JP2003055641A - Tackifier - Google Patents
TackifierInfo
- Publication number
- JP2003055641A JP2003055641A JP2001243660A JP2001243660A JP2003055641A JP 2003055641 A JP2003055641 A JP 2003055641A JP 2001243660 A JP2001243660 A JP 2001243660A JP 2001243660 A JP2001243660 A JP 2001243660A JP 2003055641 A JP2003055641 A JP 2003055641A
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- JP
- Japan
- Prior art keywords
- polysaccharide
- cooling
- stirring
- viscosity
- thickener
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Cosmetics (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、各種乳化製品、固
体分散製品に使用される乳化・分散安定化性に優れ、高
い増粘性を有する微生物多糖類系増粘剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microbial polysaccharide-based thickener which is used in various emulsified products and solid dispersion products and has excellent emulsification / dispersion stability and high viscosity.
【0002】[0002]
【従来の技術】一般に乳化製品、微細固形物の分散型製
品には、乳化系の分離防止、固形分散物の沈降防止およ
び浮上防止、取り扱い易い適度な粘性の付与等を目的に
種々の増粘剤が使用されている。例えば、乳液や化粧水
では広範囲に薄く塗るために低粘度でのびが良いこと、
クリームや美容液では部分的に塗るために適度な粘度が
あること、パック化粧料やマッサージ化粧料では流れ落
ちない程度の粘性を必要とする等、使用目的により様々
な粘度特性が要求されている。また、乳化製品や微細固
形物の分散型製品等は、水と各種油剤、高級アルコー
ル、顔料等の互いに溶け合わない原料を乳化または分散
させているため、その乳化状態や分散状態を長期間維持
し、分離を防止するために増粘剤が配合されている。In general, emulsified products and dispersion products of fine solids have various thickening properties for the purpose of preventing separation of the emulsified system, preventing sedimentation and floating of the solid dispersion, and imparting an appropriate viscosity for easy handling. Agent is used. For example, emulsions and lotions have a low viscosity and spread well because they are applied thinly over a wide area.
Various viscosity characteristics are required depending on the purpose of use, such as that a cream or a beauty essence has an appropriate viscosity for partial application, and a pack cosmetic or a massage cosmetic needs a viscosity that does not run off. In addition, since emulsified products and dispersion products of fine solids emulsify or disperse insoluble materials such as water and various oils, higher alcohols, pigments, etc., the emulsified state or dispersed state is maintained for a long time. However, a thickener is added to prevent separation.
【0003】化粧料に用いられる増粘剤には、アクリル
酸系ポリマーなどの合成ポリマー、カルボキシメチルセ
ルロースやメチルセルロースなどの天然物を加工したも
の、カラギーナン、グアーガム、ローカストビーンガ
ム、アラビアゴム、カラヤガム等の植物由来の多糖類、
キサンタンガム等の微生物由来の多糖類が用いられてい
る。特に、従来から比較的少量で高い増粘効果を得る目
的で天然物を加工したものや微生物産生多糖類が多く使
用されてきた。しかし、微生物産生多糖類系の増粘剤
は、温度が高くなると粘性が急速に低下する欠点があ
る。Thickeners used in cosmetics include synthetic polymers such as acrylic acid polymers, processed natural products such as carboxymethyl cellulose and methyl cellulose, carrageenan, guar gum, locust bean gum, gum arabic and karaya gum. Plant-derived polysaccharides,
Microorganism-derived polysaccharides such as xanthan gum are used. In particular, processed natural products and microbially produced polysaccharides have been used in many cases for the purpose of obtaining a high thickening effect with a relatively small amount. However, the polysaccharide-based thickeners produced by microorganisms have the drawback that the viscosity rapidly decreases with increasing temperature.
【0004】そこで、微生物産生多糖類の粘性特性を改
善する方法が提案され、例えば、低濃度の増粘剤配合に
より高粘性を得る方法として微生物由来の多糖類である
ジェランガムと他の多糖類を配合して粘性を高める方法
(特開平10−215795号公報)、粉末状キサンタ
ンガムを加熱処理もしくは湿熱処理して高粘性キサンタ
ンガムを得る方法(特開平10−33125号公報、特
開2000−7705号公報)等がある。しかし、未だ
十分に満足できる増粘剤は得られておらず、より高性能
化が求められている。Therefore, a method for improving the viscous properties of the microorganism-produced polysaccharide has been proposed. For example, gellan gum which is a microorganism-derived polysaccharide and other polysaccharides are used as a method for obtaining a high viscosity by blending a thickening agent at a low concentration. A method of increasing viscosity by blending (JP-A-10-215795), or a method of heat-treating or wet-heat treating powdery xanthan gum (JP-A-10-33125, JP-A-2000-7705). ) Etc. However, a sufficiently satisfactory thickener has not yet been obtained, and higher performance is required.
【0005】[0005]
【発明が解決しようとする課題】本発明者らは、上記の
問題点を改善し、少量で高い増粘性を与え、温度の上昇
による粘性の急速な低下のない優れた多糖類系増粘剤と
して、フコース、グルコース、グルクロン酸、ラムノー
スを構成単糖として含む多糖類をpHが8以上の水溶液
中、60〜180℃で加熱処理して得られる多糖類を有
効成分とする増粘剤を提案した(特願2000−313
517号)。DISCLOSURE OF THE INVENTION The inventors of the present invention have improved the above-mentioned problems, provided a high viscosity increase with a small amount, and an excellent polysaccharide-type thickener without a rapid decrease in viscosity due to an increase in temperature. As a solution, a thickener containing a polysaccharide obtained by heating a polysaccharide containing fucose, glucose, glucuronic acid, and rhamnose as constituent monosaccharides at 60 to 180 ° C. in an aqueous solution having a pH of 8 or more as an active ingredient is proposed. (Patent application 2000-313
517).
【0006】しかし、フラスコスケールでの生産は可能
であるが、そのまま工業的な規模での生産すると生産ロ
ットによって得られる増粘剤の粘度にバラツキがみられ
るという問題点があった。However, although the flask scale production is possible, there is a problem in that the viscosity of the thickener obtained varies depending on the production lot when produced on an industrial scale as it is.
【0007】本発明の目的は、かかる問題点を解決し
て、実際に工業的な規模での生産が可能であり、かつ、
乳化・分散安定化性に優れた増粘剤を提供することにあ
る。The object of the present invention is to solve the above problems and enable production on an industrial scale, and
It is to provide a thickener having excellent emulsification / dispersion stability.
【0008】[0008]
【課題を解決するための手段】本発明者らは、かかる課
題を解決するために、多糖類増粘剤の工業的な規模での
製造方法の改善について鋭意研究を重ねた結果、特定の
多糖類をアルカリ水溶液中で加熱処理した後、強い剪断
力を伴わない方式で冷却することにより、より高い粘度
を有し、しかも温度上昇による粘度の急激な低下がな
く、乳化・分散安定化性に優れた多糖類が得られること
を見いだして、本発明を完成させるに至った。In order to solve such a problem, the inventors of the present invention have conducted diligent research on improvement of a method for producing a polysaccharide thickener on an industrial scale, and as a result, have identified a specific problem. By heat-treating saccharides in an alkaline aqueous solution and then cooling by a method that does not involve strong shearing force, it has a higher viscosity, and there is no sharp decrease in viscosity due to temperature rise, and emulsion / dispersion stability is improved. The inventors have found that an excellent polysaccharide can be obtained, and completed the present invention.
【0009】すなわち、請求項1に係る発明は、実質的
にフコース、グルコース、グルクロン酸、ラムノースを
構成単糖として含む多糖類を、pHが8以上の水溶液
中、60〜180℃で加熱処理した後、撹拌翼の先端速
度が2.0m/s以下の回転速度に保持しながら冷却す
るか、または撹拌による剪断力を加えずに冷却する方法
によって得られた多糖類を有効成分として含む増粘剤で
ある。That is, the invention according to claim 1 heats a polysaccharide substantially containing fucose, glucose, glucuronic acid and rhamnose as constituent monosaccharides in an aqueous solution having a pH of 8 or more at 60 to 180 ° C. After that, a thickening containing a polysaccharide obtained as an active ingredient by a method of cooling while maintaining the tip speed of the stirring blade at a rotation speed of 2.0 m / s or less or cooling without applying shearing force by stirring. It is an agent.
【0010】請求項2に係る発明は、多糖類がモル比で
フコース:グルコース:グルクロン酸:ラムノース=1
〜2:1〜4:1〜2:1〜2である請求項1記載の増
粘剤。In the invention according to claim 2, the molar ratio of the polysaccharide is fucose: glucose: glucuronic acid: rhamnose = 1.
The thickener according to claim 1, which is from 2: 1 to 4: 1 to 2: 1 to 2.
【0011】請求項3に係る発明は、多糖類が主鎖とし
てグルコース、グルクロン酸、ラムノースにて構成さ
れ、さらにフコースが側鎖に結合している構造を有する
請求項1又は2記載の増粘剤。The invention according to claim 3 has a structure in which a polysaccharide is composed of glucose, glucuronic acid and rhamnose as a main chain, and further fucose is bonded to a side chain. Agent.
【0012】請求項4に係る発明は、多糖類が、アルカ
リゲネス レータス B−16株の産生する多糖類である
請求1ないし3のうちのいずれか記載の増粘剤の製造方
法である。[0012] The invention according to claim 4 is the method for producing a thickening agent according to any one of claims 1 to 3, wherein the polysaccharide is a polysaccharide produced by Alcaligenes Bastus strain B-16.
【0013】請求項5に係る発明は、撹拌による剪断力
を加えずに冷却する方法が、冷却した蛇管内を加圧下通
過させる方法である請求項1ないし4のうちのいずれか
記載の増粘剤。According to a fifth aspect of the present invention, the method of cooling without applying shearing force by stirring is a method of passing the inside of a cooled flexible pipe under pressure, thereby increasing the viscosity. Agent.
【0014】[0014]
【発明の実施の形態】以下に本発明を詳細に説明する。
本発明の増粘剤は、実質的にフコース、グルコース、グ
ルクロン酸、ラムノースを構成単糖として含む多糖類を
pHが8以上のアルカリ水溶液中、60〜180℃で加
熱処理した後、強い剪断力を伴わない方法で冷却して得
られた多糖類を有効成分として含む増粘剤である。アル
カリ加熱処理を施した多糖類は高温で高い粘度を保持し
ているが、これを冷却する際に、冷却効率を高める観点
から強力な撹拌下に行った場合には、無撹拌ないしは緩
慢な撹拌下に行った場合と比べて増粘効果が小さく、温
度による粘性の変化が大きくなる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The thickener of the present invention has a strong shearing force after substantially heat-treating a polysaccharide containing fucose, glucose, glucuronic acid and rhamnose as constituent monosaccharides in an alkaline aqueous solution having a pH of 8 or more at 60 to 180 ° C. It is a thickener containing as an active ingredient a polysaccharide obtained by cooling by a method without. The polysaccharide that has been subjected to alkali heat treatment retains a high viscosity at high temperatures, but when it is cooled, it is not stirred or slowly stirred if it is stirred strongly from the viewpoint of enhancing cooling efficiency. Compared to the case below, the thickening effect is small and the change in viscosity with temperature is large.
【0015】本発明に用いられる多糖類は、実質的にフ
コース、グルコース、グルクロン酸、ラムノースを構成
単糖として含む多糖類で、好ましくは下記式(1)に示
されるようなグルコース、グルクロン酸、ラムノースか
らなる繰返し構造の主鎖からなり、1つのグルコースに
1つのフコースが分岐した構造を有する多糖類である。The polysaccharide used in the present invention is a polysaccharide substantially containing fucose, glucose, glucuronic acid, and rhamnose as constituent monosaccharides, and preferably glucose, glucuronic acid represented by the following formula (1), It is a polysaccharide having a repeating main chain composed of rhamnose and having a structure in which one fucose is branched to one glucose.
【0016】[0016]
【化1】 [Chemical 1]
【0017】本発明に用いられる多糖類は、微生物産生
の多糖類として得られるものである。一般に微生物は、
2種以上の多糖類を産生することが多いために本発明に
使用される多糖類に他の多糖類が含まれていても本発明
の効果を妨げるものでなければ、他の多糖類が含まれる
ことを妨げるものではない。The polysaccharide used in the present invention is obtained as a microbially produced polysaccharide. Generally, microorganisms
Since two or more types of polysaccharides are often produced, even if the polysaccharide used in the present invention contains other polysaccharides, other polysaccharides are included as long as the effects of the present invention are not impaired. It does not prevent you from being
【0018】多糖類を産生する微生物は、特に限定され
るものではないが、例えば、アルカリゲネス レータス
B−16株細菌(FERM BP−2015号)があ
る。Microorganisms which produce polysaccharides are not particularly limited, but for example, Alcaligenes pertus
There is a B-16 strain bacterium (FERM BP-2015).
【0019】本発明の多糖類の製造は、例えば、アルカ
リゲネス レータス B−16株細菌の場合、次のように
行われる。The production of the polysaccharide of the present invention is carried out as follows, for example, in the case of Alcaligenes lettus B-16 strain bacteria.
【0020】アルカリゲネス レータス B−16株細菌
は、通常の微生物の培養方法で培養され、例えば、炭素
源にフラクトース、グルコース、シュークロースなどの
単糖類、ヘミセルロース、デンプン、コーンスターチな
どの天然高分子、オリーブ油脂などの油類を、窒素源に
尿素、塩化アンモニウム、硝酸アンモニウム、硫酸アン
モニウムなどの無機体窒素源、トリプトン、酵母エキ
ス、肉エキス、ペプトン、麦芽エキスなどの有機体窒素
源を用い、その他リン酸カリウム、硫酸マグネシウム、
塩化ナトリウムなどの無機塩類を加えた培地を用い、初
発pHが4〜10、培養温度が15〜40℃で通気攪拌
液体培養を3〜10日間行なう。培養後、該培養液に約
2倍量(容量)以上のアセトン、エタノール、イソプロ
ピルアルコールなどの有機溶媒を入れ、培養産生物を不
溶性の凝集物として回収する。The Alcaligenes lettus B-16 strain bacterium is cultivated by an ordinary microbial culturing method. For example, monosaccharides such as fructose, glucose and sucrose as carbon sources, natural polymers such as hemicellulose, starch and corn starch, and olives. Oils such as oils and fats, inorganic nitrogen sources such as urea, ammonium chloride, ammonium nitrate, ammonium sulfate, and organic nitrogen sources such as tryptone, yeast extract, meat extract, peptone, and malt extract are used as nitrogen sources. , Magnesium sulfate,
Using a medium to which an inorganic salt such as sodium chloride is added, aeration stirring liquid culture is performed for 3 to 10 days at an initial pH of 4 to 10 and a culture temperature of 15 to 40 ° C. After culturing, about 2 times (volume) or more of an organic solvent such as acetone, ethanol or isopropyl alcohol is added to the culture solution, and the culture product is recovered as an insoluble aggregate.
【0021】アルカリゲネス レータス B−16株細菌
の生産する多糖類には、少なくとも2種の多糖類が含ま
れていることが確かめられており、一つは、本発明の多
糖類である前記式(1)に示すようなグルコース、グル
クロン酸、ラムノースからなる繰返し構造の中の1つの
グルコースに1つのフコースが分岐した構造を有する多
糖類であり、他の一つは、下記(2)で示される実質的
にフコースとマンノースを構成単糖とする構造の繰り返
しの多糖類である〔1998年度日本農芸化学会大会要
旨集、371頁参照。Y.Nohata,J.Azum
a,R.Kurane,Carbohydrate R
esearch 293,213〜222(199
6))参照〕It has been confirmed that at least two kinds of polysaccharides are contained in the polysaccharide produced by Alcaligenes lettus B-16 strain bacterium, one of which is the above-mentioned formula ( A polysaccharide having a structure in which one fucose is branched to one glucose in the repeating structure consisting of glucose, glucuronic acid, and rhamnose as shown in 1), and the other one is shown in (2) below. It is a repeating polysaccharide having a structure substantially consisting of fucose and mannose as constituent monosaccharides [See 1998 Annual Meeting of the Japan Society for Agricultural Chemistry, p. 371]. Y. Nohata, J .; Azumi
a.R. Kurane, Carbohydrate R
esearch 293 , 213-222 (199)
See 6))]
【0022】[0022]
【化2】 [Chemical 2]
【0023】上記式(2)で示される多糖類が、本発明
の多糖類である上記式(1)の多糖類中に含まれていて
もその効果を妨げないため、上記式(2)で示される多
糖類を除去することなく、アルカリゲネス レータス B
−16株細菌の生産する多糖類を使用することができ
る。Even if the polysaccharide represented by the above formula (2) is contained in the polysaccharide of the above formula (1), which is the polysaccharide of the present invention, its effect is not impaired. Therefore, in the above formula (2) Alkaline Genesulators B without removal of the indicated polysaccharides
Polysaccharides produced by strain -16 can be used.
【0024】本発明に係る多糖類にアルカリ加熱処理を
施す際の多糖類水溶液のpHは、アルカリ性物質を加え
てpHを8以上、好ましくはpH11以上、さらに好ま
しくはpH12以上とする。水溶液のpHが7未満の酸
性条件下では、該多糖類の分子鎖の切断が激しく、本発
明の意図する増粘効果及び乳化・分散効果を得ることが
できない場合がある。The pH of the aqueous polysaccharide solution when the polysaccharide according to the present invention is subjected to the alkali heat treatment is adjusted to 8 or more, preferably 11 or more, more preferably 12 or more by adding an alkaline substance. Under acidic conditions where the pH of the aqueous solution is less than 7, the molecular chain of the polysaccharide is severely broken, and the thickening effect and the emulsifying / dispersing effect intended by the present invention may not be obtained.
【0025】アルカリ加熱処理温度は、60℃〜180
℃、好ましくは80〜160℃、より好ましくは100
〜140℃である。60℃未満では、加熱時間を長くし
ても増粘効果が得られない場合がある。また、180℃
を越えると、多糖類の分解が過度に進むことがあり好ま
しくないことがある。当然のことながら、100℃以上
の場合で大量に生産する場合には、加熱処理にジャーフ
ァーメンターの様な耐熱容器を用いる必要がある。加熱
時間は、pH、処理温度、目的の粘度特性によって、適
宜決定されるものであるが、通常10〜120分であ
る。又、途中でサンプリングして粘度を測定することに
よって、所定粘度の多糖類を得ることもできる。The alkali heat treatment temperature is 60 ° C to 180 ° C.
℃, preferably 80-160 ℃, more preferably 100
~ 140 ° C. If it is lower than 60 ° C, the thickening effect may not be obtained even if the heating time is extended. Also, 180 ℃
If it exceeds the range, the decomposition of the polysaccharide may proceed excessively, which is not preferable. As a matter of course, in the case of mass production at 100 ° C. or higher, it is necessary to use a heat resistant container such as a jar fermenter for the heat treatment. The heating time is appropriately determined depending on the pH, the treatment temperature and the desired viscosity characteristic, but is usually 10 to 120 minutes. In addition, a polysaccharide having a predetermined viscosity can be obtained by sampling the viscosity during the measurement and measuring the viscosity.
【0026】本発明に係る多糖類のアルカリ加熱処理に
おいて、該多糖類の水溶液濃度は0.01〜3重量%、
好ましくは0.1重量%〜1重量%の濃度である。3重
量%を越える濃度では、水溶液の粘度が高くて取り扱い
性が悪くなる場合がある。また、0.01重量%以下の
濃度では、濃度が低く製造効率が低く好ましくない。In the alkaline heat treatment of the polysaccharide according to the present invention, the aqueous solution concentration of the polysaccharide is 0.01 to 3% by weight,
The concentration is preferably 0.1% by weight to 1% by weight. If the concentration exceeds 3% by weight, the viscosity of the aqueous solution may be high and the handleability may deteriorate. Further, if the concentration is 0.01% by weight or less, the concentration is low and the production efficiency is low, which is not preferable.
【0027】多糖類にアルカリ加熱処理を施したなら
ば、引き続いて本発明に従って撹拌翼の先端速度が2.
0m/s以下の回転速度に保持しながら冷却するか、又
は撹拌による剪断力を加えずに冷却する方法が適用され
る。)具体的には、ジャーファーメンターの容器内を撹
拌することなくジャーファーメンターの容器外を水等の
冷媒で外部冷却する方法、あるいはジャーファーメンタ
ー容器内の冷却コイルに冷媒を通しながら、撹拌翼の先
端速度が2.0m/s以下の回転速度で撹拌冷却する方
法、ジャーファーメンター容器から冷媒冷却した蛇管
(冷却用コイル)内に圧入して冷却する方法等が挙げら
れる。大きなジャーファーメンター容器での冷却では、
先端速度の低い、低撹拌速度では冷却に時間がかかり、
目的とする粘度を持つ多糖類が得られなく、好ましくは
ない。撹拌冷却時の撹拌翼の形状は特に限定されるもの
ではなく、ジャーファーメンター等の容器を考慮してプ
ロペラ型、リボン型、ブレード型等の形状のものが適宜
選択される。また、冷却に用いる蛇管(冷却用コイル)
の口径、長さ、材質、形状は特に限定されるものではな
く、冷却到達温度、冷却処理量、時間等の条件を考慮し
て適宜選択されるものである。本発明の特徴は、アルカ
リ加熱処理を施した多糖類水溶液を冷却する際に、撹拌
等による剪断力を実質伴わないか、あるいは撹拌等によ
る剪断力を小さくして冷却する点にあり、好ましくは、
剪断力の伴わない蛇管(冷却用コイル)に圧入する方法
である。If the polysaccharide has been subjected to an alkali heat treatment, subsequently the tip speed of the stirring blade according to the present invention is 2.
A method of cooling while maintaining the rotation speed of 0 m / s or less, or cooling without applying shearing force by stirring is applied. ) Specifically, a method of externally cooling the outside of the jar fermenter container with a refrigerant such as water without stirring the inside of the jar fermenter container, or stirring the refrigerant while passing the refrigerant through a cooling coil in the jar fermenter container. Examples thereof include a method of stirring and cooling the blade at a tip speed of 2.0 m / s or less, and a method of press-fitting into a refrigerant cooled coil (coil for cooling) from a jar fermenter container to cool. For cooling in a large jar fermenter vessel,
Cooling takes time at low tip speed and low stirring speed,
It is not preferable because a polysaccharide having a desired viscosity cannot be obtained. The shape of the stirring blade at the time of stirring and cooling is not particularly limited, and a propeller type, ribbon type, blade type or the like is appropriately selected in consideration of a container such as a jar fermenter. A flexible pipe used for cooling (cooling coil)
The diameter, length, material and shape of the are not particularly limited, and may be appropriately selected in consideration of conditions such as the ultimate cooling temperature, the amount of cooling treatment, and the time. The feature of the present invention is that when cooling the polysaccharide aqueous solution that has been subjected to the alkali heat treatment, there is substantially no shearing force due to stirring or the like, or the shearing force due to stirring or the like is reduced to cool, and preferably ,
This is a method of press-fitting into a flexible pipe (cooling coil) that is not accompanied by shearing force.
【0028】撹拌冷却時の撹拌翼の先端速度が2.0m
/sを越えると、アルカリ加熱処理して得られる多糖類
の粘性の増加が少なく、しかもアルカリ加熱処理前の該
多糖類よりも温度による粘性の変化が大きくなるうえ
に、粘度の経時変化も大きくなり好ましくない。また、
必要以上の撹拌冷却の継続も好ましくない。The tip speed of the stirring blade during stirring and cooling is 2.0 m.
If it exceeds / s, the increase in viscosity of the polysaccharide obtained by the alkali heat treatment is small, and the change in viscosity with temperature is larger than that of the polysaccharide before the alkali heat treatment, and the change in viscosity with time is also large. It is not preferable. Also,
It is not preferable to continue stirring and cooling more than necessary.
【0029】冷却目標温度は、特に限定されたものでは
ないが、通常、40℃〜室温を目安に適宜選択されれば
良い。The target cooling temperature is not particularly limited, but it may be appropriately selected usually from 40 ° C. to room temperature.
【0030】アルカリ加熱処理を施した多糖類水溶液の
冷却温度が40℃〜室温に達したならば、無機酸(硫
酸、塩酸)の水溶液を加えて中和し、次いで攪拌下に約
3倍量(容量)のアセトン、エタノール、イソプロピル
アルコールなどの有機溶媒を加えて、加熱処理された多
糖類を凝集物として析出させ、ろ過、減圧乾燥すること
により、目的とする増粘剤が容易に単離される。When the cooling temperature of the aqueous solution of the polysaccharide subjected to the alkali heat treatment reaches 40 ° C. to room temperature, an aqueous solution of an inorganic acid (sulfuric acid, hydrochloric acid) is added to neutralize it, and then about 3 times the amount is added with stirring. By adding (volume) of an organic solvent such as acetone, ethanol, or isopropyl alcohol, the heat-treated polysaccharide is precipitated as an agglomerate, and the target thickener is easily isolated by filtration and drying under reduced pressure. Be done.
【0031】アルカリ加熱処理を施した多糖類は、これ
を強い剪断力を伴わない方式で冷却することにより)少
量で高い増粘性を持ち、さらに乳化製品の乳化安定化
性、個体分散製品の分散安定化性に優れるために、化粧
品、医薬品、食品、塗料、インク、農薬などの広い分野
で適用できるようになった。The polysaccharide which has been subjected to the alkali heat treatment has a high thickening property in a small amount (by cooling the polysaccharide in a manner not accompanied by strong shearing force), and further, the emulsion stability of the emulsified product and the dispersion of the solid dispersed product. Due to its excellent stability, it has become applicable to a wide range of fields such as cosmetics, pharmaceuticals, foods, paints, inks and agricultural chemicals.
【0032】また、本発明の増粘剤には、本発明の効果
を損なわない範囲で、他の増粘剤と混合して用いること
も、何ら妨げるものではない。The thickener of the present invention may be used in a mixture with other thickeners as long as the effects of the present invention are not impaired.
【0033】本発明で用いられる多糖類は、分子量1千
万以上と極めて高分子であるため、アルカリ水溶液の形
態で高温処理すると、分子が伸びた状態になり、増粘性
が高くなる。しかし、冷却時に強力に撹拌して剪断力を
かけると、伸びた分子鎖が剪断力により切断し、さらに
分子の一部の立体構造に変化が起こるため、粘度が低下
し増粘効果が得られなくなると考えられる。Since the polysaccharide used in the present invention is an extremely high molecular weight polymer having a molecular weight of 10 million or more, when it is treated at a high temperature in the form of an aqueous alkaline solution, the molecule becomes elongated and the viscosity increases. However, when the mixture is vigorously stirred and subjected to shearing force during cooling, the extended molecular chain is cut by shearing force, and part of the three-dimensional structure of the molecule is changed, resulting in a decrease in viscosity and a thickening effect. It is thought to disappear.
【0034】[0034]
【実施例】以下、実施例によって本発明を具体的に説明
する。ただし、本発明はこれらに限定されるものではな
い。EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
【0035】[アルカリゲネス レータス B−16株細
菌の培養]アルカリゲネス レータス B−16(FER
M BP2015)株を肉エキス0.5%、ペプトン1
%、食塩0.3%からなる培地1Lに接種し、30℃,
24時間、振盪培養し、これを種として300L容量の
ジャーファーメンターに下記組成の培養培地200Lを
入れ、で30℃,144時間通気撹拌(通気量:200
L/min、撹拌数:250rpm)培養した。[Culture of Alcaligenes latorus B-16 strain bacterium] Alcaligenes latorus B-16 (FER
MBP2015) strain with meat extract 0.5%, peptone 1
%, Sodium chloride 0.3%, inoculated into 1 L of medium,
After shaking culture for 24 hours, 200 L of a culture medium having the following composition was put into a 300 L jar fermenter using this as a seed, and aerated and stirred at 30 ° C. for 144 hours (aeration amount: 200
L / min, agitation number: 250 rpm) were cultured.
【0036】
<培養培地の組成>
グルコース 〔和光純薬工業(株)製 試薬〕 4.00kg
リン酸水素二カリウム 〔和光純薬工業(株)製 試薬〕 0.40kg
リン酸二水素カリウム 〔和光純薬工業(株)製 試薬〕 0.20kg
塩化ナトリウム 〔和光純薬工業(株)製 試薬〕 0.01kg
硫酸マグネシウム 〔和光純薬工業(株)製 試薬〕 0.02kg
硝酸カリウム 〔和光純薬工業(株)製 試薬〕 0.10kg
イーストエキストラクト〔オキソイド(OXOID)社製〕 0.15kg
以上の成分をイオン交換水に溶解し、水酸化ナトリウム
および硫酸を用いてpH6.5に調整し、全量を200
リットルとした。<Composition of culture medium> Glucose [Wako Pure Chemical Industries, Ltd. reagent] 4.00 kg Dipotassium hydrogen phosphate [Wako Pure Chemical Industries, Ltd. reagent] 0.40 kg potassium dihydrogen phosphate [Japanese Kojun Pure Chemicals Co., Ltd. Reagent] 0.20kg Sodium chloride [Wako Pure Chemicals Co., Ltd. Reagent] 0.01kg Magnesium Sulfate [Wako Pure Chemicals Co., Ltd. Reagent] 0.02kg Potassium Nitrate [Wako Pure Chemicals Industry] Co., Ltd. reagent] 0.10 kg yeast extract [manufactured by Oxoid (OXOID)] 0.15 kg The above components are dissolved in ion-exchanged water, and the pH is adjusted to 6.5 using sodium hydroxide and sulfuric acid. To 200
It was liter.
【0037】[B−16多糖類の調製]培養終了後、培
養物に約3倍容量のイソプロピルアルコールを加えて攪
拌混合し、析出した凝集物を濾過、回収し、減圧下にて
乾燥し、B−16多糖類を得た。[Preparation of B-16 Polysaccharide] After the completion of the culture, about 3 volumes of isopropyl alcohol were added to the culture, and the mixture was stirred and mixed. The precipitated aggregate was filtered, collected, and dried under reduced pressure. A B-16 polysaccharide was obtained.
【0038】[多糖類−1の調製]300リットル容器
に水199.9kgを入れ、撹拌下、上記の方法で得ら
れたB−16多糖類100gを加えて溶解し、0.5重
量%水溶液200kgを調製した。これを1モル/L水
酸化ナトリウム水溶液にてpHを13に調整した後、3
00リットルのジャーファーメンターに入れて、室温に
て一晩放置した。放置後、120℃で20分間、加圧加
熱処理を行ない、次いで100℃まで冷却し、常圧に戻
してアルカリ加熱処理したB−16多糖類を得た。ステ
ンレス製蛇管(内径20mm、長さ12.5m)の外部
を15℃の冷水で冷却しながら得られたアルカリ加熱処
理したB−16多糖類を加圧方式で30分間かけて通し
30℃まで冷却し、1モル/L硫酸で中和した。中和
後、該多糖類水溶液の約3倍容量のイソプロピルアルコ
ールを添加し、析出した凝集物をろ過し、減圧乾燥して
多糖類−1を得た。[Preparation of Polysaccharide-1] 199.9 kg of water was placed in a 300 liter container, 100 g of the B-16 polysaccharide obtained by the above method was added and dissolved under stirring to prepare a 0.5 wt% aqueous solution. 200 kg was prepared. This was adjusted to pH 13 with a 1 mol / L sodium hydroxide aqueous solution, and then 3
It was placed in a 00 liter jar fermenter and left overnight at room temperature. After standing, pressure heating treatment was carried out at 120 ° C. for 20 minutes, then cooling to 100 ° C. and returning to normal pressure to obtain alkali heat treated B-16 polysaccharide. While cooling the outside of a stainless steel flexible tube (inner diameter 20 mm, length 12.5 m) with cold water at 15 ° C., the alkali-heated B-16 polysaccharide was passed through the pressure system for 30 minutes and cooled to 30 ° C. Then, it was neutralized with 1 mol / L sulfuric acid. After neutralization, about 3 times the volume of the aqueous polysaccharide solution was added to isopropyl alcohol, and the precipitated aggregates were filtered and dried under reduced pressure to obtain polysaccharide-1.
【0039】[多糖類−2の調製]500リットル容器
に水99.95gを入れ、撹拌下、上記の方法で得られ
たB−16多糖類0.5gを加えて溶解し、0.5重量
%水溶液100gを調製した。これを1モル/L水酸化
ナトリウム水溶液にてpHを13に調整した後、30リ
ットルのジャーファーメンターに入れて、室温にて一晩
放置した。放置した。それを120℃で20分間、加圧
加熱処理を行った後、静置して室温まで冷却し、1モル
/L硫酸で中和した。中和後、該多糖類水溶液の約3倍
容量のイソプロピルアルコールを添加し、析出した凝集
物をろ過し、減圧乾燥してアルカリ加熱処理した多糖類
−2を得た。[Preparation of Polysaccharide-2] 99.95 g of water was placed in a 500-liter container, 0.5 g of the B-16 polysaccharide obtained by the above method was added and dissolved under stirring to obtain 0.5 wt. % 100% aqueous solution was prepared. This was adjusted to pH 13 with a 1 mol / L sodium hydroxide aqueous solution, put into a 30 liter jar fermenter, and left overnight at room temperature. I left it. It was heated at 120 ° C. for 20 minutes under pressure, then allowed to stand, cooled to room temperature, and neutralized with 1 mol / L sulfuric acid. After neutralization, about 3 times the volume of the polysaccharide aqueous solution was added to isopropyl alcohol, and the precipitated aggregate was filtered and dried under reduced pressure to obtain alkali-treated polysaccharide-2.
【0040】[多糖類−3の調製]30リットル容器に
水19.99kgを入れ、撹拌下、上記の方法で得られ
たB−16多糖類10gを加えて溶解し、0.5重量%
水溶液20kgを調製した。これを1モル/L水酸化ナ
トリウム水溶液にてpHを13に調整した後、30リッ
トルのジャーファーメンターに入れて、室温にて一晩放
置した。ジャーファーメンターを加熱し、120℃で2
0分間、加圧加熱処理を行った。次いで100℃まで冷
却し、常圧に戻した後、ジャーファーメンターのジャケ
ットに15℃の冷水を通して6時間かけて冷却した。さ
らに1モル/L硫酸で中和し、該多糖類水溶液の約3倍
容量のイソプロピルアルコールを添加し、析出した凝集
物をろ過し、減圧乾燥してアルカリ加熱処理した多糖類
−3を得た。[Preparation of Polysaccharide-3] In a 30 liter container, 19.99 kg of water was added, and 10 g of the B-16 polysaccharide obtained by the above method was added and dissolved under stirring to give 0.5% by weight.
20 kg of aqueous solution was prepared. This was adjusted to pH 13 with a 1 mol / L sodium hydroxide aqueous solution, put into a 30 liter jar fermenter, and left overnight at room temperature. Heat the jar fermenter to 120 ° C for 2
Pressure heating treatment was performed for 0 minutes. Then, after cooling to 100 ° C. and returning to normal pressure, cold water of 15 ° C. was passed through the jacket of the jar fermenter for 6 hours for cooling. Further, it was neutralized with 1 mol / L sulfuric acid, isopropyl alcohol in an amount about 3 times the volume of the polysaccharide aqueous solution was added, and the precipitated aggregate was filtered and dried under reduced pressure to obtain alkali-treated polysaccharide-3. .
【0041】[多糖類−4の製造]アルカリ加熱処理し
た多糖類−1の製造方法において、得られたアルカリ加
熱処理したB−16多糖類の入っている30リットルの
ジャーファーメンターのジャケットに15℃の冷水を通
して冷却し、同時にプロペラ型撹拌翼を持つ撹拌装置を
使い、先端速度1.88m/Sで2時間撹拌して30℃
以下に冷却し、1モル/L硫酸で中和した。中和後、該
多糖類水溶液の約3倍容量のイソプロピルアルコールを
添加し、析出した凝集物をろ過し、減圧乾燥してアルカ
リ加熱処理した多糖類−4を得た。同様に表1記載の冷
却条件で30リットルのジャーファーメンターにて多糖
類−7を得た。[Production of Polysaccharide-4] In the method for producing the alkali-heat-treated Polysaccharide-1, the obtained alkali-heat-treated B-16 polysaccharide was placed in a jacket of a 30-liter jar fermenter containing 15 It is cooled by passing cold water of ℃ at the same time, using a stirring device with a propeller-type stirring blade at the same time, stirring at a tip speed of 1.88 m / S for 2 hours and stirring at 30 °
It cooled below and neutralized with 1 mol / L sulfuric acid. After neutralization, about 3 times the volume of the polysaccharide aqueous solution was added to isopropyl alcohol, and the precipitated aggregates were filtered and dried under reduced pressure to obtain alkali-treated polysaccharide-4. Similarly, under the cooling conditions shown in Table 1, polysaccharide-7 was obtained with a 30 liter jar fermenter.
【0042】[多糖類−5の製造]300リットル容器
に水199.9kgを入れ、撹拌下、上記の方法で得ら
れたB−16多糖類100gを加えて溶解し、0.5重
量%水溶液200kgを調製した。これを1モル/L水
酸化ナトリウム水溶液にてpHを13に調整した後、3
00リットルのジャーファーメンターに入れて、室温に
て一晩放置した。ジャーファーメンターを加熱し、12
0℃で20分間、加圧加熱処理を行ない、次いで100
℃まで冷却し、常圧に戻した後、ジャーファーメンター
のジャケットに15℃の冷水を通し、同時にプロペラ型
撹拌翼を持つ撹拌装置を使い、先端速度1.88m/s
で2時間撹拌し、30℃以下に冷却した。さらに1モル
/L硫酸で中和し、該多糖類水溶液の約3倍容量のイソ
プロピルアルコールを添加し、析出した凝集物をろ過
し、減圧乾燥して多糖類−5を得た。同様に表1記載の
冷却条件で多糖類−8,9を調製した。なお、多糖類−
6は、アルカリ処理をしていないB−16多糖類であ
る。[Production of Polysaccharide-5] 199.9 kg of water was placed in a 300 liter container, 100 g of the B-16 polysaccharide obtained by the above method was added and dissolved under stirring, and a 0.5 wt% aqueous solution was prepared. 200 kg was prepared. This was adjusted to pH 13 with a 1 mol / L sodium hydroxide aqueous solution, and then 3
It was placed in a 00 liter jar fermenter and left overnight at room temperature. Heat the jar fermenter, 12
Pressure heat treatment at 0 ° C for 20 minutes, then 100
After cooling to ℃ and returning to normal pressure, cold water at 15 ℃ was passed through the jacket of the jar fermenter, and at the same time, using a stirring device with a propeller-type stirring blade, the tip speed was 1.88 m / s.
The mixture was stirred for 2 hours and cooled to below 30 ° C. Further, the mixture was neutralized with 1 mol / L sulfuric acid, isopropyl alcohol in an amount about 3 times the volume of the polysaccharide aqueous solution was added, and the precipitated aggregate was filtered and dried under reduced pressure to obtain polysaccharide-5. Similarly, polysaccharides-8 and 9 were prepared under the cooling conditions shown in Table 1. In addition, polysaccharide-
6 is a B-16 polysaccharide that has not been treated with alkali.
【0043】[多糖類−10の製造]キサンタンガム
(商標、三晶(株)製)の0.5重量%水溶液を調製
し、増粘剤−10とした。[Manufacture of Polysaccharide-10] A 0.5% by weight aqueous solution of xanthan gum (trademark, manufactured by Sansho Co., Ltd.) was prepared as a thickener-10.
【0044】[多糖類−11の製造]多糖類−1の製造
方法において、B−16多糖類をキサンタンガム(商
標、三晶(株)製)に置き換えて調製し、多糖類−11
を得た。[Production of Polysaccharide-11] Polysaccharide-11 was prepared by substituting xanthan gum (trademark, manufactured by Sansho Co., Ltd.) for B-16 polysaccharide in the method for producing Polysaccharide-1.
Got
【0045】[0045]
【表1】 [Table 1]
【0046】[増粘剤水溶液の粘度測定]200mLト
ールビーカーに増粘剤0.2g、水199.8gを加
え、小型ホモミキサーにて8000rpmで10分間攪
拌分散させて、0.1重量%水溶液とした。該水溶液を
30℃、50℃、80℃の各恒温水層につけて、24時
間静置した後、30℃にしてB型回転粘度計(30rp
m、回転開始より1分後に測定)で粘度を測定した。結
果を表2に示す。[Viscosity Measurement of Thickener Aqueous Solution] To a 200 mL tall beaker, 0.2 g of a thickener and 199.8 g of water were added, and the mixture was stirred and dispersed at 8000 rpm for 10 minutes with a small homomixer to prepare a 0.1 wt% aqueous solution. And The aqueous solution was immersed in each of the constant temperature water layers of 30 ° C., 50 ° C. and 80 ° C., allowed to stand for 24 hours, then brought to 30 ° C., and a B type rotational viscometer (30 rp).
m, and measured 1 minute after the start of rotation). The results are shown in Table 2.
【0047】[0047]
【表2】 [Table 2]
【0048】アルカリ加熱処理後のB−16多糖類を冷
却する際に、無撹拌下あるいは撹拌による剪断力2.0
0m/s以下で冷却、調製した本発明の増粘剤は、撹拌
による先端速度が2.00m/sを超えた条件で冷却、
調製した比較例7〜9よりも高い粘度を示し、高温でも
粘度を保持し、温度による経時変化も小さいことがわか
る。特に剪断力の伴わない蛇管(冷却用コイル)を用い
た冷却方法で得られた増粘剤−1、並びに500m容器
での静置による冷却で得られた増粘剤−2はいずれもB
−16多糖類に比べて、より高い粘性を示し、更に低温
から高温域までの粘性の経時変化も小さいことが分か
る。また、キサンタンガムでは同様なアルカリ加熱処
理、無撹拌下での冷却方法によっても増粘効果は全く見
られなかった。When cooling the B-16 polysaccharide after the alkali heat treatment, a shearing force of 2.0 with or without stirring is applied.
The thickener of the present invention prepared by cooling at 0 m / s or less is cooled under the condition that the tip speed by stirring exceeds 2.00 m / s.
It can be seen that the viscosity is higher than those of the prepared Comparative Examples 7 to 9, the viscosity is maintained even at high temperature, and the change with time due to temperature is small. In particular, the thickener-1 obtained by a cooling method using a flexible tube (cooling coil) without shearing force and the thickener-2 obtained by cooling by standing in a 500 m container are both B
It can be seen that the viscosity of the -16 polysaccharide is higher than that of -16 polysaccharide, and the change with time of the viscosity from a low temperature to a high temperature region is small. Also, with xanthan gum, no thickening effect was observed even by the same alkali heat treatment and cooling method without stirring.
【0049】[乳化・分散安定化性の測定]200mL
トールビーカーに増粘剤96mg、水159.904g
を加え、小型ホモミキサーにて8000rpmで20分
間撹拌分散させて、0.06重量%水溶液とした。それ
に流動パラフィン0.8gを加え、小型ホモミキサーに
て8000rpmで10分間撹拌分散させ、その液の一
部をとり、500nmの吸光度を測定し、測定値をAと
した。吸光度測定後、直径2.5mmのガラス製のサン
プル瓶2本に約40mLづつとり、30℃と50℃に静
置した。そして、1週間後、2ヶ月後にサンプル瓶の底
部からパスツールピペットで試料をとり、500nmの
吸光度を測定し、Bとした。次式のように試料液調製直
後の吸光度:Aと所定期間静置後の試料の吸光度Bの比
を乳化・分散安定率(%)とし評価し、この比が高い程
良い。その結果を表3に示した。
乳化・分散安定化率(%)={(B)/(A)}×10
0[Measurement of emulsification / dispersion stability] 200 mL
Thor beaker 96mg thickener, water 159.904g
Was added, and the mixture was stirred and dispersed at 8000 rpm for 20 minutes with a small homomixer to obtain a 0.06 wt% aqueous solution. Liquid paraffin (0.8 g) was added thereto, and the mixture was stirred and dispersed at 8000 rpm for 10 minutes with a small homomixer, a part of the liquid was taken, the absorbance at 500 nm was measured, and the measured value was set to A. After measuring the absorbance, about 40 mL each was placed in two glass sample bottles having a diameter of 2.5 mm and left at 30 ° C. and 50 ° C. Then, after 1 week and 2 months, a sample was taken from the bottom of the sample bottle with a Pasteur pipette, and the absorbance at 500 nm was measured and designated as B. The ratio of the absorbance A immediately after the preparation of the sample solution: A and the absorbance B of the sample after standing for a predetermined period was evaluated as the emulsification / dispersion stability rate (%) as in the following formula, and the higher the ratio, the better. The results are shown in Table 3. Emulsification / dispersion stabilization rate (%) = {(B) / (A)} × 10
0
【0050】[0050]
【表3】 [Table 3]
【0051】アルカリ加熱処理後の冷却時、無撹拌下あ
るいは撹拌による剪断力が小さい状態で調製した本発明
の増粘剤は、乳化・分散安定化性に優れていることが分
かる。It can be seen that the thickener of the present invention prepared without stirring or with a small shearing force by stirring during cooling after the alkali heat treatment is excellent in emulsion / dispersion stability.
【0052】[0052]
【発明の効果】本発明の増粘剤は、従来の増粘剤に比べ
て、少量で高い粘性を示し、高温、長時間でも粘性を維
持し、しかも乳化・分散安定化性に優れている。そのた
め、化粧品、医薬品、食品、塗料、インク、農薬等の乳
化製品の増粘、乳化・分散安定化に好適に使用できる。INDUSTRIAL APPLICABILITY The thickener of the present invention shows a high viscosity with a small amount, maintains the viscosity even at high temperature and for a long time, and is excellent in emulsion / dispersion stability as compared with the conventional thickeners. . Therefore, it can be suitably used for thickening and emulsifying / dispersing and stabilizing emulsified products such as cosmetics, pharmaceuticals, foods, paints, inks and agricultural chemicals.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 黒宮 友美 三重県四日市市別名六丁目6番9号 伯東 株式会社四日市研究所内 (72)発明者 久芳 啓資 大分県佐伯市字野岡11772番地81 (72)発明者 美矢 豊文 大分県佐伯市字女島6952番地3 Fターム(参考) 4C083 AD211 EE01 EE07 FF01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Tomomi Kuromiya Mie prefecture Yokkaichi city aka 6-6-9 Hakuto Yokkaichi Institute Inc. (72) Inventor Keisuke Hisayoshi 81, No. 11772, Nooka, Saiki City, Oita Prefecture (72) Inventor Toyoya Fumiya 65-2 Mejima, Saiki City, Oita Prefecture F term (reference) 4C083 AD211 EE01 EE07 FF01
Claims (5)
ロン酸、ラムノースを構成単糖として含む多糖類を、p
Hが8以上のアルカリ水溶液中、60〜180℃で加熱
処理した後、撹拌翼の先端速度が2.0m/s以下の回
転速度に保持しながら冷却するか、または撹拌による剪
断力を加えずに冷却する方法によって得られた多糖類を
有効成分として含む増粘剤。1. A polysaccharide substantially containing fucose, glucose, glucuronic acid and rhamnose as constituent monosaccharides,
After heat-treating at 60 to 180 ° C in an alkaline aqueous solution having H of 8 or more, cooling is performed while maintaining the tip speed of the stirring blade at a rotation speed of 2.0 m / s or less, or without applying shearing force by stirring. A thickener containing, as an active ingredient, a polysaccharide obtained by a cooling method.
ス:グルコース:グルクロン酸:ラムノース=1〜2:
1〜4:1〜2:1〜2である請求項1記載の増粘剤。2. The constituent monosaccharides of the polysaccharide are fucose: glucose: glucuronic acid: rhamnose = 1 to 2: in molar ratio.
The thickener according to claim 1, which is 1 to 4: 1 to 2: 1 to 2.
クロン酸、ラムノースにて構成され、さらにフコースが
側鎖に結合している構造を有する請求項1又は2記載の
増粘剤。3. The thickener according to claim 1, wherein the polysaccharide has a structure composed of glucose, glucuronic acid, and rhamnose as a main chain, and further has fucose bonded to a side chain.
−16株の産生する多糖類である請求項1ないし3のう
ちのいずれかに記載の増粘剤。4. The polysaccharide is Alkaline Genesulators B.
The thickener according to any one of claims 1 to 3, which is a polysaccharide produced by strain -16.
法が、冷却した蛇管内を加圧下通過させる方法である請
求項1ないし4のうちのいずれかに記載の増粘剤。5. The thickener according to any one of claims 1 to 4, wherein the method of cooling without applying shearing force by stirring is a method of passing the cooled flexible tube under pressure.
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JP2011238595A Division JP5320449B2 (en) | 2011-10-31 | 2011-10-31 | Method for producing thickener |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002053426A (en) * | 2001-09-28 | 2002-02-19 | Hakuto Co Ltd | Water-based cosmetic |
JP2002060314A (en) * | 2001-09-18 | 2002-02-26 | Hakuto Co Ltd | Skin care preparation |
JP2003089624A (en) * | 2001-09-18 | 2003-03-28 | Hakuto Co Ltd | Rinse for hair |
WO2003082225A1 (en) * | 2002-03-28 | 2003-10-09 | Hakuto Co., Ltd. | Method of foam stabilization for foam cosmetic |
WO2006028012A1 (en) * | 2004-09-07 | 2006-03-16 | Hakuto Co., Ltd. | Cosmetics and process for production thereof |
JP2008007491A (en) * | 2006-06-30 | 2008-01-17 | Univ Kanagawa | Cosmetic material and method for producing the same |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07184676A (en) * | 1993-12-24 | 1995-07-25 | Agency Of Ind Science & Technol | Production of polysaccharide |
JPH08336394A (en) * | 1995-06-13 | 1996-12-24 | Agency Of Ind Science & Technol | Production of polysaccharides |
JP2002030243A (en) * | 2001-01-30 | 2002-01-31 | Hakuto Co Ltd | Aqueous ink composition |
JP2002030242A (en) * | 2001-03-01 | 2002-01-31 | Hakuto Co Ltd | Aqueous ink composition for ball-point pen |
JP2002121538A (en) * | 2000-10-13 | 2002-04-26 | Hakuto Co Ltd | Thickener and cosmetic containing the same |
-
2001
- 2001-08-10 JP JP2001243660A patent/JP2003055641A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07184676A (en) * | 1993-12-24 | 1995-07-25 | Agency Of Ind Science & Technol | Production of polysaccharide |
JPH08336394A (en) * | 1995-06-13 | 1996-12-24 | Agency Of Ind Science & Technol | Production of polysaccharides |
JP2002121538A (en) * | 2000-10-13 | 2002-04-26 | Hakuto Co Ltd | Thickener and cosmetic containing the same |
JP2002030243A (en) * | 2001-01-30 | 2002-01-31 | Hakuto Co Ltd | Aqueous ink composition |
JP2002030242A (en) * | 2001-03-01 | 2002-01-31 | Hakuto Co Ltd | Aqueous ink composition for ball-point pen |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002060314A (en) * | 2001-09-18 | 2002-02-26 | Hakuto Co Ltd | Skin care preparation |
JP2003089624A (en) * | 2001-09-18 | 2003-03-28 | Hakuto Co Ltd | Rinse for hair |
JP4716476B2 (en) * | 2001-09-18 | 2011-07-06 | 伯東株式会社 | Hair rinse |
JP2002053426A (en) * | 2001-09-28 | 2002-02-19 | Hakuto Co Ltd | Water-based cosmetic |
WO2003082225A1 (en) * | 2002-03-28 | 2003-10-09 | Hakuto Co., Ltd. | Method of foam stabilization for foam cosmetic |
WO2006028012A1 (en) * | 2004-09-07 | 2006-03-16 | Hakuto Co., Ltd. | Cosmetics and process for production thereof |
JP2008007491A (en) * | 2006-06-30 | 2008-01-17 | Univ Kanagawa | Cosmetic material and method for producing the same |
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