JP2008061532A - Hydrous gel sheet, method for producing the same and applications thereof - Google Patents
Hydrous gel sheet, method for producing the same and applications thereof Download PDFInfo
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本発明は、微生物セルロースによる含水ゲルシートを、空気とよく接触する培養により連続的に製造する方法及び得られた含水ゲルシートに関する。
さらに詳しくは、本発明は、吸水シートに含水ゲルを生成せしめてスライス法では得られない短時間で含水ゲルシートを製造する方法、及び得られた該ゲルシートの自由水を化粧液と置換して含浸化粧料の取扱い性と肌への密着性に優れたシート状化粧パック材とその製造方法に関する。
The present invention relates to a method for continuously producing a hydrated gel sheet made of microbial cellulose by culturing in good contact with air and the obtained hydrated gel sheet.
More specifically, the present invention relates to a method for producing a water-containing gel sheet in a short time that cannot be obtained by a slicing method by generating a water-containing gel on a water-absorbing sheet, and impregnating the resulting free water of the gel sheet with a cosmetic liquid. The present invention relates to a sheet-type cosmetic pack material excellent in handling properties of cosmetics and adhesion to skin, and a method for producing the same.
従来、含水ゲルによるシート状パック材に関する数多くの改良技術が提案されている。例えば、特開昭５８−１８０４０８号公報に、ポリアクリル酸、及びその塩と水、架橋剤を成分とする含水ゲルによるシート状パック材があり、特開平６−３２１７３３号公報には、β−１，３−グルカンをアルカリ溶液に溶解してゲル皮膜を生成させ、水洗、乾燥して、乾燥シートに化粧液を含浸したシート状パック材がある。これらのゲルシートは引張強度が弱くて取扱い性が悪いこと、化粧料成分がゲル体に包接のように包み込まれて滲出し難い問題があった。
一方、アセトバクター属の菌により微生物セルロースが産生されることは、１８８６年にブラウン氏の報告があり、微生物セルロースによるゲル体はナタデココとして古くから知られていて特開平０７−０５９５２３号公報、特開平０７−０７９７９７号公報にも可食性ゲル体が記載されているがシート状パック材の新規の素材としても注目される。
Conventionally, many improvement techniques regarding a sheet-like pack material using a hydrous gel have been proposed. For example, Japanese Patent Application Laid-Open No. 58-180408 discloses a sheet-like pack material made of a hydrogel containing polyacrylic acid and a salt thereof, water, and a crosslinking agent, and Japanese Patent Application Laid-Open No. 6-321733 discloses β- There is a sheet-like pack material in which 1,3-glucan is dissolved in an alkaline solution to form a gel film, washed with water and dried, and a dry sheet is impregnated with a cosmetic liquid. These gel sheets have a problem that the tensile strength is weak and the handleability is poor, and the cosmetic ingredients are wrapped in the gel body like a clathrate and difficult to exude.
On the other hand, the production of microbial cellulose by bacteria of the genus Acetobacter was reported by Mr. Brown in 1886, and the gel body made of microbial cellulose has long been known as Nata de Coco and is disclosed in JP-A-07-059523. Kaihei 07-079797 discloses an edible gel body, but is also attracting attention as a new material for a sheet-like pack material.
微生物セルロースの原料として使用するナタデココのゲル構造は、ナノセルロース繊維の網目構造を有するもので、親水性高分子に基づくゲル体と疑似物性を示す。微生物セルロースによるゲル体は、一般に乾燥によるナノセルロースが収束して太くなり、網目構造の変化によりゲル復元性が悪くなるのが普通である。
そこで、ゲル復元性を高める方法として、従来、ゲルを粉砕して水溶性安定剤として、グルコース、フラクトース、シュークロース、デンプン、食塩、重曹、乳酸、クエン酸、リン酸、酒石酸、グルタミン酸又はアスパラギン酸より選ばれたものを用いることが提案された。
The gel structure of Nata de Coco used as a raw material of microbial cellulose has a network structure of nanocellulose fibers, and shows a gel body and pseudo physical properties based on a hydrophilic polymer. In general, gel bodies made of microbial cellulose are generally thickened by drying of nanocellulose due to drying, and the gel restoration properties are usually deteriorated due to changes in the network structure.
Therefore, conventionally, as a method for improving the gel recovery property, the gel is crushed and used as a water-soluble stabilizer. It was proposed to use more selected ones.
しかし、乾燥シートに有効なゲル復元剤については未だ知られておらず、特開２００２−１４２７９６号公報では、生体高分子による配向を有する基板上で培養して微生物セルロースを産生し、基板の分子の配向に沿った配向性の高い微生物セルロース膜を産生する方法が示されているが、この方法は、基板の配向をレプリカ式に移し採るセルロース膜の製造であって、本発明の目的とするような培養液に吸水性シートを連続的に浸漬して好気性の培養を行って、含水ゲルを連続的に生成する方法ではない。 However, an effective gel restoring agent for a dry sheet is not yet known. In Japanese Patent Application Laid-Open No. 2002-142996, microbial cellulose is produced by culturing on a substrate having an orientation by a biopolymer, and the molecules of the substrate Although a method for producing a highly oriented microbial cellulose film along the orientation of the substrate is shown, this method is a production of a cellulose film in which the orientation of the substrate is transferred in a replica manner, and is an object of the present invention. This is not a method of continuously generating a hydrous gel by immersing a water-absorbent sheet continuously in such a culture solution to perform aerobic culture.
従来、ナタデココのような微生物セルロースから、公知の静置培養によって含水ゲルを製造する代表的は方法としては、静置培養によって得られた微生物セルロースの含水ゲル体を形成した後、これをスライスするという、いわゆるスライス法しかなかった。
このスライス法によれば、１８〜２０mmの厚さの含水ゲル体を得るのに１２〜１３日を要する上に、ゲル体をスライスする手数がかかり、しかも薄い均一厚さのシートを得ることは不可能であり、特に厚さ３mm以下のシートを得ることは如何に鋭敏な刃のスライス形成装置を使用しても無理であった。一方、ゲルシートの厚さは、好ましくは２mm以下、さらに好ましくは１mm以下のものが求められており、仮に厚さ３mmのゲルシートを圧縮して厚さ１mm以下にしても、化粧液を注液することにより、元の３mmに戻す工程が必要であった。
また、従来の静置培養法によって得られた含水ゲルシートは、時間経過と共に一般細菌が増殖するので、衛生面の安全を保つことが難しいという問題があった。
そこで、本発明は、公知の静置培養法を採用してもスライスする必要が無く、薄い均一厚さのシートを得るが可能となり、圧縮することもなく、３mm以下の含水シートを容易に製造する方法を提供する。
Conventionally, as a typical method for producing a hydrogel from microbial cellulose such as Nata de Coco by known static culture, a hydrated gel body of microbial cellulose obtained by static culture is formed and then sliced. There was only a so-called slicing method.
According to this slicing method, it takes 12 to 13 days to obtain a water-containing gel body having a thickness of 18 to 20 mm, and it takes time and effort to slice the gel body, and a sheet having a thin uniform thickness is obtained. In particular, it was impossible to obtain a sheet having a thickness of 3 mm or less, no matter how sharp the blade slicing apparatus was used. On the other hand, the thickness of the gel sheet is preferably 2 mm or less, more preferably 1 mm or less. Even if the gel sheet having a thickness of 3 mm is compressed to a thickness of 1 mm or less, the cosmetic liquid is injected. Therefore, a process of returning to the original 3 mm was necessary.
In addition, the water-containing gel sheet obtained by the conventional static culture method has a problem that it is difficult to keep hygienic safety because general bacteria grow over time.
Therefore, the present invention does not require slicing even if a known static culture method is adopted, and a sheet having a thin uniform thickness can be obtained, and a hydrous sheet having a thickness of 3 mm or less can be easily produced without compression. Provide a way to do it.
本発明では、培養液に吸水性シートを連続的に浸漬又は含浸して、空気とよく接触する培養を行い、アセトバクター菌は好気性菌であるから活性化されて効率よく含水ゲルシートが得られる。
本発明で得られた含水ゲルシートは、薄い均一厚さのものが可能で、３mm以下、必要に応じて２mm以下、さらに必要であれば、１mm以下のものが容易に得られる。
In the present invention, the water-absorbent sheet is continuously immersed or impregnated in the culture solution, and the culture is performed in good contact with air. Since Acetobacter is an aerobic bacterium, it is activated and a hydrous gel sheet can be obtained efficiently. .
The water-containing gel sheet obtained in the present invention can have a thin and uniform thickness, and can easily be obtained with a thickness of 3 mm or less, 2 mm or less as required, and 1 mm or less if necessary.
すなわち、本発明では、以下の構成を基本として上記の課題を解決したものである。
（１）微生物により微生物セルロースを産生する培養液に、吸水性シートを浸漬する培養によって含水ゲルシートを製造する方法。
（２）上記培養液が、酢酸でｐH３〜５に調整したココナッツ水にスクロースを溶解した培地に好気性のアセトバクター・キシリナムを植菌して得られた配合液であることを特徴とする（１）に記載の含水ゲルシートの製造方法。
なお、本発明では、培養液のｐH調整は、本発明に用いるアセトバクター菌は酢酸菌を好むので、酢酸を使用するのがよい。
（３）上記培養が、吸水性シートを培養液に浸漬と引上げを繰り返す培養であることを特徴とする（１）又は（２）に記載の含水ゲルシートの製造方法。
（４）上記培養が、吸水性を有する多孔質の合成樹脂シート、不織布、織物、編物又は紙より選ばれた吸水性シートを用いた培養であることを特徴とする上記（１）〜（３）のいずれかに記載の含水ゲルシートの製造方法。
（５）上記培養が、吸水性シートの両面又は片面に含水ゲルを生成する培養であることを特徴とする（１）〜（４）のいずれかに記載の含水ゲルシートの製造方法。
（６）上記培養が、ループ状にした吸水性シートを培養液に浸漬するエンドレス回転による培養であることを特徴とする（１）〜（５）のいずれかに記載の含水ゲルシートの製造方法。
（７）上記培養が、吸水性シートを２枚重ねで培養液に浸漬し、該２枚重ねのシートの両面に含水ゲルを生成せしめた後、２枚を分離して吸水性シートのそれぞれの片面に含水ゲルを生成する培養であることを特徴とする(１)〜（５）のいずれかに記載の含水ゲルシートの製造方法。
（８）上記（１）〜（７）のいずれかに記載の方法により製造された含水ゲルシート。
（９）上記（１）〜（７）のいずれかに記載の方法による含水ゲルシートが含有する自由水を、脱水又は乾燥により２０重量％以上を除いた後、化粧液を含浸することを特徴とするシート状パック材の製造方法。
（１０）自由水が、ＨＬＢ１０以上の親水性非イオン界面活性剤又は／及び糖アルコールの少なくとも１種以上を含む水溶液であることを特徴とする（９）に記載のシート状パック剤の製造方法。
（１１）上記自由水を脱水又は乾燥により２０重量％以上を除いた後、冷蔵又は冷凍保管し、次いで化粧液を注液することを特徴とするシート状パック材の製造方法。
（１２）上記冷蔵又は冷凍保管が、０〜１０℃でおこなうことを特徴とする（１０）に記載のシート状パック材の製造方法。
（１３）上記（９）〜（１２）のいずれかに記載の方法により製造されたシート状化粧用パック材。
That is, in the present invention, the above-described problems are solved based on the following configuration.
(1) A method for producing a hydrogel sheet by culturing a water-absorbing sheet in a culture solution that produces microbial cellulose by microorganisms.
(2) The culture solution is a mixed solution obtained by inoculating aerobic Acetobacter xylinum in a medium in which sucrose is dissolved in coconut water adjusted to pH 3 to 5 with acetic acid ( The manufacturing method of the hydrogel sheet as described in 1).
In the present invention, the pH adjustment of the culture solution is preferably carried out using acetic acid since the Acetobacter bacteria used in the present invention prefer acetic acid bacteria.
(3) The method for producing a water-containing gel sheet according to (1) or (2), wherein the culture is a culture in which the water-absorbent sheet is repeatedly immersed and pulled up in a culture solution.
(4) The above cultures (1) to (3), wherein the culture is a culture using a water-absorbent sheet selected from a porous synthetic resin sheet having a water absorption property, a nonwoven fabric, a woven fabric, a knitted fabric, or paper. ) A method for producing a hydrogel sheet according to any one of the above.
(5) The method for producing a water-containing gel sheet according to any one of (1) to (4), wherein the culture is a culture that generates a water-containing gel on both sides or one side of the water-absorbent sheet.
(6) The method for producing a hydrogel sheet according to any one of (1) to (5), wherein the culture is culture by endless rotation in which a looped water-absorbent sheet is immersed in a culture solution.
(7) The above culture is performed by immersing two water-absorbing sheets in a culture solution and forming a hydrous gel on both surfaces of the two-layered sheets. The method for producing a water-containing gel sheet according to any one of (1) to (5), wherein the water-containing gel is cultured on one side.
(8) A hydrogel sheet produced by the method according to any one of (1) to (7) above.
(9) The free water contained in the water-containing gel sheet according to any one of the above (1) to (7) is impregnated with a cosmetic liquid after removing 20% by weight or more by dehydration or drying. The manufacturing method of the sheet-like pack material to perform.
(10) The method for producing a sheet-like pack according to (9), wherein the free water is an aqueous solution containing at least one kind of hydrophilic nonionic surfactant having HLB of 10 or higher and / or sugar alcohol. .
(11) A method for producing a sheet-shaped pack material, wherein the free water is removed by dehydration or drying to remove 20% by weight or more, then refrigerated or frozen, and then a cosmetic liquid is injected.
(12) The method for producing a sheet-like pack material according to (10), wherein the refrigeration or the freezing storage is performed at 0 to 10 ° C.
(13) A sheet-like cosmetic pack produced by the method according to any one of (9) to (12).
本発明において、微生物セルロースを産生する培養液に植菌する菌株には、Acetobacter属、Rhizobium属、Agrobactcrium属、Sarcina属、Achromobacter属、Alcaligenes属等が知られているが、本発明では、特にAcetobacter属のAcetobacter xylinumを用いる。
用いるAcetobacter xylinumとしては、ATCC１０８２１、ATCC３１１７４、ATCC２３７６８、ATCC２３７６９、ATCC１４８５１、ATCC１１１４２、ATCC１１１７２、IFO０３２８８、IFO１３７７２、等がある。
In the present invention, Acetobacter genus, Rhizobium genus, Agrobactcrium genus, Sarcina genus, Achromobacter genus, Alcaligenes genus, and the like are known as strains to be inoculated in a culture solution producing microbial cellulose. Use the genus Acetobacter xylinum.
Examples of Acetobacter xylinum to be used include ATCC 10821, ATCC 31174, ATCC 23768, ATCC 23769, ATCC 14851, ATCC 11142, ATCC 11172, IFO03288, IFO13777, and the like.
上記菌株を用いるには、微生物セルロースを産生する培養液、特に酢酸のような有機カルボン酸を用いてｐH３〜５に調整したココナッツ水にスクロースを溶解した培地に対して、上記Acetobacter xylinuのような菌株を３〜８重量％を植菌するのが好ましい。菌株が、３重量％以下では、微生物セルロースの産生が不足するし、８重量％以上では、多過ぎて経済的に無駄となる。
本発明の培養液に用いるスクロースは、８〜２０重量％を用いるのが適当であり、８重量％以下では菌に栄養不足となり、微生物セルロース産生が少なく、２０重量％以上では、得られた含水ゲルシートが硬くなり、肌への密着性が低下する。
In order to use the above strain, a culture solution that produces microbial cellulose, particularly a medium in which sucrose is dissolved in coconut water adjusted to pH 3 to 5 using an organic carboxylic acid such as acetic acid, is used as in the above-mentioned Acetobacter xylinu. It is preferred to inoculate 3-8% by weight of the strain. If the strain is 3% by weight or less, the production of microbial cellulose is insufficient, and if it is 8% by weight or more, it is too much and is economically wasteful.
The sucrose used in the culture solution of the present invention is suitably used in an amount of 8 to 20% by weight. When the amount is 8% by weight or less, the microorganism is undernutrition, and the production of microbial cellulose is small. The gel sheet becomes hard and the adhesion to the skin decreases.
本発明における培養液を用いる培養及び浸漬は、２８〜３０℃の培養液の温度で、好気性を満たすように空気とよく接触するような条件で、吸水性シートを培養液に浸漬して引上げることを繰り返し行う。具体的には、丸網式抄紙法の丸網部分を半分以上液面上に設けた連続装置により、吸水性シートに浸漬と引上げを連続的に繰り返す方法、又は水車様の枠周に吸水性シートをループ状にしてエンドレスに固定し回転により浸漬と引き上げを繰り返し行う方法を行う。 Cultivation and immersion using the culture solution in the present invention are performed by immersing the water-absorbent sheet in the culture solution at a temperature of the culture solution of 28 to 30 ° C. under the condition of being in good contact with air so as to satisfy aerobic properties. Repeat to raise. Specifically, a continuous device in which more than half of the round net type papermaking method is provided on the liquid surface, a method of continuously dipping and pulling up on the water absorbent sheet, or water absorption on the periphery of a watermill-like frame. A method in which the sheet is looped and fixed endlessly and is repeatedly dipped and pulled up by rotation.
本発明では、微生物によるセルロースゲルの産生は、培養液にナタデココ由来の成分を含むものを使用するのが適当であるが、微生物セルロースゲル体を製造するには、具体的には、酢酸等のカルボン酸によりｐH３〜５に調整したココナッツ水に、スクロースを８〜２０重量％を溶解して培地として、セルロース産菌としてAcetobacter xylinum、特にATCC１０８２１を３〜８重量％植菌し、２８〜３０℃で１０〜１２日の静置培養により微生物セルロースゲルを生成する。 In the present invention, the production of cellulose gel by microorganisms is suitably performed using a culture solution containing a component derived from Nata de Coco. In order to produce a microbial cellulose gel body, specifically, acetic acid or the like is used. In coconut water adjusted to pH 3-5 with carboxylic acid, 8-20% by weight of sucrose is dissolved and used as a medium. Acetobacter xylinum, especially ATCC 10821, is inoculated as 3-8% by weight as a cellulosic bacterium, and 28-30 ° C. To produce a microbial cellulose gel by static culture for 10-12 days.
上記静置培養によって得られた微生物セルロースゲルは、洗浄・殺菌・除菌処理を施すが、洗浄処理は、酢酸が検出されなくなるまで充分に水洗をする。殺菌処理は、９５〜１００℃で２０〜３０分の熱湯処理でよい。除菌処理は、水酸化ナトリウム０．１％水溶液８０℃３０分の処理でアセトバクター菌を溶出して除去することができる。
本発明では、含水ゲル体の透明度をよくするには、エタノールを培地に添加して、ナノファイバーの分散性を高めることが効果的である。
また、過剰の水分は、遠心脱水により除去するとよい。吸着水の５０％未満を脱水するには、ゲル体のままでもよいが、細かく切断して、ホモミキサーにより離解して乾燥する方法が好ましい。乾燥は、温風乾燥機又は凍結乾燥機により自由水を全量脱水して、吸着水の脱水を５０％未満とするが、脱水の品質管理は重量測定により行う。
さらに、本発明で製造されたゲルシートは、−４０℃〜１０℃の温度で冷凍又は冷蔵保存により一般細菌の増殖を押さえ、含有水分の酸化還元電位の上昇を押さえることにより衛生面の安全を保つことができる。
The microbial cellulose gel obtained by the stationary culture is subjected to washing, sterilization and sterilization treatment. The washing treatment is sufficiently washed with water until no acetic acid is detected. The sterilization treatment may be hot water treatment at 95-100 ° C. for 20-30 minutes. The sterilization treatment can be performed by eluting and removing Acetobacter bacteria by treatment with a 0.1% aqueous solution of sodium hydroxide at 80 ° C. for 30 minutes.
In the present invention, in order to improve the transparency of the water-containing gel body, it is effective to add ethanol to the medium to enhance the dispersibility of the nanofibers.
Excess water may be removed by centrifugal dehydration. In order to dehydrate less than 50% of the adsorbed water, the gel body may be used as it is, but a method of cutting it finely, separating it with a homomixer and drying it is preferable. In drying, the entire amount of free water is dehydrated by a hot air drier or freeze drier so that the adsorbed water is dehydrated to less than 50%. Quality control of dehydration is performed by weight measurement.
Furthermore, the gel sheet produced by the present invention keeps hygiene safety by suppressing the growth of general bacteria by freezing or refrigerated storage at a temperature of −40 ° C. to 10 ° C., and suppressing the increase in the redox potential of the contained water. be able to.
本発明において、微生物が産生するセルロースは、７〜１０ｎｍの太さのナノファイバーの三次元空隙構造が水を吸着して含水ゲルを構成する。含水ゲルに含まれる水は、自由水と吸着水に分けられ、自由水と吸着水の割合は、概ね、重量比で８５：１５である。
自由水及び吸着水を含む含水ゲルのミクロ構造は、図1に示すように、吸着水はナノファイバーの三次元空隙構造内に封じ込められた水分子であり、自由水はナノファイバーの三次元空隙構造の外にフリーに存在する水分子と考えられるが、三次元空隙構造内に封じ込められた水分子からなる吸着水の脱水は５０％以上になると、不可逆的に影響してゲルの復元が難しくなる。
In the present invention, the cellulose produced by the microorganism constitutes a hydrous gel by adsorbing water with a three-dimensional void structure of nanofibers having a thickness of 7 to 10 nm. The water contained in the hydrous gel is divided into free water and adsorbed water, and the ratio of free water and adsorbed water is approximately 85:15 by weight.
As shown in Fig. 1, the microstructure of the hydrous gel containing free water and adsorbed water is that the adsorbed water is water molecules confined within the three-dimensional void structure of the nanofiber, and the free water is the three-dimensional void of the nanofiber. It is thought that water molecules exist freely outside the structure, but if the dehydration of adsorbed water consisting of water molecules contained in the three-dimensional void structure exceeds 50%, it is difficult to restore the gel due to irreversible effects. Become.
上記脱水の工程は、先ず、遠心分離を利用して一時脱水を行い、第一段階として加熱乾燥して、ナノファイバーの三次元空隙構造の外にフリーに存在する水分を除去し、第二段階として三次元空隙構造内に封じ込められた吸着水の脱水を行うが、ナノファイバーの三次元空隙構造の外に存在する自由水の脱水は、ゲル物性に可逆的であるから問題はないが、三次元空隙構造内に封じ込められた水分子からなる吸着水の脱水は５０％以上になると、不可逆的に影響してゲルの復元が難しくなる。
このときの加熱乾燥時間と、重量減の関係は図２に示すところであるが、この図によれば、乾燥温度が７０℃であれば、約10分程度で、自由水の殆どが乾燥除去できるが、ナノファイバーの三次元空隙構造内に封じ込められた水分子の除去はきわめて緩慢であることがわかる。
吸着水を脱水した乾燥状態から、吸水して復元性をよくするには、糖アルコールとしてオリゴサッカライド、ソルビトール、キシリトール等から選ばれたものを含有することが有効である。
The dehydration step first performs temporary dehydration using centrifugation, and heat-drys as the first stage to remove moisture that is present outside the three-dimensional void structure of the nanofiber, and then the second stage. The water adsorbed in the three-dimensional void structure is dehydrated, but the dehydration of free water existing outside the three-dimensional void structure of the nanofiber is reversible in the gel properties, but there is no problem. When dehydration of adsorbed water composed of water molecules contained in the original void structure is 50% or more, it is difficult to restore the gel due to irreversible influence.
The relationship between the heat drying time and weight loss at this time is as shown in FIG. 2, but according to this figure, if the drying temperature is 70 ° C., most of the free water can be removed by drying in about 10 minutes. However, it can be seen that the removal of water molecules contained within the three-dimensional void structure of the nanofiber is extremely slow.
In order to absorb water from the dried state where the adsorbed water has been dehydrated and improve the restoration property, it is effective to contain a sugar alcohol selected from oligosaccharides, sorbitol, xylitol and the like.
これは、自由水、次いでの吸着水の脱水によって、微生物セルロースによるナノファイバーが接合して太くなり、三次元空隙構造が潰れるためで、吸水性が著しく低下する。吸着水が５０％以上残留する状態であれば、復元性と担持性は保持される。
担持効果を得るためには、吸着水の脱水を５０％未満として、吸着水を担持液と入れ替えることが重要である。自由水を入れ替えたのでは担持効果が得られないし、吸着水を５０％以上脱水した場合には吸水性が著しく低下して上述のように担持効果が得られない。
This is because nanofibers made of microbial cellulose are joined and thickened by dehydration of free water and then adsorbed water, and the three-dimensional void structure is crushed, so that the water absorption is significantly reduced. If the adsorbed water is in a state where 50% or more remains, the restorability and supportability are maintained.
In order to obtain the supporting effect, it is important to desorb the adsorbed water to less than 50% and replace the adsorbed water with the supporting liquid. If the free water is replaced, the supporting effect cannot be obtained. If the adsorbed water is dehydrated by 50% or more, the water absorption is remarkably lowered and the supporting effect cannot be obtained as described above.
飽和に含水したゲル体自体の重量を１００重量％とすると、水分が９９重量％、微生物セルロースが約１重量％であり、上記水分の内訳は、上述するように重量比で、自由水が８５、吸着水１５である。飽和含水ゲル重量を基準として把握するのがよい。吸着水の５０％未満を脱水した状態にするには、飽和含水状態の重量を基準として７．５〜１５重量％に乾燥すればよい。過剰の水を遠心脱水により除いて基準値を設定する。基準値に対して吸着水の残留量を乾燥の温度と時間により重量で調節する。 Assuming that the weight of the gel body containing water in saturation is 100% by weight, the water content is 99% by weight and the microbial cellulose is about 1% by weight. , Adsorbed water 15. It is good to grasp on the basis of the weight of the saturated hydrous gel. In order to dehydrate less than 50% of the adsorbed water, it may be dried to 7.5 to 15% by weight based on the weight of the saturated water-containing state. Excess water is removed by centrifugal dehydration and a reference value is set. The residual amount of adsorbed water is adjusted by weight according to the drying temperature and time with respect to the reference value.
スクロースに酵素を作用した場合、スクロースホスホリラーゼではα−１，４−グルカン（澱粉）が産生する。アセトバクター・キシリナムではβ−１，４−グルカン（セルロース）であることを確認するために、後述する実施例では、微生物産生ゲルを凍結乾燥を行い、粉末にして、ＮＭＲによるスペクトル分析をしたところ、本発明で得られた産生成分はβ−１，４−グルカン（セルロース）であることが確認された。 When an enzyme is allowed to act on sucrose, sucrose phosphorylase produces α-1,4-glucan (starch). In Acetobacter xylinum, in order to confirm that it is β-1,4-glucan (cellulose), in the examples described later, the microorganism-produced gel was freeze-dried, powdered, and subjected to NMR spectrum analysis. The production component obtained in the present invention was confirmed to be β-1,4-glucan (cellulose).
吸水性シートには、吸水性を有する多孔質の合成樹脂シートを用いることができる、例えば、ポリエチレン、ポリスチレン、ポリウレタン等による柔軟な多孔質に加えて濡れ易くするために界面活性剤やグラフト処理により親水化したものも好ましい。吸水性を有する不織布、織物、編物、紙も使用することができる。吸水性は、浸漬と引上げの繰り返しにより空気に触れる培養をする培養液の均一な含浸に必要なことである。吸水性シートの内部及び表面に含水ゲルが生成するが、表面には両面でも片面でもよい。片面に培養液を塗布して培養してもよいが、２枚のシートを重ねて、浸漬と引上げを繰り返して含水ゲルを両面に生成させて２枚に分離する方法が合理的である。 As the water absorbent sheet, a porous synthetic resin sheet having water absorbency can be used. For example, in order to make it easy to get wet in addition to a flexible porous material such as polyethylene, polystyrene, polyurethane, etc. A hydrophilized product is also preferred. Nonwoven fabrics, woven fabrics, knitted fabrics, and papers having water absorption can also be used. Water absorption is necessary for uniform impregnation of a culture solution for culturing in contact with air by repeated immersion and pulling. A hydrogel is formed inside and on the surface of the water-absorbent sheet, but the surface may be double-sided or single-sided. A culture solution may be applied on one side and cultured. However, it is reasonable to stack two sheets and repeat soaking and pulling to form a hydrous gel on both sides and separate them into two.
吸水性シートに、肌色やピンク色、その他美容に好ましい色や柄又は化粧に必要な情報を印刷することにより従来になかった情報を有するパック材とすることができる。
酢酸が検出されなくなるまで洗浄し、１００℃３０分の殺菌処理を行う。過剰の水分を除くには遠心脱水又はマングルを用いればよい。遠心脱水により過剰な水分を除いた含水シートは、図１に示すようにに８５％の自由水と１５％の吸着水の水分より成る。含水ゲルに化粧液を注液するには、注液相当分の自由水を除いて化粧液と入れ替える。自由水の２０％以上、好ましくは４０％以上を除いて除去部分を作って、除去部分に化粧液を注入する。自由水により化粧液が希釈されることになるので、化粧液の配合と注液量に応じて自由水を除く量を定めればよく、４０重量％脱水した注液化粧料の濃度に対して、２０％脱水した場合は、化粧料の濃度は２倍にする必要があるが、２０重量％未満の脱水にはそれ以上の高濃度になるため、増粘剤など配合が適合しなくなり２０重量％以上を可とする。
It is possible to obtain a pack material having information which has not been conventionally obtained by printing information necessary for skin color, pink color, and other colors and patterns preferable for cosmetics or makeup on the water absorbent sheet.
Wash until acetic acid is no longer detected and sterilize at 100 ° C. for 30 minutes. Centrifugal dehydration or mangles may be used to remove excess water. The water-containing sheet from which excess water has been removed by centrifugal dehydration is composed of 85% free water and 15% adsorbed water as shown in FIG. In order to inject the cosmetic liquid into the water-containing gel, the free liquid corresponding to the liquid injection is removed and replaced with the cosmetic liquid. A removal part is made by removing 20% or more, preferably 40% or more of free water, and a cosmetic liquid is injected into the removal part. Since the cosmetic liquid is diluted with free water, the amount excluding free water may be determined according to the composition of the cosmetic liquid and the amount of liquid to be injected. When 20% is dehydrated, the concentration of cosmetics must be doubled. However, dehydration of less than 20% by weight results in a higher concentration, which makes the blending of thickeners incompatible and 20%. % Or more is acceptable.
含水ゲルシートを用いてシート状パック材とする場合には、化粧液を注液しても受け入れる容積がないので脱水して受入れ部を作成するが、該受入れ部作成の管理基準値には遠心脱水による重量を基準として用いる。
乾燥シートを用いてシート状パック材とする場合には、化粧液を含浸してゲルシートに復元させることになるが、乾燥によりゲル復元性が低下するので、HLB１０以上の親水性の非イオン界面活性剤又は/及び糖アルコール含有させて乾燥する。乾燥は温風乾燥でも凍結乾燥であってもよい。HLB１０未満の非イオン界面活性剤の含有により微生物セルロースを包み込んで、ナノファイバーの収束を防ぐことができる。糖アルコールを単独又は非イオン界面活性剤と併用しても有効である。糖アルコールとしては、オリゴサッカライド、ソルビトール等を用いることができる。
When a hydrous gel sheet is used to form a sheet-like pack material, there is no capacity to accept a cosmetic liquid even if it is injected, so the receiving part is created by dehydration. The weight by is used as a reference.
In the case of using a dry sheet as a sheet-like pack material, the gel sheet is impregnated with a cosmetic liquid, but the gel recovery property is reduced by drying. Add agent and / or sugar alcohol and dry. Drying may be hot air drying or freeze drying. By containing a nonionic surfactant of less than HLB10, microbial cellulose can be encapsulated to prevent nanofiber convergence. It is also effective to use a sugar alcohol alone or in combination with a nonionic surfactant. As sugar alcohols, oligosaccharides, sorbitol and the like can be used.
従来、公知の静置培養法では、上述するように、１８〜２０mmの厚さの含水ゲル体を得るのに１２〜１３日を要する上に、スライスしてシート状とするにしても、３mm以下の均一な薄い厚さのシート状は得ることができなかった。また、従来の静置培養法で得られた含水ゲル体は、時間経過と共に一般細菌が増殖するので、安全を保つことが難しかった。
本発明によれば、短時間に吸水性シートの両面又は片面に含水ゲルを生成させることが可能で、しかも得られた吸水性シートは、厚さは３mm以下、好ましくは２mm以下、さらに好ましくは１mm以下のゲルシートを１日以内に生産することができる。
また、本発明で製造されたゲルシートは、−４０℃〜１０℃に冷凍又は冷蔵又保存により一般細菌の増殖を押さえ、容易に衛生面の安全を確保することができる。
さらに、本発明の微生物セルロースによる含水ゲルシートの製造法では、従来法に比して取扱い性が抜群によくなる。また、得られたゲルシートは、破れたり変形することがなく、従来得られなかった３mm以下の厚さにすることにより、密着性をさらに高めて、且つ質量の低減とスライス工程の削除により安価になる。
さらに、親水性高分子ではなくナノセルロース繊維による擬似ゲル構造を用いることで、ゲル体を用いても成分の拘束性が向上し、化粧用シートとして、ゲル体を使用して化粧液に含浸させたときに、化粧成分を包接のように拘束することを改善する。
Conventionally, in the known stationary culture method, as described above, it takes 12 to 13 days to obtain a hydrogel body with a thickness of 18 to 20 mm, and even if it is sliced into a sheet, it is 3 mm. The following uniform thin sheet could not be obtained. In addition, it is difficult to maintain safety in a hydrogel body obtained by a conventional static culture method because general bacteria grow over time.
According to the present invention, a water-containing gel can be formed on both sides or one side of a water-absorbent sheet in a short time, and the resulting water-absorbent sheet has a thickness of 3 mm or less, preferably 2 mm or less, more preferably A gel sheet of 1 mm or less can be produced within one day.
Moreover, the gel sheet manufactured by this invention can suppress the proliferation of general bacteria by refrigeration, refrigeration, or storage at -40 ° C to 10 ° C, and can easily ensure hygiene safety.
Furthermore, in the method for producing a hydrogel sheet with microbial cellulose of the present invention, the handleability is outstanding as compared with the conventional method. In addition, the obtained gel sheet is not torn or deformed, and has a thickness of 3 mm or less, which has not been obtained in the past. Become.
Furthermore, by using a pseudo gel structure made of nanocellulose fibers instead of a hydrophilic polymer, the restraint property of the components is improved even if the gel body is used, and the cosmetic liquid is impregnated with the gel body as a cosmetic sheet. Improve the binding of cosmetic ingredients like inclusion.
ココナッツ水にショ糖１０重量％を配合して酢酸でｐH４に調整した水溶液に、アセトバクターキシリナム５重量％を植菌して、温度を２９℃に保って培養液とした。
円周３mの水車型の枠に、メッシュ調のコットン不織布厚さ０．２mm、幅５０cm、長さ３mの吸水性シートを固定した。水車の１/３を培養液に浸漬して、最初吸水性シート全体を培養液で湿潤して、毎分５０cmの速度で回転した。８時間の培養で厚さ０．８mmの含水ゲルシートを生成した。該含水ゲルシートを流水により酢酸のなくなるまで洗浄し、１００℃３０分の殺菌処理を行った水冷して遠心脱水を行い、その重量は６g/１００cｍ２であった。その８５％が自由水であるので、自由水５０％を除くために、マングルで絞り２．５ｇ/１００cｍ２を脱水して３℃に冷蔵した。次いで、フェイスマスクの形状に型抜きして、脱水部に相当する化粧液の２．５g/１００cｍ２量を注液してシート状パック材を得た。
注液した化粧液は、精製水：８１部、１．３−ＢＧ：１７．４部、キサンタンガム：０．３５部、アクリル酸ナトリウム：０．１部、メチルパラペン：０．１４部、ＰＥＧ−６０水添ヒマシ油：０．５部、ヒヤルロンサンナトリウム：０．００４部、ソウハクエキス；０．００１４部、メリッサエキス０．０００６部、を配合した液を用いた。
得られたシート状のパック材は厚さ０．８mmである。従来のパック材より取扱い性が優れており、顔の凹凸に密着性が抜群であった。
比較例として、脱水を１０重量％の０．５ｇ/１００cｍ２としたものは、化粧液の注液適量が僅かで、それ以上の注液は困難でありパック化粧料として有効なものは得られなかった。
5% by weight of Acetobacter xylinum was inoculated into an aqueous solution in which 10% by weight of sucrose was mixed with coconut water and adjusted to pH 4 with acetic acid, and the temperature was maintained at 29 ° C. to obtain a culture solution.
A water-absorbent sheet having a mesh-like cotton nonwoven fabric thickness of 0.2 mm, width of 50 cm, and length of 3 m was fixed to a watermill-type frame having a circumference of 3 m. One third of the water wheel was immersed in the culture solution, and the entire water-absorbent sheet was first wetted with the culture solution and rotated at a speed of 50 cm per minute. A water-containing gel sheet having a thickness of 0.8 mm was produced by culturing for 8 hours. The hydrogel sheet was washed with running water until it was free of acetic acid, sterilized at 100 ° C. for 30 minutes, cooled with water, centrifuged and dehydrated, and its weight was 6 g / 100 cm 2 . Since 85% of that was free water, 2.5 g / 100 cm 2 was squeezed with mangles and refrigerated to 3 ° C. to remove 50% of the free water. Subsequently, it was die-cut into the shape of a face mask, and a 2.5 g / 100 cm 2 amount of a cosmetic liquid corresponding to the dewatering part was injected to obtain a sheet-like pack material.
The injected cosmetic liquid was purified water: 81 parts, 1.3-BG: 17.4 parts, xanthan gum: 0.35 parts, sodium acrylate: 0.1 parts, methylparapene: 0.14 parts, PEG-60 Hydrogenated castor oil: 0.5 part, hyaluronic acid sodium: 0.004 part, Soraku extract; 0.0014 part, Melissa extract 0.0006 part was used.
The obtained sheet-like pack material has a thickness of 0.8 mm. It is easier to handle than conventional pack materials, and has excellent adhesion to facial irregularities.
As a comparative example, when 10% by weight of dehydration was 0.5 g / 100 cm 2 , the cosmetic liquid injection amount was very small, and it was difficult to inject more than that, and an effective pack cosmetic was obtained. There wasn't.
肌色の薄葉紙厚さ０．０２mmの大きさ５０cm×５０cmを２枚重ねて用い、実施例１に記載の如く培養液に浸漬して、６時間で厚さ０．６mmの含水ゲルシートを得て２枚に分離して片面に含水ゲルを０．３mm有するゲルシートを得た。洗浄、殺菌処理を行って、HLB１２の非イオン界面活性剤としてポリオキシエチレン（３０）ポリオキシプロピレン（６）デシルテトラデシルエーチル０．５重量％水溶液に浸漬・絞液として７０℃で乾燥して乾燥シートとした。フェイスマスクの形状に型抜きして、シート重量と同量の実施例１に用いた化粧液を注液した。３０分後には厚さ０．６mmの含水ゲルシートが復元して、密着性の優れたシート状パックが得られた。
比較例として非イオン界面活性剤を含浸しないものは、該化粧液を注液して常温で１週間後でも風合が硬く含水ゲルに復元することがなかった。
Two sheets of flesh-colored thin paper with a thickness of 0.02 mm and a size of 50 cm × 50 cm were used, and immersed in a culture solution as described in Example 1 to obtain a hydrous gel sheet having a thickness of 0.6 mm in 6 hours. Separated into sheets, a gel sheet having a water-containing gel of 0.3 mm on one side was obtained. It is washed and sterilized, and dipped in a 0.5% by weight aqueous solution of polyoxyethylene (30) polyoxypropylene (6) decyltetradecylethyl as a nonionic surfactant for HLB12 and dried at 70 ° C as a squeezed solution. To obtain a dry sheet. The face mask was cut into a shape, and the same amount of the cosmetic liquid used in Example 1 as the sheet weight was injected. After 30 minutes, the water-containing gel sheet having a thickness of 0.6 mm was restored, and a sheet-like pack having excellent adhesion was obtained.
As a comparative example, a sample not impregnated with a nonionic surfactant was hard to be restored to a water-containing gel even after 1 week at room temperature after the cosmetic solution was poured.
Claims (13)
A sheet-shaped cosmetic pack produced by the method according to claim 9.
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| DE102008046644A1 (en) * | 2008-09-09 | 2010-03-11 | Friedrich-Schiller-Universität Jena | Process for the production of bacterially synthesized cellulose and cellulosic material in a flat form |
| KR101109034B1 (en) | 2009-06-17 | 2012-01-31 | 김홍남 | Method for mass production of microbial cellulose and method for mask pack using there of |
| KR101300625B1 (en) * | 2013-02-26 | 2013-08-27 | 농업회사법인 주식회사 자담 | Fabrication method of bacterial cellulose gel |
| KR101385501B1 (en) | 2013-10-10 | 2014-04-15 | (주)이지코스텍 | Manufacturing method of cosmetic biocellulose sheet and cosmetic biocellulose sheet by using therof |
| KR101407348B1 (en) | 2012-04-09 | 2014-06-17 | 하태석 | The manufacturing method of bio cellulose pack having natural ganulated powder |
| JP2014111639A (en) * | 2014-02-10 | 2014-06-19 | Toyo Shinyaku Co Ltd | Transparent sheet-like cosmetic |
| JP2015504845A (en) * | 2011-12-19 | 2015-02-16 | ロレアル | Beauty sheet for lips |
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| JP2019503995A (en) * | 2015-11-25 | 2019-02-14 | イェナセル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Cellulose-containing articles for skin |
| KR102013769B1 (en) * | 2018-02-20 | 2019-10-21 | 에임즈마이크론 주식회사 | Hybrid skin-covering sheet and skin covering mask comprising hybrid skin-covering sheet |
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| JP2021532283A (en) * | 2018-09-27 | 2021-11-25 | エルジー・ケム・リミテッド | Biocellulose sheet and its manufacturing method |
| CN117482023A (en) * | 2023-10-27 | 2024-02-02 | 养生堂（安吉）化妆品有限公司 | Method for preparing biological fiber mask cloth and biological fiber mask cloth obtained by same |
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| JP2006298846A (en) * | 2005-04-21 | 2006-11-02 | Toyo Shinyaku:Kk | Base material |
| JP2007169242A (en) * | 2005-12-26 | 2007-07-05 | Toyo Shinyaku:Kk | Cosmetic |
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| DE102008046644A1 (en) * | 2008-09-09 | 2010-03-11 | Friedrich-Schiller-Universität Jena | Process for the production of bacterially synthesized cellulose and cellulosic material in a flat form |
| KR101109034B1 (en) | 2009-06-17 | 2012-01-31 | 김홍남 | Method for mass production of microbial cellulose and method for mask pack using there of |
| JP2015504845A (en) * | 2011-12-19 | 2015-02-16 | ロレアル | Beauty sheet for lips |
| KR101407348B1 (en) | 2012-04-09 | 2014-06-17 | 하태석 | The manufacturing method of bio cellulose pack having natural ganulated powder |
| KR101300625B1 (en) * | 2013-02-26 | 2013-08-27 | 농업회사법인 주식회사 자담 | Fabrication method of bacterial cellulose gel |
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| JP2014111639A (en) * | 2014-02-10 | 2014-06-19 | Toyo Shinyaku Co Ltd | Transparent sheet-like cosmetic |
| JP2016147825A (en) * | 2015-02-12 | 2016-08-18 | 嬌▲ぽん▼生技股▲分▼有限公司 | Biological fiber composite dressing material |
| US10682257B2 (en) | 2015-07-29 | 2020-06-16 | Evophancie Biotech Ltd | Biological fiber composite dressing |
| JP2019503995A (en) * | 2015-11-25 | 2019-02-14 | イェナセル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Cellulose-containing articles for skin |
| JP2022025089A (en) * | 2015-11-25 | 2022-02-09 | イェナセル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Cellulose-containing article for skin |
| US11529433B2 (en) | 2015-11-25 | 2022-12-20 | JeNaCell GmbH | Biotechnologically-produced cellulose-containing article for dermatological use |
| JP7382373B2 (en) | 2015-11-25 | 2023-11-16 | イェナセル ゲゼルシャフト ミット ベシュレンクテル ハフツング | Cellulose-containing articles for skin |
| KR102013769B1 (en) * | 2018-02-20 | 2019-10-21 | 에임즈마이크론 주식회사 | Hybrid skin-covering sheet and skin covering mask comprising hybrid skin-covering sheet |
| JP2021532283A (en) * | 2018-09-27 | 2021-11-25 | エルジー・ケム・リミテッド | Biocellulose sheet and its manufacturing method |
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