WO1997008208A1 - Process for producing sprayable cationic biopolymers - Google Patents

Process for producing sprayable cationic biopolymers Download PDF

Info

Publication number
WO1997008208A1
WO1997008208A1 PCT/EP1996/003635 EP9603635W WO9708208A1 WO 1997008208 A1 WO1997008208 A1 WO 1997008208A1 EP 9603635 W EP9603635 W EP 9603635W WO 9708208 A1 WO9708208 A1 WO 9708208A1
Authority
WO
WIPO (PCT)
Prior art keywords
chitosans
cationic biopolymers
hydrogen peroxide
process according
weight
Prior art date
Application number
PCT/EP1996/003635
Other languages
German (de)
French (fr)
Inventor
Peter Horlacher
Rolf Wachter
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP96929271A priority Critical patent/EP0847403A1/en
Priority to AU68739/96A priority patent/AU6873996A/en
Publication of WO1997008208A1 publication Critical patent/WO1997008208A1/en
Priority to NO975791A priority patent/NO975791D0/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/736—Chitin; Chitosan; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring

Definitions

  • the invention relates to a method for producing sprayable cationic biopolymers by degrading chitosan powders with hydrogen peroxide.
  • Chitosans are biopolymers and belong to the group of hydrocolloids. Chemically speaking, they are partially deacetylated chitins of different molecular weights that contain the - idealized - following idealized monomer building block:
  • chitosans are cationic biopolymers under these conditions.
  • the positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products
  • a problem in the production of chitosans is that the aqueous or glycolic acid solutions of the products have too high a viscosity for the production of spray formulations even when diluted strongly (1 to 3% by weight), so that the incorporation of Chitosan, an excellent film-forming agent, for example in hair sprays, is not readily possible.
  • Another disadvantage is that the chitosans have a reddish color due to the production process, which is not desirable for a large number of cosmetic applications
  • the object of the invention was therefore to develop a process for the production of cationic biopolymers, especially chitosans, whose solutions are low-viscosity at the same time, can be easily sprayed and have an advantageously high color quality.
  • the invention relates to a process for the preparation of sprayable cationic biopolymers, in which powdered chitosans are broken down in a mixing device with an aqueous hydrogen peroxide solution and then dissolved in polar media
  • the selection of the chitosans to which the degradation process extends is not critical in itself. This means that neither the degree of deacylation nor the average molecular weight of the biopolymers have a significant influence on the resulting viscosity, color and stability of the products.
  • the grain size of the chitosan used there have been slight advantages for microcrystalline products, but the use of chitosans of conventional grain size distribution, such as those that occur in spray drying, steam drying or freeze drying, if necessary after subsequent mechanical comminution and autoclaving, leads to excellent product qualities .
  • the method is also applicable to derivatized chitosans such as e.g. quaternary products of the type of hydroxypropylchitosan and applicable to anionic reaction products of chitosans with dicarboxylic anhydrides.
  • the chitosan powder which may have a residual moisture content of 5 to 35% by weight, is placed in a mixer, for example a ploughshare mixer from Lödige or a Drais mixer, and the corresponding amount of hydrogen peroxide solution is added. If necessary, the product can then be subjected to further drying. The degradation is usually carried out over a period of 0.5 to 5, preferably 1 to 3, hours. Practically colorless, storage-stable products are obtained whose solutions can be easily sprayed.
  • Polar media for example a ploughshare mixer from Lödige or a Drais mixer
  • Suitable solvents for the degraded chitosan powder are water and organic acids, preferably glycolic or acetic acid.
  • the powders are usually dissolved in amounts of 0.5 to 5 and preferably 1 to 3% by weight.
  • the chitosan additives obtainable by the process according to the invention are dissolved in water or organic acids, the 1 to 5% by weight solutions show a surprisingly low viscosity and can be sprayed easily. They are also practically colorless and stable in storage.
  • the cationic biopolymers obtainable by the process according to the invention are therefore suitable • both as powder and in the form of said solutions - as raw materials for the preparation of hair and body preparations, in which they are present in amounts of 0.5 to 10, preferably 1 to 5 wt .-% - based on the agent - may be included.
  • Another object of the invention therefore relates to the use of the chitosans obtainable by the process described for the production of spray formulations, in particular hair sprays.
  • a typical spray formulation is shown in Table 1; Percentages as% by weight.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Molecular Biology (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

A process is disclosed for producing sprayable cationic biopolymers. Chitosan powder is decomposed in a mixer together with an aqueous hydrogen peroxide solution, then dissolved in polar media. The thus obtained products are very fluid and may also be used in spray preparations, for example hair sprays.

Description

Verfahren zur Herstellung versprühbarer kationischer Biopoiymere Process for the preparation of sprayable cationic biopolymers
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft ein Verfahren zur Herstellung versprühbarer kationischer Biopolymere durch Abbau von Chitosanpulvern mit Wasserstoffperoxid.The invention relates to a method for producing sprayable cationic biopolymers by degrading chitosan powders with hydrogen peroxide.
Stand der TechnikState of the art
Chitosane stellen Biopolymere dar und werden zur Gruppe der Hydrokolloide gezählt Chemisch betrachtet handelt es sich um partiell deacetylierte Chitine unterschiedlichen Molekulargewichtes, die den - idealisierten - folgenden idealisierten Monomerbaustein enthalten:Chitosans are biopolymers and belong to the group of hydrocolloids. Chemically speaking, they are partially deacetylated chitins of different molecular weights that contain the - idealized - following idealized monomer building block:
Figure imgf000003_0001
Figure imgf000003_0001
Im Gegensatz zu den meisten Hydrokolloiden, die im Bereich biologischer pH-Werte negativ geladen sind, stellen Chitosane unter diesen Bedingungen kationische Biopoiymere dar. Die positiv geladenen Chitosane können mit entgegengesetzt geladenen Oberflächen in Wechselwirkung treten und werden daher in kosmetischen Haar- und Köφeφflegemitteln eingesetztIn contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products
Obersichten zu diesem Thema sind beispielsweise von B.Gesslein et al. in HAPPI 27, 57 (1990), O.Skaugrud in Drug Cosm. Ind. 148, 24 (1991) und EOnsoyen et al. in Seifen-Öle-Fette-Wachse 117. 633 (1991) erschienen. Zur Herstellung der Chitosane geht man von Chitin, vorzugsweise den Schalenresten von Krustentieren aus, die als billige Rohstoffe in großen Mengen zur Verfügung stehen. Das Chitin wird dabei in einem Verfahren das erstmals von Hackmann et al. beschrieben worden ist üblicherweise zunächst durch Zusatz von Basen deproteiniert durch Zugabe von Mineralsäuren demineraiisiert und schließlich durch Zugabe von starken Basen deacetyiiert, wobei die Mole¬ kulargewichte über ein breites Spektrum verteilt sein können. Entsprechende Verfahren sind bei¬ spielsweise aus Makromol. Chem. 177, 3589 (1976) oder der französischen Patentanmeldung FR-A 2701 266 bekanntOverviews on this topic are, for example, by B. Gesslein et al. in HAPPI 27, 57 (1990), O.Skaugrud in Drug Cosm. Ind. 148, 24 (1991) and EOnsoyen et al. in soap-oil-fat waxes 117, 633 (1991). The production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials. The chitin is used in a process that was first developed by Hackmann et al. It has usually been described first as deproteinized by adding bases, by adding mineral acids, and finally deacetyiated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum. Corresponding methods are made, for example, of macromol. Chem. 177, 3589 (1976) or French patent application FR-A 2701 266
Ein Problem bei der Herstellung von Chitosanen besteht allerdings darin, daß die wäßrigen oder gly- colsauren Lösungen der Produkte selbst bei starker Verdünnung (1 bis 3 Gew.-%) für die Herstellung von Sprayrezepturen eine zu hohe Viskosität aufweisen, so daß die Einarbeitung von Chitosan, einem vorzüglichen Fiimbildner, beispielsweise in Haarsprays nicht ohne weiteres möglich ist Weiterhin von Nachteil ist es, daß die Chitosane hersteilungsbedingt eine rötliche Färbung aufweisen, die für eine Vielzahl von kosmetischen Anwendungen nicht erwünscht istA problem in the production of chitosans, however, is that the aqueous or glycolic acid solutions of the products have too high a viscosity for the production of spray formulations even when diluted strongly (1 to 3% by weight), so that the incorporation of Chitosan, an excellent film-forming agent, for example in hair sprays, is not readily possible. Another disadvantage is that the chitosans have a reddish color due to the production process, which is not desirable for a large number of cosmetic applications
Die Aufgabe der Erfindung hat daher darin bestanden, ein Verfahren zur Herstellung von kationischen Biopolymeren, speziell Chitosanen, zu entwickeln, deren Lösungen gleichzeitig niedrigviskos sind, sich einfach versprühen lassen und eine vorteilhaft hohe Farbqualität aufweisen.The object of the invention was therefore to develop a process for the production of cationic biopolymers, especially chitosans, whose solutions are low-viscosity at the same time, can be easily sprayed and have an advantageously high color quality.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung ist ein Verfahren zur Herstellung versprühbarer kationischer Biopolymere, bei dem man pulverförmige Chitosane in einer Mischvoπichtung mit einer wäßrigen Wasserstoff- peroxidlösung abbaut und anschließend in polaren Medien auflöstThe invention relates to a process for the preparation of sprayable cationic biopolymers, in which powdered chitosans are broken down in a mixing device with an aqueous hydrogen peroxide solution and then dissolved in polar media
Überraschenderweise wurde gefunden, daß die nachträgliche Behandlung von trockenen Chitosan- pulvern mit Wasserstoffperoxid beispielsweise in Pflugscharmischern schon bei niedrigen Tempera¬ turen nicht nur zu einer deutlichen Farbaufhellung führt, sondern gleichzeitig auch ein Abbau stattfindet so daß Produkte erhalten werden, deren verdünnte wäßrigen oder organisch sauren Lösungen nun eine so geringe Viskosität aufweisen, daß sie sich problemlos versprühen lassen. Da das Verfahren vorzugsweise bei neutralem bzw. durch das Chitosan schwach alkalischem pH-Wert durchgeführt wird, ist mit dem Peroxidabbau auch keine zusätzliche Salzbelastung verbunden. ChitosaneSurprisingly, it was found that the subsequent treatment of dry chitosan powders with hydrogen peroxide, for example in ploughshare mixers, not only leads to a clear lightening of the color even at low temperatures, but also degradation takes place at the same time, so that products are obtained whose dilute aqueous or organically acidic Solutions now have such a low viscosity that they can be sprayed without problems. Since the process is preferably carried out at a neutral pH or slightly alkaline due to the chitosan, there is no additional salt load associated with the peroxide degradation. Chitosane
Die Auswahl der Chitosane, auf die sich das Abbauverfahren erstreckt ist an sich unkritisch. Das bedeutet daß weder Deacylierungsgrad noch das mittlere Molekulargewicht der Biopolymere einen signifikanten Einfluß auf die resultierende Viskosität Farbe und Stabilität der Produkte haben. Im Hinblick auf die Korngröße des eingesetzten Chitosans haben sich leichte Vorteile für mikrokristalline Produkte ergeben, doch auch der Einsatz von Chitosanen konventioneller Korngrößenverteilung, wie sie beispielsweise bei der Sprühtrocknung, Heißdampftrocknung oder Gefriertrocknung, gegebenenfalls nach anschließender mechanischer Zerkleinerung und Autokiavierung anfälen, führt zu ausgezeichneten Produktqualitäten. Des weiteren ist das Verfahren auch auf derivatisierte Chitosane wie z.B. quartäre Produkte vom Typ des Hydroxypropylchitosans sowie auf anionische Umsetzungsprodukte von Chitosanen mit Dicarbonsäureanhydriden anwendbar.The selection of the chitosans to which the degradation process extends is not critical in itself. This means that neither the degree of deacylation nor the average molecular weight of the biopolymers have a significant influence on the resulting viscosity, color and stability of the products. With regard to the grain size of the chitosan used, there have been slight advantages for microcrystalline products, but the use of chitosans of conventional grain size distribution, such as those that occur in spray drying, steam drying or freeze drying, if necessary after subsequent mechanical comminution and autoclaving, leads to excellent product qualities . The method is also applicable to derivatized chitosans such as e.g. quaternary products of the type of hydroxypropylchitosan and applicable to anionic reaction products of chitosans with dicarboxylic anhydrides.
WasserstoffperoxidlösunqenHydrogen peroxide solutions
Als Abbaumittel kommen Wasserstoffperoxidlösungen des Handels in Betracht die einen Aktiv¬ substanzgehalt von 25 bis 55 und vorzugsweise 35 bis 50 Gew.-% aufweisen. Sie werden üblicher¬ weise in einer Konzentration von 0,05 bis 30, vorzugsweise 0,1 bis 10 und insbesondere 0,5 bis 5 Gew.-% - berechnet als 100%iges Wasserstoffperoxid und bezogen auf die Trockensubstanz der Chitosane - eingesetztCommercial hydrogen peroxide solutions which have an active substance content of 25 to 55 and preferably 35 to 50% by weight are suitable as degradation agents. They are usually used in a concentration of 0.05 to 30, preferably 0.1 to 10 and in particular 0.5 to 5% by weight, calculated as 100% hydrogen peroxide and based on the dry substance of the chitosans
Durchführung des PeroxidabbausImplementation of peroxide degradation
Es hat sich als besonders vorteilhaft erwiesen, den Peroxidabbau bei niedrigen Temperaturen, bei¬ spielsweise im Bereich von 30 bis 70 und vorzugsweise 45 bis 55βC durchzuführen. Hierzu legt man das Chitosanpulver, das eine Restfeuchte von 5 bis 35 Gew.-% aufweisen kann, in einem Mischer, beispielsweise einem Pflugscharmischer der Fa. Lödige oder einem Drais-Mischer vor und gibt die entsprechende Menge Wasserstoffperoxidlösung zu. Falls erforderlich, kann das Produkt anschließend einerweiteren Trocknung unterworfen werden. Üblicherweise wird der Abbau über einen Zeitraum von 0,5 bis 5, vorzugsweise 1 bis 3 h durchgeführt Es werden praktisch farblose, lagerstabile Produkte erhalten, deren Lösungen sich leicht versprühen lassen. Polare MedienIt has proved to be particularly advantageous, peroxide decomposition at low temperatures, spielsweise in the range of 30 to 70 and preferably 45 to 55 perform β C. For this purpose, the chitosan powder, which may have a residual moisture content of 5 to 35% by weight, is placed in a mixer, for example a ploughshare mixer from Lödige or a Drais mixer, and the corresponding amount of hydrogen peroxide solution is added. If necessary, the product can then be subjected to further drying. The degradation is usually carried out over a period of 0.5 to 5, preferably 1 to 3, hours. Practically colorless, storage-stable products are obtained whose solutions can be easily sprayed. Polar media
Als geeignete Lösungsmittel für die abgebauten Chitosanpuiver kommen Wasser und organische Säuren, vorzugsweise Glycol- oder Essigsäure in Frage. Üblicherweise löst man die Pulver in Mengen von 0,5 bis 5 und vorzugsweise 1 bis 3 Gew.-%.Suitable solvents for the degraded chitosan powder are water and organic acids, preferably glycolic or acetic acid. The powders are usually dissolved in amounts of 0.5 to 5 and preferably 1 to 3% by weight.
Gewerbliche AnwendbarkeitIndustrial applicability
Löst man die nach dem erfindungsgemäßen Verfahren erhältlichen Chitosanpuiver in Wasser oder organischen Säuren, zeigen die 1 bis 5 Gew.-%igen Lösungen eine überraschend niedrige Viskosität und lassen sich leicht versprühen. Sie sind zudem praktisch farblos und lagerstabil. Die nach dem erfindungsgemäßen Verfahren erhältlichen kationischen Biopolymere eignen sich daher • sowohl ais Pulver als auch in Form besagter Lösungen - als Rohstoffe für die Herstellung von Mitteln zur Haar- und Köφβφfiege, in denen sie in Mengen von 0,5 bis 10, vorzugsweise 1 bis 5 Gew.-% - bezogen auf die Mittel - enthalten sein können. Ein weiterer Gegenstand der Erfindung betrifft daher die Verwen¬ dung der nach dem beschriebenen Verfahren erhältlichen Chitosane zur Herstellung von Sprayrezep¬ turen, insbesondere Haarsprays. If the chitosan additives obtainable by the process according to the invention are dissolved in water or organic acids, the 1 to 5% by weight solutions show a surprisingly low viscosity and can be sprayed easily. They are also practically colorless and stable in storage. The cationic biopolymers obtainable by the process according to the invention are therefore suitable • both as powder and in the form of said solutions - as raw materials for the preparation of hair and body preparations, in which they are present in amounts of 0.5 to 10, preferably 1 to 5 wt .-% - based on the agent - may be included. Another object of the invention therefore relates to the use of the chitosans obtainable by the process described for the production of spray formulations, in particular hair sprays.
BeispieleExamples
Beispiel 1example 1
In einem Flugscharmischer der Fa. Lödige wurden 100 g eines leicht rosagefärbten Chitosanpulvers (Restfeuchte 10,3 Gew.-%, Viskosität der 1 Gew.-%igen wäßrigen Lösung bei pH = 5 : 3.500 mPas) und 27,5 g Wasser vorgelegt Hierzu wurden 0,9 g einer 50 Gew.-%igen Wasserstoffperoxidlösung bei einer Temperatur von 55βC gegeben. Der Ansatz wurde über einen Zeitraum von 90 min intensiv ver¬ mischt Anschließend wurde ein praktisch farbloses Produkt erhalten. Die 1 Gew.-%ige wäßrige Lösung zeigte nur noch eine Viskosität von 63 mPas (Brookfield RVF, Spindel 4 bzw. 1, 10 UpM, 20βC).100 g of a slightly pink-colored chitosan powder (residual moisture 10.3% by weight, viscosity of the 1% by weight aqueous solution at pH = 5: 3,500 mPas) and 27.5 g of water were placed in a flight shear mixer from Lödige 0.9 g of a 50 wt .-% hydrogen peroxide solution were added at a temperature of 55 ° C. The batch was mixed intensively over a period of 90 min. A practically colorless product was then obtained. The 1% by weight aqueous solution only had a viscosity of 63 mPas (Brookfield RVF, spindle 4 or 1, 10 rpm, 20 ° C.).
Beispiel 2Example 2
In einem Flugscharmischer der Fa. Lödige wurden 100 g eines leicht rosagefärbten Chitosanpulvers (Restfeuchte 10,3 Gew.-%, Viskosität der 1 Gew.-%igen wäßrigen Lösung bei pH = 5 : 3.500 mPas) und 27,5 g Wasser vorgelegt Hierzu wurden 9 g einer 50 Gew.-%igen Wasserstoffperoxidlösung bei einer Temperatur von 55βC gegeben. Der Ansatz wurde über einen Zeitraum von 90 min intensiv venmischt Anschließend wurde ein praktisch farbloses Produkt erhalten. Die 1 Gew.-%ige wäßrige Lösung zeigte nur noch eine Viskosität von 20 mPas (Brookfield RVF, Spindel 4 bzw. 1 , 10 UpM, 20*C).100 g of a slightly pink-colored chitosan powder (residual moisture 10.3% by weight, viscosity of the 1% by weight aqueous solution at pH = 5: 3,500 mPas) and 27.5 g of water were placed in a flight shear mixer from Lödige 9 g of a 50% by weight hydrogen peroxide solution were added at a temperature of 55 ° C. The mixture was intensively mixed over a period of 90 min. A practically colorless product was then obtained. The 1% by weight aqueous solution only showed a viscosity of 20 mPas (Brookfield RVF, spindle 4 or 1, 10 rpm, 20 * C).
Beispiel 3Example 3
In Tabelle 1 ist eine typische Sprayrezeptur wiedergegeben; Prozentangaben als Gew.-%.A typical spray formulation is shown in Table 1; Percentages as% by weight.
Tabelle 1 SprayrezepturTable 1 Spray formulation
Figure imgf000007_0001
Figure imgf000007_0001

Claims

Patentansprüche claims
1. Verfahren zur Herstellung versprühbarer kationischer Biopolymere, dadurch gekennzeichnet daß man pulverförmige Chitosane in einer Mischvorrichtung mit einer wäßrigen Wasserstoff¬ peroxidlösung abbaut und anschließend in polaren Medien auflöst1. A process for the preparation of sprayable cationic biopolymers, characterized in that powdery chitosans are broken down in a mixing device with an aqueous hydrogen peroxide solution and then dissolved in polar media
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet daß man den Abbau bei Tempera¬ turen im Bereich von 30 bis 70βC durchführt2. The method according to claim 1, characterized in that the degradation is carried out at temperatures in the range from 30 to 70 β C.
3. Verfahren nach den Ansprüchen 1 und 2, dadurch gekennzeichnet daß man ais polare Me¬ dien Wasser, Glycol- oder Essigsäure einsetzt3. Process according to claims 1 and 2, characterized in that water, glycolic or acetic acid is used as polar media
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet daß man die Wasserstoff¬ peroxidlösungen in Konzentrationen von 0,05 bis 30 Gew.-% - berechnet als 100%iges Was¬ serstoffperoxid und bezogen auf die Trockensubstanz der Chitosane - eingesetzt4. Process according to claims 1 to 3, characterized in that the hydrogen peroxide solutions in concentrations of 0.05 to 30 wt .-% - calculated as 100% Was¬ peroxide and based on the dry matter of the chitosans - used
5. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß man die abgebauten Chitosanpuiver in Mengen von 0,1 bis 5 Gew.-% löst5. Process according to claims 1 to 4, characterized in that the degraded chitosan puiver is dissolved in amounts of 0.1 to 5% by weight
6. Verwendung der nach dem Verfahren nach den Ansprüchen 1 bis 5 erhältlichen kationischen Biopolymere zur Herstellung von Sprayrezepturen. 6. Use of the cationic biopolymers obtainable by the process according to claims 1 to 5 for the production of spray formulations.
PCT/EP1996/003635 1995-08-28 1996-08-19 Process for producing sprayable cationic biopolymers WO1997008208A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96929271A EP0847403A1 (en) 1995-08-28 1996-08-19 Process for producing sprayable cationic biopolymers
AU68739/96A AU6873996A (en) 1995-08-28 1996-08-19 Process for producing sprayable cationic biopolymers
NO975791A NO975791D0 (en) 1995-08-28 1997-12-09 Process for the preparation of sprayable cationic biopolymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19537001A DE19537001C2 (en) 1995-08-28 1995-08-28 Hair sprays
DE19537001.5 1995-08-28

Publications (1)

Publication Number Publication Date
WO1997008208A1 true WO1997008208A1 (en) 1997-03-06

Family

ID=7774028

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/003635 WO1997008208A1 (en) 1995-08-28 1996-08-19 Process for producing sprayable cationic biopolymers

Country Status (5)

Country Link
EP (1) EP0847403A1 (en)
AU (1) AU6873996A (en)
DE (1) DE19537001C2 (en)
NO (1) NO975791D0 (en)
WO (1) WO1997008208A1 (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ335974A (en) 1996-11-28 2000-06-23 Henkel Kgaa Hypocholesteremic agents containing tocopherols and phytostanol (phytosterols)
DE19730649C1 (en) 1997-07-17 1998-09-24 Henkel Kgaa Skin-compatible detergent mixture with good cleaning, rewetting and conditioning power
JP2002520511A (en) 1998-07-16 2002-07-09 コグニス・ドイチュラント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Use of PIT emulsion
DE19911040A1 (en) 1999-03-12 2000-09-21 Cognis Deutschland Gmbh Surfactant granules
ES2247749T3 (en) 1999-07-02 2006-03-01 Cognis Ip Management Gmbh MICROCAPSULES III.
EP1064912B1 (en) 1999-07-02 2004-01-28 Cognis Iberia, S.L. Microcapsules
DE59908471D1 (en) 1999-07-02 2004-03-11 Cognis Iberia Sl Microcapsules - II
DE59912558D1 (en) 1999-07-02 2005-10-20 Cognis Ip Man Gmbh Microcapsules - IV
DE19960632A1 (en) * 1999-12-16 2001-07-05 Cognis Deutschland Gmbh Cosmetics containing natural chitosans
DE10014529A1 (en) 2000-03-23 2001-09-27 Cognis Deutschland Gmbh Cosmetic deodorant compositions, comprise chitosan and/or chitosan derivatives in the form of nanoparticles
DE10018812A1 (en) 2000-04-15 2001-10-25 Cognis Deutschland Gmbh Nonionic surfactant granulate, used in surfactant, cosmetic or pharmaceutical formulation or laundry or other detergent, is obtained by granulating and simultaneously drying aqueous surfactant paste in presence of organic polymeric carrier
FR2814380B1 (en) 2000-09-25 2002-11-08 Serobiologiques Lab Sa MICROCAPSULES POWDER AND PROCESS FOR OBTAINING
DE10105623A1 (en) 2001-02-08 2002-08-14 Cognis Deutschland Gmbh Process for antibacterial finishing of fibers or nonwovens
DE102004007115A1 (en) 2004-02-13 2005-08-25 Cognis Deutschland Gmbh & Co. Kg Chitosan-containing wound dressings

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0222301A (en) * 1988-07-12 1990-01-25 Nippon Kayaku Co Ltd Production of water-soluble chitosan
CN1082883A (en) * 1993-05-18 1994-03-02 国家海洋局杭州水处理技术开发中心 A kind of hair jelly of chitosan-containing

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3903797A1 (en) * 1989-02-09 1990-08-16 Hoechst Ag METHOD FOR THE PRODUCTION OF ACTIVATED CHITOSANS AND THE USE THEREOF IN THE PRODUCTION OF CHITOSAN DERIVATIVES
FI86068C (en) * 1989-10-20 1992-07-10 Firextra Oy Process for the production of chitosan and other products from shells of organisms, in particular from shells of marine organisms
JP2779555B2 (en) * 1991-04-05 1998-07-23 花王株式会社 Hair cosmetics
DE4343378C1 (en) * 1993-12-18 1995-03-30 Kao Corp Gmbh Hair care composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0222301A (en) * 1988-07-12 1990-01-25 Nippon Kayaku Co Ltd Production of water-soluble chitosan
CN1082883A (en) * 1993-05-18 1994-03-02 国家海洋局杭州水处理技术开发中心 A kind of hair jelly of chitosan-containing

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 117, no. 26, 28 December 1992, Columbus, Ohio, US; abstract no. 258043, "Oxidative degradation of chitosan in the presence of hydroperoxide" XP002019681 *
CHEMICAL ABSTRACTS, vol. 122, no. 4, 23 January 1995, Columbus, Ohio, US; abstract no. 38524, "Hair sprays containing chitosan and surfactants" XP002019682 *
CHEMICAL ABSTRACTS, vol. 92, no. 18, 1980, Columbus, Ohio, US; abstract no. 148883, page 121; column r; XP002019680 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 171 (C - 706)<4114> 3 April 1990 (1990-04-03) *
SHENG Y. ET AL., ZHONGGUO YAOKE DAXUE XUEBAO, vol. 23, no. 3, 1992, CHINA, pages 173 - 176 *

Also Published As

Publication number Publication date
NO975791L (en) 1997-12-09
AU6873996A (en) 1997-03-19
EP0847403A1 (en) 1998-06-17
DE19537001A1 (en) 1997-03-06
NO975791D0 (en) 1997-12-09
DE19537001C2 (en) 1997-12-11

Similar Documents

Publication Publication Date Title
EP0807127B1 (en) Method of preparing low-viscosity cationic biopolymers
WO1997008208A1 (en) Process for producing sprayable cationic biopolymers
DE4442987C2 (en) Cationic chitin breakdown products
WO1996015155A1 (en) Process for preparing light-coloured chitosans
DE2840011C2 (en) Process for the production of highly substituted polysaccharides
DE69132166T2 (en) FILM-FORMING COMPOSITIONS FROM WET POWDER
DE69704360T2 (en) COMPOSITION CONTAINING NANOFIBRILLS OF CELLULOSE AND CARBOXYLATED CELLULOSE WITH A LOW DEGREE OF SUBSTITUTION
DE69716917T2 (en) COMPOSITION OF NANOFIBRILLS OF CELLULOSE WITH CARBOXYLATED CELLULOSE WITH A HIGH DEGREE OF SUBSTITUTION
DE4303415C2 (en) Emulsion containing chitosan
DE102006057904A1 (en) Production of cellulose nanoparticles
DE69024366T2 (en) Stable, liquid, aqueous pigment dispersions
CH637989A5 (en) INORGANIC BINDING AGENT AND METHOD FOR THE PRODUCTION THEREOF.
DE4242949A1 (en) Fine-particle, high-purity, neutral zinc oxide powder, process for its production and its use
DE3141165A1 (en) INCLUDING COMPLEXES OF CYCLODEXTRINES AND STRONG, INORGANIC, OXYGEN-CONTAINING ACIDS, AND METHOD FOR THE PRODUCTION THEREOF
EP0518175A2 (en) Preparation of a neutral metal oxide sol
DE19816362A1 (en) Matting agent based on coated silicon dioxide
DE19520906A1 (en) Modified material from renewable raw materials
DE3783781T2 (en) AQUEOUS COATING COMPOSITION CONTAINING FINE PARTICLES FROM A SOLUTION OF A WATER-INSOLUBLE RESIN.
DE69917218T2 (en) WATER REPELLENT ACTIVE INGREDIENTS AND WATER DISPERSIBLE GRAINS
EP1000122B1 (en) Aqueous shellac solution or dispersion
DE1592865C3 (en) Process for the production of organically modified silicas
DE1145735B (en) cleaning supplies
EP1211942B1 (en) Method for the production of polyvinylpyrrolidone-iodine in an aqueous solution
EP0776656B1 (en) Cosmetic and/or pharmaceutical emulsions
EP0549865B1 (en) Preparation process of siccatives for fluid coating materials; siccatives and use thereof

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 1996929271

Country of ref document: EP

AK Designated states

Kind code of ref document: A1

Designated state(s): AU BG BR BY CA CN CZ HU IS JP KR LT LV MX NO NZ PL RO RU SI SK UA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 1996929271

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

WWW Wipo information: withdrawn in national office

Ref document number: 1996929271

Country of ref document: EP