TW201012482A - Thickening composition and process for production thereof - Google Patents

Thickening composition and process for production thereof Download PDF

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Publication number
TW201012482A
TW201012482A TW98117531A TW98117531A TW201012482A TW 201012482 A TW201012482 A TW 201012482A TW 98117531 A TW98117531 A TW 98117531A TW 98117531 A TW98117531 A TW 98117531A TW 201012482 A TW201012482 A TW 201012482A
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Taiwan
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composition
polyamino acid
acid
mass
viscosity
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TW98117531A
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Chinese (zh)
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Hideki Nakata
Tetsuo Miyayama
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Idemitsu Technofine Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/735Mucopolysaccharides, e.g. hyaluronic acid; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48Thickener, Thickening system
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A thickening composition characterized by comprising 100 parts by mass of a crosslinked polyamino acid and 0.01 part by mass or above of a natural polysaccharide. The composition can dramatically enhance the viscosity of an aqueous medium when added to the aqueous medium. When used as cosmetics, the composition is nongreasy to the touch and excellent in spreadability on the skin, and exerts high humectant effect. Further, the composition exhibits high safety to the human body and excellent biodegradability by virtue of its natural-ingredient-base prescription.

Description

201012482 六、發明說明: 【發明所屬之技術領域】 本發明係關於-種於分散於水介質中時發揮增黏效果之 增黏性組合物及其製造方法。 【先前技術】 作為用於化妝料等之增黏劑,已知有添加丙稀酸系聚合 物(合成高分子化合物)之組合物(例如參照文獻丨:日本專 利再公表WO 2〇〇5/〇44216號公報卜包含該組合物之化妝 ❹’料對皮膚鬆他及皺紋之改善效果及保濕效果優異,無黏腻 感且對皮膚之抹勻性亦良好。然而,如丙婦酸系聚合物之 類之合成系化合物,由於其生物降解性低且對人體之不良 影響亦令人擔憂,因此尋求非合成系之增黏劑之天然系之 增黏劑。 作為天然系之增黏性多糖類,已知有三仙膠(xamhan gum)或玻尿酸(hyaluronic acid)(例如參照文獻2 :曰本專利 特開2000443477號公報 '文獻3 :日本專利特開2〇〇4_ 149463號公報三仙膠或玻尿酸不僅保濕效果優異,並 且具有廢棄時之生物降解性,因此廣泛用作化妝料之素 , 材。又,亦已知將含有多糖類與聚胺基酸類之增黏性組合 .物(例如參照文獻4:日本專利特開2〇〇3_1287〇2號公報)、 或包含半乳甘露聚糖或其衍生物之交聯體作為保濕成分之 化妝品組合物(例如參照文獻5 :日本專利特開2〇〇4 21759〇 號公報)。 然而,於上述先前技術中,增黏效果未必充分,例如於 140609.doc 201012482 用作化妝料之情形時,關於無黏腻感且對皮膚之抹勻性優 異、進而保濕性亦優異等各種性質,不能平衡性良好地發 揮優異效果。 因此本發明之目的在於提供一種增黏性組合物及其製 造方法,該增黏性組合物不僅具有生物降解性,並且增黏 陡優異,即使於用作化妝料之情形,使用時亦無黏腻感、 對皮膚之抹勻性優異’進而保濕效果亦優異。 【發明内容】 為解決上述問題,本發明係提供如下所述之增黏性組合 物。 [1] 一種增黏性組合物,其特徵在於··其係將聚胺基酸 類交聯體與天然高分子調配而成。 [2] 如上述本發明之增黏性組合物,其中上述天然高分 子為天然多糖類。 [3 ]如上述本發明之增黏性組合物,其中上述天然多糖 類為玻尿酸。 [4] 如上述本發明之增黏性組合物’其係相對於聚胺基 酸類交聯體之調配量100質量份’調配天然高分子〇.〇1質 量份以上而成。 [5] 如上述本發明之增黏性組合物’其中上述聚胺基酸 類交聯體為聚-γ-麩胺酸或其鹽。 [6] 如上述本發明之增黏性組合物,其中上述聚胺基酸 類交聯體係分子量為1〇〜3000 kDa之聚胺基酸類之放射線 交聯體。 140609.doc 201012482 [7]如上述本發明之增黏性組合物,其中上述聚胺基酸 類交聯體之平均粒徑為〇 U00 μηι 〇 又’本發明亦提供一種增黏性組合物之製造方法,其特 徵在於.使聚胺基酸類交聯而製作聚胺基酸類交聯體之 後,調配天然高分子。 根據本發明之增黏性組合物,藉由將聚胺基酸類交聯體 與天然高分子、尤其係天然多糖類併用,可飛躍性地提高 分散於水介質中時之黏度。因此,可對通常單獨未表現出 尚黏度之天然高分子例如具有各種功能之天然多糖類亦賦 予適度之黏度,從而可擴大利用範圍。又,本發明之增黏 性組合物由於為天然系之配方’故對人體之安全性高生 物降解性亦優異。 因此’本發明之增黏性組合物可廣泛應用於以化妝料為 代表之生活用品、化妝用品、衛生用品、醫療用品、農業 /園藝領域、食品領域及環境領域。 尤其於將玻尿酸用作天然多糖類之情形時,不僅可期待 增黏性之大幅提高’並且除聚胺基酸類交聯體之保濕效果 以外’亦可獲得玻尿酸之保濕效果。 又’作為天然多糖類之三仙膠,其作為具有耐鹽性、对 酸性及耐熱性優異等特徵之增黏劑而廣為人知,但於用作 化妝料之情形時’有黏腻感或對皮膚之抹勻性差等使用感 不良’使用範圍受限。對此,本發明中藉由將三仙膠與聚 胺基酸類交聯體併用而獲得優異之使用感。 根據本發明之增黏性組合物之製造方法,於使聚胺基酸 140609.doc 201012482 類父聯而製作聚胺基酸類交聯體之後調配天然高分子藉 此可飛躍性地提高分散於水介質中時之黏度。 【實施方式】 本發明之增黏性組合物(以下亦稱為「本組合物」)之特 徵在於:其係將聚胺基酸類交聯體與天然高分子調配而 成。以下對上述聚胺基酸類交聯體與天然高分子、進而對 包含該等之本組合物進行詳細說明。 [聚胺基酸類交聯體] 於本發明中,所謂聚胺基酸類並不限定於游離酸,可為 納、卸、鐘等之驗金屬鹽,亦可為録鹽、乙醇胺鹽、二乙 醇胺鹽'。乙醇胺鹽等驗性胺鹽。因此,聚胺基酸類交聯 體中不僅包含游離之聚胺基酸之交聯體,亦包含聚胺基酸 鹽之交聯體。作為鹽,自氣味之觀點而言較好的是納鹽或 =鹽。以下若無特別需要,則不對游離之酸及其鹽加以區 分,而表述為「聚胺基酸類」、「聚胺基酸類交聯體」。 本發明之聚胺基酸類交聯體可將包含如下所述之各種胺 基酸之聚胺基酸作為原料而應用。 例如,作為具有非極性即疏水性原子團之胺基酸,可舉 出:丙胺酸、纈胺酸、白胺酸、#白胺酸、甲硫胺酸、色 胺酸、苯丙胺酸、及脯胺酸等。作為極性但無電荷之胺基 酸’可舉出:甘胺酸、絲胺酸'蘇胺酸、半胱胺酸、酪胺 酸、天冬醯胺、及麵醯胺等。作為具有持正電荷之原子團 <胺基酸’可舉出:離胺酸、組胺酸、及精胺酸等。作為 、、負電荷之原子團之胺基酸,可舉出:天冬胺酸或麩 140609.doc 201012482 胺酸等。 作為胺基酸之其他例,可舉出:L-鳥胺酸、一系列之α-胺基酸、β-丙胺酸、γ-胺基丁酸、中性胺基酸、酸性胺基 酸、酸性胺基酸之ω-酯、鹼性胺基酸、鹼性胺基酸之Ν_取 代體、天冬胺酸-L-苯丙胺酸二聚物(阿斯巴甜)等胺基酸及 胺基酸衍生物,L-半胱胺酸等胺基磺酸等。α_胺基酸可為 光學活性物質(L體、D體),亦可為外消旋物。又,聚胺基 酸亦可為含有其他單體成分之共聚物。 本發明中所使用之聚胺基酸類交聯體可為均聚物,亦可 為共聚物。於共聚物之情形時,共聚形式並無特別限定, 可採取嵌段共聚物、無規共聚物、接枝共聚物等任意形 式。 作為聚胺基酸類交聯體為共聚物之情形時之共聚物成分 (胺基酸以外之單體成分)之具體例,例如可舉出:胺基羧 酸、胺基磺酸、胺基膦酸、羥基羧酸、酼基羧酸、巯基磺 酸、巯基膦酸等。 本發明中較好的是使用均聚物。其中,為了表現出優異 之生物降解性,較好的是將聚天冬胺酸、聚麩胺酸(以 下亦稱為「γ-PGA」)、或聚離胺酸之均聚物作為基本骨架 之交聯體。就吸水性之觀點而言,該等之中較好的是聚天 冬胺酸交聯體或γ-PGA交聯體。此外,例如若為作為化妝 料之用途,則就無黏腻感且對皮膚之抹勻性良好的方面而 言’較好的是使用γ-PGA交聯體。 此處,聚胺基酸類交聯體較好的是藉由放射線交聯而獲 140609.doc 201012482 付。其原因在於’若藉由放射線交聯,則與過氧化物交聯 相比較,聚胺基酸類交聯體之凝膠化率之確定變得容易。 對於放射線並無特別限制,例如可舉出丫射線' 電子束 等。其中,較好的是操作性良好之電子束。γ射線與電子 束相比較,穿透力高但照射劑量較小,電子束之穿透力小 於γ射線但可將照射劑量設定為較大。因此’若為與加速 電壓相對應之試料厚度,則比丫射線更短時間之照射即 可’因此較好的是使用電子束。於使用電子束作為放射線 之情形時,照射劑量較好的是10〜300 kGy之範圍,更好的 是20〜200 kGy。又,藉由並非一次施加特定之照射劑量而 係分割照射,可使其均勻交聯,且可抑制反應熱而減少分 解物。作為照射時間,較好的是總計〖秒以上。若照射時 間總計未滿1秒,則有交聯體之形成變得不充分之虞。 又為了製備本發明所使用之增黏組合物而調配之聚胺 基酸類交聯體之形態並無特別限定。例如於使用聚胺基酸 類交聯體之粉末之情形時,較好的是平均粒徑為0 1〜300 μπι之範圍,更好的是平均粒徑之範圍為卜⑽進而好 的疋平均粒徑之範圍為5〜3〇 μηι。又,於使用聚胺基酸類 交聯體之水溶液之情形時,較好的是平均粒徑為〇. 1 ρ以 上。 若為該範圍外之粒徑,則於將組合物用作化妝料之情形 時會殘存粒感,無法獲得較好之使用感及適當之黏度。平 句粒L 了藉由應用夫朗和斐(Fraunhofer)之繞射原理之雷 射式粒度分布測定器(清新(Seishin)企業股份有限公司製 140609.doc 201012482 造,LMS-30)而測定。[Technical Field] The present invention relates to a viscosity-increasing composition which exhibits a viscosity-increasing effect when dispersed in an aqueous medium, and a method for producing the same. [Prior Art] As a tackifier for cosmetics and the like, a composition in which an acrylic polymer (synthetic polymer compound) is added is known (for example, Japanese Patent Laid-Open Publication No. WO 2〇〇5/ 〇 No. 44216, the composition of the composition comprising the composition has an excellent effect of improving the skin and wrinkles and moisturizing effect, has no sticky feeling and is good for the smoothness of the skin. Synthetic compounds such as substances, because of their low biodegradability and adverse effects on the human body, are therefore a natural tackifier for non-synthetic tackifiers. For the saccharide, there is known a xamhan gum or a hyaluronic acid (for example, reference 2: 曰本专利专开 2000443477号] Document 3: Japanese Patent Laid-Open Publication No. 2-4-149463 Hyaluronic acid is not only excellent in moisturizing effect, but also has biodegradability at the time of disposal, and therefore is widely used as a pigment and material for cosmetics. Further, it is also known to combine a polysaccharide with a polybasic acid to enhance adhesion. Reference 4: Japanese Patent Laid-Open Publication No. 2〇〇3_1287〇2, or a cosmetic composition comprising a crosslinked body of galactomannan or a derivative thereof as a moisturizing component (for example, Reference 5: Japanese Patent Laid-Open 2〇〇4 21759〇)) However, in the above prior art, the viscosity-increasing effect is not necessarily sufficient, for example, when 140609.doc 201012482 is used as a cosmetic material, regarding the non-sticky feeling and the smoothness to the skin. It is excellent in various properties such as excellent and moisturizing properties, and it is not excellent in balance. Therefore, an object of the present invention is to provide a thickening composition and a method for producing the same, which are not only biodegradable, It is excellent in viscosity-increasing viscosity, and it is excellent in moisturizing effect even when it is used as a cosmetic material, and it is excellent in moisturizing effect when it is used. [Invention] In order to solve the above problems, the present invention provides A tackifying composition as described below. [1] A tackifying composition characterized in that it is prepared by blending a polyamino acid crosslinked body with a natural polymer. [2] The above-mentioned tackifying composition of the present invention, wherein the natural polymer is a natural polysaccharide. [3] The above-mentioned thickening composition of the present invention, wherein the natural polysaccharide is hyaluronic acid. [4] The above-mentioned tackifying composition of the present invention is prepared by blending 100 parts by mass of the polyamino acid crosslinked body with 1 part by mass or more of the natural polymer. [5] The tackifying composition 'wherein the above-mentioned polyamino acid crosslinked body is poly-γ-glutamic acid or a salt thereof. [6] The above-mentioned tackifying composition of the present invention, wherein the above polyamino acid crosslinking system A radiation crosslinked body of a polyamino acid having a molecular weight of from 1 〇 to 3000 kDa. [14] The above-mentioned tackifying composition of the present invention, wherein the above-mentioned polyamino acid crosslinked body has an average particle diameter of 〇U00 μηι 〇 and the present invention also provides a viscosifying composition. The method is characterized in that after the polyamino acid is crosslinked to form a polyamino acid crosslinked body, a natural polymer is formulated. According to the thickening composition of the present invention, the polyamino acid crosslinked body can be used in combination with a natural polymer, particularly a natural polysaccharide, to greatly improve the viscosity when dispersed in an aqueous medium. Therefore, it is possible to impart a moderate viscosity to a natural polymer which usually does not exhibit a viscosity alone, for example, a natural polysaccharide having various functions, thereby expanding the range of utilization. Further, since the tackifying composition of the present invention is a natural-based formulation, it is excellent in biodegradability against human body safety. Therefore, the tackifying composition of the present invention can be widely applied to daily necessities, cosmetics, sanitary articles, medical supplies, agricultural/horticultural fields, food fields, and environmental fields represented by cosmetics. In particular, when hyaluronic acid is used as the natural polysaccharide, not only the viscosity-increasing property can be expected to be greatly improved, but also the moisturizing effect of hyaluronic acid can be obtained in addition to the moisturizing effect of the polyurethane-based crosslinked body. Also, as a natural polysaccharide, Sanxian Gum is widely known as a tackifier having characteristics such as salt tolerance and excellent acidity and heat resistance, but it is sticky or skin when used as a cosmetic. The use of poor uniformity, such as poor use, is limited in use. On the other hand, in the present invention, an excellent feeling of use is obtained by using a crosslinked body of trisin and a polyamino acid. According to the method for producing a thickening composition of the present invention, the polyamine acid 140900.doc 201012482 is used to form a polyamino acid crosslinked body, and then the natural polymer is blended to thereby rapidly increase the dispersion in water. Viscosity in the medium. [Embodiment] The tackifying composition of the present invention (hereinafter also referred to as "the present composition") is characterized in that it is prepared by blending a polyamino acid crosslinked body with a natural polymer. Hereinafter, the above-mentioned polyamino acid crosslinked body, natural polymer, and the present composition containing the above will be described in detail. [Polyamino acid crosslinked body] In the present invention, the polyamino acid is not limited to the free acid, and may be a metal salt such as sodium, hydride, or the like, or a salt, an ethanolamine salt or a diethanolamine. salt'. An amine salt such as an ethanolamine salt. Therefore, the polyamino acid crosslinked body contains not only a crosslinked body of a free polyamino acid but also a crosslinked body of a polyamino acid salt. As the salt, a sodium salt or a salt is preferred from the viewpoint of odor. Unless otherwise specified, the free acid and its salt are not distinguished, and are described as "polyamino acid" and "polyamino acid crosslinked body". The polyamino acid crosslinked body of the present invention can be applied as a raw material using a polyamino acid containing various amino acids as described below. For example, as the amino acid having a nonpolar or hydrophobic atomic group, alanine, lysine, leucine, #leucine, methionine, tryptophan, phenylalanine, and guanamine may be mentioned. Acid, etc. Examples of the polar but non-charged amino acid include glycine, serine 'threonine, cysteine, tyrosine, aspartame, and decylamine. Examples of the atomic group having a positive charge <amino acid' include lysine, histidine, and arginine. Examples of the amino acid of the negatively charged atomic group include aspartic acid or bran 140609.doc 201012482 Aminic acid and the like. Other examples of the amino acid include L-ornithine, a series of α-amino acids, β-alanine, γ-aminobutyric acid, neutral amino acid, acid amino acid, Amino acid and amine such as ω-ester of acidic amino acid, basic amino acid, Ν-substituent of basic amino acid, aspartic acid-L-phenylalanine dimer (aspartame) A base acid derivative, an amine sulfonic acid such as L-cysteine or the like. The α-amino acid may be an optically active substance (L body, D body) or a racemate. Further, the polyamino acid may be a copolymer containing other monomer components. The polyamino acid crosslinked body used in the present invention may be a homopolymer or a copolymer. In the case of the copolymer, the copolymerization form is not particularly limited, and any form such as a block copolymer, a random copolymer or a graft copolymer may be employed. Specific examples of the copolymer component (monomer component other than the amino acid) when the crosslinked product of the polyamino acid is a copolymer include, for example, an aminocarboxylic acid, an aminosulfonic acid, and an aminophosphine. An acid, a hydroxycarboxylic acid, a mercaptocarboxylic acid, a mercaptosulfonic acid, a mercaptophosphonic acid or the like. It is preferred in the present invention to use a homopolymer. Among them, in order to exhibit excellent biodegradability, it is preferred to use polyaspartic acid, polyglutamic acid (hereinafter also referred to as "γ-PGA"), or a homopolymer of poly-amino acid as a basic skeleton. Cross-linking body. From the viewpoint of water absorption, among these, a polyaspartic acid crosslinked body or a γ-PGA crosslinked body is preferred. Further, for example, in the case of use as a cosmetic, it is preferable that a γ-PGA crosslinked body is used in terms of no stickiness and good skin smoothness. Here, the polyamino acid crosslinked body is preferably obtained by radiation crosslinking of 140609.doc 201012482. The reason for this is that the 'gelation ratio of the polyamino acid crosslinked body is easily determined by cross-linking with the peroxide. The radiation is not particularly limited, and examples thereof include a x-ray electron beam. Among them, an electron beam having good operability is preferred. Compared with the electron beam, the gamma ray has a high penetration force but a small irradiation dose, and the penetration force of the electron beam is smaller than that of the gamma ray, but the irradiation dose can be set to be large. Therefore, if the thickness of the sample corresponding to the accelerating voltage is shorter than that of the x-ray, it is preferable to use an electron beam. In the case where 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, by dividing the irradiation by not applying a specific irradiation dose at a time, it is possible to uniformly crosslink, and it is possible to suppress the heat of reaction and reduce the decomposition product. As the irradiation time, it is preferred that the total is s or more. If the total irradiation time is less than one second, the formation of the crosslinked body may be insufficient. Further, the form of the polyamino acid crosslinked body to be prepared in order to prepare the tackifying composition used in the present invention is not particularly limited. For example, in the case of using a powder of a polyamino acid crosslinked body, it is preferred that the average particle diameter is in the range of from 0 1 to 300 μm, and more preferably, the average particle diameter is in the range of (10) and thus the fine average particle size. The range of the diameter is 5~3〇μηι. Further, in the case of using an aqueous solution of a polyamino acid crosslinked body, it is preferred that the average particle diameter is 〇.1 ρ or more. If it is a particle size outside the range, when the composition is used as a cosmetic, the graininess remains, and a good feeling of use and an appropriate viscosity cannot be obtained. The flat particle L was measured by a laser particle size distribution analyzer (manufactured by Seishin Co., Ltd., 140609.doc 201012482, LMS-30) using the diffraction principle of Fraunhofer.

此外’本發明中用於放射線交聯之聚胺基酸之分子量, 較好的是於凝膠過濾層析法之測定下為ι〇〜3_心之範 圍’就吸保濕性之觀點而言更好的是5(Κι_他。分子 量可藉由賴料溶解於純水中並直接進行㈣過滤分析而 測定。具體而言’將分子量已知之標準支鍵殿粉(昭和電 工製造)溶解於純水中而製備標準溶液,根據凝膠過遽中 之溶出時間與標準溶液之分子量而製作校正曲線之後,對 試料同樣地進行敎。試料之分子量可根據凝膠過滤曲線 中之峰值位置(溶出時間)而求得。 [天然兩分子] 作為用於本發明之增黏性組合物中之天然高分子,可舉 f天然多糖類、蛋自質及脂質等。就增黏效果之觀點而 言’尤其好的是使用天然多糖類。 天然多糖類中’作為植物系高分子,例如可舉出:阿拉 伯膠I蓍膠、半乳聚糖、古亞膠、刺槐豆膠、刺梧桐 膠、鹿角菜膠、果膠、瓊脂、棍樟籽(棍棹(marmelo))、海 藻膠(褐藻萃取物)、澱粉(米、玉米、馬鈴薯、小麥)、甘 草酸,作為微生物系高分子,例如可舉出:三仙膠、聚葡 萄糖、琥珀醯聚糖、支鏈澱粉等,作為動物系高分子,例 如可舉出:玻尿酸、硫酸黏多糖、栝樓仁酸、膠原蛋白、 酪蛋白、白蛋白、明膠等。 尤其自增黏效果之觀點而言’較好的是使用玻尿酸作為 天然多糖類。此處,用作天然多糖類之玻尿酸並無特別限 140609.doc 201012482 定,但自增黏效果之觀點而言,較好的是使用分子量為工 萬以上之玻尿酸,更好的是使用分子量為50萬以上之玻尿 酸’進而好的是使用分子量為100萬以上之玻尿酸。 [本組合物] 為了構成本發明之增黏性組合物,較好的是於將聚胺基 酸類父聯體設為10 0質量份時,以〇. 〇 1質量份以上之比例 調配天然多糖類等。藉由於該範圍内調配聚胺基酸類交聯 體與天然高分子’可有效獲得增黏效果。此處,考慮到增 黏效果’較好的是將天然高分子之調配比例設為001質量 瘳 份以上。若天然高分子之調配比例未滿〇〇 i質量份,則無 法獲得聚胺基酸類交聯體與天然高分子之相乘效果,增黏 性未提高。考慮到增黏效果’天然高分子之調配比例較好 的是1質量份以上、100質量份以下。 又’於實際使用本發明之增黏性組合物時,可預先決定 如8型黏度計(轉子N〇.4 ’ 6 rpm,25。〇)之聚胺基酸類交聯 體(早獨)之黏度成為0.1〜1〇〇 pa.s之範圍之條件A,同樣 地’亦預先決定如天然多糖類等天然高分子(單獨)之黏度 ❿ 成為0.01〜1〇〇 Pa.s之範圍之條件B。並且,藉由以同時滿 足條件A與條件b之比例來調配聚胺基酸類交聯體與天然 南分子’可較好地製造黏度為1 Pa.s以上之高黏度液體。 若聚胺基酸類交聯體及天然高分子(天然多糖類等)之黏度 · 為不滿足上述條件A或條件B中之任一項之範圍,則於調 配兩種成分之情形時,有變得無法獲得較好之使用感(無 作為化妝料之黏膩感)之虞。 140609.doc •10- 201012482 此處,為了進一步發揮本發明之增黏性組合物之效果, 可於使聚胺基酸類交聯並使聚胺基酸類交聯體交聯之後, 調配天然尚分子。藉由士在丨】 稭由如此之製造方法,可飛躍性地提高 所得混合液體之黏度。 [任意成分] >本組合物中’除上述之必需成分以外,在不損及本發明 效果之範圍内’可調配可於化妝料等之組合物中調配之其 他成分。 ' 例如可於本組合物中適當調配:液態石蠟、角鯊烷凡 士林等碳氫化合物類;澳洲胡桃油、橄欖油、羊毛脂等油 脂類;荷荷芭油、巴西棕櫚蠟、堪地里拉蠟(cande出la wax)等蝶U基聚硬氧烧、甲基苯基梦氧炫等聚石夕氧 類;辛醇、月桂醇、肉豆蔻醇、鯨蠟醇、膽固醇、植物固 醇等高級醇類;癸酸、肉豆蔻酸、棕櫚酸、硬脂酸、二十 二酸、羊毛脂脂肪酸、亞麻油酸、次亞麻油酸等高級脂肪 酸;聚乙二醇、甘油、〗,3_丁二醇、赤藻糖醇、山梨糖 醇、木糖醇、麥芽糖醇、黏多醣、玻尿酸、硫酸軟骨素、 甲殼素、殼聚糖等保濕劑;乙醇等低級醇;丁基羥基甲 苯、生育盼、植酸等抗氧化劑;苯甲酸、水揚酸、山梨 酸、對羥基苯甲酸烷基酯、六氣酚等抗菌劑等。 又,可於本組合物中調配:甘胺酸、丙胺酸、纈胺酸、 白胺酸、蘇胺酸、苯丙胺酸、酪胺酸、天冬胺酸、天冬醯 胺、麩醯胺、牛磺酸、精胺酸、組胺酸等胺基酸及該等之 鹼金屬鹽與鹽酸鹽;醯基肌胺酸(例如月桂醯肌胺酸鈉)、 140609.doc 201012482 楚胱甘肽;檸檬酸、蘋果酸、酒錢、乳酸等有機酸;維 生素A及其衍生物;維生素B6鹽酸鹽、維生素組棕櫚酸 酯、維生素B6二辛酸醋 '維生素贮及其衍生物維生素 B12、維生素B15及其衍生物等維生素_ ;抗壞血酸抗 壞血酸硫酸酯(鹽)、抗壞血酸磷酸酯(鹽)、抗壞血酸二棕 櫊酸醋等維生素C類;《_生育盼、p_生育紛、mm、維 生素E醋酸鹽等維生素£類;維生素D類;維生素Η、泛 酸、泛硫乙胺等維生素類;於驗醢胺、终驗酸节醋、讀 維素、尿囊素、甘草酸(鹽)、甘草次酸及其衍生物、曰本 扁柏油、甜沒藥醇、桉樹油、瑞香草盼、肌醇、柴胡皂 "蔘44瓜皁苦、無患子皂芽等皂脊類;泛醇乙 醚乙块雌一醇、傳明酸、熊果芽、頭花千金藤驗、胎盤 :取物等各種藥劑;羊蹄、苦參、萍蓬草、橙子、鼠尾 卓二鋸葉草、錦葵、當藥、麝香草、當歸、橙皮、樺木、 ^刑絲瓜、七葉樹、虎耳草山金車、百合、艾草、芍 φ 薈、梔子、花柏等各種在溶劑中萃取出之天然萃取 和劑、抗氧化劑、色素、香料、純水等。 :::合物中,由於形成充分穩定之組合物故為了使 掛於太纟人 禾义需要調配界面活性劑。然而 妨礙口物’並不妨礙界面活性劑之調配。又,亦並非 妨礙马了其它·夕一 匕爻目的而調配界面活性劑者。 其:夕二本組合物中為了特意提高穩定性而調配或者為了 具他目的而可 當選擇如 =&之界面活性劑並無特別限定,例如可適 界面活性劑來調配:山梨糖醇酐單月桂酸酯、 140609.doc •12· 201012482 山梨糖醇酐單棕搁酸酯、山 _ Μ _ 糸糖醇酐倍半油酸酯、山梨糖 酵酐二油酸酯、聚氧乙烯 _ ^ ^ 银糖醇酐皁月桂酸酯、聚氧乙 二醇単油酸酯、聚氧乙烯燒基 丞吸眾乙一醇二脂肪酸酯、 月桂醯胺二乙醇醯胺、 曰肪酸—丙醇醯胺、麥芽糖醇羥基 脂肪族醚、烷基化多糖、焓 -土葡糖♦、糖醋、聚謎改質梦 酮等非離子界面活性劑 削,硬知醯二甲基氣化銨、氯化苯二 甲烴錄、月桂基氧化胺等陽離子界面活性劑;棕棚酸納、 月桂酸納、月桂基硫酸納、月桂基硫酸鉀、烷基硫酸三乙 醇胺、酿甲基牛魏鹽等陰離子界面活性劑;兩性界面活 性劑。Further, the molecular weight of the polyamino acid used for radiation crosslinking in the present invention is preferably in the range of ι〇~3_heart in the measurement by gel filtration chromatography. More preferably, it is 5 (Κι_他. The molecular weight can be determined by dissolving the raw material in pure water and directly performing (4) filtration analysis. Specifically, 'the standard molecular weight powder (manufactured by Showa Denko) having a known molecular weight is dissolved in The standard solution is prepared in pure water, and the calibration curve is prepared according to the elution time in the gel and the molecular weight of the standard solution, and the sample is similarly enthalpy. The molecular weight of the sample can be based on the peak position in the gel filtration curve (dissolution) [Natural two molecules] The natural polymer used in the thickening composition of the present invention may, for example, be a natural polysaccharide, an egg or a lipid, or the like. 'It is particularly preferable to use a natural polysaccharide. Among the natural polysaccharides, 'as a plant-based polymer, for example, gum arabic I guar gum, galactan, guar gum, locust bean gum, karaya gum, antlers Vegetable gum Pectin, agar, stick seed (marmelo), seaweed gum (hay algae extract), starch (rice, corn, potato, wheat), glycyrrhizic acid, as a microorganism-based polymer, for example, three Examples of the animal-based polymer include celery, polydextrose, amber sterol, amylopectin, and the like, and examples thereof include hyaluronic acid, sulfated polysaccharide, quercetin, collagen, casein, albumin, and gelatin. In particular, from the viewpoint of the viscosity-increasing effect, it is preferred to use hyaluronic acid as the natural polysaccharide. Here, the hyaluronic acid used as the natural polysaccharide is not particularly limited to 140609.doc 201012482, but from the viewpoint of the viscosity-increasing effect It is preferred to use a hyaluronic acid having a molecular weight of not more than 10,000, more preferably a hyaluronic acid having a molecular weight of 500,000 or more, and further preferably a hyaluronic acid having a molecular weight of 1,000,000 or more. [This composition] In order to constitute the present invention In the viscosity-increasing composition, it is preferred to formulate a natural polysaccharide or the like in a ratio of 质量. 〇1 part by mass or more when the polyamino acid-based parent complex is set to 100 parts by mass. It is effective to obtain a viscosity-increasing effect by blending a polyurethane-based crosslinked body with a natural polymer. Here, in consideration of the viscosity-increasing effect, it is preferable to set the ratio of the natural polymer to 001 mass or more. If the blending ratio of the natural polymer is less than 质量i by mass, the synergistic effect of the polyamino acid crosslinked body and the natural polymer cannot be obtained, and the viscosity increasing property is not improved. Considering the viscosity increasing effect 'natural polymer The blending ratio is preferably 1 part by mass or more and 100 parts by mass or less. Further, when the tackifying composition of the present invention is actually used, it is possible to predetermine, for example, an 8-type viscometer (rotor N〇.4 '6 rpm, 25 The viscosity of the polyamino acid crosslinked body (as early as possible) is a condition A in the range of 0.1 to 1 〇〇 pa.s, and similarly, a natural polymer such as a natural polysaccharide (individually) is also determined in advance. The viscosity ❿ becomes the condition B in the range of 0.01 to 1 〇〇Pa.s. Further, by mixing the polyamino acid crosslinked body and the natural south molecule at the same time to satisfy the ratio of the condition A to the condition b, a highly viscous liquid having a viscosity of 1 Pa.s or more can be preferably produced. If the viscosity of the polyamino acid crosslinked body and the natural polymer (natural polysaccharide, etc.) does not satisfy the range of any of the above conditions A or B, the case may be changed when the two components are blended. It is impossible to obtain a good feeling of use (no sticky feeling as a cosmetic material). 140609.doc •10-201012482 Here, in order to further exert the effect of the tackifying composition of the present invention, the natural molecules can be formulated after cross-linking the polyamino acid and crosslinking the polyamino acid cross-linking body. . By using this method, the viscosity of the resulting mixed liquid can be dramatically improved. [Optional component] > In the present composition, in addition to the above-mentioned essential components, other components which can be formulated in a composition such as a cosmetic can be blended in a range which does not impair the effects of the present invention. ' For example, it can be appropriately formulated in the present composition: hydrocarbons such as liquid paraffin and squalane petroleum jelly; oils such as Australian walnut oil, olive oil and lanolin; jojoba oil, carnauba wax and canary wax (cande la wax) and other butterfly U-based polyoxygen burning, methyl phenyl oxyxan and other polyoxanthoxy; octanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, cholesterol, plant sterol and other advanced Alcohols; higher fatty acids such as citric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lanolin fatty acid, linoleic acid, linoleic acid; polyethylene glycol, glycerin, 〗 〖 Diglyceride, erythritol, sorbitol, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, chitin, chitosan and other humectants; lower alcohol such as ethanol; butyl hydroxy toluene, fertility Antioxidants such as phytic acid; antibacterial agents such as benzoic acid, salicylic acid, sorbic acid, alkyl p-hydroxybenzoate, and hexa-phenol. Moreover, it can be formulated in the composition: glycine, alanine, valine, leucine, sulphate, phenylalanine, tyrosine, aspartic acid, aspartame, glutamine, Amino acids such as taurine, arginine, histidine, and the alkali metal salts and hydrochlorides; thiocreatinine (eg, sodium laurate), 140609.doc 201012482 chytripeptide ; citric acid, malic acid, alcohol, lactic acid and other organic acids; vitamin A and its derivatives; vitamin B6 hydrochloride, vitamin palmitate, vitamin B6 dioctanoate vinegar 'vitamin storage and its derivatives vitamin B12, vitamin B15 And its derivatives and other vitamins _; ascorbyl ascorbyl sulfate (salt), ascorbyl phosphate (salt), ascorbic acid, palmitic acid vinegar and other vitamin C; "_ fertility, p_ fertility, mm, vitamin E acetate Such as vitamins; vitamin D; vitamins, pantothenic acid, pantethine and other vitamins; in the test of guanamine, final acid vinegar, reading vitamins, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid And its derivatives, sputum tar, sweet myrrh, Tree oil, thyme hope, inositol, saikosapon soap " 蔘44 melon bitter, sapindus soap scent and other soap ridges; panthenol ether b block estradiol, tranexamic acid, bear fruit bud, head flower Qianjin Teng, Placenta: a variety of medicines such as extracts; sheep's hoof, sophora, fluster, orange, rat tail, sawmill, mallow, medicine, thyme, angelica, orange peel, birch, squash, horse chestnut, horse chestnut, Saussurea chinensis, lily, wormwood, 芍 栀, 栀子, cypress, and other natural extracts extracted from solvents, antioxidants, pigments, spices, pure water, etc. In the ::: compound, since a sufficiently stable composition is formed, it is necessary to formulate a surfactant in order to hang on the Taiyi people. However, obstructing the mouth does not interfere with the formulation of the surfactant. Moreover, it is not the case that the surfactant is formulated to interfere with other things. It is not particularly limited in the composition of the present invention for the purpose of intentionally improving the stability or for the purpose of selecting a surfactant such as = & the surfactant may be formulated with a suitable surfactant: sorbitan Monolaurate, 140609.doc •12· 201012482 sorbitan monopalmitate, _ _ _ sucrose anhydride sesquioleate, sorbitan dioleate, polyoxyethylene _ ^ ^ Silver saponin soap laurate, polyoxyethylene glycol oleate, polyoxyethylene sulphonate, succinyl alcohol fatty acid ester, lauric acid diethanol decylamine, fatty acid - propanol oxime Amine, maltitol hydroxy aliphatic ether, alkylated polysaccharide, strontium-sucking sugar ♦, sweet and sour vinegar, non-mystery modified ketone and other non-ionic surfactants, hard know 醯 dimethyl carbamide, chlorination Cationic surfactants such as benzoic acid, lauryl amine oxide; anionic interfaces such as sodium sulphate, sodium laurate, sodium lauryl sulfate, potassium lauryl sulfate, triethanolamine alkyl sulfate, and methyl bovine Wei salt Active agent; amphoteric surfactant.

將本組合物用作化妝料之情形時,適宜作為例如皮膚化 妝料、臉部化妝料及毛髮化妝料等。本組合物之劑型並無 特別限定’可採取任意之劑型。於將本組合物用於例如皮 膚化妝料之情形時,可與一般用作皮膚化妝料成分之界面 活性劑、油分、保濕劑、皮膜形成劑、油凝膠化劑、金屬 氧化物、有機紫外線吸收劑、無機金屬鹽類、有機金屬鹽 類、醇類、螯合劑、pH值調整劑、防腐劑、其他增黏劑、 藥效成分、色素、香料等添加劑成分任意組合調配。又, 亦可採取例如水溶液系、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(〇/w)型乳化化 妝料、水/油(W/0)型乳化化妝料等各種形態。再者,作為 具體之用途’可舉出乳霜、化妝乳液、化妝水、油性化妝 水、口紅、粉底、皮膚清潔劑等。 [實施例] 140609.doc •13· 201012482 其次,藉由實施例而進一步對本發明進行詳細說明。此 外,本發明並不限定於實施例之内容。 [實施例π 將γ-PGA交聯體(出光精密科技(Idemitsu Technofine)股 份有限公司製造,商品名:Gel Protein A-8002,平均粒徑 26·5 μιη)調配於純水中,以分別成為1.〇質量%及2.0質量% 之方式首先製備2種γ-ρ〇Α交聯體分散液。 繼而,將平均分子量不同之2種玻尿酸(ΗΑ)(紀文Food Chemifa股份有限公司製造,商品名:玻尿酸FCH120),混 合於上述2種γ-PGA交聯體分散液及純水中,製備表1所示 之12種試料液。然後使用B型黏度計(轉子No.4,6 rpm, 25°C )測定各試料液之黏度。將其結果示於表1中。各黏度 數值之右側之括號内表示相對於γ-PGA交聯體100質量份之 玻尿酸(ΗΑ)之各質量份。 再者’本實施形態中所使用之γ—PGA交聯體係藉由對分 子量70 kDa之聚-γ-麩胺酸進行丨4〇 kGy之電子束照射處理 而得者。 [表1] (試料液之黏度(Pa-S)) γ-PGA 0.0質量% γ-PGA 1.0質量% γ-PGA 2.0質量% HA 〇質量% 〇〇(-) 1.3(-) 14.1 ㈠ HA(分子量110萬)0.1質量% 〇·〇(-) 3.1(10質量份) 23.0(5質量份> HA(分子量200萬>0.1質量% 0.1(-) 6.2(1〇質量份) 28.1(5質量份) HA(分子量200萬)0.2質量% 0.3(-) 11.6(20質量份) 37.6(10質量份) 140609.doc 201012482 根據表1之結果,若為單獨之y_pga交聯體,則即使提 尚八、辰又亦未明顯看出黏度之增加。又,玻尿酸單獨之 清形亦相/¾ 使增加其量亦未明顯看出黏度之增加。然 而,於混合有該等雙方之試料液之情形時,可明顯看出黏 度之增加,從而可知γ-ρ〇Α交聯體與玻尿酸起相乘作用。 又藉由增大玻尿酸之平均分子量,或增多相對於丫_ PGA父聯體1〇〇質量份之調配量,可獲得更顯著之增黏效 果。 此外,對將調配有γ-PGA交聯體與玻尿酸之組合物用作 化妝料之情形時之使用感進行確認,結果:與單獨之γ_ PGA交聯體或單獨之玻尿酸之情形時的組合物相比較,不 僅對鬆他及敵紋之改善效果優異’並且具有充分之保濕效 果,無黏腻感且對皮膚之抹勻性良好。 [實施例2] 將與實施例1所使用之γ-PGA交聯體相同者混合於純水 中,以分別成為0.5質量%、1 ·〇質量%及2.〇質量%之方式製 備3種γ-PGA交聯體分散液。 繼而,將三仙膠(XG)(曰清〇iiii〇製造,商品名:Nomcort ZZ)混合於上述3種γ-PGA交聯體分散液及純水中,製備表 2所示之12種試料液。然後以與實施例1相同之方式測定出 各試料液之黏度。將其結果不於表2中。各黏度數值之右 侧之括號内表示相對於γ-PGA交聯體1〇〇質量份之三仙膠 (XG)之各質量份。 140609.doc -15- 201012482 [表2] 試料液之黏度(Pa-s)) γ-PGA 0.0質量% γ-PGA 0.5質量% γ-PGA 1.0質量% γ-PGA 2.0質量% 叉〇〇.〇質量% 〇·〇(-) 0.0(-) 1.3(-) 14.1 ㈠ 叉〇0.1質量% 0.1(-) 1.5(20質量份) 7.9(10質量份) 31.4(5質量份) 乂6 0.5質量% 4.9(-) 22.1(100質量份> 36.5(50質量份) 66.6(25質量份) 根據表2之結果可知,若為單獨之γ-PGA交聯體或單獨 之三仙膠,則即使提高其濃度,亦未明顯看出黏度之增 加。然而,於調配有三仙膠與γ-PGA交聯體雙方之試料液 之情形時,可明顯看出黏度之增加,從而可知γ-PGA交聯 體與三仙膠起相乘作用。 又,對將調配有γ-PGA交聯體與三仙膠之組合物用作化 妝料之情形時之使用感進行確認,結果:與單獨之γ-PGA 交聯體之情形時之組合物相比較,不僅對鬆弛及皺紋之改 善效果優異,並且具有充分之保濕效果,無黏膩感且對皮 膚之抹勻性良好。 [實施例3] 將與實施例1所使用之γ-PGA交聯體相同者混合於純水 中,以成為2.0質量%之方式製備1種γ-PGA交聯體分散 液。 繼而,將蛋白質(高研股份有限公司製造,製品名: Atelocollagen)混合於上述γ-PGA交聯體分散液及純水中, 製備表3所示之4種試料液。然後,以與實施例1相同之方 式測定各試料液之黏度。將其結果示於表3中。各黏度數 值之右側之括號内表示相對於γ-PGA交聯體100質量份之蛋 140609.doc -16· 201012482 白質之各質量份。 [表3]When the present composition is used as a cosmetic, it is suitably used as, for example, a skin cosmetic, a facial cosmetic, a hair cosmetic, and the like. The dosage form of the composition is not particularly limited, and any dosage form may be employed. When the composition is used in, for example, a skin cosmetic, it can be used as a surfactant, an oil component, a moisturizer, a film forming agent, an oil gelling agent, a metal oxide, or an organic ultraviolet ray which are generally used as a skin cosmetic component. Additives such as absorbents, inorganic metal salts, organic metal salts, alcohols, chelating agents, pH adjusters, preservatives, other tackifiers, medicinal ingredients, pigments, and perfumes are blended in any combination. Further, for example, an aqueous solution, a solubilized system, an emulsified system, a powder dispersion system, a water-oil two-layer system, a water-oil-powder three-layer system, an oil/water (〇/w) type emulsified cosmetic, and water may be used. / Oil (W / 0) type emulsion cosmetics and other forms. Further, as a specific use, a cream, a lotion, a lotion, an oily lotion, a lipstick, a foundation, a skin cleanser, and the like can be given. [Embodiment] 140609.doc • 13· 201012482 Next, the present invention will be further described in detail by way of examples. Further, the present invention is not limited to the contents of the embodiments. [Example π] γ-PGA crosslinked body (manufactured by Idemitsu Technofine Co., Ltd., trade name: Gel Protein A-8002, average particle diameter: 26.5 μm) was formulated in pure water to become 1. 〇 Mass % and 2.0% by mass First, two kinds of γ-ρ〇Α crosslinked body dispersions were prepared. Then, two kinds of hyaluronic acid (ΗΑ) (manufactured by Jiwen Food Chemifa Co., Ltd., trade name: hyaluronic acid FCH120) having different average molecular weights were mixed in the above two kinds of γ-PGA crosslinked dispersions and pure water to prepare Table 1 The 12 sample solutions shown. Then, the viscosity of each sample liquid was measured using a B-type viscometer (rotor No. 4, 6 rpm, 25 ° C). The results are shown in Table 1. The parentheses on the right side of each viscosity value indicate the respective parts by mass of hyaluronic acid (ΗΑ) with respect to 100 parts by mass of the γ-PGA crosslinked body. Further, the γ-PGA crosslinking system used in the present embodiment was obtained by subjecting a poly-γ-glutamic acid having a molecular weight of 70 kDa to electron beam irradiation treatment of 丨4 〇 kGy. [Table 1] (Viscosity of sample liquid (Pa-S)) γ-PGA 0.0% by mass γ-PGA 1.0% by mass γ-PGA 2.0% by mass HA 〇% by mass 〇〇(-) 1.3(-) 14.1 (I) HA ( Molecular weight: 1.1 million) 0.1% by mass 〇·〇(-) 3.1 (10 parts by mass) 23.0 (5 parts by mass) HA (molecular weight: 2 million > 0.1% by mass 0.1 (-) 6.2 (1 part by mass) 28.1 (5) Parts by mass) HA (molecular weight 2 million) 0.2% by mass 0.3 (-) 11.6 (20 parts by mass) 37.6 (10 parts by mass) 140609.doc 201012482 According to the results of Table 1, if it is a separate y_pga crosslinked body, even if Shang Ba and Chen did not clearly see the increase in viscosity. Moreover, the hyaluronic acid alone had a clear shape/3⁄4, so that the increase in the amount did not clearly show the increase in viscosity. However, in the case of mixing the sample liquids of the two sides In the case, it is obvious that the viscosity increases, so that the γ-ρ〇Α cross-linker is multiplied by hyaluronic acid, and by increasing the average molecular weight of hyaluronic acid, or increasing relative to the 丫_PGA parent complex. A more significant viscosity-increasing effect can be obtained by adjusting the amount of the 〇 mass. In addition, a composition in which a γ-PGA crosslinked body and hyaluronic acid are formulated is used as a cosmetic material. In the case of the use, the feeling of use was confirmed. As a result, compared with the composition of the γ_PGA crosslinked body alone or the hyaluronic acid alone, the effect of improving the pine and the enemy pattern was excellent, and the moisturizing effect was sufficient. It has no sticky feeling and is good to the skin. [Example 2] The same γ-PGA crosslinked body as used in Example 1 was mixed in pure water to have a mass ratio of 0.5% by mass, respectively. Three types of γ-PGA crosslinked dispersions were prepared in a manner of 〇 mass % and 2. 〇 mass %. Then, Sanxian gum (XG) (manufactured by 曰清〇iiii〇, trade name: Nomcort ZZ) was mixed in the above 3 The γ-PGA crosslinked dispersion and pure water were prepared, and 12 kinds of sample liquids shown in Table 2 were prepared. Then, the viscosity of each sample liquid was measured in the same manner as in Example 1. The results are not shown in Table 2. The parentheses on the right side of each viscosity value indicate the mass parts of the three masses (XG) with respect to 1 part by mass of the γ-PGA crosslinked body. 140609.doc -15- 201012482 [Table 2] Sample liquid Viscosity (Pa-s)) γ-PGA 0.0% by mass γ-PGA 0.5% by mass γ-PGA 1.0% by mass γ-PGA 2.0% by mass Fork 〇质量% 〇·〇(-) 0.0(-) 1.3(-) 14.1 (1) Fork 0.1% by mass 0.1(-) 1.5 (20 parts by mass) 7.9 (10 parts by mass) 31.4 (5 parts by mass) 乂6 0.5 Mass % 4.9 (-) 22.1 (100 parts by mass) 36.5 (50 parts by mass) 66.6 (25 parts by mass) According to the results of Table 2, it is understood that if it is a separate γ-PGA crosslinked body or a separate Sanxian gum, Even if the concentration is increased, the increase in viscosity is not apparent. However, in the case where the sample liquid of both the sacral gum and the γ-PGA crosslinked body was prepared, the increase in viscosity was apparent, and it was found that the γ-PGA crosslinked body was multiplied by the Sanxian gum. Further, the feeling of use in the case where a composition in which a γ-PGA crosslinked body and a sinica compound were blended was used as a cosmetic was confirmed, and as a result, a composition phase in the case of a crosslinked body of γ-PGA alone was used. In comparison, it not only has an excellent effect on the improvement of slack and wrinkles, but also has a sufficient moisturizing effect, a non-sticky feeling and a good smoothness to the skin. [Example 3] The same γ-PGA crosslinked body was used in the same manner as in the case of the γ-PGA crosslinked body used in Example 1, and a γ-PGA crosslinked dispersion was prepared in an amount of 2.0% by mass. Then, the protein (manufactured by Takahashi Co., Ltd., product name: Atelocollagen) was mixed in the above-mentioned γ-PGA crosslinked dispersion liquid and pure water to prepare four kinds of sample liquids shown in Table 3. Then, the viscosity of each sample liquid was measured in the same manner as in Example 1. The results are shown in Table 3. The parentheses on the right side of each viscosity number indicate the mass parts of the white matter with respect to 100 parts by mass of the γ-PGA crosslinked body 140609.doc -16· 201012482. [table 3]

f料液之黏度(PaW γ-PGA 0·0質量% γ-PGA 2.0質量% 27/7(15質量份) 白質0·0質量% ll·白質0.3質量。/〇 據表3之結果可知,若為單獨之γ-PGA交聯體或單獨 • 之蛋白質,則即使提高其濃度,亦未明顯看出黏度之增 加。然而’於調配有蛋白質與γ·Ρ(}Α交聯體雙方之試料液 之情形時,可明顯看出黏度之增加,從而可知γ-PGA交聯 體與蛋白質起相乘作用。 又,對將調配有γ-PGA交聯體與蛋白質之組合物用作化 ^料之It形時之使用感進行確認,結果:與單獨之 交聯體之情形時之組合物相比較,不僅對鬆他及敏紋之改 果優異,並且具有充分之保濕效果,無黏腻感且對皮 φ 膚之抹勻性良好。 [實施例4] .將與實施例1所使用々_PGA交聯體相同者混合於純水 :’以成為2.0質量%之方式製備,_pGA交聯體分散 繼而,將脂質(日油股份有限公司製造,商〇名· Lip^dure)混合於上述尸PGA交聯體分散液及純水中製備 f 4所示之4種試料液。然後,以與實施例丨相同之方式调 定各試料液之黏度。將其結果示於表4中。各黏度數 140609.doc •17- 201012482 右側之括號内表示相對於γ-PGA交聯體100質量份之脂質之 各質量份。 [表4] (試料液之黏度(Pa-s)) γ-PGA 〇.〇質量% γ-PGA 2.0質量% 脂質〇.〇質量% 0·0(-) 12.1(-) 脂質1.0質量% 0.0㈠ 21.2(50質量份) 根據表4之結果可知,若為單獨之γ-PGA交聯體或單獨 之脂質,則即使提高其濃度,亦未明顯看出黏度之增加。 然而,於調配有脂質與γ-PGA交聯體雙方之試料液之情形 時,可明顯看出黏度之增加,從而可知γ-PGA交聯體與脂 質起相乘作用。 又,對將調配有γ-PGA交聯體與脂質之組合物用作化妝 料之情形時之使用感進行確認,結果:與單獨之γ-PGA交 聯體之情形時之組合物相比較,不僅對鬆弛及皺紋之改善 效果優異,並且具有充分之保濕效果,無黏膩感且對皮膚 之抹勻性良好。 140609.doc 18-f Viscosity of the liquid (PaW γ-PGA 0·0% by mass γ-PGA 2.0% by mass 27/7 (15 parts by mass) White matter 0·0% by mass ll· White matter 0.3 mass. / According to the results of Table 3, In the case of a single γ-PGA crosslinked body or a separate protein, even if the concentration is increased, the increase in viscosity is not apparent. However, the sample containing both the protein and the γ·Ρ(}Α crosslinked body is prepared. In the case of liquid, the increase in viscosity is apparent, so that the γ-PGA cross-linker is multiplied by the protein. Further, the composition in which the γ-PGA cross-linked body and protein are formulated is used as a chemical material. It was confirmed by the feeling of use in the shape of It, and as a result, compared with the composition in the case of the single crosslinked body, not only the modified fruit of the pine and the sensitive grain was excellent, but also had a sufficient moisturizing effect and no sticky feeling. Moreover, it was excellent in the smoothness of the skin of the skin. [Example 4] The same as the 々_PGA crosslinked body used in Example 1 was mixed with pure water: 'prepared in a manner of 2.0% by mass, _pGA crosslinked Body dispersion, followed by mixing lipids (made by Nippon Oil Co., Ltd., 〇 〇 Name · Lip^dure) in the above-mentioned cadaver PGA Four kinds of sample liquids shown by f 4 were prepared in the crosslinked body dispersion liquid and pure water. Then, the viscosity of each sample liquid was adjusted in the same manner as in Example 。. The results are shown in Table 4. 140609.doc •17- 201012482 The parentheses on the right side indicate the mass parts of the lipid relative to 100 parts by mass of the γ-PGA crosslinked body. [Table 4] (Viscosity of the sample solution (Pa-s)) γ-PGA 〇. 〇% by mass γ-PGA 2.0% by mass Lipid 〇.〇% by mass 0·0(-) 12.1(-) Lipid 1.0% by mass 0.0 (1) 21.2 (50 parts by mass) According to the results of Table 4, if it is a single γ- PGA cross-linking or lipid alone, even if the concentration is increased, the viscosity is not clearly observed. However, when the sample liquid having both the lipid and the γ-PGA cross-linking body is prepared, the viscosity is clearly observed. In addition, it was found that the γ-PGA crosslinked body was multiplied by the lipid. Further, the feeling of use when the composition in which the γ-PGA crosslinked body and the lipid were formulated was used as a cosmetic was confirmed. Compared with the composition of the γ-PGA crosslinked body alone, it not only improves the relaxation and wrinkles Different, and it has sufficient moisturizing effect, non-stickiness and good to help spread the skin. 140609.doc 18-

Claims (1)

201012482 七、申請專利範圍: 種增黏性組合物,其特徵在於:其係將聚胺基酸類交 聯體與天然高分子調配而成。 2·如°月求項1之增黏性組合物,其中上述天然高分子為天 然多糖類。 3.如明求項2之增黏性組合物,《中上述天然多糖類為玻 尿酸15201012482 VII. Patent application scope: A kind of viscosity-increasing composition, which is characterized in that it is prepared by blending a polyamino acid crosslinked body with a natural polymer. 2. The viscosity-increasing composition of claim 1, wherein the natural polymer is a natural polysaccharide. 3. The viscosity-increasing composition of claim 2, wherein the above natural polysaccharide is hyaluronic acid 15 月求項1之增黏性組合物,其係相對於上述聚胺基酸 類交聯體之調配量刚質量份,調配上述天然高分子0.01 質量伤以'上而成者。 如叫求項2之增黏性組合物,其係相對於上述聚胺基酸 _交聯體之調配量1GG質量份,調配上述天然高分子0.01 質量份以上而成者。 如叫求項3之增黏性組合物,其係相對於上述聚胺基酸 类員交聯體之調配量1〇〇質量份,調配上述天然高分子〇 〇1 質量份以上而成者。 7 青求項1至6中任-項之增黏性組合物’其中上述聚胺 基酸類交聯體為聚个麩胺酸或其鹽。 8 · 如請求項1 5 < 士 / 甲任一項之增黏性組合物,其中上述聚胺 基酸類交聯體係分子量為10〜3000 kDa之聚胺基酸類之 放射線交聯體。 用求項7之增黏性組合物,其中上述聚胺基酸類交聯 體係刀子X為10〜3000 kDa之聚胺基酸類之放射線交聯 體。 140609.doc 201012482 ίο. 11. 12. 13. 14. 请求項1至6中任一項之增黏性組合物,其中上述聚胺 基酸類交聯體之平均粒徑為〇μιη。 如請求項7之增黏性組合物 體之平均粒徑為0.U00 μΓη 如》s求項8之增黏性組合物 體之平均粒徑為0.1〜300 μιη 如清求項9之增黏性組合物 體之平均粒徑為〇1〜3〇〇μιη 一種增勒性組合物之製造方 酸類交聯而製作聚胺基酸類 子0 ’其中上述聚胺基酸類交聯 〇 ’其中上述聚胺基酸類交聯 0 ’其中上述聚胺基酸類交聯 0 法’其特徵在於:使聚胺基 交聯體之後,調配天然高分 140609.doc 201012482 四、指定代表圖: (一) 本案指定代表圖為:(無) (二) 本代表圖之元件符號簡單說明: 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式:The tackifying composition of the item 1 of the present invention is prepared by blending the above-mentioned natural polymer with 0.01 mass of the above-mentioned natural polymer with respect to the amount of the above-mentioned polyamino acid crosslinked body. The tackifying composition of claim 2 is prepared by blending the above-mentioned natural polymer with 0.01 parts by mass or more with respect to 1 GG parts by mass of the above-mentioned polyamino acid-crosslinking body. The tackifying composition of the above-mentioned item 3 is prepared by blending the above-mentioned natural polymer 〇 〇 1 part by mass or more with respect to the above-mentioned polyamino acid-based cross-linking compound. (7) The tackifying composition of any one of Items 1 to 6, wherein the polyamino acid crosslinked body is a polyglutamic acid or a salt thereof. The adhesion-promoting composition according to any one of claims 1 to 5, wherein the polyamino acid crosslinking system has a molecular weight of 10 to 3000 kDa of a polyamine-based radiation crosslinked body. The adhesion-promoting composition of claim 7, wherein the polyamino acid crosslinking system knife X is a radiation crosslinker of a polyamino acid of 10 to 3000 kDa. The viscosifying composition according to any one of claims 1 to 6, wherein the polyamino acid crosslinked body has an average particle diameter of 〇μηη. The average particle diameter of the viscosity-increasing composite object of claim 7 is 0. U00 μΓη such as the average particle diameter of the viscosity-increasing composite object of the item 8 is 0.1 to 300 μιη, such as the viscosity-increasing combination of the item 9 The average particle diameter of the object is 〇1~3〇〇μιη. The squaric acid cross-linking of a reinforced composition produces a polyamino acid group 0' wherein the polyamino acid cross-linking 〇' wherein the polyamino acid Cross-linking 0 'the above-mentioned polyamino acid cross-linking 0 method' is characterized by: after the polyamine-based cross-linking body, the natural high score is adjusted 140609.doc 201012482 IV. Designated representative figure: (1) The representative representative figure of the case is :(None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (無)(no) 140609.doc140609.doc
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