EP0460036B1 - Single-bath degumming and decolorizing of natural silks - Google Patents

Single-bath degumming and decolorizing of natural silks Download PDF

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Publication number
EP0460036B1
EP0460036B1 EP90903801A EP90903801A EP0460036B1 EP 0460036 B1 EP0460036 B1 EP 0460036B1 EP 90903801 A EP90903801 A EP 90903801A EP 90903801 A EP90903801 A EP 90903801A EP 0460036 B1 EP0460036 B1 EP 0460036B1
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alkyl
alkali metal
weight
ammonium salts
carboxylic acid
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French (fr)
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EP0460036A1 (en
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Irmhild Goebel
Berthold Popp
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
    • D01C3/00—Treatment of animal material, e.g. chemical scouring of wool
    • D01C3/02—De-gumming silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs

Definitions

  • the invention relates to agents for the one-bath degassing and decolorization of natural silk, a process for the degassing and decolorization of natural silk as well as the use of certain surfactants in certain amounts for the one-bath degassing and decolorization of natural silk.
  • the double thread made of fibroin produced by the silk spinner is covered by sericin, the silk bast. Since the sericin shell gives the raw silk a hard and rough feel, a matt appearance and a brown to yellow / yellow-green color, the sericin must be removed from the raw silk thread by boiling to achieve a shiny, soft silk thread (International textile practice 739 - 747 ( 1988)). Sericin removal, the so-called degreasing, often takes place in soap baths at bath temperatures between 90 and 98 ° C in two successive baths. The first bath contains soaps in amounts, for example, between 12 and 20 g per liter. In the second bath, the repassing bath, the soap concentration is between 5 and 15 g per liter, for example.
  • the degassing takes between 3 and 6 hours, in some cases the degassing time can be over 6 hours.
  • other disadvantages have to be accepted in the case of soap degassing.
  • the degreasing must be carried out in softening water to avoid the formation of insoluble calcium soaps.
  • a separate bleaching step is required due to unsatisfactory discoloration results.
  • the aqueous agents for degumming silk described in DE-OS 32 47 095 contain polyacrylic acids with average molecular weights between 3,500 and 4,500, sequestering agents, boric acid, one or more wetting agents and alkali in the form of sodium hydroxide solution.
  • Ethoxylated fatty alcohols with 8 to 18 carbon atoms, C 8-18 fatty alcohol ether sulfates, sulfochlorinated C, 5- paraffin, 2-ethylhexyl sulfate, sodium salt and / or nonylphenol with 4 to 18 moles of ethylene oxide are mentioned as wetting agents.
  • degreasing agents whose wetting agent content is between 2 and 10 parts by weight, are used in degreasing baths in amounts between 10 and 15 g per liter.
  • the disadvantage of these agents is that in the case of natural silk no satisfactory decolorization can be achieved, so that the use of bleaching agents in the degreasing bath or a separate bleaching step is required.
  • the object of the present invention was to develop a composition which, in addition to a good degree of degreasing, causes such a good decolorization on natural silk, that the use of bleaching agents in degassing baths or a separate bleaching step becomes superfluous. Furthermore, when using the agent to be developed, the raw silk thread is to be completely debased and decolorized within a short period of time and the fibroin thread should not be damaged.
  • Ethoxylated and / or propoxylated C 10-22 alkyl and / or C 10-22 alkenyl alcohols with iodine numbers between 0 and 60 can be obtained by reacting straight and / or branched chain C 10-22 alkyl and / or C 10 -22 -Alkenyl alcohols of natural and / or synthetic origin with ethylene oxide and / or propylene oxide according to known industrial processes (see, for example, in "Chemical Technology", Volume 7, pages 131 to 132, Carl Hanser Verlag, Kunststoff-Vienna (1986)).
  • the average degree of oxalkylation of the oxalkylates obtained which corresponds to the molar amount of the alkylene oxides added, is between 2 and 40, preferably between 2 and 10.
  • alkyl and / or alkenyl alcohols having 10 to 22 carbon atoms, preferably having 12 to 22 carbon atoms.
  • atoms for example, are decyl, iso-tridecyl, myristyl, cetyl, stearyl and / or behenyl alcohol, cetyl further technical / Oleylalkoholgemische and / or technical alcohol mixtures with predominantly C, 2 - 14 alkyl and / or C 12-14 alkenyl alcohols, C 12-18 alkyl and / or C 12-18 alkenyl alcohols and / or C 18-22 alkyl and / or C 18-22 -Alkenylalkohole, for example coconut fatty alcohol, tallow fatty alcohol and / or rapeseed oil alcohol.
  • the iodine number of ethoxylated and / or propoxylated alkyl and / or alkenyl alcohols is preferably between 0 and 50.
  • Polyethers of the general formula can be prepared by alkoxylation of alkylphenols or Guerbet alcohols with ethylene oxide using known industrial processes ("Chemical Technology", volume 7, pages 129 to 133, Carl Hanser Verlag, Kunststoff-Vienna (1986)).
  • the average degree of oxalkylation of the oxalkylates obtained is between 2 and 10, preferably between 4 and 8.
  • Nonylphenols are preferably used as alkylphenols.
  • Suitable Guerbet alcohols are accessible by condensation of primary C 8-12 fatty alcohols in the presence of alkali at temperatures between 200 and 300 ° C (Angew. Chem. 64, 213 to 220 (1952)).
  • the hydroxyl group of the ethoxylated Guerbet alcohols is preferably etherified with C 1-5 alkyl halides.
  • Aliphatic C 10-22 carboxylic acid alkyl esters are accessible by transesterification of fats and oils with excess C 1-4 alkyl alcohols in the presence of alkaline catalysts (Winnacker / Küchler in "Chemische Technologie", Volume 7, page 105, Carl Hanser Verlag, Kunststoff-Vienna 1986).
  • Carboxylic acid methyl esters having 12 to 18 carbon atoms for example methyl lauric acid, myristic acid, palmitic acid, stearic acid and / or oleic acid, are preferably used.
  • C 10-22 alkyl and / or C 10-22 alkenyl sulfates in the form of their alkali, ammonium and / or amine salts are prepared in a manner known per se by sulfating the corresponding alkyl and / or alkenyl alcohols with chlorosulfonic acid or sulfur trioxide .
  • the resulting sulfuric acid half-esters of the alcohols are then neutralized with, for example, alkali metal hydroxide solution, such as sodium hydroxide solution, ammonia or alkanolamines, such as monoethanolamine or triethanolamine (Winnacker / ippochler in "Chemische Technologie", Volume 7, pages 120 to 123, Carl Hanser Verlag, Kunststoff-Vienna ( 1986)).
  • alkyl and / or alkenyl alcohols can be straight or branched, natural or synthetic in origin and have 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • alkyl and / or alkenyl alcohols are decyl, lauryl, myristyl, cetyl, stearyl, oleyl, behenyl alcohol and mixtures of these alcohols.
  • lauryl, myristyl alcohol or stearyl alcohol mixtures of these alcohols or alcohol mixtures with predominantly C12 - C18 alkyl and / or C 12-18 alkenyl alcohols and / or C 2 - 14 alkyl and / or C12 - 14 - Alkenyl alcohols, for example coconut oil alcohol and / or tallow oil alcohol, are used.
  • Aliphatic C 10-22 -Carbonkladiethanolamide and / or-polydiethanolamide be prepared by reaction of aliphatic, linear and / or branched chain C 10-22 carboxylic acids of natural and / or synthetic origin with diethanolamine at temperatures between 150 and 180 ° C to produce ( "Chemistry and Technology ", Volume 7, page 129, Carl Hanser Verlag, Kunststoff-Vienna (1986)).
  • coconut fatty acid diethanolamide and / or polydiethanolamide, lauric acid diethanolamide, lauric / myristic acid diethanolamide and / or oleic acid diethanolamide and / or polydiethanolamide are examples of suitable diethanolamides and / or polydiethanolamides.
  • Alkali, alkaline earth and / or ammonium salts of sulfosuccinic acid mono- and / or di-C 8-18 alkyl esters are obtained by esterification of straight-chain and / or branched-chain alkyl alcohols of natural and / or synthetic origin with maleic anhydride and subsequent reaction with sodium hydrogen sulfite produced (Winnacker / Küchler: "Chemische Technologie", volume 7, pages 119 to 120, Carl Hanser Verlag, Kunststoff-Vienna, (1986)).
  • alkyl alcohols with 8 to 18 carbon atoms are iso-octanol, iso-nonanol, iso-decanol, lauryl alcohol, myristyl alcohol and / or stearyl alcohol.
  • the agents according to the invention preferably contain alkali salts of sulfosuccinic acid mono-C10-18 alkyl esters, for example sulfosuccinic acid monolauryl ester, sodium salt.
  • Another subject of the invention is a process for the degumming and decolorization of natural silk with aqueous, alkaline liquors, containing polyacrylic acids with average molecular weights between 3,500 and 4,500, sequestering agents, wetting agents and buffer salts, which is characterized in that natural silk in a bath at temperatures between 90 and 98 ° C treated with bleach-free aqueous liquors with pH values between 10 and 12, the 2.5 to 10 g of surfactants from one or more of the following groups per liter of liquor
  • the invention furthermore relates to the use of surfactants from one or more of groups a) to f) in bleach-free aqueous, alkaline liquors in amounts of between 2.5 and 10 g of active substance per liter for single-bath degassing and decolorization of natural silk.
  • the pH of the liquors is adjusted to between 10 and 12 using alkali lye, for example sodium and / or potassium lye.
  • Surfactants from groups a) and / or b) are particularly preferably used in the liquors.
  • the liquors of the process according to the invention are prepared in such a way that demineralized water or water with up to 26 ° dH either the agents according to the invention as such or surfactants and optionally alkali metal hydroxide solution are added separately from polyacrylic acids, sequestering agents, boric acid and alkanesulfonates.
  • Natural silk for example tussah silk, Vietnamese wild silk or Chinese mountain silk, can be debossed as yarn on spray arm dyeing machines or on the bark, as a fabric on the star, on the silk reel runner or on the silk jet.
  • the liquor ratio is between 1:25 and 1: 100.
  • the method according to the invention it is possible to use natural silk within a short time, i. H. Decolorize in a bath within 30 to 60 minutes and completely degrease. Very light silk without fibroin damage is obtained, so that bleaching is unnecessary in most cases.
  • the silk is characterized by a full, soft and smooth feel and can be dyed evenly with all dyes suitable for silk, for example direct, acid, metal complex, noun and / or reactive dyes.
  • Thai wild silk with a liquor containing no surfactant additive was 0.43 g of polyacrylic acid with an average molecular weight of 3,800, 0.32 g of 1-hydroxyethane-1,1-diphosphonic acid, sodium salt, and 0.6 g of crystallized boric acid and 0.36 g of C 15 alkanesulfonate, sodium salt (50% by weight monosulfonate and 50% by weight disulfonate) were debased.
  • the degree of whiteness was determined on an Elrepho device from Zeiss with filter R 46, measured as% remission (the greater the% remission value, the better the decolorization).
  • EO means ethylene oxide, PO propylene oxide.

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Abstract

Agents for single-bath degumming and decolorizing of natural silks contain, in addition to 1 to 4 wt. % of alkane sulphonates, at least 10 to 55 wt. % of one additional tenside.

Description

Die Erfindung betrifft Mittel zum einbadigen Entbasten und Entfärben von Naturseiden, ein Verfahren zum Entbasten und Entfärben von Naturseiden sowie die Verwendung von bestimmten Tensiden in bestimmten Mengen zum einbadigen Entbasten und Entfärben von Naturseiden.The invention relates to agents for the one-bath degassing and decolorization of natural silk, a process for the degassing and decolorization of natural silk as well as the use of certain surfactants in certain amounts for the one-bath degassing and decolorization of natural silk.

Der vom Seidenspinner erzeugte Doppelfaden aus Fibroin ist von Sericin, dem Seidenbast, umhüllt. Da die Sericinhülle der Rohseide einen harten und rauhen Griff, ein mattes Aussehen und eine braune bis gelb/gelb-grüne Farbe verleiht, muß zur Erzielung eines glänzenden, weichen Seidenfadens das Sericin von dem Rohseidenfaden durch Abkochen entfernt werden (Textilpraxis international 739 - 747 (1988)). Die Sericinentfernung, die sogenannte Entbastung, erfolgt häufig in Seifenbädern bei Badtemperaturen zwischen 90 und 98 °C in zwei aufeinanderfolgenden Bädern. Das erste Bad enthält Seifen in Mengen beispielsweise zwischen 12 und 20 g pro Liter. Im zweiten Bad, dem Repassierbad, liegt die Seifenkonzentration beispielsweise zwischen 5 und 15 g pro Liter. In Abhängigkeit von der zu entbastenden Seidenart dauert die Seifenentbastung zwischen 3 und 6 Stunden, in einigen Fällen kann die Entbastungszeit über 6 Stunden betragen. Neben diesen langen Entbastungszeiten, die zur Schädigung des Seidenfadens führen kann, müssen bei der Seifenentbastung weitere Nachteile in Kauf genommen werden. So muß die Entbastung in enthärtendem Wasser durchgeführt werden, um die Bildung unlöslicher Calciumseifen zu vermeiden. Ferner ist aufgrund unbefriedigender Entfärbungsergebnisse ein separater Bleichschritt erforderlich.The double thread made of fibroin produced by the silk spinner is covered by sericin, the silk bast. Since the sericin shell gives the raw silk a hard and rough feel, a matt appearance and a brown to yellow / yellow-green color, the sericin must be removed from the raw silk thread by boiling to achieve a shiny, soft silk thread (International textile practice 739 - 747 ( 1988)). Sericin removal, the so-called degreasing, often takes place in soap baths at bath temperatures between 90 and 98 ° C in two successive baths. The first bath contains soaps in amounts, for example, between 12 and 20 g per liter. In the second bath, the repassing bath, the soap concentration is between 5 and 15 g per liter, for example. Depending on the type of silk to be degassed, the degassing takes between 3 and 6 hours, in some cases the degassing time can be over 6 hours. In addition to these long degassing times, which can lead to damage to the silk thread, other disadvantages have to be accepted in the case of soap degassing. The degreasing must be carried out in softening water to avoid the formation of insoluble calcium soaps. In addition, a separate bleaching step is required due to unsatisfactory discoloration results.

Die in DE-OS 32 47 095 beschriebenen wäßrigen Mittel zum Entbasten von Seiden enthalten Polyacrylsäuren mit mittleren Molekulargewichten zwischen 3.500 und 4.500, Sequestrierungsmittel, Borsäure, ein oder mehrere Netzmittel sowie Alkali in Form von Natronlauge. Als Netzmittel werden ethoxylierte Fettalkohole mit 8 bis 18 C-Atomen, C8-18-Fettalkoholethersulfate, sulfochloriertes C,5-Paraffin, 2-Ethylhexylsulfat, Natriumsalz und/oder Nonylphenol mit 4 bis 18 Mol Ethylenoxid genannt. Diese Entbastungsmittel, deren Netzmittelgehalt zwischen 2 und 10 Gewichtsteilen liegt, werden in Entbastungsbädern in Mengen zwischen 10 und 15 g pro Liter eingesetzt. Der Nachteil dieser Mittel besteht darin, daß im Falle von Naturseiden keine zufriedenstellende Entfärbung erzielt werden kann, so daß die Verwendung von Bleichmitteln im Entbastungsbad oder ein separater Bleichschritt erforderlich ist.The aqueous agents for degumming silk described in DE-OS 32 47 095 contain polyacrylic acids with average molecular weights between 3,500 and 4,500, sequestering agents, boric acid, one or more wetting agents and alkali in the form of sodium hydroxide solution. Ethoxylated fatty alcohols with 8 to 18 carbon atoms, C 8-18 fatty alcohol ether sulfates, sulfochlorinated C, 5- paraffin, 2-ethylhexyl sulfate, sodium salt and / or nonylphenol with 4 to 18 moles of ethylene oxide are mentioned as wetting agents. These degreasing agents, whose wetting agent content is between 2 and 10 parts by weight, are used in degreasing baths in amounts between 10 and 15 g per liter. The disadvantage of these agents is that in the case of natural silk no satisfactory decolorization can be achieved, so that the use of bleaching agents in the degreasing bath or a separate bleaching step is required.

Die Aufgabe dervorliegenden Erfindung bestand in der Entwicklung eines Mittel, welches, in Entbastungsbädern eingesetzt, neben einem guten Entbastungsgrad eine so gute Entfärbung auf Naturseiden hervorruft, daß der Einsatz von Bleichmitteln in Entbastungsbädern oder ein separater Bleichschritt überflüssig wird. Des weiteren soll bei Verwendung des zu entwickelnden Mittels innerhalb kurzer Zeit eine vollständige Entbastung und Entfärbung des Rohseidenfadens erzielt werden und der Fibroinfaden nicht geschädigt werden.The object of the present invention was to develop a composition which, in addition to a good degree of degreasing, causes such a good decolorization on natural silk, that the use of bleaching agents in degassing baths or a separate bleaching step becomes superfluous. Furthermore, when using the agent to be developed, the raw silk thread is to be completely debased and decolorized within a short period of time and the fibroin thread should not be damaged.

Überraschenderweise wurde gefunden, daß die an Mittel zum Entbasten und Entfärben von Naturseiden gestellten hohen Anfoderungen von Mitteln erfüllt werden, die neben 1 - 4 Gew.-% C12-18-Alkansulfonaten mindestens ein weiteres Tensid in Mengen von 10 bis 55 Gew.-% enthalten.Surprisingly, it was found that the imposed on means for degumming and decoloring of natural silk high POTENTIALS be fulfilled by agents that in addition to 1-4 wt .-% C 12-18 alkane sulfonates least one further surfactant in amounts of 10 to 55 parts by weight % contain.

Gegenstand der Erfindung sind dementsprechend wäßrige Mittel zum einbadigen Entbasten und Entfärben von Naturseiden, enthaltend - bezogen auf die wäßrigen Mittel 10 bis 55 Gew.-% Tenside aus einer oder mehreren der folgenden Gruppen:

  • a) C10-22-Alkyl- und/oder C10-22-Alkenylalkohole, alkoxyliert mit 2 bis 40 Mol Ethylenoxid und/oder Propylenoxid mit Jodzahlen zwischen 0 und 60
  • b) Polyether der allgemeinen Formel
    Figure imgb0001
    in der R1 einen Alkylrest mit 1 bis 5 C-Atomen oder einen Alkylarylrest mit 8 bis 12 C-Atomen in der Alkylgruppe, R2 H oder einen verzweigtkettigen Alkylrest mit 16 bis 24 C-Atomen und n eine Zahl zwischen 2 und 10 bedeutet,
  • c) aliphatische Carbonsäurealkylester mit 10 bis 22 C-Atomen im Säurerest und 1 - 4 C-Atomen im Alkoholrest,
  • d) C10-22-Alkyl- und/oder C10-22-Alkenylsulfate in Form ihrer Alkali-, Erdalkali- und/oder Ammoniumsalze,
  • e) aliphatische C10-22-Carbonsäurediethanolamide und/oder -polydiethanolamide und/oder
  • f) Sulfobernsteinsäuremono- und/oder -di-C8-18-alkylester in Form ihrerAlkali-, Erdalkali- und/oderAmmoniumsalze,
    • 1 bis 7 Gew.-% Polyacrylsäuren mit mittleren Molekulargewichten zwischen 3.500 und 4.500,
    • 1 bis 5 Gew.-% Sequestrierungsmittel,
    • 1 bis 6 Gew.-% Borsäure
    • 1 bis 4 Gew.-% C12-18-Alkansulfonate in Form ihrer Alkali- und/oderAmmoniumsalze und
    • 12 bis 35 Gew.-% 25 bis 35 Gew.-%ige Alkalilauge.
The invention accordingly relates to aqueous agents for single-bath debinding and decolorization of natural silk, comprising - based on the aqueous agents, 10 to 55% by weight of surfactants from one or more of the following groups:
  • a) C 10-22 alkyl and / or C 10-22 alkenyl alcohols, alkoxylated with 2 to 40 moles of ethylene oxide and / or propylene oxide with iodine numbers between 0 and 60
  • b) polyethers of the general formula
    Figure imgb0001
     in which R 1 is an alkyl radical with 1 to 5 C atoms or an alkylaryl radical with 8 to 12 C atoms in the alkyl group, R 2 H or a branched chain alkyl radical with 16 to 24 C atoms and n is a number between 2 and 10 ,
  • c) aliphatic carboxylic acid alkyl esters with 10 to 22 carbon atoms in the acid residue and 1 to 4 carbon atoms in the alcohol residue,
  • d) C 10-22 alkyl and / or C 10 22 alkenyl sulfates in the form of their alkali, alkaline earth and / or ammonium salts,
  • e) aliphatic C 10-22 carboxylic acid diethanolamides and / or polydiethanolamides and / or
  • f) sulfosuccinic acid mono- and / or di-C 8-18 alkyl esters in the form of their alkali metal, alkaline earth metal and / or ammonium salts,
    • 1 to 7% by weight of polyacrylic acids with average molecular weights between 3,500 and 4,500,
    • 1 to 5% by weight of sequestering agent,
    • 1 to 6% by weight boric acid
    • 1 to 4% by weight of C 12-18 alkanesulfonates in the form of their alkali and / or ammonium salts and
    • 12 to 35 wt .-% 25 to 35 wt .-% alkali.

Vorzugsweise enthalten die erfindungsgemäßen Mittel - bezogen auf die wäßrigen Mittel 10 bis 50 Gew.-% Tenside aus einer oder mehreren der Gruppen a) bis f)

  • 1 bis 5 Gew.-% Polyacrylsäuren mit mittleren Molekulargewichten zwischen 3.500 und 4.500
  • 1 bis 4 Gew.-% Sequestrierungsmittel, beispielsweise Nitrilotriessigsäure, Alkalisalze von Ethylendiamintetraacetat und/oder Alkalisalze von Phosphonsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure, Natriumsalz
  • 2 bis 5 Gew.-% Borsäure
  • 1 bis 3 Gew.-% C12-18-Alkansulfonate in Form ihrerAlkali- und/oderAmmoniumsalze und
  • 13 bis 30 Gew.-% 25 bis 35 Gew.-%ige Alkalilauge, beispielsweise Natron- und/oder Kalilauge.
The agents according to the invention preferably contain - based on the aqueous agents 10 to 50% by weight of surfactants from one or more of groups a) to f)
  • 1 to 5% by weight of polyacrylic acids with average molecular weights between 3,500 and 4,500
  • 1 to 4% by weight of sequestering agents, for example nitrilotriacetic acid, alkali metal salts of ethylenediaminetetraacetate and / or alkali metal salts of phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, sodium salt
  • 2 to 5 wt .-% boric acid
  • 1 to 3% by weight of C 12-18 alkanesulfonates in the form of their alkali and / or ammonium salts and
  • 13 to 30 wt .-% 25 to 35 wt .-% alkali, for example sodium and / or potassium hydroxide.

Ethoxylierte und/oder propoxylierte C10-22-Alkyl- und/oder C10-22-Alkenylalkohole mit Jodzahlen zwischen 0 und 60 lassen sich durch Umsetzung von gerad- und/oder verzweigtkettigen C10-22-Alkyl-und/oder C10-22-Alkenylalkoholen natürlichen und/odersynthetischen Ursprungs mit Ethylenoxid und/oder Propylenoxid nach bekannten großtechnischen Verfahren herstellen (s. beispielsweise in "Chemische Technologie", Band 7, Seiten 131 bis 132, Carl Hanser Verlag, München-Wien (1986)). Der mittlere Oxalkylierungsgrad der erhaltenen Oxalkylate, der der molaren Menge der angelagerten Alkylenoxide entspricht, liegt zwischen 2 und 40, vorzugsweise zwischen 2 und 10. Als Alkyl- und/oder Alkenylalkohole mit 10 bis 22 C-Atomen, vorzugsweise mit 12 bis 22 C-Atomen, eignen sich beispielsweise Decyl-, Lauryl-, iso-Tridecyl-, Myristyl-, Cetyl-, Stearyl-und/oder Behenylalkohol, ferner technische Cetyl-/Oleylalkoholgemische und/oder technische Alkoholgemische mit überwiegend C,2-14-Alkyl- und/oder C12-14-Alkenylalkoholen, C12-18-Alkyl- und/oder C12-18-Alkenylalkoholen und/oder C18-22-Alkyl- und/oder C18-22-Alkenylalkohole, beispielsweise Kokosfettalkohol, Talgfettalkohol und/oder Rübölalkohol. Die Jodzahl ethoxylierter und/oder propoxylierter Alkyl- und/oder Alkenylalkohole liegt vorzugsweise zwischen 0 und 50.Ethoxylated and / or propoxylated C 10-22 alkyl and / or C 10-22 alkenyl alcohols with iodine numbers between 0 and 60 can be obtained by reacting straight and / or branched chain C 10-22 alkyl and / or C 10 -22 -Alkenyl alcohols of natural and / or synthetic origin with ethylene oxide and / or propylene oxide according to known industrial processes (see, for example, in "Chemical Technology", Volume 7, pages 131 to 132, Carl Hanser Verlag, Munich-Vienna (1986)). The average degree of oxalkylation of the oxalkylates obtained, which corresponds to the molar amount of the alkylene oxides added, is between 2 and 40, preferably between 2 and 10. As alkyl and / or alkenyl alcohols having 10 to 22 carbon atoms, preferably having 12 to 22 carbon atoms. atoms, for example, are decyl, iso-tridecyl, myristyl, cetyl, stearyl and / or behenyl alcohol, cetyl further technical / Oleylalkoholgemische and / or technical alcohol mixtures with predominantly C, 2 - 14 alkyl and / or C 12-14 alkenyl alcohols, C 12-18 alkyl and / or C 12-18 alkenyl alcohols and / or C 18-22 alkyl and / or C 18-22 -Alkenylalkohole, for example coconut fatty alcohol, tallow fatty alcohol and / or rapeseed oil alcohol. The iodine number of ethoxylated and / or propoxylated alkyl and / or alkenyl alcohols is preferably between 0 and 50.

Polyether der allgemeinen Formel können durch Alkoxylierung von Alkylphenolen oder Guerbetalkoholen mit Ethylenoxid nach bekannten großtechnischen Verfahren hergestellt werden ("Chemische Technologie", Band 7, Seiten 129 bis 133, Carl Hanser Verlag, München-Wien (1986)). Der mittlere Oxalkylierungsgrad der erhaltenen Oxalkylate liegt zwischen 2 und 10, vorzugsweise zwischen 4 und 8. Als Alkylphenole werden vorzugsweise Nonylphenole eingesetzt. Geeignete Guerbetalkohole sind durch Kondensation von primären C8-12-Fettalkoholen in Gegenwart von Alkali bei Temperaturen zwischen 200 und 300 °C zugänglich (Angew. Chem. 64, 213 bis 220 (1952)). Vorzugsweise wird die Hydroxylgruppe der ethoxylierten Guerbetalkohole mit C1-5-Alkylhalogeniden verethert.Polyethers of the general formula can be prepared by alkoxylation of alkylphenols or Guerbet alcohols with ethylene oxide using known industrial processes ("Chemical Technology", volume 7, pages 129 to 133, Carl Hanser Verlag, Munich-Vienna (1986)). The average degree of oxalkylation of the oxalkylates obtained is between 2 and 10, preferably between 4 and 8. Nonylphenols are preferably used as alkylphenols. Suitable Guerbet alcohols are accessible by condensation of primary C 8-12 fatty alcohols in the presence of alkali at temperatures between 200 and 300 ° C (Angew. Chem. 64, 213 to 220 (1952)). The hydroxyl group of the ethoxylated Guerbet alcohols is preferably etherified with C 1-5 alkyl halides.

Aliphatische C10-22-Carbonsäurealkylester sind durch Umesterung von Fetten und Ölen mit überschüssigen C1-4-Alkylalkoholen in Gegenwart alkalischer Katalysatoren zugänglich (Winnacker/Küchler in "Chemische Technologie", Band 7, Seite 105, Carl Hanser Verlag, München-Wien 1986). Vorzugsweise werden Carbonsäuremethylester mit 12 bis 18 C-Atomen, zum Beispiel Laurinsäure-, Myristinsäure-, Palmitinsäure-, Stearin-und/oder Ölsäuremethylester, eingesetzt.Aliphatic C 10-22 carboxylic acid alkyl esters are accessible by transesterification of fats and oils with excess C 1-4 alkyl alcohols in the presence of alkaline catalysts (Winnacker / Küchler in "Chemische Technologie", Volume 7, page 105, Carl Hanser Verlag, Munich-Vienna 1986). Carboxylic acid methyl esters having 12 to 18 carbon atoms, for example methyl lauric acid, myristic acid, palmitic acid, stearic acid and / or oleic acid, are preferably used.

Die Herstellung von C10-22-Alkyl- und/oder C10-22-Alkenylsulfaten in Form ihrer Alkali-, Ammonium- und/oder Aminsalze erfolgt in an sich bekannter Weise durch Sulfatierung der entsprechenden Alkyl-und/oderAlkenylalkohole mit Chlorsulfonsäure oder Schwefeltrioxid. Die dabei entstehenden Schwefelsäurehalbester der Alkohole werden anschließend mit beispielsweise Alkalilauge, wie Natronlauge, Ammoniak oder Alkanolaminen, wie Monoethanolamin oder Triethanolamin neutralisiert (Winnacker/Küchler in "Chemische Technologie", Band 7, Seiten 120 bis 123, Carl Hanser Verlag, München-Wien (1986)). Die Edukte Alkyl- und/oder Alkenylalkohole können gerad- oder verzweigtkettig, natürlichen oder synthetischen Ursprungs sein und besitzen 10 bis 22 C-Atome, vorzugsweise 12 bis 18 C-Atome. Beispiele für Alkyl- und/oder Alkenylalkohole sind Decyl-, Lauryl-, Myristyl-, Cetyl-, Stearyl-, Oleyl-, Behenylalkohol sowie Mischungen dieser Alkohole. Vorzugsweise werden Lauryl-, Myristyl-oder Stearylalkohol, Mischungen dieserAlkohole oderAlkoholgemische mit überwiegend C12-18-Alkyl- und/oder C12-18-Alkenylalkoholen und/oder C,2-14-Alkyl- und/oder C12-14-Alkenylalkoholen, beispielsweise Kokosfettalkohol und/oder Talgfettalkohol, eingesetzt.C 10-22 alkyl and / or C 10-22 alkenyl sulfates in the form of their alkali, ammonium and / or amine salts are prepared in a manner known per se by sulfating the corresponding alkyl and / or alkenyl alcohols with chlorosulfonic acid or sulfur trioxide . The resulting sulfuric acid half-esters of the alcohols are then neutralized with, for example, alkali metal hydroxide solution, such as sodium hydroxide solution, ammonia or alkanolamines, such as monoethanolamine or triethanolamine (Winnacker / Küchler in "Chemische Technologie", Volume 7, pages 120 to 123, Carl Hanser Verlag, Munich-Vienna ( 1986)). The starting materials alkyl and / or alkenyl alcohols can be straight or branched, natural or synthetic in origin and have 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. Examples of alkyl and / or alkenyl alcohols are decyl, lauryl, myristyl, cetyl, stearyl, oleyl, behenyl alcohol and mixtures of these alcohols. Preferably, lauryl, myristyl alcohol or stearyl alcohol, mixtures of these alcohols or alcohol mixtures with predominantly C12 - C18 alkyl and / or C 12-18 alkenyl alcohols and / or C 2 - 14 alkyl and / or C12 - 14 - Alkenyl alcohols, for example coconut oil alcohol and / or tallow oil alcohol, are used.

Aliphatische C10-22-Carbonsäurediethanolamide und/oder-polydiethanolamide lassen sich durch Umsetzung von aliphatischen, gerad- und/oderverzweigtkettigen C10-22-Carbonsäuren natürlichen und/odersynthetischen Ursprungs mit Diethanolamin bei Temperaturen zwischen 150 und 180 °C herstellen ("Chemische Technologie", Band 7, Seite 129, Carl Hanser Verlag, München-Wien (1986)). Kokosfettsäurediethanolamid und/oder -polydiethanolamid, Laurinsäurediethanolamid, Laurin-/Myristinsäurediethanolamid und/oderÖlsäurediethanolamid und/oder -polydiethanolamid sind Beispiele für geeignete Diethanolamide und/oder Polydiethanolamide.Aliphatic C 10-22 -Carbonsäurediethanolamide and / or-polydiethanolamide be prepared by reaction of aliphatic, linear and / or branched chain C 10-22 carboxylic acids of natural and / or synthetic origin with diethanolamine at temperatures between 150 and 180 ° C to produce ( "Chemistry and Technology ", Volume 7, page 129, Carl Hanser Verlag, Munich-Vienna (1986)). Coconut fatty acid diethanolamide and / or polydiethanolamide, lauric acid diethanolamide, lauric / myristic acid diethanolamide and / or oleic acid diethanolamide and / or polydiethanolamide are examples of suitable diethanolamides and / or polydiethanolamides.

Alkali-, Erdalkali- und/oderAmmoniumsalze von Sulfobernsteinsäuremono- und/oder -di-C8-18-alkylestern werden durch Veresterung von geradkettigen und/oderverzweigtkettigen Alkylalkoholen natürlichen und/oder synthetischen Ursprungs mit Maleinsäureanhydrid und anschließende Umsetzung mit Natriumhydrogensulfit hergestellt (Winnacker/Küchler: "Chemische Technologie", Band 7, Seiten 119 bis 120, Carl Hanser Verlag, München-Wien, (1986)). Beispiele für Alkylalkohole mit 8 bis 18 C-Atomen, vorzugsweise mit 10 bis 18 C-Atomen sind iso-Octanol, iso-Nonanol, iso-Decanol, Laurylalkohol, Myristylalkohol und/oder Stearylalkohol. Die erfindungsgemäßen Mittel enthalten vorzugsweise Alkalisalze von Sulfobernsteinsäuremono-C10-18-alkylester, beispielsweise Sulfobernsteinsäuremonolaurylester, Natriumsalz.Alkali, alkaline earth and / or ammonium salts of sulfosuccinic acid mono- and / or di-C 8-18 alkyl esters are obtained by esterification of straight-chain and / or branched-chain alkyl alcohols of natural and / or synthetic origin with maleic anhydride and subsequent reaction with sodium hydrogen sulfite produced (Winnacker / Küchler: "Chemische Technologie", volume 7, pages 119 to 120, Carl Hanser Verlag, Munich-Vienna, (1986)). Examples of alkyl alcohols with 8 to 18 carbon atoms, preferably with 10 to 18 carbon atoms, are iso-octanol, iso-nonanol, iso-decanol, lauryl alcohol, myristyl alcohol and / or stearyl alcohol. The agents according to the invention preferably contain alkali salts of sulfosuccinic acid mono-C10-18 alkyl esters, for example sulfosuccinic acid monolauryl ester, sodium salt.

Weiterer Erfindungsgegenstand ist ein Verfahren zum Entbasten und Entfärben von Naturseiden mitwäßrigen, alkalischen Flotten, enthaltend Polyacrylsäuren mit mittleren Molekulargewichten zwischen 3.500 und 4.500, Sequestrierungsmittel, Netzmittel und Puffersalze, welches dadurch gekennzeichnet ist, daß man Naturseiden in einem Bad bei Temperaturen zwischen 90 und 98 °C mit bleichmittelfreien wäßrigen Flotten mit pH-Werten zwischen 10 und 12 behandelt, die pro Liter Flotte 2,5 bis 10 g Tenside aus einer oder mehreren der folgenden GruppenAnother subject of the invention is a process for the degumming and decolorization of natural silk with aqueous, alkaline liquors, containing polyacrylic acids with average molecular weights between 3,500 and 4,500, sequestering agents, wetting agents and buffer salts, which is characterized in that natural silk in a bath at temperatures between 90 and 98 ° C treated with bleach-free aqueous liquors with pH values between 10 and 12, the 2.5 to 10 g of surfactants from one or more of the following groups per liter of liquor

  • a) C10-22-Alkyl- und/oder C10-22-Alkenylalkohole, alkoxyliert mit 2 bis 40 Mol Ethylenoxid und/oder Propylenoxid mit Jodzahlen zwischen 0 und 60,a) C 10-22 alkyl and / or C 10-22 alkenyl alcohols, alkoxylated with 2 to 40 moles of ethylene oxide and / or propylene oxide with iodine numbers between 0 and 60,
  • b) Polyether der allgemeinen Formel
    Figure imgb0002
    in der R1 eine Alkylgruppe mit 1 bis 5 C-Atomen oder einen Alkylarylrest mit 8 bis 12 C-Atomen in der Alkylgruppe, R2 H oder einen verzweigtkettigen Alkylrest mit 16 bis 24 C-Atomen und n eine Zahl zwischen 2 und 10 bedeutet,    b) polyethers of the general formula
    Figure imgb0002
     in which R 1 is an alkyl group having 1 to 5 C atoms or an alkylaryl radical having 8 to 12 C atoms in the alkyl group, R 2 H or a branched chain alkyl radical having 16 to 24 C atoms and n is a number between 2 and 10 ,
  • c) aliphatische Carbonsäurealkylester mit 10 bis 22 C-Atomen im Säurerest und 1 - 4 C-Atomen im Alkoholrest,c) aliphatic carboxylic acid alkyl esters with 10 to 22 carbon atoms in the acid residue and 1 to 4 carbon atoms in the alcohol residue,
  • d) C10-22-Alkyl- und/oder C10-22-Alkenylsulfate in Form ihrer Alkali-, Erdalkali- und/oder Ammoniumsalze,d) C 10-22 alkyl and / or C 10-22 alkenyl sulfates in the form of their alkali, alkaline earth and / or ammonium salts,
  • e) aliphatische C10-22-Carbonsäurediethanolamide und/oder -polydiethanolamide und/odere) aliphatic C 10-22 carboxylic acid diethanolamides and / or polydiethanolamides and / or
  • f) Sulfobernsteinsäuremono- und/oder -di-C8-18-alkylester in Form ihrer Alkali-, Erdalkali- und/oderAmmoniumsalze,
    • 0,25 bis 1,3 g Polyacrylsäuren mit mittleren Molekulargewichten zwischen 3.500 und 4.500,
    • 0,25 bis 1 g Sequestrierungsmittel
    • 0,25 bis 1,1 g Borsäure und
    • 0,25 bis 0,75 g C,2-18-Alkansulfonate in Form ihrer Alkali- und/oderAmmoniumsalze
    • enthalten.
    • Vorzugsweise enthalten die wäßrigen Flotten des erfindungsgemäßen Verfahrens pro Liter
    • 3 bis 7 g Tenside aus einer oder mehreren der Gruppen a) bis f)
    • 0,25 bis 1,0 g Polyacrylsäuren mit mittleren Molekulargewichten zwischen 3.500 und 4.500
    • 0,25 bis 0,7 g Sequestrierungsmittel, beispielsweise Nitrilotri essigsäure, Alkalisalze von Ethylendiamintetraacetat und/oder Alkalisalze von Phosphonsäuren, wie 1-Hydroxyethan-1,1-di- phopshonsäure, Natriumsalz
    • 0,25 bis 1,0 g Borsäure und
    • 0,25 bis 0,6 g C,2-18-Alkansulfonate in Form ihrer Alkali- und/ oderAmmoniumsalze.
    f) sulfosuccinic acid mono- and / or di-C 8-18 alkyl esters in the form of their alkali, alkaline earth and / or ammonium salts,
    • 0.25 to 1.3 g polyacrylic acids with average molecular weights between 3,500 and 4,500,
    • 0.25 to 1 g sequestering agent
    • 0.25 to 1.1 g of boric acid and
    • 0.25 to 0.75 g C 2-18 alkane sulfonates in the form of their alkali and / or ammonium salts
    • contain.
    • The aqueous liquors of the process according to the invention preferably contain per liter
    • 3 to 7 g of surfactants from one or more of groups a) to f)
    • 0.25 to 1.0 g of polyacrylic acids with average molecular weights between 3,500 and 4,500
    • 0.25 to 0.7 g sequestering agent, for example nitrilotriacetic acid, alkali metal salts of ethylenediaminetetraacetate and / or alkali metal salts of phosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid, sodium salt
    • 0.25 to 1.0 g of boric acid and
    • 0.25 to 0.6 g of C 2-18 alkane sulfonates in the form of their alkali and / or ammonium salts.

Ferner ist Gegenstand der Erfindung die Verwendung von Tensiden aus einer oder mehreren der Gruppen a) bis f) in bleichmittelfreien wäßrigen, alkalischen Flotten in Mengen zwischen 2,5 und 10 g Aktivstubstanz pro Liter zum einbadigen Entbasten und Entfärben von Naturseiden.The invention furthermore relates to the use of surfactants from one or more of groups a) to f) in bleach-free aqueous, alkaline liquors in amounts of between 2.5 and 10 g of active substance per liter for single-bath degassing and decolorization of natural silk.

Der pH-Wert der Flotten wird mit Alkalilaugen, beispielsweise Natron- und/oder Kalilauge auf Werte zwischen 10 und 12 eingestellt.The pH of the liquors is adjusted to between 10 and 12 using alkali lye, for example sodium and / or potassium lye.

Besonders bevorzugt werden in den Flotten Tenside aus den Gruppen a) und/oder b) eingesetzt.Surfactants from groups a) and / or b) are particularly preferably used in the liquors.

Die Herstellung der Flotten des erfindungsgemäßen Verfahrens erfolgt in der Weise, daß demineralisiertem Wasser oder Wasser mit bis zu 26 °dH entweder die erfindungsgemäßen Mittel als solche oder aber Tenside und gegebenenfalls Alkalilauge separat von Polyacrylsäuren, Sequestrierungsmitteln, Borsäure und Alkansulfonaten zugesetzt werden. Naturseiden, beispielsweise Tussahseide, thailändische Wildseide oderchinesische Bergseide, können als Garne auf Spritzarmfärbe-Maschinen oder auf der Barke, als Gewebe auf dem Stern, auf der Seidenhaspelkufe oder auf dem Seidenjet entbastetwerden. In Abhängigkeit vom Maschinentyp liegt das Flottenverhältnis zwischen 1 : 25 und 1 : 100.The liquors of the process according to the invention are prepared in such a way that demineralized water or water with up to 26 ° dH either the agents according to the invention as such or surfactants and optionally alkali metal hydroxide solution are added separately from polyacrylic acids, sequestering agents, boric acid and alkanesulfonates. Natural silk, for example tussah silk, Thai wild silk or Chinese mountain silk, can be debossed as yarn on spray arm dyeing machines or on the bark, as a fabric on the star, on the silk reel runner or on the silk jet. Depending on the machine type, the liquor ratio is between 1:25 and 1: 100.

Mit dem erfindungsgemäßen Verfahren ist es möglich, Naturseiden innerhalb kurzer Zeit, d. h. innerhalb von 30 bis 60 Minuten in einem Bad zu entfärben und vollständig zu entbasten. Es werden sehr helle Seiden ohne Fibroinschädigungen erhalten, so daß in den meisten Fällen eine Bleiche überflüssig ist. Die Seiden zeichnen sich durch einen vollen, weichen und glatten Griff aus und können mit allen für Seiden geeigneten Farbstoffen, beispielsweise Direkt-, Säure-, Metallkomplex-, Substantiv- und/oder Reaktivfarbstoffen gleichmäßig angefärbt werden.With the method according to the invention it is possible to use natural silk within a short time, i. H. Decolorize in a bath within 30 to 60 minutes and completely degrease. Very light silk without fibroin damage is obtained, so that bleaching is unnecessary in most cases. The silk is characterized by a full, soft and smooth feel and can be dyed evenly with all dyes suitable for silk, for example direct, acid, metal complex, noun and / or reactive dyes.

BeispieleExamples

Thailändische Wildseide mit intensiver gelber Eigenfarbe (10,1 % Remission) und einem Bastgehalt von ca. 36 Gew.-% wurde bei 98 °C in 1 Stunde mit einer wäßrigen Flotte, enthaltend pro Liter 5 g Tensid, 0,43 g Polyacrylsäure mit einem mittleren Molekulargewicht von 3.800, 0,32 g 1-Hydroxyethan-1,1-diphosphonsäure, Natriumsalz, 0,6 g kristallisierte Borsäure und 0,36 g C15-Alkansulfonat, Natriumsalz (50 Gew.-% Monosulfonat und 50 Gew.-% Disulfonat), auf der Barke entbastet. Der pH-Wert des Entbastungsbades wurde mit Natronlauge auf einen Wert von 11 bis 11,5 eingestellt. Das Flottenverhältnis betrug 1 : 40.Thai wild silk with an intense yellow inherent color (10.1% remission) and a bast content of approx. 36% by weight was mixed with an aqueous liquor at 98 ° C. in 1 hour, containing 5 g of surfactant and 0.43 g of polyacrylic acid per liter an average molecular weight of 3,800, 0.32 g of 1-hydroxyethane-1,1-diphosphonic acid, sodium salt, 0.6 g of crystallized boric acid and 0.36 g of C 15 alkane sulfonate, sodium salt (50% by weight monosulfonate and 50% by weight -% disulfonate), debarked on the barge. The pH of the degumming bath was adjusted to a value of 11 to 11.5 with sodium hydroxide solution. The liquor ratio was 1:40.

Zum Vergleich wurde unter denselben Bedingungen thailändische Wildseide mit einer Flotte, enthaltend keinen Tensidzusatz, 0,43 g Polyacrylsäure mit einem mittleren Molekulargewicht von 3.800, 0,32 g 1-Hydroxyethan-1,1-diphosphonsäure, Natriumsalz, 0,6 g kristallisierte Borsäure und 0,36 g C15-Alkansulfonat, Natriumsalz (50 Gew.-% Monosulfonat und 50 Gew.-% Disulfonat) entbastet.For comparison, under the same conditions, Thai wild silk with a liquor containing no surfactant additive was 0.43 g of polyacrylic acid with an average molecular weight of 3,800, 0.32 g of 1-hydroxyethane-1,1-diphosphonic acid, sodium salt, and 0.6 g of crystallized boric acid and 0.36 g of C 15 alkanesulfonate, sodium salt (50% by weight monosulfonate and 50% by weight disulfonate) were debased.

Die Ergebnisse sind in der nachfolgenden Tabelle zusammengefaßt. Der Weißgrad wurde auf dem Elrepho-Gerät der Firma Zeiss mit Filter R 46, gemessen als % Remission, bestimmt (je größer der % Remissionswert ist, um so besser ist die Entfärbung).The results are summarized in the table below. The degree of whiteness was determined on an Elrepho device from Zeiss with filter R 46, measured as% remission (the greater the% remission value, the better the decolorization).

EO bedeutet Ethylenoxid, PO Propylenoxid.

Figure imgb0003
EO means ethylene oxide, PO propylene oxide.
Figure imgb0003

Claims (10)

1. Aqueous preparations for the single-bath degumming and decoloring of natural silk containing, based on the aqueous preparation, 10 to 55% by weight surfactants from one or more of the following groups:
a) C10-22 alkyl and/or C10-22 alkenyl alcohols alkoxylated with 2 to 40 mol ethylene oxide and/or propylene oxide and having iodine values of 0 to 60
b) polyethers corresponding to the following general formula
Figure imgb0009
in which R1 is a C1-5 alkyl radical or an alkylaryl radical containing 8 to 12 carbon atoms in the alkyl group, R2 is H or a branched C16-24 alkyl radical and n is a number of 2 to 10,
c) aliphatic carboxylic acid alkyl esters containing 10 to 22 carbon atoms in the acid part and 1 to 4 carbon atoms in the alcohol part,
d) C10-22 alkyl and/or C10-22 alkenyl sulfates in the form of their alkali metal, alkaline earth metal and/or ammonium salts,
e) aliphatic C10-22 carboxylic acid diethanolamides and/or polydiethanolamides and/or
f) sulfosuccinic acid mono- and/or di-C8-18-alkyl esters in the form of their alkali metal , alkaline earth metal and/or ammonium salts,
1 to 7% by weight polyacrylic acids having average molecular weights in the range from 3,500 to 4,500,
1 to 5 % by weight sequestering agents,
1 to 6% by weight boric acid,
1 to 4% by weight C12-16 alkane sulfonates in the form of their alkali metal and/or ammonium salts and
12 to 35% by weight 25 to 35% by weight alkali metal hydroxide.
2. Preparations as claimed in claim 1, characterized in that they contain, based on the aqueous preparation,
10 to 50% by weight surfactants from one or more of groups a) to f),
1 to 5% by weight polyacrylic acids,
1 to 4% by weight sequestering agents,
2 to 5% by weight boric acid,
1 to 3% by weight C12-18 alkane sulfonates in the form of their alkali metal and/or ammonium salts and
13 to 30% by weight 25 to 35% by weight alkali metal hydroxide.
3. Preparation as claimed in one or both of claims 1 and 2, characterized in that they contain surfactants from one or more of the following groups:
a) C12-22 alkyl and/or C12-22 alkenyl alcohols alkoxylated with 2 to 10 mol ethylene oxide and/or propylene oxide and having iodine values of 0 to 50
b) polyethers corresponding to the following general formula
Figure imgb0010
in which R1 is a C1-5 alkyl radical, R2 is a branched C16-24 alkyl radical and n is a number of 4 to 8,
c) aliphatic carboxylic acid methyl esters containing 12 to 18 carbon atoms,
d) C12-18 alkyl and/or C12-18 alkenyl sulfates in the form of their alkali metal salts and/or
e) aliphatic C10-18 carboxylic acid diethanolamides and/or polydiethanolamides and/or
f) sulfosuccinic acid mono-C10-18-alkyl esters in the form of their alkali metal salts.
4. Preparations as claimed in one or more of claims 1 to 3, characterized in that they contain surfactants from one or more of groups a) and/or b).
5. A process for the degumming and decoloring of natural silk with aqueous alkaline liquors containing polyacrylic acids having molecular weights in the agents from 3,500 to 4,500, sequestering agents, wetting agents and buffer salt, characterized in that natural silk is treated in one bath at temperatures of 90 to 98°C with bleach-free aqueous liquors having pH values of 10 to 12 which contain per liter liquor 2.5 to 10 g surfactants from one or more of the following groups
a) C10-22 alkyl and/or C10-22 alkenyl alcohols alkoxylated with 2 to 40 mol ethylene oxide and/or propylene oxide and having iodine values of 0 to 60
b) polyethers corresponding to the following general formula
Figure imgb0011
in which R1 is a C1-5 alkyl radical or an alkylaryl radical containing 8 to 12 carbon atoms in the alkyl group, R2 is H or a branched C16-24 alkyl radical and n is a number of 2 to 10,
c) aliphatic carboxylic acid alkyl esters containing 10 to 22 carbon atom in the acid part and 1 to4 carbon atoms in the alcohol part,
d) C10-22 alkyl and/or C10-22 alkenyl sulfates in the form of their alkali metal, alkaline earth metal and/or ammonium salts,
e) aliphatic C10-22 carboxylic acid diethanolamides and/or polydiethanolamides and/or
f) sulfosuccinic acid mono- and/or di-C8-18-alkyl esters in the form of their alkali metal, alkaline earth metal and/or ammonium salts,
0.25 to 1.3 g polyacrylic acids having average molecular weights in the range from 3,500 to 4,500,
0.25 to 1 g sequestering agents,
0.25 to 1.1 g boric acid and
0.25 to 0.75 g C12-18 alkane sulfonates in the form of their alkali metal and/or ammonium salts.
6. A process as claimed in claim 5, characterized in that the liquors contain per liter
3 to 7 g surfactants from one or more of groups a) to f),
0.25 to 1.0 g polyacrylic acids,
0.25 to 0.7 g sequestering agents,
0.25 to 1.0 g boric acid,
0.25 to 0.6 g C12-18 alkane sulfonates in the form of their alkali metal and/or ammonium salts.
7. A process as claimed in one or both of claims 5 and 6, characterized in that the liquors contain surfactants from one or more of the following groups:
a) C12-22 alkyl and/or C12-22 alkenyl alcohols alkoxylated with 2 to 10 mol ethylene oxide and/or propylene oxide and having iodine valurs of 0 to 50
b) polyethers corresponding to the following general formula
Figure imgb0012
in which R1 is a C1-5 alkyl radical, R2 is a branched C16-24 alkyl radical and n in a number of 4 to 8,
c) aliphatic carboxylic acid methyl esters containing 12 to 18 carbon atoms,
d) C12-18 alkyl and/or C12-18 alkenyl sulfates in the form of their alkali metal salts and/or
e) aliphatic C10-18 carboxylic acid diethanolamides and/or polydiethanolamides and/or
f) sulfosuccinic acid mono-C10-18-alkyl esters in the form of their alkali metal salts.
8. A process as claimed in one or more of claim 5 to 7, characterized in that the liquors contain surfactants from one or more of groups a) and/or b).
9. The use of surfactants from one or more of the following groups:
a) C10-22 alkyl and/or C10-22 alkenyl alcohols alkoxylated with 2 to 40 mol ethylene oxide and/or propylene oxide and having iodine values of 0 to 60
b) polyethers corresponding to the following general formula
Figure imgb0013
in which R1 is a C1-5 alkyl radical or an alkylaryl radical containing 8 to 12 carbon atoms in the alkyl group, R2 is H or a branched C16-24 alkyl radical and n is a number of 2 to 10,
c) aliphatic carboxylic acid alkyl esters containing 10 to 22 carbons atoms in the acid part and 1 to 4 carbon atom in the alcohol part,
d) C10-22 alkyl and/or C10-22 alkenyl sulfates in the form of their alkali metal, alkaline earth metal and/or ammonium salts,
e) aliphatic C10-22 carboxylic acid diethanolamides and/or polydiethanolamides and/or
f) sulfosuccinic acid mono- and/or di-C8-18-alkyl esters in the form of their alkali metal, alkaline earth
metal and/or ammonium salts, in bleach-free, aqueous alkaline liquors in quantities of 2.5 to 10 g per liter for the single-bath degumming and decoloring of natural silk.
10. The use claimed in claim 9, characterized in that bleach-free liquors having surfactant contents of 3 to 7 g per liter liquor are used.
EP90903801A 1989-02-27 1990-02-19 Single-bath degumming and decolorizing of natural silks Expired - Lifetime EP0460036B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3906045A DE3906045A1 (en) 1989-02-27 1989-02-27 ONE-BATHED DEGREASING AND DEFINITION OF NATURAL SILK
DE3906045 1989-02-27

Publications (2)

Publication Number Publication Date
EP0460036A1 EP0460036A1 (en) 1991-12-11
EP0460036B1 true EP0460036B1 (en) 1993-09-01

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ID=6375015

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Application Number Title Priority Date Filing Date
EP90903801A Expired - Lifetime EP0460036B1 (en) 1989-02-27 1990-02-19 Single-bath degumming and decolorizing of natural silks

Country Status (7)

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EP (1) EP0460036B1 (en)
KR (1) KR920700317A (en)
CN (1) CN1045136A (en)
BR (1) BR9007170A (en)
CA (1) CA2011013A1 (en)
DE (1) DE3906045A1 (en)
WO (1) WO1990010099A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069706C (en) * 1998-04-09 2001-08-15 俞祥根 Silk fiber pretreatment process and product thereof
CN102199792B (en) * 2011-05-26 2013-09-04 江苏泗绢集团有限公司 Mulberry silk spinning raw material degreasing and degumming washing machine
CN106455544B (en) 2014-03-04 2021-02-02 巴斯夫欧洲公司 Method for removing cotton linters from cotton seeds
CN104074047B (en) * 2014-07-11 2016-03-02 上海多纶化工有限公司 Weaving scouring agent
CN110029401A (en) * 2019-04-12 2019-07-19 苏州丝之源纺织科技有限公司 A kind of low temperature degumming agent and its Degumming method for natural colorful silk

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1151601B (en) * 1982-06-08 1986-12-24 Henkel Chimica Spa PRODUCT AND PROCEDURE FOR THE FOAMING OF NATURAL SILK

Also Published As

Publication number Publication date
EP0460036A1 (en) 1991-12-11
WO1990010099A1 (en) 1990-09-07
DE3906045A1 (en) 1990-09-06
CA2011013A1 (en) 1990-08-27
KR920700317A (en) 1992-02-19
CN1045136A (en) 1990-09-05
BR9007170A (en) 1991-12-17

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