成した液晶フィルムは、ラメラ相を形成していた。 Liquid crystal formation was observed in all of the emulsifiers and cosmetics of Examples 1 to 12. In addition, the cosmetics of Examples 1 to 12 are liquid crystal films on the skin without breakage of the liquid crystal even after 8 hours after application, even by mechanical load, water evaporation, contact with sweat or sebum, etc. Maintained its shape. Furthermore, in the cosmetics of Examples 1 to 12, the formation of liquid crystals was observed even after storage for 1 month, and the stability of the liquid crystals was excellent. The liquid crystal films formed by applying the cosmetics of Example 1, Example 2, Example 6 and Example 11 to the skin had a lamellar phase.
液晶形成及び安定性に関する典型的な例として、被験試料について、偏光顕微鏡観察及びX線小角散乱解析による結果を図1及び図2に示す。すなわち、実施例1の化粧料について、皮膚塗布前の水分を多量に含んだクリーム状の化粧料における液晶形成性に係る偏光顕微鏡の観察写真及び液晶構造に係るX線小角散乱解析の結果をそれぞれ図1A及び図2Aに示す。同様に、皮膚塗布後8時間の水分が自然蒸発しフィルム形成後の化粧料における液晶形成性に係る偏光顕微鏡の観察写真及び液晶構造に係るX線小角散乱解析の結果をそれぞれ図1B及び図2Bに示す。これらの図が示すとおり、実施例1の化粧料について、皮膚塗布前後において、フィトステロールの残留物や結晶の析出物は観察できず、液晶の存在が確認できた。 As a typical example of liquid crystal formation and stability, the results of a test sample by polarization microscope observation and X-ray small angle scattering analysis are shown in FIGS. 1 and 2. That is, regarding the cosmetic of Example 1, an observation photograph of a polarization microscope relating to the liquid crystal forming property in a creamy cosmetic containing a large amount of water before skin application and the results of X-ray small angle scattering analysis relating to the liquid crystal structure are respectively shown. It is shown in FIGS. 1A and 2A. Similarly, 8 hours after the skin application, water naturally evaporates and the observation result of the polarization microscope concerning the liquid crystal forming property in the cosmetic material after the film formation and the result of the X-ray small angle scattering analysis concerning the liquid crystal structure are shown in FIGS. 1B and 2B, respectively. Shown in. As shown in these figures, with respect to the cosmetic material of Example 1, before and after application to the skin, no residue of phytosterols or a precipitate of crystals was observed, and the presence of liquid crystals could be confirmed.
より詳細には、図1A及び図1Bの偏光顕微鏡結果より、実施例1の化粧料について、分散した微小液晶滴(LC Microdroplet;約30μm)としての安定な液晶相の存在を、マルターゼクロスとして確認できた。特に、水分蒸発した後のフィルムは、数多くの微小液晶滴がポリマーフィルム内に安定に濃度の高い状態で固定化されているため、保湿性及び閉塞性の機能を効率的に発揮できることがわかる。 More specifically, the presence of a stable liquid crystal phase as dispersed micro liquid crystal droplets (LC Microdroplets: about 30 μm) in the cosmetic material of Example 1 was confirmed as maltase cross from the results of the polarization microscope of FIGS. 1A and 1B. did it. In particular, it can be seen that since the film after water evaporation has a large number of minute liquid crystal droplets stably immobilized in the polymer film in a highly concentrated state, the moisturizing and clogging properties can be efficiently exhibited.
図2A及び図2BのSAXS解析結果からは、実施例1の化粧料について、クリーム状にある場合(含水量>80質量%)は柱状構造を有する液晶相が形成され、フィルム状にある場合(含水量<50重量%)はラメラ相による液晶構造が形成されていることがわかった。化粧料がクリーム状にある場合は柱状構造を有する液晶であることから、水分を強固に保持し容器中で処方を安定化する。一方で、化粧料がフィルム状にある場合はラメラ液晶であることから、水分の捕獲及び排出ができるので、フィルムを通して水分を肌に与えることが期待できる。形成されたフィルムには安定なラメラ液晶滴を数多く含有しており、このラメラ液晶相の層間隔は約7〜8nmであった。これは角層の細胞間脂質中の短周期ラメラの層間隔(6nm)に類似している。このような層間隔を有するラメラ液晶相は、周囲からの水分の貯蔵及び再捕獲に有益であり、フィルムの質感としては湿潤性、柔軟性及び弾性を持続することが期待される。 From the SAXS analysis results of FIG. 2A and FIG. 2B, regarding the cosmetic of Example 1, in the case of a cream (water content>80% by mass), a liquid crystal phase having a columnar structure was formed, and in the case of a film ( It was found that a water content <50% by weight) formed a liquid crystal structure by a lamella phase. When the cosmetic is in the form of cream, it is a liquid crystal having a columnar structure, so that it firmly holds water and stabilizes the formulation in the container. On the other hand, when the cosmetic material is in the form of a film, since it is a lamellar liquid crystal, water can be captured and discharged, so that it can be expected to give water to the skin through the film. The formed film contained a large number of stable lamellar liquid crystal droplets, and the layer spacing of this lamellar liquid crystal phase was about 7 to 8 nm. This is similar to the interlamellar spacing (6 nm) of short-period lamellae in the intercellular lipids of the stratum corneum. The lamellar liquid crystal phase having such a layer interval is useful for storage and re-capture of moisture from the surroundings, and is expected to maintain wettability, flexibility and elasticity as a film texture.
比較例1及び比較例5の化粧料は、いずれにおいても、液晶の形成が認められなかった。 No liquid crystal formation was observed in any of the cosmetics of Comparative Example 1 and Comparative Example 5.
比較例2の乳化剤及び化粧料は、いずれも液晶の形成が認められた。しかし、比較例2の化粧料は、1ヵ月間保管することにより、結晶の析出が認められるものであった。 Liquid crystal formation was observed for both the emulsifier and the cosmetic of Comparative Example 2. However, the cosmetic of Comparative Example 2 was found to show crystal precipitation when stored for one month.
比較例3の乳化剤は液晶の形成が認められたものの、比較例3の化粧料は結晶の析出が認められるものであった。 The emulsifier of Comparative Example 3 was found to form liquid crystals, whereas the cosmetic of Comparative Example 3 was found to have crystal precipitation.
比較例4の乳化剤及び化粧料は、フィトステロールが完全に溶解せずに、フィトステロールの残留物が観察されるものであった。 In the emulsifier and cosmetics of Comparative Example 4, phytosterol was not completely dissolved, and a phytosterol residue was observed.
実施例13〜実施例14の乳化剤及び比較例6の乳化剤について、液晶形成性に係る偏光顕微鏡の観察写真を図3に示す。図3が示すとおり、実施例13〜実施例14の乳化剤は液晶の形成が認められた。それに対して、比較例6の乳化剤は、多くのフィトステロールの残留物が認められるものであった。 FIG. 3 shows observation photographs of a liquid crystal forming property of the emulsifiers of Examples 13 to 14 and Comparative Example 6 with a polarization microscope. As shown in FIG. 3, liquid crystal formation was observed in the emulsifiers of Examples 13 to 14. On the other hand, in the emulsifier of Comparative Example 6, many phytosterol residues were observed.
以上の結果より、実施例1〜実施例14の乳化剤及び化粧料は、調製時において液晶の形成が認められるものであった。また、実施例1〜実施例12の化粧料は、液晶の安定性に優れたものであり、皮膚上に塗布することによりラメラ相の液晶フィルムを形成し得るものであった。 From the above results, it was confirmed that the emulsifiers and cosmetics of Examples 1 to 14 formed liquid crystals at the time of preparation. Further, the cosmetics of Examples 1 to 12 were excellent in liquid crystal stability, and were capable of forming a lamella phase liquid crystal film when applied on the skin.
(3−2)フィルム特性
in vivo保湿性について、実施例1の化粧料と比較例1の化粧料とを、及び実施例11の化粧料と比較例5の化粧料とを比較した結果を、それぞれ図4A及び図4Bに示す。これらの図が示すとおり、実施例1及び実施例11の化粧料は、それぞれ比較例1及び比較例5の化粧料と比べて、保湿効果が高いことがわかった。
(3-2) Regarding film property in vivo moisture retention, the results of comparing the cosmetics of Example 1 and the cosmetics of Comparative Example 1 and the cosmetics of Example 11 and the cosmetics of Comparative Example 5 were compared, They are shown in FIGS. 4A and 4B, respectively. As shown in these figures, the cosmetics of Examples 1 and 11 were found to have a higher moisturizing effect than the cosmetics of Comparative Example 1 and Comparative Example 5, respectively.
閉塞性について、実施例1の化粧料と比較例1の化粧料とを比較した結果を図5に示す。図5が示すとおり、実施例1の化粧料は、比較例1の化粧料と比べて、高分子フィルム中に液晶が存在することにより耐水性及び水分保持力が向上したために精製水の蒸発量が少なく、閉塞性の高いものであった。 Regarding the occlusivity, the results of comparing the cosmetics of Example 1 and the cosmetics of Comparative Example 1 are shown in FIG. As shown in FIG. 5, compared with the cosmetic of Comparative Example 1, the cosmetic of Example 1 had improved water resistance and water retention due to the presence of liquid crystal in the polymer film, and thus the amount of evaporation of purified water. The number was low and the occlusivity was high.
接着性について、実施例1の化粧料と比較例1の化粧料とを比較した結果を図6に示す。図6が示すとおり、実施例1の化粧料及び比較例1の化粧料により形成したフィルムを皮膚上に長時間接着させた際、比較例1の化粧料では剥がれかかっている様子が観察されたが、実施例1の化粧料は皮膚への接着性が高く、8時間を経過しても密着している様子が観察された。高分子フィルム中の液晶滴は保湿性や閉塞性だけではなく、充填剤としても機能することから、液晶滴が存在することにより、汗や皮脂への耐性が向上し、長時間の接着が可能になったと推測される。また、フィルムの上からパウダーファンデーションや口紅などのメーキャップ化粧料などを接着させることも可能であった。 Regarding the adhesiveness, the results of comparing the cosmetics of Example 1 and the cosmetics of Comparative Example 1 are shown in FIG. As shown in FIG. 6, when the film formed of the cosmetic of Example 1 and the film of Comparative Example 1 was adhered to the skin for a long time, it was observed that the cosmetic of Comparative Example 1 was about to come off. However, the cosmetic of Example 1 had high adhesiveness to the skin, and it was observed that the cosmetic adhered even after 8 hours. Since the liquid crystal droplets in the polymer film not only have moisturizing and blocking properties, but also function as a filler, the presence of liquid crystal droplets improves the resistance to sweat and sebum and enables long-term adhesion. It is speculated that It was also possible to adhere powder foundation, makeup cosmetics such as lipstick, etc. onto the film.
[4.処方例]
上記(1−1)の手順にしたがって、それぞれ種々の濃度の両親媒性脂質、ステロール及び直鎖飽和脂肪酸からなるA相を調製し、次いでA相にB相を加えて乳化剤を調製し、液晶形成性を評価した。
[4. Prescription example]
According to the procedure of (1-1) above, phase A comprising amphipathic lipid, sterol and linear saturated fatty acid in various concentrations, respectively, was prepared, and then phase B was added to phase A to prepare an emulsifier. The formability was evaluated.
A相における両親媒性脂質、直鎖飽和脂肪酸及びステロールの濃度が下記表2〜表4に記載の濃度範囲にある場合には、液晶形成性を有するもの(「◎」)として評価できた。また、B相として、表5に記載のものが使用可能であることを確認した。 When the concentrations of the amphipathic lipid, the linear saturated fatty acid and the sterol in the phase A were in the concentration ranges shown in Tables 2 to 4 below, it could be evaluated as having liquid crystal formation (“⊚”). In addition, it was confirmed that the phase B described in Table 5 could be used.
水溶性高分子として表6に記載の水溶性高分子を用い、水溶性高分子の濃度範囲を2〜10wt%とした以外は、実施例1の処方及び上記(1−1)の手順に従って、化粧料を調製し、液晶形成性を評価した。結果、いずれの化粧料も液晶形成性を有するもの(「◎」)として評価できた。また、得られた化粧料を皮膚上に塗布したところ、フィルムの形成を確認できた。形成されたフィルムは安定なラメラ液晶滴を数多く含有していた。被膜形成高分子とラメラ液晶滴との組み合わせは、角層のバリア機能を担う細胞間脂質と類似した構造となっていることから、角層と同じような機能を果たすことが期待できる。 According to the formulation of Example 1 and the procedure of (1-1) above, except that the water-soluble polymer shown in Table 6 was used as the water-soluble polymer and the concentration range of the water-soluble polymer was 2 to 10 wt %. Cosmetics were prepared and liquid crystal forming properties were evaluated. As a result, all the cosmetics could be evaluated as those having a liquid crystal forming property (“⊚”). When the obtained cosmetic was applied on the skin, formation of a film could be confirmed. The film formed contained many stable lamellar liquid crystal droplets. Since the combination of the film-forming polymer and the lamellar liquid crystal droplets has a structure similar to that of the intercellular lipid that has the barrier function of the stratum corneum, it can be expected to perform the same function as that of the stratum corneum.
本発明の一態様の組成物及び乳化剤は、容器中では液状で、及び皮膚上ではフィルム状で安定的に液晶構造を保持する化粧料を調製するために利用可能である。本発明の一態様の化粧料は、皮膚表面に塗布することにより、ラメラ液晶構造を備えた複合体フィルムを形成し得ることから、クリーム、乳液、パックなどの化粧品として利用することができるものである。使用者は、本発明の一態様に係る化粧料を使用することにより、日常的に快適に、皮膚の乾燥を低減又は防止すること、皮膚の状態の改善、さらに皮膚の保護ができるようになる。
The composition and emulsifier of one embodiment of the present invention can be used for preparing a cosmetic that stably holds a liquid crystal structure in a liquid state in a container and in a film form on the skin. The cosmetic of one embodiment of the present invention can be used as a cosmetic such as a cream, an emulsion or a pack because it can form a composite film having a lamellar liquid crystal structure by applying it to the skin surface. is there. By using the cosmetics according to one aspect of the present invention, the user can comfortably reduce or prevent the dryness of the skin, improve the condition of the skin, and further protect the skin on a daily basis. ..
Claims (11)
The cosmetic according to claim 10, wherein the cosmetic exhibits a film-like shape when applied to the skin and has a water content of 50% or less, and contains a stable liquid crystal phase.
Priority Applications (1)
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