EP1570123B1 - Pfropfpolymerisaten als hilfsmittel für die textilfärberei und den textildruck - Google Patents

Pfropfpolymerisaten als hilfsmittel für die textilfärberei und den textildruck Download PDF

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Publication number
EP1570123B1
EP1570123B1 EP03785689A EP03785689A EP1570123B1 EP 1570123 B1 EP1570123 B1 EP 1570123B1 EP 03785689 A EP03785689 A EP 03785689A EP 03785689 A EP03785689 A EP 03785689A EP 1570123 B1 EP1570123 B1 EP 1570123B1
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Prior art keywords
graft polymer
textile
monoethylenically unsaturated
process according
butyl
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German (de)
English (en)
French (fr)
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EP1570123A1 (de
Inventor
Pia Baum
Nicola Ulrike KÜLZER
Frank Funke
Andreas Bastian
Markus Ringelsbacher
Heinz Heissler
Gerhard Reuther
Rouven Konrad
James David Carnahan
Karl Siemensmeyer
Birgit Potthoff-Karl
Tanja Schneider
Johann Müller
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BASF SE
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BASF SE
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Priority claimed from DE2002156618 external-priority patent/DE10256618A1/de
Priority claimed from DE2002161190 external-priority patent/DE10261190A1/de
Priority claimed from DE2003121396 external-priority patent/DE10321396A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1570123A1 publication Critical patent/EP1570123A1/de
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/13—Fugitive dyeing or stripping dyes
    • D06P5/137—Fugitive dyeing or stripping dyes with other compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular

Definitions

  • the present invention relates to stripping agents and leveling agents comprising at least one graft polymer composed of a polymeric graft base A containing no monoethylenically unsaturated units and polymeric side chains B formed from copolymers of at least two monoethylenically unsaturated monomers B1 and B2, wherein B1 and B2 each contain at least one nitrogen-containing heterocycle, and optionally further comonomers B3, wherein the proportion of side chains B is greater than 35 wt .-%. Furthermore, the present invention relates to a process for the post-cleaning of dyed or printed textile.
  • auxiliaries for textile dyeing are usually used. Desired effects of textile dyeing auxiliaries are, for example, the removal of undesired dyeings.
  • Other auxiliaries for textile dyeing provide, inter alia, for particularly good and uniform dyeing and / or good wasting of the colorants.
  • auxiliaries for textile dyeing are known to the person skilled in the art as leveling agents.
  • auxiliaries for textile dyeing are known to the person skilled in the art as stripping agents.
  • auxiliaries for textile dyeing are known to the person skilled in the art as secondary soaping agents.
  • Textiles - for example natural and synthetic textiles - are often not completely homogeneous in their composition, but have different composition or thickness over the length of the threads. This can result in the fabric having stronger and weaker colored spots after dyeing, which is generally undesirable.
  • leveling agents are used. These are understood to mean those agents which produce uniform coloring over the surface of the textile to be dyed and especially over the length of the thread. From the prior art, oil sulfonates, fatty alcohol sulfonates, fatty acid condensation products, alkyl and alkylaryl polyglycol ethers are known as leveling agents.
  • leveling agents influence the dyeing behavior of the dyes, in particular the Aufzieh .
  • Very fiber-based dyes should be retained longer in the liquor and easier to migrate on the fiber. It is desirable that leveling agents result in more uniform (“more episcopitarian”) dyeings.
  • leveling agents based on polyvinylpyrrolidone s. Ullmann's Encyclopedia of Industrial Chemistry (5th Edition) Volume A26, page 291, left column.
  • Other commercially available leveling agents are condensates of adipic acid and amines such as
  • stripping agents generally those agents which are suitable for the elimination of, for example, dyeings, imprints and impregnations by redissolving, changing or destroying a dye.
  • a particularly important application for peel-off is the repair of false coloration. This dye is lightened to false color, so that the false color can be re-dyed.
  • Peel-off agents are also known as a component of etching pastes. These are used to remove certain colors in the etching pressure. In etching, a color is usually printed over the entire surface. Then it is overprinted with a subsequent color. The subsequent color is then removed in places with the aid of an etching printing paste.
  • dyed textiles are usually cleaned with the aid of reactive dyes, direct dyes or vat dyes in order to remove the remaining on the fiber, unfixed dye to achieve a sufficient level of fastness.
  • at least one soap bath and several rinse and neutralization baths are used for this purpose.
  • the result of the subsequent cleaning is influenced by the chemicals present in the dyebath, in particular the salt load.
  • a compound is used for post-purification, which disperses the dye or decomposition products of the dye, and which is generally referred to as secondary soaping agent.
  • the known Nachseifstoff show disadvantages, in many known Nachseifmitten one notes an insufficient effect, especially in the presence of salts such as Glauber's salt and / or sodium chloride in the soap bath. Furthermore, the known Nachseifsch at high temperatures, ie 98 ° C, must be used. The effect of the used as Nachseifstoff polyacrylic acids and polyvinylpyrrolidones can be improved.
  • the known Nachseifstoff show disadvantages, in many known Nachseifmitten to provide an insufficient effect, especially in the presence of salts such. Glauber's salt and / or sodium chloride in a soap bath. Furthermore, the known post-sifting agents must be heated at high temperatures, i. at 98 ° C. The effect of the used as Nachseifstoff polyacrylic acids and polyvinylpyrrolidones can be improved.
  • textiles or textiles are to be understood as meaning textile fibers, semi-finished and finished finished products and finished goods made thereof, which in addition to textiles for the clothing industry also include, for example, carpets and other home textiles as well as textile structures serving technical purposes. These include unshaped structures such as flakes, linear structures such as twine, threads, yarns, linen, cords, ropes, threads and body structures such as felts, fabrics, nonwovens and wadding.
  • the textiles may be of natural origin, for example cotton, wool or flax, or synthetic, for example polyamide.
  • copolymers used in the novel auxiliaries for textile dyeing and textile printing which are also referred to below as copolymers according to the invention, are characterized in that they contain at least 2 monoethylenically unsaturated monomers B1 and B2 in copolymerized form, each containing at least one nitrogen-containing Heterocycle included.
  • copolymers used according to the invention may be random copolymers, block copolymers or graft polymers.
  • copolymerized monomer B1 examples include N-vinylpyrrolidone, N-vinyl- ⁇ -valerolactam and N-vinyl- ⁇ -caprolactam, with N-vinylpyrrolidone being preferred.
  • the copolymers used according to the invention comprise at least one monomer B2 which comprises a nitrogen-containing heterocycle selected from the group consisting of pyrroles, pyrrolidines, pyridines, quinolines, isoquinolines, purines, pyrazoles, imidazoles, triazoles, tetrazoles, indolizines, pyridazines , Pyrimidines, pyrazines, indoles, isoindoles, oxazoles, oxazolidones, oxazolidines, morpholines, piperazines, piperidines, isoxazoles, thiazoles, isothiazoles, indoxyls, isatins, dioxindoles and hydanthoines and derivatives thereof, for example barbituric acid and uracil and derivatives thereof.
  • a nitrogen-containing heterocycle selected from the group consisting of pyrroles, pyrrolidines, pyridines,
  • Preferred heterocycles are imidazoles, pyridines and pyridine N-oxides, with imidazoles being particularly preferred.
  • Examples of particularly suitable comonomers B2 are N-vinylimidazoles, Alkylvinylimidaiole, in particular methylvinylimidazoles such as 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridines, 2- and 4-vinylpyridine N-oxides and betaine derivatives and quaternization products of these monomers.
  • Especially preferred comonomers interpolymerized 82 are N-vinylimidazoles of the formula II a, betaine N-vinylimidazoles of the formula II b, 2- and 4-vinyl pyridines of the general formula II c and d II and betaine 2- and 4-vinyl pyridines of the general formula II e, and f II
  • Examples of particularly preferred betaine copolymerized monomers B2 are monomers of the formula II b, II e, and f II, in which the group A 1 - X - - CH 2 -COO -, - (CH 2) 2 -SO 3 - or - (CH 2 ) 3 -SO 3 - and the remaining variables are each hydrogen.
  • Vinylimidazoles and vinylpyridines are also suitable as copolymerized monomers B2 which have been quaternized before or after the polymerization.
  • alkylating agents such as alkyl halides, which generally have 1 to 24 C atoms in the alkyl radical, or dialkyl sulfates, which generally contain alkyl radicals having 1 to 10 C atoms.
  • alkylating agents from these groups are methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride and lauryl chloride, as well as dimethyl sulfate and diethyl sulfate.
  • alkylating agents include: benzyl halides, especially benzyl chloride and benzyl bromide; Chloroacetic acid; Methyl fluorohydride, diazomethane; Oxonium compounds such as trimethyloxonium tetrafluoroborate; Alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichlorohydrins.
  • Preferred quaternizing agents are methyl chloride, dimethyl sulfate and diethyl sulfate.
  • copolymerized quaternized monomers B2 are 1-methyl-3-vinylimidazolium methosulfate and methochloride.
  • the weight ratio of the copolymerized monomers B1 and B2 is generally 99: 1 to 1:99, preferably 90:10 to 30:70, more preferably 90:10 to 50:50, most preferably 80:20 to 50:50 and especially 80:20 to 60:40.
  • the C 1 -C 24 -alkyl radicals in formula III a to III d can be branched or unbranched C 1 -C 24 -alkyl radicals, preference being given to C 1 -C 12 -alkyl radicals and C 1 -C 6 -alkyl radicals being particularly preferred , Examples are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methyl-propyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl , 2,2-dimethyl-propyl, 1-ethyl-propyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methyl-pentyl, 3-methylpentyl, 4-methylpentyl, 1,1 Dimethylbutyl, 1,2-dimethyl
  • the process according to the invention is characterized in that one or more graft polymers are used as the copolymer in the process according to the invention.
  • Graft polymers which are preferably used are, for example, those which, in addition to the monomers B1 and B2, also contain in copolymerized form such comonomers B3 which correspond to the formulas IIIa to IIId.
  • graft polymers which are composed a polymeric graft base A, which has no monoethylenically unsaturated units, and
  • polymeric side chains B formed from copolymers of at least two monoethylenically unsaturated monomers B1 and B2, each containing at least one nitrogen-containing heterocycle, and optionally further comonomers B3.
  • the graft polymers used in the below-described embodiment of the process according to the invention can be characterized by their ratio of side chains B to polymeric graft base A.
  • the proportion of side chains B in the graft polymers must be greater than 35 wt .-%, based on the total graft polymer. Preferably, the proportion is 55 to 95 wt .-%, particularly preferably 70 to 90 wt .-%.
  • the side chains B of the graft polymers preferably contain at least one cyclic amide of the general formula I as monomer B1 copolymerized, wherein in formula I they are variables as defined above.
  • copolymerized monomer B1 examples include N-vinylpyrrolidone, N-vinyl- ⁇ -valerolactam and N-vinyl- ⁇ -caprolactam, with N-vinylpyrrolidone being preferred.
  • the side chains B preferably contain at least one monoethylenically unsaturated monomer B2 which comprises a nitrogen-containing heterocycle selected from the group consisting of pyrroles, pyrrolidines, pyridines, quinolines, isoquinalines, purines, pyrazoles, imidazoles, triazoles, tetrazoles, indolizines , Pyridazines, pyrimidines, pyrazines, indoles, isoindoles, oxazoles, oxazolidones, oxazolidines, morpholines, piperazines, piperidines, isoxazoles, thiazoles, isothiazoles, indoxyls, isatins, dioxindoles and hydanthoines and derivatives thereof, eg Barbituric acid and uracil and their derivatives.
  • a nitrogen-containing heterocycle selected from the group consisting of pyrroles, pyrrol
  • Preferred heterocycles are imidazoles, pyridines and pyridine N-oxides, with imidazoles being particularly preferred.
  • Examples of particularly suitable comonomers B2 are N-vinylimidazoles, alkylvinylimidazoles, especially methylvinylimidazoles such as 1-vinyl-2-methylimidazole, 3-vinylimidazole N-oxide, 2- and 4-vinylpyridines, 2- and 4-vinylpyridine N-oxides and betaine derivatives and quaternization products of these monomers.
  • Very particularly preferred copolymerized comonomers B2 are N-vinylimidazoles of the formula II a, betaine N-vinylimidazoles of the formula II b, 2- and 4-vinyl pyridines of the general formula II c and d II and betaine 2- and 4-vinylpyridines of the general formula II II e and f.
  • Examples of very particularly preferred betaine copolymerized monomers B2 are monomers of the formula II b, II e, and f II, in which the group A 1 - X - is -CH 2 -COO -, - (CH 2) 2 -SO 3 - or - (CH 2 ) 3 -SO 3 - and the remaining variables are each hydrogen. Also suitable are vinylimidazoles and vinylpyridines as copolymerized monomers B2, which were quaternized before or after the polymerization.
  • the quaternization can be carried out in particular as described above.
  • copolymerized quaternized monomers B2 are 1-methyl-3-vinylimidazolium methosulfate and methoxloride.
  • the weight ratio of the copolymerized monomers B1 and B2 is generally 99: 1 to 1:99, preferably 90:10 to 30:70, more preferably 90:10 to 50:50, most preferably 80:20 to 50:50 and especially 80:20 to 60:40.
  • the graft polymers used according to the invention may contain one or more further monomers B3 in the side chains in copolymerized form, for example carboxyl-containing monoethylenically unsaturated monomers, for example C 2 -C 10 -unsaturated mono- or dicarboxylic acids and their derivatives such as salts, esters, anhydrides and those as defined above are.
  • the polymeric graft base A of the graft polymers used according to the invention is preferably a polyether.
  • the term "polymer” is intended to include also oligomeric compounds.
  • Particularly preferred polymeric graft bases A have an average molecular weight M n of at least 300 g / mol.
  • copolymers are suitable, it being possible for the copolymers to be random copolymers or block copolymers.
  • the terminal primary hydroxyl groups of the polyethers prepared on the basis of alkylene oxides or glycerol and the secondary OH groups of polyglycerol can be free or etherified 24 alcohols, esterified with C 1 -C 24 carboxylic acids or with isocyanates to form urethanes and with C 1 -C be implemented.
  • suitable alcohols for this purpose are: primary aliphatic alcohols, such as methanol, ethanol, propanol and butanol, primary aromatic alcohols, such as phenol, isopropylphenol, tert-butylphenol, octylphenol, nonylphenol and naphthol, secondary aliphatic alcohols, such as isopropanol, tertiary aliphatic alcohols Alcohols such as tert-butanol and polyhydric alcohols, for example, diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol and butanediol, and triols such as glycerol and trimethylolpropane.
  • primary aliphatic alcohols such as methanol, ethanol, propanol and butanol
  • primary aromatic alcohols such as phenol, isopropylphenol, tert-butylphenol, octylphenol, nony
  • the hydroxyl groups can also be exchanged by reductive amination with hydrogen-ammonia mixtures under pressure for primary amino groups or be converted by cyanethylation with acrylonitrile and hydrogenation in Aminopropylenend phenomenon.
  • the conversion of the hydroxyl end groups can not only subsequently by reaction with alcohols or alkali metal, amines and hydroxylamines but these compounds can be used as Lewis acids, such as boron trifluoride, also at the beginning of the polymerization as a starter.
  • the hydroxyl end groups can also be etherified by reaction with alkylating agents, such as dimethyl sulfate.
  • the C 1 -C 24 -alkyl radicals in formula IVa and IVb may be branched or unbranched C 1 -C 24 -alkyl radicals, preference being given to C 1 -C 12 -alkyl radicals and C 1 -C 6 -alkyl radicals being particularly preferred.
  • Examples are methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methyl-propyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl , 2,2-dimethyl-propyl, 1-ethyl-propyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methyl-pentyl, 3-methylpentyl, 4-methylpentyl, 1,1 Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl , 1,2,2-trimethylpropyl, 1-e
  • the average molecular weight M n of the polyethers of the general formula IV a is at least 300 g / mol and is generally ⁇ 100 000 g / mol. It is preferably 500 g / mol to 50,000 g / mol, more preferably up to 10,000 / mol g and most preferably up to 2000 g / mol.
  • the polydispersity of the polyethers of general formula IV a is low in most cases, for example in the range of 1.1 to 1.8.
  • homopolymers and copolymers of ethylene oxide, propylene oxide, butylene oxide and isobutylene oxide, which may be linear or branched can be used as polymeric graft base A.
  • homopolymers in the context of the present invention also encompasses those polymers which, in addition to the polymerized alkylene oxide unit, also contain the reactive molecules which were used to initiate the polymerization of the cyclic ethers or to cap the polymer end-capping.
  • Branched polymers can be prepared by, for example, low molecular weight polyols (radicals R 7 in formula IV a and IV b), for example pentaerythritol, glycerol and sugar or sugar alcohols such as sucrose, D-sorbitol and D-mannitol, disaccharides, ethylene oxide and if desired, attaches propylene oxide and / or butylene oxides or polyglycerol.
  • low molecular weight polyols for example pentaerythritol, glycerol and sugar or sugar alcohols such as sucrose, D-sorbitol and D-mannitol, disaccharides, ethylene oxide and if desired, attaches propylene oxide and / or butylene oxides or polyglycerol.
  • polymers in which at least one, preferably one to eight, more preferably one to five, of those present in the polyhydric alcohol molecule are formed Hydroxyl groups may be linked in the form of an ether bond with the polyether radical according to formula IVa or IVb.
  • Four-armed polymers can be obtained by attaching the alkylene oxides to diamines, preferably ethylenediamine.
  • branched polymers can be prepared by reacting alkylene oxides with higher-value amines, for example triamines, or in particular polyethyleneimines.
  • Polyethyleneimines suitable for this purpose generally have average molecular weights M n of 300 to 20 000 g, preferably 500 to 10000 g and particularly preferably 500 to 5000 g.
  • the weight ratio of alkylene oxide to polyethyleneimine is usually in the range of 100: 1 to 0.1: 1, preferably in the range of 20: 1 to 0.5: 1.
  • IV a and IV b produced by phosgenation polycarbonates of polyalkylene oxides or polyurethanes of polyalkylene oxides and aliphatic C 1 -C 12 -, preferably C 1 -C 6 diisocyanates or aromatic diisocyanates, for example hexamethylene diisocyanate or phenylene diisocyanate, to be used as the polymeric graft base A.
  • polyesters, polycarbonates or polyurethanes may contain up to 500, preferably up to 100 polyalkylene oxide units, wherein the polyalkylene oxide units may consist of both homopolymers and copolymers of different alkylene oxides.
  • An effect of polyethylene oxide and copolymeric alkylene oxides having a high ethylene oxide content is that, when the grafting and grafting density are the same as for polypropylene oxide, the weight ratio of side chain to polymeric graft base is greater.
  • the K values of the graft polymers are usually from 10 to 150, preferably from 10 to 80 and more preferably from 15 to 60 (determined by H. Fikentscher, Cellulosic Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 ) in water or 3 wt .-% aqueous sodium chloride solutions at 25 ° C and polymer concentrations, depending on the K value range from 0.1 wt .-% to 5 wt .-% are).
  • the respective desired K value can be adjusted by the composition of the starting materials.
  • the molecular weight of the products is given by the molecular weight of the graft base and the proportion of comonomers which react as side chains. The more molecules you use as a grafting base, the more end molecules you have and vice versa.
  • the side chain density is adjustable by the amount of starter and the reaction conditions.
  • the monomers B1 and B2 and optionally further comonomers B3 are radically polymerized in the presence of the polymeric graft base A.
  • the polymerization may be conducted, for example, in terms of solution polymerization, bulk polymerization, emulsion polymerization, reverse emulsion polymerization, suspension polymerization, reverse suspension polymerization, or precipitation polymerization. Preference is given to the polymerization in bulk and above all the solution polymerization, which is carried out in particular in the presence of water.
  • polymerization in bulk it is possible to proceed by dissolving the monomers B1 and B2 in the polymeric grafting base A, heating the mixture to the polymerization temperature and polymerizing it out after addition of a free radical initiator.
  • the polymerization can also be carried out semicontinuously by first heating a part, e.g.
  • the mixture of polymeric graft base A, monomer B1 and B2 and free radical initiator presents and heated to polymerization and after the onset of polymerization, the remainder of the mixture to be polymerized after the progress of the polymerization admits
  • the polymeric graft A in to a reactor and heated to polymerization temperature and monomer B1 and B2 (separately or as a mixture) and the radical initiator either all at once, batchwise or preferably continuously adding and polymerizing.
  • Suitable organic solvents are, for example aliphatic and cycloaliphatic monohydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol, polyhydric alcohols, for example glycols, such as ethylene glycol, propylene glycol and butylene glycol, and glycerol, alkyl ethers of polyhydric alcohols, for example methyl and ethyl ethers of said dihydric alcohols, and also ether alcohols, such as diethylene glycol and triethylene glycol, and cyclic ethers, such as dioxane.
  • aliphatic and cycloaliphatic monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butano
  • the graft polymerization is carried out in water as a solvent.
  • A, B1 and B2 and optionally further comonomers B3 are more or less well dissolved, depending on the amount of water used.
  • the water can also be added - partly or wholly - during the course of the polymerization.
  • mixtures of water and the above-mentioned organic solvents can also be used.
  • solutions or dispersions of the graft polymers according to the invention obtained by means of various drying methods, e.g. Spray drying, fluidized spray drying, drum drying or freeze drying, can be converted into powder form. By being introduced into water, an aqueous solution or dispersion can then easily be prepared again at the desired time.
  • radical initiators are peroxo compounds, azo compounds, redox initiator systems and reducing compounds. Of course you can also use mixtures of radical starters.
  • radical initiators are: alkali metal peroxodisulfates, for example sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, organic peroxides, such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide tert-butyl peracetate, tert-butyl per-maleate, tert-butyl per-pivalate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butylperneodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl
  • droperoxide tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate; Azobisisobutyronitrile, azobis (2-amidopropane) dihydrochloride and 2,2'-azobis (2-methylbutyronitrile); Sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxilate and hydrazine, and combinations of the foregoing with hydrogen peroxide; Ascorbic acid / ferrous sulfate / Na 2 S 2 O B , tert-butyl hydroperoxide / sodium disulfite and tertiary butyl hydroperoxide / sodium hydroxymethanesulfinate.
  • Preferred radical initiators are e.g. tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perodecanoate, tert-butyl peroxide, tert-butyl hydroperoxide, azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methylbutyronitrile), hydrogen peroxide and sodium peroxodisulfate , which redox metal salts, z.
  • iron salts can be added in small quantities.
  • radical initiator used.
  • polymerization regulators can also be used. Suitable compounds known to those skilled in the art, e.g. Sulfur compounds, such as mercaptoethanol,
  • 2-ethylhexyl thioglycolate, thioglycolic acid and dodecyl mercaptan but also other types of regulators, e.g. Bisulfite and hypophosphite.
  • polymerization regulators When polymerization regulators are used, their amount used is usually 0.1 to 15 wt .-%. preferably 0.1 to 5 wt.% and particularly preferably 0.1 to 2.5 wt.%, based on monomers B1 and B2.
  • the polymerization temperature is usually at 30 to 200 ° C, preferably at 50 to 150 ° C and particularly preferably at 75 to 110 ° C.
  • the polymerization is usually carried out under atmospheric pressure, but may also be carried out under reduced or elevated pressure, e.g. at 0.5 or 5 bar, expire.
  • the graft polymers described above can be used, for example, as stripping agents. According to the invention, the above-described graft polymers can be used as leveling agents.
  • At least one graft polymer is used as auxiliaries for textile dyeing and textile printing which has a copolymer as the graft base which comprises monomers B1 and B2 in copolymerized form and optionally further comonomers B3, where the monomers B1, B2 and B3 as defined above.
  • auxiliaries for textile dyeing and textile printing for example, stripping agents and leveling agents containing the graft polymers described above.
  • Auxiliaries according to the invention for textile dyeing and textile printing contain at least one graft polymer which is composed of a polymeric graft base A which has no monoethylenically unsaturated units and polymeric side chains B formed of copolymers of at least two monoethylenically unsaturated Monomers B1 and B2, each containing at least one nitrogen-containing heterocycle, and optionally further comonomers B3, wherein the proportion of side chains B greater than 35 wt .-%.
  • Preferred auxiliaries according to the invention for textile dyeing and textile printing contain, in addition to the above-described copolymers and in particular the above-described graft polymers, further components, for example phosphorus compounds, complexing agents and ionic or nonionic surfactants, particularly suitable phosphorus compounds being, for example, phosphonic acid compounds, for example hydroxymethylidenediphosphonic acid.
  • suitable complexing agents are aminocarboxylic acid derivatives and their alkali metal salts, for example nitrilotriacetic acid, ethylenediaminetetraacetic acid and the corresponding di- and trisodium salts, and the tetrasodium salt of ethylenediaminetetraacetic acid.
  • Suitable nonionic surfactants are, for example, ethoxylation products of long-chain alcohols.
  • Preferred alcohols are, for example, from the series of 1-alkanols having 8 to 30 carbon atoms, preferably 8 to 18 carbon atoms, or the series of 2-alkanols having 8 to 30, preferably 8 to 18 carbon atoms.
  • the degree of ethoxylation is 4 to 30, preferably 6 to 15.
  • alkoxylation of the above alkanols with a mean degree of alkoxylation of 8 to 30, preferably 8 to 18, wherein at least 1 mol of propylene oxide was used.
  • alkoxylation products obtained by reacting alkanols first with propylene oxide and then with ethylene oxide.
  • Suitable ionic surfactants are based, for example, on mono- or diesters of sulfosuccinic acid.
  • Suitable alcohols for the preparation of the esters are branched or unbranched alcohols having a chain length of 2 to 30 carbon atoms, preferably 4 to 18 carbon atoms.
  • the inventive auxiliaries for textile dyeing and textile printing can be used as a powder. But you can also use them as an aqueous formulation, wherein the water content in the range of 5 to 95, preferably 20 to 90 wt .-%, based on the sum of the components, may be.
  • the use as a liquid formulation the dosage can be done for example by means of an automatic dosing.
  • Another object of the present invention is a method for leveling off false colorations or unlevel dyeings in textile materials, hereinafter also referred to as leveling process according to the invention, characterized in that the leveling agent used is at least one graft polymer which copolymerizes at least 2 monoethylenically unsaturated monomers B1 and B2 contains, wherein B1 and B2 each contain at least one nitrogen-containing heterocycle.
  • the leveling process of the invention relates to the elimination of off-color or uneven coloration by vat, direct, reactive or sulfur dyes.
  • the graft polymers described above are used.
  • the leveling process according to the invention can be carried out under otherwise known conditions.
  • the leveling process according to the invention is carried out in an aqueous liquor, wherein the liquor ratio can be in the range from 1: 100 to 1: 5, preferably in the range from 1:25 to 1: 5.
  • the concentration of the leveling agents according to the invention is in the range from 0.01 to 10 g / l liquor, in particular in the range from 0.1 to 1 g / l and in particular to 1 g / l liquor.
  • the liquor is admixed with one or more dispersants.
  • suitable dispersants are naphthalenesulfonic acid-formaldehyde condensation products which can be prepared, for example, by sulfonation of naphthalene with oleum, partial or complete neutralization with, for example, aqueous alkali metal hydroxide and reaction with formaldehyde.
  • dispersants are, for example, in US 4,218,218 described. In general, amounts of 0.1 to 5 g of dispersant / l liquor, preferably 1 to 2 g / l are suitable.
  • one or more reducing agents are added to the liquor, for example sodium dithionite Na 2 S 2 O 4 .
  • amounts of 0.1 to 10 g of reducing agent / l liquor, in particular 1 to 6 g / l are suitable.
  • the liquor is admixed with protective colloids, for example protective colloids based on partially or completely neutralized polyacrylic acids.
  • Suitable polyacrylic acids have an average molecular weight M w of, for example, 1000 to 200 000 g / mol, preferably 1000 to 100 000 g / mol and in particular 3000 to 70 000 g / mol. Very particularly preferred are the completely neutralized polyacrylic acids.
  • amounts of 0.1 to 5 g protective colloid / l liquor, in particular 1 to 2 g / l are suitable.
  • the leveling process according to the invention is usually carried out at a pH of 9 to 13.
  • the leveling process according to the invention is usually carried out at a temperature above room temperature. Particularly suitable are temperatures in the range of 50 ° C to boiling temperature, preferably at least 60 ° C.
  • the duration of the leveling process according to the invention is usually at least 5 minutes to 2 hours, preferably 30 to 90 minutes.
  • Another object of the present invention is a process for the removal of false coloration of textile materials, hereinafter also referred to as the inventive stripping process, characterized in that as a stripping agent at least one graft polymer is used, which contains at least 2 monoethylenically unsaturated monomers B1 and B2 in copolymerized form, wherein B1 and B2 each contain at least one nitrogen-containing heterocycle.
  • the stripping process of the invention relates to the removal of spotting from vat, direct, reactive or sulfur dyes.
  • the graft polymers described above are used.
  • the stripping process according to the invention can be carried out under otherwise known conditions.
  • the removal process according to the invention is preferably carried out in an aqueous liquor, it being possible for the liquor ratio to be in the range from 1: 100 to 1: 5, preferably in the range from 1:25 to 1: 5.
  • the concentration of the stripping agents according to the invention is in the range from 0.5 to 10 g / l liquor, in particular in the range from 2 to 4 g / l liquor.
  • the liquor is admixed with one or more dispersants.
  • suitable dispersants are naphthalenesulfonic acid-formaldehyde condensation products which can be prepared, for example, by sulfonation of naphthalene with oleum, partial or complete neutralization with, for example, aqueous alkali metal hydroxide and reaction with formaldehyde.
  • suitable dispersants are, for example, in US 4,218,218 described.
  • amounts of 0.1 to 5 g of dispersant / l liquor, preferably 1 to 2 g / l are suitable.
  • one or more reducing agents are added to the liquor, for example sodium dithionite Na 2 S 2 O 4 .
  • the liquor is admixed with protective colloids, for example protective colloids based on partially or completely neutralized polyacrylic acids.
  • Suitable polyacrylic acids have an average molecular weight M w of, for example, 1000 to 200 000 g / mol, preferably 1000 to 100 000 g / mol and in particular 3000 to 70 000 g / mol. Very particularly preferred are the completely neutralized polyacrylic acids.
  • amounts of 0.1 to 5 g protective colloid / l liquor, in particular 1 to 2 g / l are suitable.
  • the stripping process according to the invention is usually carried out at a pH of 9 to 13.
  • the stripping process according to the invention is usually carried out at a temperature above room temperature. Particularly suitable are temperatures in the range of 50 ° C to boiling temperature, preferably at least 60 ° C.
  • the duration of the stripping process according to the invention is usually at least 5 minutes to 2 hours, preferably 30 to 90 minutes.
  • Another object of the present invention is a process for the post-cleaning of dyed or printed textile, hereinafter also referred to as Nachtherapiesbacter or nachseifbacter according to the invention
  • the after-sifting process according to the invention is carried out using one or more after-saponification agents according to the invention in a usually aqueous liquor.
  • the liquor may contain foreign salts, for example NaCl or Glauber's salt, in amounts of up to 15% by weight, based on the liquor.
  • the water used to make the aqueous liquor need not be softened; Water hardnesses of up to 30 ° dH (German hardness) are conceivable.
  • the after-sifting process according to the invention can be carried out under atmospheric pressure, but elevated pressures such as, for example, 1.1 to 5 bar are also conceivable.
  • the after-sifting process it is possible to treat dyed or printed textiles in one or more soap baths, wherein temperature, pressure and pH conditions in the soap baths can be chosen to be the same or different.
  • temperature, pressure and pH conditions in the soap baths can be chosen to be the same or different.
  • pressure and temperature conditions are the same in each case different Seifbädem.
  • At least one soap bath must contain one or more of the afterseing agents according to the invention.
  • the concentration of the afterseing agents used in the soap bath or baths according to the invention is usually 1 to 8 g / l, preferably 1 to 4 g / l.
  • Nonionic surfactants for example polyalkoxylated fatty alcohols
  • ethylene oxide, propylene oxide or butylene oxide is suitable or mixtures of the abovementioned epoxides; preferred is ethylene oxide.
  • Suitable alcohols are C 10 -C 24 -alcohols, in particular C 12 -C 18 -alcohols.
  • Alkoxyllêtsgrade are 10 to 40 equivalents of alkoxide per equivalent of fatty alcohol, in particular 15 to 30 equivalents of alkoxide per equivalent of fatty alcohol and in particular 20 to 25 equivalents of alkoxide per equivalent of fatty alcohol mentioned.
  • the degree of alkoxylation should be understood as an average value.
  • phosphorus-containing compounds such as polyphosphates or alkylidene bisphosphonic such as hydroxymethylidene bisphosphonic.
  • amino acetic acid derivatives such as nitrilotriacetic acid or ethylenediaminetetraacetic acid and the respective corresponding alkali metal salts.
  • the pH of the soap bath or baths used in the process according to the invention is in the range from 4 to 12, preferably 5 to 11. Particularly preferably, the pH is neutral or slightly acidic.
  • organic carboxylic acids are usually used, for example aliphatic monocarboxylic acids such as acetic acid, formic acid, propionic acid, furthermore aliphatic dicarboxylic acids such as adipic acid, succinic acid, citric acid or polycarboxylic acids.
  • carboxylic acids which only have a very low vapor pressure Have room temperature. Accordingly, aliphatic dicarboxylic acids, citric acid and polycarboxylic acids are preferred
  • Preferably used aliphatic dicarboxylic acids have the general formula HO 2 C- (CH 2 ) i - (O- (CH 2 ) j ) k -CO 2 H in which the variables i, j, k can independently of one another mean 0 to 9. Particular preference is given to carboxylic acids in which k is 0 or 1 and i and j independently of one another are from 1 to 6. Very particular preference is given to carboxylic acids in which i and j, independently of one another, are 1 to 4 and k is 0 or 1. Particular preference is given to mixtures of these carboxylic acids or mixtures of these carboxylic acids with citric acid.
  • Preferred aliphatic dicarboxylic acids are succinic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid.
  • polycarboxylic acids originate from the class of polyacrylic acids or their copolymers with maleic acids. They have an average molecular weight M n in the range from 1000 to 150000 g / mol, preferably 2000 to 70000 g / mol.
  • the afterseeding process according to the invention is usually carried out at elevated temperatures. Possible temperatures are 50 to 100 ° C and under pressure even higher temperatures. Preference is given to temperatures of 60 to 98 ° C.
  • the Massenverphasettnis of liquor to nachreiinigendem dyed or printed textile is usually 1: 4 to 1:40, preferably 1: 6 to 1:20. During the cleaning, you can move the fleet with the textile.
  • the duration of action per soaping bath is not critical per se; it is usual to use 5 minutes to 10 hours, preferably 10 to 30 minutes.
  • the textiles are usually rinsed with water. Usually one to 6, preferably 2 to 4 rinses. Rinsing usually takes place in the first rinse bath or baths with warm water, i. Water from a temperature of 35 to 70 ° C. The last rinses often take place at room temperature up to 40 ° C.
  • the subject of the present invention is a process for the post-purification of textiles printed with reactive dyes, direct dyes or vat dyes, the post-cleaning being followed by the dyeing and serving to remove dye not bound to the textile.
  • the K value was after H. Fikentscher, Cellulosic Chemistry Vol. 13, pp. 58-64 and 71-74 determined at 25 ° C in 3 wt.% Aqueous NaCl solution and was 40.
  • Percentage quantities are based on the weight of the fabric. Quantities not given in percentages are to be taken from the volume of the liquor.
  • Example 1 Twenty-five grams of bleached cotton nettle (Sample 1) was wound on a perforated metal basket and dyed in an airtight stainless steel cylinder 15 cm in diameter and 30 cm high which served as a dyeing vessel for 40 seconds at 60 ° C for 3 minutes. Subsequently, the dyeing vessel was opened and after a total of 4 min dyeing time another 25 g of bleached cotton nettle (sample 2) wound on a perforated metal basket placed in the dyeing vessel. The staining vessel was closed again and dyed at 60 ° C. for a further 45 min. The dyed cotton nettle was then removed and rinsed three times by immersion in 1 l of cold water.
  • the dyed cotton seed (samples 1 and 2) in 1 liter of liquor entnumbered 2 ml / l 50 wt .-% hydrogen peroxide solution was oxidized for 5 min at 55 ° C followed by rinsing at room temperature with water in the overflow for 5 min.
  • samples 1 and 2 were cleaned for 15 minutes at 98 ° C. in a soapy bath.
  • the soap bath was composed as follows: volume of liquid 1 l containing 1 g / l 90 wt .-% aqueous C 13 H 27 - (OCH 2 CH 2) 4 -OH and 0.5 g / l Na 2 CO 3.
  • the sample was again rinsed for 1 min at 55 ° C.
  • Samples 1 and 2 were spun and dried. Obtained in this way equalized samples 1 and 2.
  • the reflectance spectrum was recorded from sample 1 as a reference and then from the bleached cottonweed with a spectrometer (X-rite CA22).
  • K / S values were calculated according to Kubelka-Munk. Then the K / S values of the bleached cotton hemp were subtracted from that of the sample 1 to obtain the pure dye content of the K / S value of the sample 1.
  • the obtained pure dye fractions of the K / S values were then compared in the region of the maximum of the wavelength-dependent representation of the K / S values of sample 2.
  • the K / S value of Sample 1 was set equal to 100%.
  • sample 1 and sample 2 should have the same color depth.
  • Example 2.1.1 was repeated, but graft polymer 1 was replaced by polyvinylpyrrolidone 1 having a molecular weight M w of 45,000 g / mol and a Fikentscher K value of 31, determined in 1% by weight aqueous solution.
  • the mixture was then heated from room temperature to 60 ° C. over the course of 10 minutes, and this temperature was maintained for 45 minutes. Subsequently, the pre-dyed cotton nettle was removed and rinsed three times with 1 liter of water at room temperature
  • the pre-dyed cotton nettle was oxidized for 5 min at 55 ° C. in 1 l of liquor containing 2 ml / l of 50% strength by weight hydrogen peroxide solution, rinsed for 1 min at room temperature in the overflow and then spun and dried.
  • a blind dyeing liquor ie a dye liquor without colorant, was prepared containing 12 ml / l sodium hydroxide solution 38 ° Be, 6 g / l Na 2 S 2 O 4 and 2 g / l graft polymer 1.
  • 50 g of the pre-dyed cotton nettle described above were placed in the blind dyeing liquor, heated to 80 ° C. within 20 minutes and then treated at 80 ° C for 45 minutes. The mixture was then cooled to 60 ° C. in the course of 10 minutes and the pretreated cotton nettle was removed at this temperature. It was again rinsed 3 times in about 1 liter of cold water and then oxidized with 1 liter of liquor containing 2 ml / l of 50 wt .-% hydrogen peroxide solution at 55 ° C for 5 min.
  • the remission spectrum was recorded on a pre-dyed cotton-seed as reference and then on the bleached cotton-nettle with a spectrometer (X-rite CA22).
  • K / S values were calculated according to Kubelka-Munk. Then the K / S values of the bleached cotton hemp were subtracted from that of the pre-dyed cotton hemp to obtain the pure dye content of the K / S value of the precolored cotton hothead.
  • the pure dye contents of the K / S values obtained were then compared in the region of the maximum of the wavelength-dependent representation of the K / S values of the pre-dyed cotton nettle.
  • the K / S value of the pre-dyed cotton seed was set equal to 100%. The higher the K / S value of the treated cotton nettle compared to the K / S value of the pre-dyed cotton nettle, the worse the peel result was evaluated.
  • the sample In the case of a very good peeling result, the sample should have a color depth comparable to the cotton used or no coloration can be detected any more.
  • the values for the removal result are given in% color depth of the pre-dyed cotton nettle.
  • the resulting from Table 3 amount of dye hydrolyzate was made up to 1 liter with water and adjusted with CaCl 2 to 20 ° DH.
  • a padder manufactured by a padder (manufacturer Mathis, type no. HVF12085)
  • the diluted hydrolysates were applied to cotton fabric.
  • the contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 80%.
  • the application speed was 2 m / min.
  • the textile was dried at 125 ° C. in a circulating air oven (manufacturer: Mathis, Type No. LTF89534) at 125 ° C. for 4 minutes without circulating air.
  • the color depth of the padded textile thus obtained was determined by means of a reflectance spectrometer (X-rite CA22) and the calculation was carried out as described above.
  • the padded, non-cleaned textile is also referred to below as padded textile.
  • the reflectance spectrum was recorded on the padded, dried textile as reference and then on the untreated textile with a spectrometer (X-rite CA22).
  • the K / S values were calculated according to Kubelka-Munk. Subsequently, the K / S values of the untreated fabric were subtracted from the padded, dried fabric to obtain the pure dye content of the K / S value of the padded, dried fabric.
  • the procedure was analogous to the subsequently cleaned sample.
  • the pure dye content of the K / S value of the post-purified textile was obtained.
  • the obtained pure dye contents of the K / S values were then compared in the region of the maximum of the wavelength-dependent representation of the K / S values of the padded, dried textile.
  • the K / S value of the padded, dried textile was set to 100%. The higher the K / S value of the post-cleaned fabric compared to the non-post-cleaned, padded, dried fabric, the worse the post-soing effect was evaluated.
  • the after-sifting agents used were the substances or mixtures S1 to S8 given in Table 4 below.
  • Table 4 Composition of the after-sizing agents S2 to S7 according to the invention and of the comparative after-sifting agent S1 Aftersoaping S1 S2 S3 S4 S5 S6 S7 polyacrylic acid 100 1-Hydroxymethylidenbisphosphonklare 25 10 31.5 Copolymer 1 100 Graft polymer 1 25 10 35 35 100 nC 16 H 33 - (OCH 2 CH 2 ) 25 -OH 2.5 2.5 3.5 water 47.5 77.5 30 65
  • the polyacrylic acid used for the after-sifting agent S1 used in comparative examples is NaOH-neutralized polyacrylic acid having an M w of 70,000 g, as determined by gel permeation chromatography; pH 8.5, as 45 wt .-% aqueous solution.
  • Post-soap-free soap baths were used in Comparative Examples C2, V4, V6 and V8, ie the padded textile was treated with hot water at the indicated pH.
  • NC 16 H 33 - (OCH 2 CH 2 ) -OH is hexadecanol ethoxylated with ethylene oxide, prepared according to the following procedure:
  • Printing pastes D1 to D8 were prepared by mixing 80 g of the alginate Manutex F 700), 10 g of sodium salt of p-nitrosulfonic acid, 100 g of urea and 25 g of Na 2 CO 3 and 5 g of sodium hexametaphosphate for water softening and 20 g of dyestuff hydrolyzate according to Table 1 were stirred to a printing paste.
  • the printing pastes D1 to D8 thus obtained had a dynamic viscosity of 3 Pa ⁇ s.
  • Each printing paste D1 to D8 was printed on a 100% cotton fabric on a MBK flat-film printing table with magnetic doctor blade system (doctor blade diameter 10 mm, 12 m / min, draw 6) using a flat stencil (gauze E50-55) ) at 80 ° C until complete dryness of the pressure.
  • the amount of post-soap shown in Table 6 from Table 4 was dissolved with 50 g of sodium chloride in 1 liter of water and adjusted to 10 ° DH with CaCl 2 . 200 ml of the resulting liquor were heated to 60 ° C. If necessary, the pH was adjusted to the value indicated in Table 3 with the aid of citric acid. 10 g of a printed textile were added to the liquor and heated to the temperature indicated in Table 3 within 10 minutes. It was allowed to act for 15 minutes per Seifbad and then cooled to 60 ° C, wherein in the examples in which several Seifbäder were used, respectively disposed of the liquor after the first Seifbad and a new Seifbad was set. In the experiments, the second soap bath of identical composition was used for this purpose. The textile was removed and squeezed by hand. The mixture was then rinsed twice with 200 ml of cold water for 5 minutes each time. It was then spun and the sample was dried at room temperature
  • the reflectance spectrum was recorded on the printed, dried textile as reference and then on the untreated textile with a spectrometer (X-rite CA22).
  • X-rite CA22 a spectrometer
  • K / S values were calculated according to Kubelka-Munk.
  • the K / S values of the untreated textile were subtracted from the printed, dried textile to obtain the pure dye content of the K / S value of the printed, dried textile.
  • the procedure was analogous to the subsequently cleaned sample.
  • the pure dye content of the K / S value of the post-purified textile was obtained.
  • the obtained pure dye contents of the K / S values were then compared in the region of the maximum of the wavelength-dependent representation of the K / S values of the printed, dried textile.
  • the K / S value of the printed, dried textile was set to 100%. The higher the K / S value of the post-cleaned fabric compared to the non-post-printed printed dried fabric, the worse the post-sifting effect was evaluated.
  • the after-sifting agents used were the substances or mixtures S1 to S8 given in Table 6 below.
  • Table 6 Nachmassbeitician according to invention and comparative examples V61 V62 V63 64 65 66 67 Hydrolyzate no H5 H5 H5 H5 H5 H5 H5 Amount of hydrolyzate [g / l] 20 20 20 20 20 20 20 Color depth printed textile% 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

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EP03785689A 2002-12-03 2003-11-28 Pfropfpolymerisaten als hilfsmittel für die textilfärberei und den textildruck Expired - Lifetime EP1570123B1 (de)

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DE2002156618 DE10256618A1 (de) 2002-12-03 2002-12-03 Verfahren zum Nachreinigen von gefärbtem Textil
DE2002161190 DE10261190A1 (de) 2002-12-20 2002-12-20 Verwendung von Copolymerisaten als Hilfsmittel für die Textilfärberei
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DE2003121396 DE10321396A1 (de) 2003-05-12 2003-05-12 Verwendung von Copylymerisaten als Hilfsmittel für die Textilfärberei
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DE10156134A1 (de) * 2001-11-16 2003-05-28 Basf Ag Pfropfpolymerisate mit cyclische N-Vinylamide enthaltenden Seitenketten
DE10156135A1 (de) * 2001-11-16 2003-06-05 Basf Ag Pfropfpolymerisate mit Stickstoffheterocyclen enthaltenden Seitenketten
DE10156133A1 (de) * 2001-11-16 2003-05-28 Basf Ag Pfropfpolymerisate mit Stickstoffheterocyclen enthaltenden Seitenketten

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ATE434076T1 (de) 2009-07-15
US20060116311A1 (en) 2006-06-01
DE50311617D1 (de) 2009-07-30
EP1570123A1 (de) 2005-09-07
BR0316848A (pt) 2005-10-18
WO2004050982A1 (de) 2004-06-17
PT1570123E (pt) 2009-07-23
ES2327114T3 (es) 2009-10-26
BR0316848B1 (pt) 2013-07-02
AU2003294749A1 (en) 2004-06-23

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