JP5840838B2 - Thickening composition and method for producing the same - Google Patents
Thickening composition and method for producing the same Download PDFInfo
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- JP5840838B2 JP5840838B2 JP2010515827A JP2010515827A JP5840838B2 JP 5840838 B2 JP5840838 B2 JP 5840838B2 JP 2010515827 A JP2010515827 A JP 2010515827A JP 2010515827 A JP2010515827 A JP 2010515827A JP 5840838 B2 JP5840838 B2 JP 5840838B2
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- GJPYYNMJTJNYTO-UHFFFAOYSA-J sodium aluminium sulfate Chemical compound [Na+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJPYYNMJTJNYTO-UHFFFAOYSA-J 0.000 description 1
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- GYDJEQRTZSCIOI-LJGSYFOKSA-N tranexamic acid Chemical compound NC[C@H]1CC[C@H](C(O)=O)CC1 GYDJEQRTZSCIOI-LJGSYFOKSA-N 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/735—Mucopolysaccharides, e.g. hyaluronic acid; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/88—Polyamides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
Description
本発明は、水性媒体に分散させたときに増粘効果を発揮する増粘性組成物およびその製造方法に関する。 The present invention relates to a thickening composition that exhibits a thickening effect when dispersed in an aqueous medium, and a method for producing the same.
化粧料などに用いられる増粘剤として、アクリル系ポリマー（合成高分子化合物）を添加した組成物が知られている（例えば、特許文献１参照）。この組成物からなる化粧料は、皮膚のはりおよびしわの改善効果や保湿効果に優れ、べたつかず肌へののびもよい。しかし、アクリル系ポリマーのような合成系の化合物は、生分解性が低く人体への悪影響も懸念されることから、合成系の増粘剤ではなく天然系の増粘剤が求められてきた。
天然系の増粘性多糖類としては、キサンタンガムやヒアルロン酸が知られている（例えば特許文献２、３参照）。キサンタンガムやヒアルロン酸は、保湿効果に優れるとともに廃棄時の生分解性を有するため、化粧料の素材として広く用いられている。また、多糖類とポリアミノ酸類を含有する増粘剤組成物（例えば、特許文献４参照）や、ガラクトマンナンまたはその誘導体からなる架橋物を保湿成分とする化粧品組成物も知られている（例えば、特許文献５参照）。As a thickener used in cosmetics and the like, a composition to which an acrylic polymer (synthetic polymer compound) is added is known (see, for example, Patent Document 1). A cosmetic comprising this composition is excellent in the improvement and moisturizing effects of skin creases and wrinkles, and is not sticky and spreads well on the skin. However, a synthetic compound such as an acrylic polymer has low biodegradability and may be adversely affected by the human body. Therefore, a natural thickener is required instead of a synthetic thickener.
Xanthan gum and hyaluronic acid are known as natural thickening polysaccharides (see, for example, Patent Documents 2 and 3). Xanthan gum and hyaluronic acid are widely used as cosmetic materials because they have excellent moisturizing effects and biodegradability upon disposal. In addition, thickener compositions containing polysaccharides and polyamino acids (see, for example, Patent Document 4) and cosmetic compositions containing a cross-linked product composed of galactomannan or a derivative thereof as a moisturizing component are also known (for example, , See Patent Document 5).
しかしながら、前記した従来の技術においては、必ずしも増粘効果が十分ではなく、例えば化粧料として使用した場合に、べたつかず肌へののびが優れ、さらに保湿性にも優れるといった各種の性質についてバランスよく優れた効果を発揮することはできなかった。
そこで、本発明は、生分解性を有するとともに、増粘性に優れ、化粧料として使用した場合にも使用時にべたつかず肌へののびが優れ、さらに保湿効果にも優れる増粘性組成物およびその製造方法を提供することを目的とする。However, in the above-described conventional technology, the thickening effect is not always sufficient. For example, when used as a cosmetic, it has a well-balanced balance of various properties such as non-stickiness, excellent skin extension, and excellent moisture retention. An excellent effect could not be exhibited.
Accordingly, the present invention has a biodegradable, excellent thickening property, a non-sticky skin when used as a cosmetic, has excellent skin spreading properties, and also has a moisturizing effect and its production It aims to provide a method.
前記した課題を解決すべく、本発明は、以下のような増粘性組成物を提供するものである。
〔１〕ポリアミノ酸類架橋体と、天然高分子とを配合してなることを特徴とする増粘性組成物。
〔２〕前述した本発明の増粘性組成物において、前記天然高分子が天然多糖類であることを特徴とする増粘性組成物。
〔３〕前述した本発明の増粘性組成物において、前記天然多糖類がヒアルロン酸であることを特徴とする増粘性組成物。
〔４〕前述した本発明の増粘性組成物において、ポリアミノ酸類架橋体の配合量１００質量部に対し、天然高分子が０．０１質量部以上配合されてなることを特徴とする増粘性組成物。
〔５〕前述した本発明の増粘性組成物において、前記ポリアミノ酸類架橋体がポリ−γ−グルタミン酸またはその塩であることを特徴とする増粘性組成物。
〔６〕前述した本発明の増粘性組成物において、前記ポリアミノ酸類架橋体が、分子量１０〜３０００ｋＤａのポリアミノ酸類の放射線架橋体であることを特徴とする増粘性組成物。
〔７〕前述した本発明の増粘性組成物において、前記ポリアミノ酸類架橋体の平均粒径が０．１〜３００μｍであることを特徴とする増粘性組成物。
本発明はまた、ポリアミノ酸類を架橋させてポリアミノ酸類架橋体を作製した後、天然高分子を配合することを特徴とする増粘性組成物の製造方法を提供するものである。In order to solve the above-mentioned problems, the present invention provides the following thickening composition.
[1] A thickening composition comprising a crosslinked polyamino acid and a natural polymer.
[2] The thickening composition of the present invention described above, wherein the natural polymer is a natural polysaccharide.
[3] The thickening composition according to the invention, wherein the natural polysaccharide is hyaluronic acid.
[4] The thickening composition of the present invention described above, wherein the natural polymer is blended in an amount of 0.01 parts by mass or more with respect to 100 parts by mass of the polyamino acid crosslinked product. object.
[5] The above thickening composition of the present invention, wherein the cross-linked polyamino acid is poly-γ-glutamic acid or a salt thereof.
[6] The thickening composition according to the invention, wherein the polyamino acid crosslinked product is a radiation crosslinked product of a polyamino acid having a molecular weight of 10 to 3000 kDa.
[7] The thickening composition according to the present invention, wherein the polyamino acid crosslinked product has an average particle size of 0.1 to 300 μm.
The present invention also provides a method for producing a thickening composition characterized in that a polyamino acid is crosslinked to produce a crosslinked polyamino acid compound, and then a natural polymer is blended.
本発明に係る増粘性組成物によれば、ポリアミノ酸類架橋体と、天然高分子、特に天然多糖類とを併用することにより、水性媒体に分散させたときの粘度を飛躍的に高める事ができる。それ故、通常単独では高粘度を発現しない天然高分子、例えば種々の機能を持った天然多糖類にも適度な粘度を付与することができ利用範囲を拡大することができる。また、本発明の増粘性組成物は、天然系の処方であることから、人体への安全性が高く、生分解性にも優れている。
それ故、本発明の増粘性組成物は、化粧料をはじめ、生活用品、トイレタリー用品、衛生用品、医療用品、農業／園芸分野、食品分野および環境分野に広く適用できる。
特に、天然多糖類としてヒアルロン酸を用いた場合には、大幅な増粘性の向上を期待できるとともに、ポリアミノ酸類架橋体による保湿効果に加えて、ヒアルロン酸による保湿効果も得られる。
また、天然多糖類としてのキサンタンガムは、耐塩性、耐酸性および耐熱性に優れる等の特徴を有する増粘剤として良く知られているが、化粧料として使用した場合に、べたつきがあったり肌へののびが劣るというように使用感が優れず、使用範囲が限定されていた。これに対して、本発明においては、キサンタンガムをポリアミノ酸類架橋体と併用することにより優れた使用感が得られるようになる。
本発明に係る増粘性組成物の製造方法によれば、ポリアミノ酸類を架橋させてポリアミノ酸類架橋体を作製した後、天然高分子を配合することで、水性媒体に分散させたときの粘度を飛躍的に高めることができる。According to the thickening composition of the present invention, the combined use of a polyamino acid crosslinked product and a natural polymer, particularly a natural polysaccharide, can dramatically increase the viscosity when dispersed in an aqueous medium. it can. Therefore, an appropriate viscosity can be imparted to a natural polymer that does not normally exhibit high viscosity, for example, a natural polysaccharide having various functions, and the range of use can be expanded. In addition, since the thickening composition of the present invention is a natural formulation, it has high safety to the human body and excellent biodegradability.
Therefore, the thickening composition of the present invention can be widely applied to cosmetics, daily necessities, toiletries, hygiene products, medical supplies, agriculture / horticultural fields, food fields and environmental fields.
In particular, when hyaluronic acid is used as a natural polysaccharide, a significant increase in viscosity can be expected, and a moisturizing effect by hyaluronic acid can be obtained in addition to a moisturizing effect by a crosslinked polyamino acid.
In addition, xanthan gum as a natural polysaccharide is well known as a thickener having characteristics such as excellent salt resistance, acid resistance and heat resistance. The feeling of use was not so good that the spread was inferior, and the range of use was limited. On the other hand, in the present invention, an excellent feeling of use can be obtained by using xanthan gum in combination with a crosslinked polyamino acid.
According to the method for producing a thickening composition according to the present invention, after a polyamino acid is cross-linked to produce a polyamino acid cross-linked product, the viscosity when dispersed in an aqueous medium is obtained by blending a natural polymer. Can be dramatically improved.
本発明の増粘性組成物（以下、「本組成物」ともいう。）は、ポリアミノ酸類架橋体と、天然高分子とを配合してなることを特徴とする。以下、前記のポリアミノ酸類架橋体と天然高分子、さらにこれらから構成される本組成物について詳細に説明する。
〔ポリアミノ酸類架橋体〕
本発明において、ポリアミノ酸類とは、遊離酸であるものに限らず、ナトリウム、カリウム、リチウムなどのアルカリ金属塩であってもよく、アンモニウム塩、エタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩などの塩基性アミン塩であってもよい。従って、ポリアミノ酸類架橋体には、遊離のポリアミノ酸の架橋体だけでなく、ポリアミノ酸塩の架橋体も含まれる。塩としては、匂いの観点からナトリウム塩またはカリウム塩が好ましい。以下、特に必要がなければ、遊離の酸とその塩とを区別しないで、「ポリアミノ酸類」、「ポリアミノ酸類架橋体」のように表記する。The thickening composition of the present invention (hereinafter also referred to as “the present composition”) is characterized by blending a crosslinked polyamino acid and a natural polymer. Hereinafter, the polyamino acid cross-linked product, the natural polymer, and the composition composed of these will be described in detail.
[Polyamino acid cross-linked product]
In the present invention, polyamino acids are not limited to free acids, but may be alkali metal salts such as sodium, potassium, lithium, ammonium salts, ethanolamine salts, diethanolamine salts, triethanolamine salts, etc. The basic amine salt may be used. Accordingly, the crosslinked polyamino acids include not only crosslinked polyamino acids but also crosslinked polyamino acid salts. The salt is preferably a sodium salt or a potassium salt from the viewpoint of odor. Hereinafter, unless otherwise required, the free acid and its salt are not distinguished from each other and expressed as “polyamino acids” or “crosslinked polyamino acids”.
本発明のポリアミノ酸類架橋体は、以下のような各種のアミノ酸からなるポリアミノ酸を原料として適用できる。
例えば、非極性すなわち疎水性の原子団を持つアミノ酸として、アラニン、バリン、ロイシン、イソロイシン、メチオニン、トリプトファン、フェニルアラニン、およびプロリンなどが挙げられる。極性であるが電荷のないアミノ酸としては、グリシン、セリン、トレオニン、システイン、チロシン、アスパラギン、およびグルタミンなどが挙げられる。正電荷を持つ原子団を有するアミノ酸としては、リジン、ヒスチジン、およびアルギニンなどが挙げられる。負電荷を持つ原子団を有するアミノ酸としては、アスパラギン酸やグルタミン酸などが挙げられる。The polyamino acids cross-linked product of the present invention can be applied using polyamino acids composed of the following various amino acids as raw materials.
For example, amino acids having non-polar or hydrophobic atomic groups include alanine, valine, leucine, isoleucine, methionine, tryptophan, phenylalanine, and proline. Examples of polar but uncharged amino acids include glycine, serine, threonine, cysteine, tyrosine, asparagine, and glutamine. Examples of amino acids having a positively charged atomic group include lysine, histidine, and arginine. Examples of amino acids having a negatively charged atomic group include aspartic acid and glutamic acid.
アミノ酸の他の例としては、Ｌ−オルニチン、一連のα−アミノ酸、β−アラニン、γ−アミノ酪酸、中性アミノ酸、酸性アミノ酸、酸性アミノ酸のω−エステル、塩基性アミノ酸、塩基性アミノ酸のＮ−置換体、アスパラギン酸−Ｌ−フェニルアラニン２量体（アスパルテーム）等のアミノ酸およびアミノ酸誘導体、Ｌ−システイン酸等のアミノスルホン酸等を挙げることができる。α−アミノ酸は、光学活性体（Ｌ体、Ｄ体）であっても、ラセミ体であってもよい。またポリアミノ酸は他のモノマー成分を含むコポリマーであってもよい。 Other examples of amino acids include L-ornithine, a series of α-amino acids, β-alanine, γ-aminobutyric acid, neutral amino acids, acidic amino acids, ω-esters of acidic amino acids, basic amino acids, N of basic amino acids -Substituents, amino acids such as aspartic acid-L-phenylalanine dimer (aspartame) and amino acid derivatives, aminosulfonic acids such as L-cysteic acid, and the like. The α-amino acid may be an optically active substance (L form, D form) or a racemic form. The polyamino acid may be a copolymer containing other monomer components.
本発明で用いられるポリアミノ酸類架橋体は、ホモポリマーであっても、コポリマーであってもよい。コポリマーの場合、共重合形式は特に限定されるものでなく、ブロックコポリマー、ランダムコポリマー、グラフトコポリマー等、任意の形式をとり得る。
ポリアミノ酸類架橋体がコポリマーである場合のコポリマー成分（アミノ酸以外のモノマー成分）の具体例としては、例えばアミノカルボン酸、アミノスルホン酸、アミノホスホン酸、ヒドロキシカルボン酸、メルカプトカルボン酸、メルカプトスルホン酸、メルカプトホスホン酸等が挙げられる。The polyamino acid crosslinked product used in the present invention may be a homopolymer or a copolymer. In the case of a copolymer, the copolymerization format is not particularly limited, and may take any format such as a block copolymer, a random copolymer, a graft copolymer, and the like.
Specific examples of copolymer components (monomer components other than amino acids) when the polyamino acid cross-linked product is a copolymer include, for example, aminocarboxylic acid, aminosulfonic acid, aminophosphonic acid, hydroxycarboxylic acid, mercaptocarboxylic acid, mercaptosulfonic acid And mercaptophosphonic acid.
本発明ではホモポリマーが好ましく用いられる。中でも、優れた生分解性を発現させるためには、ポリアスパラギン酸、ポリ−γ−グルタミン酸（以下、「γ-ＰＧＡ」ともいう。）、あるいはポリリジンのホモポリマーを基本骨格とした架橋体が好ましい。吸水性の観点からは、これらの中でも、ポリアスパラギン酸架橋体やγ-ＰＧＡ架橋体が好ましい。さらに、例えば化粧料としての用途であれば、べたつかず肌へののびがよいことからγ-ＰＧＡ架橋体を用いることが好ましい。 In the present invention, a homopolymer is preferably used. Among these, in order to develop excellent biodegradability, a cross-linked product having polyaspartic acid, poly-γ-glutamic acid (hereinafter also referred to as “γ-PGA”), or a polylysine homopolymer as a basic skeleton is preferable. . Among these, a polyaspartic acid crosslinked body and a γ-PGA crosslinked body are preferable from the viewpoint of water absorption. Furthermore, for use as a cosmetic, for example, it is preferable to use a γ-PGA crosslinked product because it is non-sticky and spreads well on the skin.
ここで、ポリアミノ酸類架橋体は、放射線架橋により得ることが好ましい。放射線架橋によれば、過酸化物架橋に比べてポリアミノ酸類架橋体のゲル化率の特定が容易になるからである。放射線については、特に制限はなく、例えば、γ線、電子線等が挙げられる。中でも、操作性の良い電子線が好適である。γ線は電子線より透過力が高いが照射線量が小さく、電子線の透過力はγ線より小さいが照射線量を大きく設定できる。それ故、加速電圧に対応した試料厚みであれば、γ線よりも短時間の照射でよいので、電子線を用いることが好ましい。放射線として、電子線を用いる場合には、照射線量として１０〜３００ｋＧｙの範囲が好ましく、より好ましくは２０〜２００ｋＧｙである。また、一度に所定の照射線量を加えるのではなく、分割して照射する事で均一に架橋させ、反応熱を抑えて分解物を減少させることができる。照射時間としては通算１秒以上が好ましい。照射時間が通算で１秒未満であると、架橋体の形成が不十分となるおそれがある。 Here, it is preferable to obtain the crosslinked polyamino acids by radiation crosslinking. This is because radiation cross-linking makes it easier to specify the gelation rate of the crosslinked polyamino acids compared to peroxide cross-linking. There is no restriction | limiting in particular about a radiation, For example, a gamma ray, an electron beam, etc. are mentioned. Among these, an electron beam with good operability is preferable. Although γ-rays have higher transmission power than electron beams, the irradiation dose is small, and the transmission power of electron beams is smaller than γ-rays, but the irradiation dose can be set larger. Therefore, it is preferable to use an electron beam because the sample thickness corresponding to the acceleration voltage can be irradiated in a shorter time than γ rays. When an electron beam is used as the radiation, the irradiation dose is preferably in the range of 10 to 300 kGy, more preferably 20 to 200 kGy. Further, instead of applying a predetermined irradiation dose at a time, it is possible to uniformly cross-link by dividing and irradiating, and to reduce the reaction heat and reduce decomposition products. The irradiation time is preferably 1 second or longer. If the irradiation time is less than 1 second in total, the formation of a crosslinked product may be insufficient.
また、本発明で用いる増粘組成物を調製するために配合するポリアミノ酸類架橋体の形態は特に限定しない。例えば、ポリアミノ酸類架橋体の粉末を用いる場合は、平均粒径が０．１〜３００μｍの範囲であることが好ましく、より好ましくは平均粒径の範囲が1〜５０μｍであり、さらに好ましくは平均粒径の範囲が５〜３０μｍである。また、ポリアミノ酸類架橋体の水溶液を用いる場合は、平均粒径が０．１μ以上であることが好ましい。
この範囲外の粒径であると、組成物を化粧料として用いる場合に粒感が残ってしまい、好ましい使用感および適切な粘度が得られない。平均粒径は、フラウンホーファーの回折原理を応用した、レーザー式粒度分布測定器（セイシン企業株式会社製 ＬＭＳ−３０）により測定できる。
さらに、本発明で放射線架橋に用いるポリアミノ酸の分子量は、ゲルろ過クロマトグラフィーによる測定で１０〜３０００ｋＤａの範囲であることが好ましく、吸保湿性の観点から５０〜１０００ｋＤａとすることがより好ましい。分子量は、試料を純水に溶解しそのままゲルろ過分析を行うことで測定できる。具体的には、分子量既知の標準プルラン(昭和電工製)を純水に溶解して標準溶液を調製し、ゲルろ過における溶出時間と標準溶液の分子量により校正曲線を作製した後、試料について同様に測定を行う。試料の分子量は、ゲルろ過曲線におけるピーク位置（溶出時間）から求められる。Moreover, the form of the crosslinked polyamino acids compounded for preparing the thickening composition used in the present invention is not particularly limited. For example, when using a polyamino acid powder, the average particle size is preferably in the range of 0.1 to 300 μm, more preferably the average particle size is in the range of 1 to 50 μm, and even more preferably the average The range of the particle size is 5 to 30 μm. Moreover, when using the aqueous solution of a polyamino acid crosslinked body, it is preferable that an average particle diameter is 0.1 micrometer or more.
When the particle size is outside this range, a grainy feeling remains when the composition is used as a cosmetic, and a preferable feeling of use and an appropriate viscosity cannot be obtained. The average particle diameter can be measured with a laser particle size distribution analyzer (LMS-30 manufactured by Seishin Enterprise Co., Ltd.) that applies Fraunhofer's diffraction principle.
Furthermore, the molecular weight of the polyamino acid used for radiation crosslinking in the present invention is preferably in the range of 10 to 3000 kDa as measured by gel filtration chromatography, and more preferably 50 to 1000 kDa from the viewpoint of moisture absorption and retention. The molecular weight can be measured by dissolving a sample in pure water and performing gel filtration analysis as it is. Specifically, a standard pullulan (manufactured by Showa Denko) with a known molecular weight is dissolved in pure water to prepare a standard solution, and after preparing a calibration curve based on the elution time in gel filtration and the molecular weight of the standard solution, the same applies to the sample. Measure. The molecular weight of the sample is determined from the peak position (elution time) in the gel filtration curve.
〔天然高分子〕
本発明の増粘性組成物に用いられる天然高分子としては、天然多糖類、タンパク質および脂質などが挙げられる。増粘効果の観点からは天然多糖類を用いることが特に好ましい。
天然多糖類のうち、植物系高分子としては、例えば、アラビアガム、トラガカントガム、ガラクタン、グアーガム、キャロブガム、カラヤガム、カラギーナン、ペクチン、カンテン、クインスシード（マルメロ）、アルゲコロイド（カッソウエキス）、デンプン（コメ、トウモロコシ、バレイショ、コムギ）、グリチルリチン酸が挙げられ、微生物系高分子としては、例えば、キサンタンガム、デキストラン、サクシノグルカン、ブルラン等が挙げられ、動物系高分子としては、例えば、ヒアルロン酸、ムコイチン硫酸、カロニン酸、コラーゲン、カゼイン、アルブミン、ゼラチン等が挙げられる。
特に、増粘効果の観点より、天然多糖類としてヒアルロン酸を用いることが好ましい。ここで、天然多糖類として使用するヒアルロン酸は特に限定しないが、増粘効果の観点より分子量が１万以上のヒアルロン酸を用いることが好ましく、分子量が５０万以上のヒアルロン酸を用いることがより好ましく、分子量１００万以上のヒアルロン酸を用いることがさらに好ましい。[Natural polymer]
Examples of the natural polymer used in the thickening composition of the present invention include natural polysaccharides, proteins and lipids. From the viewpoint of thickening effect, it is particularly preferable to use natural polysaccharides.
Among natural polysaccharides, as plant polymers, for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (gypsum extract), starch (rice, rice, Corn, potato, wheat) and glycyrrhizic acid. Examples of the microbial polymer include xanthan gum, dextran, succinoglucan, and bullulan. Examples of the animal polymer include hyaluronic acid and mucoitin sulfate. , Caronic acid, collagen, casein, albumin, gelatin and the like.
In particular, hyaluronic acid is preferably used as the natural polysaccharide from the viewpoint of thickening effect. Here, hyaluronic acid used as the natural polysaccharide is not particularly limited, but hyaluronic acid having a molecular weight of 10,000 or more is preferably used from the viewpoint of a thickening effect, and hyaluronic acid having a molecular weight of 500,000 or more is more preferably used. Preferably, hyaluronic acid having a molecular weight of 1 million or more is more preferably used.
〔本組成物〕
本発明の増粘性組成物を構成するには、ポリアミノ酸類架橋体を１００質量部としたとき、天然多糖類等を０．０１質量部以上の割合で配合することが好ましい。ポリアミノ酸類架橋体と天然高分子をこの範囲で配合することで、効果的に増粘効果が得られる。ここで、増粘効果を考慮して、天然高分子の配合割合を０．０１質量部以上とすることが好ましい。天然高分子の配合割合が０．０１質量部未満であると、ポリアミノ酸類架橋体と天然高分子との相乗効果が得られず、増粘性が向上しない。天然高分子の配合割合は、増粘効果を考慮して、１質量部以上１００質量以下とすることが好ましい。
また、本発明の増粘性組成物を実際に使用する際には、Ｂ型粘度計（ローターＮｏ．４、６ｒｐｍ、２５℃)におけるポリアミノ酸類架橋体（単独）の粘度が０．１〜１００Ｐａ・ｓの範囲になるような条件Ａを前もって決めておき、同様に、天然多糖類等の天然高分子（単独）の粘度が０．０１〜１００Ｐａ・ｓの範囲になるような条件Ｂも前もって決めておくとよい。そして、条件Ａと条件Ｂをともに満たすような割合でポリアミノ酸類架橋体と天然高分子とを配合することで、粘度が１Ｐａ・ｓ以上である高粘度液体を好ましく製造することができる。ポリアミノ酸類架橋体および天然高分子（天然多糖類等）の粘度が前記した条件Ａあるいは条件Ｂのいずれかを満たさない範囲であると、両成分を配合した場合に好ましい使用感（化粧料としてのべたつきがないこと）が得られなくなるおそれがある。
ここで、本発明の増粘性組成物の効果をより発揮させるためには、ポリアミノ酸類を架橋させてポリアミノ酸類架橋体を架橋させた後、天然高分子を配合させるとよい。このような製造方法により、得られる混合液体の粘度を飛躍的に高めることができる。[This composition]
In order to constitute the thickening composition of the present invention, it is preferable to blend a natural polysaccharide or the like in a proportion of 0.01 parts by mass or more when the polyamino acid crosslinked product is 100 parts by mass. By blending the polyamino acid crosslinked product and the natural polymer within this range, a thickening effect can be effectively obtained. Here, in consideration of the thickening effect, the blending ratio of the natural polymer is preferably 0.01 parts by mass or more. When the blending ratio of the natural polymer is less than 0.01 parts by mass, the synergistic effect between the polyamino acid crosslinked product and the natural polymer cannot be obtained, and the viscosity increase is not improved. The blending ratio of the natural polymer is preferably 1 part by mass or more and 100 parts by mass or less in consideration of the thickening effect.
When the thickening composition of the present invention is actually used, the viscosity of the crosslinked polyamino acid (single) in a B-type viscometer (rotor No. 4, 6 rpm, 25 ° C.) is 0.1 to 100 Pa. -Predetermining the condition A to be in the range of s in advance, and similarly, the condition B in which the viscosity of the natural polymer such as natural polysaccharide (single) is in the range of 0.01 to 100 Pa · s It is good to decide. And the high viscosity liquid whose viscosity is 1 Pa * s or more can be preferably manufactured by mix | blending polyamino acid bridge | crosslinking body and a natural polymer in the ratio which satisfy | fills both the conditions A and the conditions B. FIG. When the viscosity of the crosslinked polyamino acids and natural polymer (natural polysaccharides, etc.) is in a range not satisfying either of the above conditions A or B, it is preferable when both components are blended (as a cosmetic) There is a risk that it will not be possible to obtain.
Here, in order to exhibit the effect of the thickening composition of the present invention more, it is preferable to crosslink the polyamino acids to crosslink the crosslinked polyamino acids, and then blend a natural polymer. By such a manufacturing method, the viscosity of the obtained mixed liquid can be dramatically increased.
〔任意成分〕
本組成物には、上記の必須成分に加えて、化粧料等の組成物に配合され得る他の成分を、本発明の効果を損なわない限りにおいて配合することができる。[Optional ingredients]
In addition to the above essential components, other components that can be blended in the composition such as cosmetics can be blended in the present composition as long as the effects of the present invention are not impaired.
例えば、流動パラフィン、スクワラン、ワセリン等の炭化水素類；マカデミアナッツ油、オリーブ油、ラノリン等の油脂類；ホホバ油、カルナバロウ、キャンデリラロウ等のロウ類；ジメチルポリシロキサン、メチルフェニルシロキサン等のシリコーン類；カプリルアルコール、ラウリルアルコール、ミリスチルアルコール、セチルアルコール、コレステロール、フィトステロール等の高級アルコール類；カプリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、ラノリン脂肪酸、リノール酸、リノレン酸等の高級脂肪酸；ポリエチレングリコール、グリセリン、１，３−ブチレングリコール、エリスリトール、ソルビトール、キシリトール、マルチトール、ムコ多糖、ヒアルロン酸、コンドロイチン硫酸、キチン、キトサン等の保湿剤；エタノール等の低級アルコール；ブチルヒドロキシトルエン、トコフェロール、フィチン等の酸化防止剤；安息香酸、サリチル酸、ソルビン酸、パラオキシ安息香酸アルキルエステル、ヘキサクロロフェン等の抗菌剤等を本組成物中に適宜配合することができる。 For example, hydrocarbons such as liquid paraffin, squalane and petrolatum; fats and oils such as macadamia nut oil, olive oil and lanolin; waxes such as jojoba oil, carnauba wax and candelilla wax; silicones such as dimethylpolysiloxane and methylphenylsiloxane; Higher alcohols such as capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cholesterol, phytosterol; higher fatty acids such as capric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lanolin fatty acid, linoleic acid, linolenic acid; polyethylene Glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, chitin, chitosan Moisturizers such as: lower alcohols such as ethanol; antioxidants such as butylhydroxytoluene, tocopherol, phytin; It can mix | blend suitably.
また、グリシン、アラニン、バリン、ロイシン、トレオニン、フェニルアラニン、チロシン、アスパラギン酸、アスパラギン、グルタミン、タウリン、アルギニン、ヒスチジン等のアミノ酸およびこれらのアルカリ金属塩と塩酸塩；アシルサルコシン酸（例えばラウロイルサルコシンナトリウム）、グルタチオン；クエン酸、リンゴ酸、酒石酸、乳酸等の有機酸；ビタミンＡおよびその誘導体；ビタミンＢ６塩酸塩、ビタミンＢ６トリパルミテート、ビタミンＢ６ジオクタノエート、ビタミンＢ２およびその誘導体、ビタミンＢ１２、ビタミンＢ１５およびその誘導体等のビタミンＢ類；アスコルビン酸、アスコルビン酸硫酸エステル（塩）、アスコルビン酸リン酸エステル（塩）、アスコルビン酸ジパルミテート等のビタミンＣ類；α−トコフェロール、β−トコフェロール、γ−トコフェロール、ビタミンＥアセテート等のビタミンＥ類；ビタミンＤ類；ビタミンＨ、パントテン酸、パンテチン等のビタミン類；ニコチン酸アミド、ニコチン酸ベンジル、γ−オリザノール、アラントイン、グリチルリチン酸（塩）、グリチルレチン酸およびその誘導体、ヒノキチオール、ビサボロール、ユーカリプトール、チモール、イノシトール、サイコサポニン、ニンジンサポニン、ヘチマサポニン、ムクロジサポニン等のサポニン類、パントテニルエチルエーテル、エチニルエストラジオール、トラネキサム酸、アルブチン、セファランチン、プラセンタエキス等の各種薬剤；ギシギシ、クララ、コウホネ、オレンジ、セージ、ノコギリソウ、ゼニアオイ、センブリ、タイム、トウキ、トウヒ、バーチ、スギナ、ヘチマ、マロニエ、ユキノシタ、アルニカ、ユリ、ヨモギ、シャクヤク、アロエ、クチナシ、サワラ等の各種の溶媒で抽出した天然エキス；中和剤、酸化防止剤、色素、香料、精製水等を、本組成物中に配合することができる。 In addition, amino acids such as glycine, alanine, valine, leucine, threonine, phenylalanine, tyrosine, aspartic acid, asparagine, glutamine, taurine, arginine, histidine and their alkali metal salts and hydrochlorides; acyl sarcosine acid (for example, lauroyl sarcosine sodium) Glutathione; organic acids such as citric acid, malic acid, tartaric acid and lactic acid; vitamin A and its derivatives; vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B12, vitamin B15 and Vitamin B such as derivatives thereof; Vitamin C such as ascorbic acid, ascorbic acid sulfate (salt), ascorbic acid phosphate (salt), ascorbic acid dipalmitate; α-to Vitamin E such as ferrol, β-tocopherol, γ-tocopherol, vitamin E acetate; vitamin D; vitamins such as vitamin H, pantothenic acid, pantethine; nicotinamide, benzyl nicotinate, γ-oryzanol, allantoin, glycyrrhizin Acid (salt), glycyrrhetinic acid and its derivatives, hinokitiol, bisabolol, eucalyptol, thymol, inositol, saikosaponin, carrot saponin, hechisaponin, muclodisaponin, saponins, pantothenyl ethyl ether, ethinyl estradiol, tranexamic acid, Various drugs such as arbutin, cephalanthin, placenta extract; borage, clara, corn, orange, sage, yarrow, mallow, assembly, thyme, toki, tow Natural extracts extracted with various solvents such as baboon, birch, horsetail, loofah, maronier, yukinoshita, arnica, lily, mugwort, peonies, aloe, gardenia, sawara; neutralizers, antioxidants, pigments, fragrances, purified water Etc. can be blended in the composition.
本組成物においては、十分に安定な組成物が形成されるので、本組成物の安定性を向上させる目的で、あえて界面活性剤を配合する必要はない。ただし本組成物に対し、界面活性剤の配合を妨げるものではない。また、他の目的のために界面活性剤を配合することを妨げるものでもない。 In the present composition, since a sufficiently stable composition is formed, it is not necessary to add a surfactant for the purpose of improving the stability of the present composition. However, the composition of the surfactant is not hindered with respect to the present composition. Moreover, it does not prevent mixing a surfactant for other purposes.
なお、本組成物において、あえて安定性の向上のために配合するか、他の目的のために配合し得る界面活性剤は、特に限定されず、例えば、モノラウリン酸ソルビタン、モノパルミチン酸ソルビタン、セスキオレイン酸ソルビタン、トリオレイン酸ソルビタン、モノラウリン酸ポリオキシエチレンソルビタン、ポリオキシエチレングリコールモノオレート、ポリオキシエチレンアルキルエーテル、ポリエチレングリコールジ脂肪酸エステル、ラウロイルジエタノールアミド、脂肪酸ジプロパノールアミド、マルチトールヒドロキシ脂肪族エーテル、アルキル化多糖、アルキルグルコシド、シュガーエステル、ポリエーテル変性シリコーン等の非イオン界面活性剤；ステアリルトリメチルアンモニウムクロライド、塩化ベンザルコニウム、ラウリルアミンオキサイド等のカチオン界面活性剤；パルミチン酸ナトリウム、ラウリン酸ナトリウム、ラウリル硫酸ナトリウム、ラウリル硫酸カリウム、アルキル硫酸トリエタノールアミン、アシルメチルタウリン塩等のアニオン界面活性剤；両性界面活性剤等を適宜選択して配合することができる。 In the present composition, the surfactant that can be added for the purpose of improving the stability or can be added for other purposes is not particularly limited. For example, sorbitan monolaurate, sorbitan monopalmitate, Sorbitan oleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene glycol monooleate, polyoxyethylene alkyl ether, polyethylene glycol difatty acid ester, lauroyl diethanolamide, fatty acid dipropanolamide, maltitol hydroxy aliphatic ether , Non-ionic surfactants such as alkylated polysaccharides, alkyl glucosides, sugar esters, polyether-modified silicones; stearyl trimethyl ammonium chloride, benzalkonium chloride, laur Cationic surfactants such as ruamine oxide; anionic surfactants such as sodium palmitate, sodium laurate, sodium lauryl sulfate, potassium lauryl sulfate, triethanolamine alkyl sulfate, and acylmethyl taurate; Can be blended.
本組成物を化粧料として用いる場合、例えば皮膚化粧料、メーキャップ化粧料、および毛髪化粧料等として好適である。本組成物の剤型は特に限定されるものでなく、任意の剤型をとり得る。本組成物を、例えば皮膚化粧料に使用する場合には、皮膚化粧料成分として一般に使用されている界面活性剤、油分、保湿剤、皮膜形成剤、油ゲル化剤、金属酸化物、有機紫外線吸収剤、無機金属塩類、有機金属塩類、アルコール類、キレート剤、ｐＨ調整剤、防腐剤、他の増粘剤、薬効成分、色素、香料等の添加剤成分と任意に組み合わせて配合すればよい。また、例えば水溶液系、可溶化系、乳化系、粉末分散系、水−油２層系、水−油−粉末３層系、油／水（Ｏ／Ｗ）型乳化化粧料、水／油（Ｗ／Ｏ）型乳化化粧料等の種々の形態をとることもできる。なお、具体的な用途としては、クリーム、化粧乳液、化粧水、油性化粧水、口紅、ファンデーション、皮膚洗浄剤などが挙げられる。 When this composition is used as a cosmetic, it is suitable as, for example, a skin cosmetic, a makeup cosmetic, and a hair cosmetic. The dosage form of this composition is not particularly limited, and can be any dosage form. When this composition is used for skin cosmetics, for example, surfactants, oils, moisturizers, film forming agents, oil gelling agents, metal oxides, organic ultraviolet rays generally used as skin cosmetic ingredients. Absorbents, inorganic metal salts, organic metal salts, alcohols, chelating agents, pH adjusters, preservatives, other thickeners, medicinal ingredients, pigments, fragrances and other additive components may be combined in any combination. . Further, for example, aqueous solution system, solubilization system, emulsion system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, oil / water (O / W) type emulsified cosmetic, water / oil ( Various forms such as (W / O) type emulsified cosmetics can also be taken. Specific applications include creams, cosmetic emulsions, lotions, oily lotions, lipsticks, foundations, skin cleansing agents, and the like.
次に、実施例によって本発明をさらに詳細に説明する。なお、本発明は実施例の内容に限定されるものではない。
〔実施例１〕
γ-ＰＧＡ架橋体（出光テクノファイン株式会社製、商品名：ジェルプロテインＡ-８００２、平均粒径 ２６．５μｍ）を、純水に配合して、各々１．０質量％および２．０質量％になるように２種のγ-ＰＧＡ架橋体分散液をまず調製した。
次に、平均分子量の異なる２種のヒアルロン酸(ＨＡ）（株式会社紀文フードケミファ製、商品名：ヒアルロン酸ＦＣＨ１２０)を、前記した２種のγ-ＰＧＡ架橋体分散液および純水に混合して、表１に示す１２種類の試料液を調製した。そして、各試料液の粘度を、Ｂ型粘度計(ローターＮｏ．４、６ｒｐｍ、２５℃)を用いて測定した。その結果を表１に示す。各粘度数値の右隣のかっこ内はγ-ＰＧＡ架橋体１００質量部に対するヒアルロン酸（ＨＡ）の各質量部を示している。
なお、本実施形態で用いたγ-ＰＧＡ架橋体は、分子量７０ｋＤａのポリ−γ−グルタミン酸に、１４０ｋＧｙの電子線照射処理を行うことで得られたものである。Next, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to the content of the Example.
[Example 1]
γ-PGA cross-linked product (manufactured by Idemitsu Techno Fine Co., Ltd., trade name: Gel Protein A-8002, average particle size 26.5 μm) is blended in pure water and 1.0% by mass and 2.0% by mass, respectively. First, two kinds of γ-PGA cross-linked dispersion liquids were prepared.
Next, two kinds of hyaluronic acid (HA) having different average molecular weights (trade name: hyaluronic acid FCH120, manufactured by Kibun Food Chemifa Co., Ltd.) are mixed with the two kinds of γ-PGA crosslinked dispersion and pure water described above. Thus, 12 types of sample solutions shown in Table 1 were prepared. And the viscosity of each sample liquid was measured using the B-type viscosity meter (rotor No. 4, 6 rpm, 25 degreeC). The results are shown in Table 1. The parenthesis next to each viscosity value indicates each part by mass of hyaluronic acid (HA) with respect to 100 parts by mass of the γ-PGA crosslinked body.
The crosslinked γ-PGA used in this embodiment is obtained by subjecting poly-γ-glutamic acid having a molecular weight of 70 kDa to an electron beam irradiation treatment of 140 kGy.
表１の結果から、γ-ＰＧＡ架橋体単独では、その濃度を上げても粘度の増加はさほど認められない。また、ヒアルロン酸単独の場合も同様に、その量を増やしても粘度の増加はさほど認められない。しかし、これら双方を混合した試料液においては顕著に粘度の増加が認められ、γ-ＰＧＡ架橋体とヒアルロン酸とが相乗的に働いていることが理解できる。
また、ヒアルロン酸の平均分子量を大きくしたり、γ−ＰＧＡ架橋体１００質量部に対する配合量を多くすることで、より顕著な増粘効果が得られた。
さらに、γ-ＰＧＡ架橋体とヒアルロン酸を配合した組成物を化粧料として用いた場合の使用感を確認したところ、γ-ＰＧＡ架橋体単独やヒアルロン酸単独の場合の組成物と比べて、はりやしわの改善効果に優れるとともに、十分な保湿効果を有し、べたつきがなく、肌へののびが良好であった。From the results shown in Table 1, with the γ-PGA crosslinked product alone, even if the concentration is increased, the increase in viscosity is not recognized so much. Similarly, in the case of hyaluronic acid alone, the increase in viscosity is not appreciably observed even if the amount is increased. However, in the sample solution in which both are mixed, the viscosity is remarkably increased, and it can be understood that the γ-PGA crosslinked product and hyaluronic acid work synergistically.
Moreover, the more remarkable thickening effect was acquired by enlarging the average molecular weight of hyaluronic acid, or increasing the compounding quantity with respect to 100 mass parts of (gamma) -PGA crosslinked bodies.
Furthermore, when the feeling of use when a composition containing a crosslinked γ-PGA and hyaluronic acid was used as a cosmetic was confirmed, compared to the composition in the case of a crosslinked γ-PGA alone or hyaluronic acid alone, It was excellent in improving wrinkles and wrinkles, had a sufficient moisturizing effect, had no stickiness, and spread well on the skin.
〔実施例２〕
実施例１で用いたγ-ＰＧＡ架橋体と同じものを純水に混合して、各々０．５質量％、１．０質量％、および２．０質量％となるように３種のγ-ＰＧＡ架橋体分散液を調製した。
次に、キサンタンガム（ＸＧ）（日清オイリオ製、商品名：ノムコートＺＺ）を前記した３種のγ-ＰＧＡ架橋体分散液および純水に混合して、表２に示す１２種類の試料液を調製した。そして、各試料液の粘度を、実施例１と同様にして測定した。その結果を表２に示す。各粘度数値の右隣のかっこ内はγ-ＰＧＡ架橋体１００質量部に対するキサンタンガム（ＸＧ）の各質量部を示している。[Example 2]
The same γ-PGA crosslinked product used in Example 1 was mixed with pure water, so that three kinds of γ- A PGA crosslinked dispersion was prepared.
Next, xanthan gum (XG) (manufactured by Nisshin Eulio, trade name: Nomcoat ZZ) was mixed with the above-mentioned three γ-PGA cross-linked dispersion liquids and pure water, and 12 kinds of sample liquids shown in Table 2 were prepared. Prepared. And the viscosity of each sample liquid was measured like Example 1. FIG. The results are shown in Table 2. The inside of the parenthesis on the right side of each viscosity value indicates each part by mass of xanthan gum (XG) with respect to 100 parts by mass of the γ-PGA crosslinked body.
表２の結果からわかるように、γ-ＰＧＡ架橋体単独やキサンタンガム単独では、その濃度を上げても粘度の増加はさほど認められない。しかし、キサンタンガムとγ-ＰＧＡ架橋体の双方を配合した試料液においては顕著に粘度の増加が認められ、γ-ＰＧＡ架橋体とキサンタンガムとが相乗的に働いていることが理解できる。
また、γ-ＰＧＡ架橋体とキサンタンガムを配合した組成物を化粧料として用いた場合の使用感を確認したところ、γ-ＰＧＡ架橋体単独の場合の組成物と比べて、はりやしわの改善効果に優れるとともに、十分な保湿効果を有し、べたつきがなく、肌へののびが良好であった。As can be seen from the results in Table 2, with the γ-PGA crosslinked body alone or xanthan gum alone, the viscosity is not significantly increased even when the concentration is increased. However, in the sample solution in which both xanthan gum and γ-PGA cross-linked product are mixed, the viscosity is remarkably increased, and it can be understood that the γ-PGA cross-linked product and xanthan gum work synergistically.
Moreover, when the feeling of use at the time of using the composition which mix | blended the (gamma) -PGA crosslinked body and xanthan gum as cosmetics was confirmed, compared with the composition in the case of only a (gamma) -PGA crosslinked body, the improvement effect of a wrinkle and wrinkle In addition to being excellent in moisture, it has a sufficient moisturizing effect, has no stickiness, and spreads well on the skin.
〔実施例３〕
実施例１で用いたγ-ＰＧＡ架橋体と同じものを純水に混合して、２．０質量％となるように１種のγ-ＰＧＡ架橋体分散液を調製した。
次に、タンパク質（株式会社高研製、製品名：アテロコラーゲン）を前記したγ-ＰＧＡ架橋体分散液および純水に混合して、表３に示す４種類の試料液を調製した。そして、各試料液の粘度を、実施例１と同様にして測定した。その結果を表３に示す。各粘度数値の右隣のかっこ内はγ-ＰＧＡ架橋体１００質量部に対するタンパク質の各質量部を示している。Example 3
The same γ-PGA crosslinked product used in Example 1 was mixed with pure water to prepare one kind of γ-PGA crosslinked product dispersion to 2.0% by mass.
Next, the protein (product name: Atelocollagen, manufactured by Koken Co., Ltd.) was mixed with the above-mentioned γ-PGA crosslinked dispersion and pure water to prepare four types of sample solutions shown in Table 3. And the viscosity of each sample liquid was measured like Example 1. FIG. The results are shown in Table 3. In the parentheses on the right side of each viscosity value, each part by mass of the protein with respect to 100 parts by mass of the γ-PGA crosslinked body is shown.
表３の結果からわかるように、γ―ＰＧＡ架橋体単独やタンパク質単独では、その濃度を上げても粘度の増加はさほど認められない。しかし、タンパク質とγ-ＰＧＡ架橋体の双方を配合した試料液においては顕著に粘度の増加が認められ、γ-ＰＧＡ架橋体とタンパク質とが相乗的に働いていることが理解できる。
また、γ-ＰＧＡ架橋体とタンパク質を配合した組成物を化粧料として用いた場合の使用感を確認したところ、γ-ＰＧＡ架橋体単独の場合の組成物と比べて、はりやしわの改善効果に優れるとともに、十分な保湿効果を有し、べたつきがなく、肌へののびが良好であった。As can be seen from the results in Table 3, with the γ-PGA cross-linked substance alone or with the protein alone, the increase in viscosity is not appreciably observed even when the concentration is increased. However, in the sample solution in which both the protein and the γ-PGA cross-linked product are blended, the viscosity is remarkably increased, and it can be understood that the γ-PGA cross-linked product and the protein work synergistically.
Moreover, when the usability when using a composition containing a crosslinked γ-PGA and a protein as a cosmetic was confirmed, the effect of improving the wrinkles and wrinkles compared to the composition of the crosslinked γ-PGA alone. In addition to being excellent in moisture, it has a sufficient moisturizing effect, has no stickiness, and spreads well on the skin.
〔実施例４〕
実施例１で用いたγ-ＰＧＡ架橋体と同じものを純水に混合して、２．０質量％となるように１種のγ-ＰＧＡ架橋体分散液を調製した。
次に、脂質(日油株式会社製、商品名：リピジュア）を前記したγ-ＰＧＡ架橋体分散液および純水に混合して、表４に示す４種類の試料液を調製した。そして、各試料液の粘度を、実施例１と同様にして測定した。その結果を表４に示す。各粘度数値の右隣のかっこ内はγ-ＰＧＡ架橋体１００質量部に対する脂質の各質量部を示している。Example 4
The same γ-PGA crosslinked product used in Example 1 was mixed with pure water to prepare one kind of γ-PGA crosslinked product dispersion to 2.0% by mass.
Next, lipids (manufactured by NOF Corporation, trade name: Lipidure) were mixed with the above-mentioned γ-PGA crosslinked body dispersion and pure water to prepare four types of sample solutions shown in Table 4. And the viscosity of each sample liquid was measured like Example 1. FIG. The results are shown in Table 4. In the parentheses on the right of each viscosity value, each part by mass of lipid with respect to 100 parts by mass of the γ-PGA crosslinked body is shown.
表４の結果からわかるように、γ−ＰＧＡ架橋体単独や脂質単独では、その濃度を上げても粘度の増加はさほど認められない。しかし、脂質とγ-ＰＧＡ架橋体の双方を配合した試料液においては顕著に粘度の増加が認められ、γ-ＰＧＡ架橋体と脂質とが相乗的に働いていることが理解できる。
また、γ-ＰＧＡ架橋体と脂質を配合した組成物を化粧料として用いた場合の使用感を確認したところ、γ-ＰＧＡ架橋体単独の場合の組成物と比べて、はりやしわの改善効果に優れるとともに、十分な保湿効果を有し、べたつきがなく、肌へののびが良好であった。As can be seen from the results in Table 4, with the γ-PGA crosslinked body alone or with the lipid alone, the increase in viscosity is not appreciably observed even when the concentration is increased. However, in the sample solution in which both the lipid and the γ-PGA crosslinked product are blended, the viscosity is remarkably increased, and it can be understood that the γ-PGA crosslinked product and the lipid work synergistically.
Moreover, when the feeling of use at the time of using the composition which mix | blended the gamma-PGA crosslinked body and lipid as cosmetics was confirmed, compared with the composition in the case of a gamma-PGA crosslinked body alone, the improvement effect of a wrinkle and wrinkle In addition to being excellent in moisture, it has a sufficient moisturizing effect, has no stickiness, and spreads well on the skin.
本発明の増粘性組成物は増粘効果が極めて高く、化粧料や衛生用品等の分野に好適に利用できる。 The thickening composition of the present invention has an extremely high thickening effect and can be suitably used in the fields of cosmetics and hygiene products.
Claims (2)
前記ポリアミノ酸類架橋体は、分子量１０〜３０００ｋＤａ、平均粒径が０．１〜３００μｍのポリ−γ−グルタミン酸の架橋体又はその塩であり、
前記天然高分子は、ヒアルロン酸、脂質から選ばれたものであり、
前記天然高分子は、前記ポリアミノ酸類架橋体１００質量部に対し、０．０１質量部以上で混合されて相乗的に増粘性が増大してなることを特徴とする増粘性組成物。 A thickening composition having a synergistically increased viscosity obtained by mixing a natural polymer with an aqueous dispersion of a crosslinked polyamino acid,
The polyamino acid cross-linked product is a cross-linked product of poly-γ-glutamic acid having a molecular weight of 10 to 3000 kDa and an average particle size of 0.1 to 300 μm, or a salt thereof,
The natural polymer is selected from hyaluronic acid and lipid,
The thickening composition, wherein the natural polymer is mixed in an amount of 0.01 parts by mass or more with respect to 100 parts by mass of the crosslinked polyamino acids, and the viscosity is increased synergistically.
前記ポリアミノ酸類架橋体は、分子量１０〜３０００ｋＤａ、平均粒径が０．１〜３００μｍのポリ−γ−グルタミン酸の架橋体又はその塩であり、
前記天然高分子は、ヒアルロン酸、脂質から選ばれたものであり、
前記天然高分子は、前記ポリアミノ酸類架橋体１００質量部に対し、０．０１質量部以上混合することにより相乗的に増粘性を増大させることを特徴とする増粘性組成物の製造方法。 A polyamino acid is cross-linked to produce a polyamino acid cross-linked product, and the resulting polyamino acid cross-linked product is dispersed in water to obtain an aqueous dispersion, and then the natural dispersion is mixed with the aqueous dispersion. A method for producing a thickening composition having increased thickening,
The polyamino acid cross-linked product is a cross-linked product of poly-γ-glutamic acid having a molecular weight of 10 to 3000 kDa and an average particle size of 0.1 to 300 μm, or a salt thereof,
The natural polymer is selected from hyaluronic acid and lipid,
The method for producing a thickening composition, wherein the natural polymer is synergistically increased in viscosity by mixing 0.01 parts by mass or more with respect to 100 parts by mass of the crosslinked polyamino acids.
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| CN112063221B (en) * | 2020-09-18 | 2022-11-15 | 山东华熙海御生物医药有限公司 | Coloring auxiliary agent containing hyaluronic acid, preparation method and application thereof |
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| JP2003146830A (en) * | 2001-11-08 | 2003-05-21 | Sakata Kyoko | Cosmetic |
| JP2005179534A (en) * | 2003-12-19 | 2005-07-07 | Tung Hai Biotechnology Corp | Three-dimensionally crosslinked, high water-absorptivity gamma polyglutamic acid hydrogel with stable biodegradability, and method for producing the same |
| JP2006342164A (en) * | 2005-06-07 | 2006-12-21 | Goldschmidt Gmbh | Topical cosmetic formulations for regulating and improving moisture content in skin |
| WO2007135801A1 (en) * | 2006-05-23 | 2007-11-29 | Toyo Boseki Kabushiki Kaisha | MICROORGANISM CAPABLE OF PRODUCING γ-L-PGA, METHOD FOR PRODUCTION OF γ-L-PGA USING THE MICROORGANISM, CROSSLINKED PRODUCT, AND AGENT FOR EXTERNAL APPLICATION TO THE SKIN |
| JP2007320889A (en) * | 2006-05-31 | 2007-12-13 | Umo Inc Co Ltd | Method for preparing face-beautifying medicine |
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| JP2003146830A (en) * | 2001-11-08 | 2003-05-21 | Sakata Kyoko | Cosmetic |
| JP2005179534A (en) * | 2003-12-19 | 2005-07-07 | Tung Hai Biotechnology Corp | Three-dimensionally crosslinked, high water-absorptivity gamma polyglutamic acid hydrogel with stable biodegradability, and method for producing the same |
| JP2006342164A (en) * | 2005-06-07 | 2006-12-21 | Goldschmidt Gmbh | Topical cosmetic formulations for regulating and improving moisture content in skin |
| WO2007135801A1 (en) * | 2006-05-23 | 2007-11-29 | Toyo Boseki Kabushiki Kaisha | MICROORGANISM CAPABLE OF PRODUCING γ-L-PGA, METHOD FOR PRODUCTION OF γ-L-PGA USING THE MICROORGANISM, CROSSLINKED PRODUCT, AND AGENT FOR EXTERNAL APPLICATION TO THE SKIN |
| JP2007320889A (en) * | 2006-05-31 | 2007-12-13 | Umo Inc Co Ltd | Method for preparing face-beautifying medicine |
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