EP2313550A1 - Procédé de post-traitement ménagé de textiles teints - Google Patents

Procédé de post-traitement ménagé de textiles teints

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Publication number
EP2313550A1
EP2313550A1 EP09781304A EP09781304A EP2313550A1 EP 2313550 A1 EP2313550 A1 EP 2313550A1 EP 09781304 A EP09781304 A EP 09781304A EP 09781304 A EP09781304 A EP 09781304A EP 2313550 A1 EP2313550 A1 EP 2313550A1
Authority
EP
European Patent Office
Prior art keywords
mol
polypropylene
units
carbon atoms
radicals
Prior art date
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Granted
Application number
EP09781304A
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German (de)
English (en)
Other versions
EP2313550B1 (fr
Inventor
Pia Baum
Klaus Scheuermann
Dieter Boeckh
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BASF SE
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BASF SE
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Priority to EP09781304A priority Critical patent/EP2313550B1/fr
Priority to PL09781304T priority patent/PL2313550T3/pl
Publication of EP2313550A1 publication Critical patent/EP2313550A1/fr
Application granted granted Critical
Publication of EP2313550B1 publication Critical patent/EP2313550B1/fr
Active legal-status Critical Current
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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02After-treatment
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/52General 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/60General 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34Material containing ester groups
    • D06P3/52Polyesters
    • D06P3/54Polyesters using dispersed dyestuffs
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79Polyolefins
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79Polyolefins
    • D06P3/794Polyolefins using dispersed dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02After-treatment
    • D06P5/04After-treatment with organic compounds
    • D06P5/08After-treatment with organic compounds macromolecular

Definitions

  • the invention relates to a process for the aftertreatment of dyed and / or printed textiles for removing excess amounts of colorants, in which an aqueous formulation is used which comprises at least one graft copolymer having a hydrophilic main chain and also surfactants.
  • Polyester fibers are widely used raw materials for the production of textile materials. Textiles made of polyester fibers can be colored by means of various dyeing processes from aqueous baths and / or printed by means of suitable textile printing inks. Polyesters can be dyed, for example, with disperse dyes at 120 ° - 130 0 C in Ausziehverfahen.
  • the residual on the surface, excess dye may be removed, for example advertising by a reductive after-washing with hydrosulphite and NaOH at 60-70 0 C to. Thereafter, the fabric is usually rinsed, depending on the color depth 1 to 3 times. In the last rinse, the pH of the textile material is preferably adjusted to 4-7 with acetic acid.
  • a third known method is the use of surfactants for after-washing.
  • Surfactants alone generally do not have a sufficient effect.
  • WO 2006/098730 discloses a disperse dye-dyeable fiber comprising a blend of a polyolefin and an amorphous, glycol-modified PET (PET-G).
  • PET-G amorphous, glycol-modified PET
  • preference is given to using maleic anhydride.
  • WO 2006/128796 discloses a process for dyeing polyolefins, in which polyolefins are used which are reacted with a block copolymer of at least one nonpolar block, which is composed essentially of isobutene units, and at least one polar block, which is essentially composed of oxyalkylene units, are blinded.
  • a block copolymer of at least one nonpolar block which is composed essentially of isobutene units
  • at least one polar block which is essentially composed of oxyalkylene units
  • polyesters and / or polyamides can also be incorporated as auxiliaries.
  • Dyeing of such textiles from doped polypropylene can be done in a similar way to the dyeing of polyesters.
  • the object of the invention was therefore to provide a gentle process for after-washing, which avoids discoloration of the textiles.
  • a process has been found for the post-treatment of colored and / or printed textile materials, the textile materials comprising polyester and / or polypropylene fibers, and in which the said materials with an aqueous formulation of at least one anionic and / or nonionic surfactant (A) a temperature of 20 to 100 0 C, and wherein the aqueous solution further contains at least one graft copolymer (B) comprising a straight-chain or branched, hydrophilic N and / or O atoms comprising main chain and grafted on side chains , More specifically, the following is to be accomplished for the invention:
  • dyed and / or printed textile, polyester and / or polypropylene fibers comprising materials are aftertreated with an aqueous formulation.
  • textile materials can be all types of textile materials, such as fibers for textile use, for example filaments or staple fibers, as well as semi-finished products or intermediate products such as yarns, fabrics, knitted fabrics, knitted fabrics, nonwovens or nonwovens also be finished products, such as clothing or home textiles.
  • the textile materials include polyester and / or polypropylene fibers. They may consist solely of polyester fibers and / or polypropylene fibers, but of course may also be used in combination with other materials such as polyamide fibers or natural fibers. A combination can be made at different stages of production. For example, it is already possible to produce filaments of a plurality of polymers with a defined geometric arrangement at the melt-spinning stage. In the manufacture of yarn, fibers of other polymers may be incorporated, or fiber blends may be made of staple fibers. Furthermore, various yarns may be processed together and, finally, fabrics, knits or the like comprising polyester and / or polypropylene fibers may be joined together with chemically dissimilar fabrics.
  • Suitable polypropylene grades for the production of fibers are known in principle to the person skilled in the art. These are relatively high molecular weight, viscous products, which are characterized in the usual way by their melt flow index (determined according to ISO 1 133). According to the invention, at least one polypropylene having a melt flow index MFR (230 ° C., 2.16 kg) of 0.1 to 60 g / 10 min is used.
  • polypropylene homopolymers may also be polypropylene copolymers which comprise, in addition to the propylene, small amounts of other comonomers.
  • Suitable comonomers may in particular be other olefins such as, for example, ethylene and 1-butene, 2-butene, isobutene. thene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene or ⁇ -methylstyrene, dienes and / or polyenes.
  • the proportion of comonomers in the polypropylene is generally not more than 20% by weight, preferably not more than 10% by weight.
  • polypropylene having a melt flow index MFR (230 ° C., 2.16 kg) of 1 to 50 g / 10 min, more preferably 10 to 45 g / 10 min and, for example, 30 to 40 g / 10 min.
  • the amount of the polypropylene is 80 to 99 wt.%, Based on the sum of all components of the undyed fiber, preferably 85 to 99 wt.%, Particularly preferably 90 to 98 wt.% And for example 93 to 97 wt.%.
  • the polypropylene fiber for improving the dyeability comprises 1 to 20% by weight of at least one polyester.
  • This may be conventional PET with a melting point of 255 to 265 ° C. It is particularly advantageous to use modified PET which has additional soft segments and accordingly has a lower degree of crystallization or melting point.
  • PHg polyesters are used, which have a melting point of 50 to 200 0 C.
  • Lower melting point polyesters can be obtained by substituting a portion of the terephthalic acid units in the PET for aliphatic dicarboxylic acid units, especially adipic acid units, to synthesize the polyesters.
  • the ethylene glycol units can also be replaced by longer-chain diols, in particular C 3 to C 6 alkanediols, such as, for example, 1,4-butanediol or 1,6-hexanediol.
  • Polyesters preferred for carrying out the invention have at least two different dicarboxylic acid units (X). They comprise at least 5 to 80 mol% of terephthalic acid units (X1) and 20 to 95 mol% of units of aliphatic 1, ⁇ -dicarboxylic acids (X2) having 4 to 10 carbon atoms. The total amount of (X1) and (X2) is at least 80 mol%, the% figures being based on the total amount of all dicarboxylic acid units in the polyester.
  • the aliphatic 1, ⁇ -dicarboxylic acid units (X2) may, for example, be succinic acid, glutaric acid, adipic acid or sebacic acid. It is preferably adipic acid.
  • dicarboxylic acid units (X1) and (X2) various dicarboxylic acid units may still be present therefrom.
  • other aromatics see dicarboxylic acid units and / or cycloaliphatic dicarboxylic acid units.
  • mixtures of different dicarboxylic acid units can be used.
  • the amount of terephthalic acid units (X1) is 20 to 70 mol% and the amount of (X2) is 30 to 80 mol%.
  • the sum of (X1) and (X2) is at least 90 mol%, more preferably at least 98 mol%, and most preferably 100 mol%.
  • the diol units (Y) are selected from the group of aliphatic, cyclic and / or polyether diols, wherein 50 to 100 mol% of aliphatic 1, ⁇ -diols (Y1) are present, and the% data based on the total amount of all diols are.
  • the aliphatic diols having 4 to 10 carbon atoms (Y1) may be, for example, 1,4-butanediol, 1,5-butanediol or 1,6-hexanediol.
  • (Y1) is 1,4-butanediol.
  • polyether diols examples include diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol.
  • cycloaliphatic diols examples include cyclopentane or cyclohexanediols. Of course, aliphatic diols which do not correspond to the definition (Y1) can also be used. Examples include in particular ethylene glycol or propylene glycol.
  • polyesters may also include other components for fine control of the properties.
  • examples include building blocks which have additional functional groups. Particular mention should be made here of amino groups. Also to be mentioned are building blocks for chain extension.
  • Preferred polyesters of the type mentioned have a melting point of 50 to 200 0 C.
  • the melting point is preferably 60 to 180 0 C, particularly preferably 80 to 160 0 C, most preferably 100 to 150 ° C and, for example 110-130 0 C.
  • the glass transition temperature is preferably 20-35 ° C, preferably 25-30 ° C without the invention being restricted thereto.
  • the number average molecular weight M n should generally be 5000 to 50 000 g / mol, preferably 10000 to 30 000 g / mol. Have proven particularly useful 20,000 to 25,000 g / mol.
  • the ratio M w / M n is preferably 3 to 6, for example 4 to 5. It is furthermore advantageous for the polyester to have a melt flow rate MFR of 2 to 6 g / 10 min (ISO 1 133, 190 ° C., 2.16 kg).
  • a preferred bulk density is 1, 2 - 1, 35 g / cm 3, more preferably 1, 22 - 1. 30 g / cm3
  • the preferred Vicat softening temperature is 75 to 85 ° C, more preferably 78-82 ° C (VST A / 50, ISO 306). Further details for the preparation of such polyesters are disclosed in WO 2008/65185.
  • polyesters can be used as an additive.
  • the amount of the polyesters is preferably from 1 to 15% by weight, more preferably from 2 to 10% by weight and, for example, from 3 to 7% by weight.
  • the polypropylene preferably used as an additive in addition to 0.1 to 10 wt.% Of at least one block copolymer having at least one non-polar block having a number average molar mass M n of at least 200 g / mol and a polar block with a number average molar mass M n of at least 500 g / mol includes.
  • the amount of block copolymer is preferably from 0.2 to 6% by weight, more preferably from 0.5 to 4% by weight, and for example from 0.75 to 3% by weight.
  • non-polar block which is composed essentially of isobutene units
  • a polar block which is composed essentially of oxyalkylene units, and whose average molar mass M n is at least 1000 g / mol.
  • the oxyalkylene units are preferably ethylene oxide units.
  • the block copolymers are preferably triblock copolymers having a middle block of oxyalkylene units and two terminal blocks of isobutene, the blocks being linked together via suitable linking moieties.
  • the polar blocks each have an average molar mass M n of
  • M n is preferably from 1250 to 18000 g / mol, more preferably from 1500 to 15000 g / mol, and most preferably from 2500 to 8000 g / mol.
  • the non-polar blocks generally each have an average molar mass M n of 200 to 10,000 g / mol.
  • M n is preferably from 300 to 8000 g / mol, particularly preferably from 400 to 6000 g / mol and very particularly preferably from 500 to 5000 g / mol.
  • the block copolymers may be diblock, triblock or multiblock copolymers. Preference is given to diblock and triblock copolymers, in particular triblock copolymers which have a central polar block and two terminal nonpolar blocks. It may also be mixtures of diblock and triblock copolymers.
  • block copolymers and their preparation are shown in detail in WO 2006/128796 page 4 to page 10.
  • the abovementioned block copolymers interact synergistically with the polyester and bring about particularly good dyeability. Preference is therefore given to an additive system comprising at least one polyester and at least one block copolymer of the type mentioned. But it is also possible to use only a polyester or only said block copolymer as an additive.
  • disperse dyes may preferably be used.
  • the term "disperse dye” is known to the person skilled in the art. Disperse dyes are dyes having a low water solubility which are used in disperse, colloidal form for dyeing, in particular for dyeing fibers and textile materials are described, for example, in WO 2006/128796, page 15 to page 20.
  • an aqueous formulation of at least one anionic and / or nonionic surfactant (A) and at least one graft copolymer (B) is used.
  • formulations for treating textiles are often referred to as "liquor”.
  • the aqueous formulation used essentially comprises water as solvent.
  • optional water-miscible solvents may be present, for example, alcohols such as methanol, ethanol or propanol.
  • the solvent comprises at least 80% by weight of water with respect to the sum of all solvents of the aqueous formulation, preferably at least 90% by weight, more preferably at least 95% by weight, and very particularly preferably only water is used as solvent.
  • the formulation furthermore contains at least one anionic and / or nonionic surfactant (A). At least one nonionic surfactant is preferred. used. Of course, mixtures of several different surfactants can be used.
  • nonionic surfactants include surfactants (A1) of the general formula (I) R 1 -O- (CH 2 -CH (R 2 ) -O) n H.
  • n is a number from 3 to 25, preferably 4 to 15 and more preferably 5 to 10.
  • R 1 is an aliphatic and / or aromatic, straight-chain or branched hydrocarbon radical having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms and especially preferably 12 to 16 carbon atoms.
  • R 1 is preferably a straight-chain or branched, aliphatic hydrocarbon radical.
  • R 1 may be radicals derived from fatty alcohols or preferably oxoalcohols.
  • radicals R 2 independently of one another represent hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen or methyl and particularly preferably hydrogen. If several different radicals R 2 are present, it should be at least 60%, preferably at least 80% of the radicals R 2 is hydrogen, this statement being based on the total number of all radicals R 2 .
  • Nonionic surfactants (A1) are commercially available.
  • surfactants include low-foaming nonionic surfactants (A2). Such surfactants are known in principle to the person skilled in the art.
  • (A2) may be nonionic surfactants of the general formula (II) R 1 -O- (CH 2 -CH (R 3 ) -O) m -R 4 , wherein R 1 is as defined above.
  • m is a number from 3 to 30, preferably 5 to 25 and particularly preferably 10 to 20.
  • R 3 may be hydrogen, or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen or methyl, wherein at least 60%, preferably at least 80% of the radicals R 3 , based on the total number of all radicals R 3 is hydrogen. Particularly preferably, R 3 is exclusively hydrogen.
  • the group R 4 is a group which is more hydrophobic than the group - (CH 2 -CH (R 3 ) -O) m - in formula (II).
  • R 4 may be a group - (CH 2 -CH (R 5 ) -O) Z -H, where z is a number from 1 to 15, preferably from 2 to 10.
  • R 5 is hydrogen or an alkyl radical having 1 to 6 carbon atoms, preferably hydrogen, methyl or ethyl, with the proviso that at least 60% of the groups R 5, based on the total number of all groups R 5, is an alkyl radical having 1 to 6 Carbon atoms is.
  • R 5 is methyl.
  • Such block copolymers can be obtained by first alkoxylating the starter alcohol with ethylene oxide or at least 60 mol% of ethylene oxide-containing alkylene oxide mixtures and the resulting alkoxy alcohol in a second stage with propylene oxide and / or higher alkylene oxides or at least 60 mol% propylene oxide and / or higher alkylene oxides further alkoxylated alkylene oxide mixtures.
  • R 4 include straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, preferably 6 to 14 carbon atoms, or groups of the formula --CO-R 4 , where R 4 has the meaning mentioned.
  • Such structures can be obtained by etherification or esterification of corresponding nonionic surfactants.
  • low-foam nonionic surfactants are disclosed, for example, in WO 92/14808, WO 01/77276 or WO 2006/097435. Low-foaming nonionic surfactants are commercially available.
  • graft copolymers is used in the usual sense for copolymers which have a straight-chain or branched polymer backbone (main chain) and branched off (grafted) side chains, which in their own right can already be termed oligomers or polymers Polymer backbone and the side chains are chemically different nature.
  • the straight-chain or branched main chain is hydrophilic. It has N and / or O atoms, which are preferably part of the main chain itself.
  • the N and / or O atoms of the main chain are separated from each other by groups of hydrocarbons, preferably from 2 to 4 hydrocarbon groups. They may preferably be 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene or 1,4-butylene groups.
  • the graft copolymer (B) is a graft copolymer (B1) having a main chain which consists essentially of alkylene oxide units, the main chain having a number average molecular weight M n of 300 to 60,000 g / mol, preferably 600 to 10,000 g / mol and more preferably 2000 to 8000 g / mol.
  • the term "substantially” is intended to mean that the main chain as a rule comprises at least 90 mol% of alkylene oxide units, preferably ethylene oxide and / or propylene oxide units, which is generally at least 50 mol%, preferably at least 70 mol% and particularly preferably at least 90 mol% of the alkylene oxide units are ethylene oxide units.
  • the side chains consist essentially of ethylenically unsaturated monomers. These are preferably functional groups containing ethylenically unsaturated monomers. Suitable monomers include vinyl derivatives or acyl derivatives such as, for example, vinyl acetate, vinylamine, vinylpyrrolidone, vinylimidazole, vinyl esters, acrylic acid or acrylic acid esters. In a preferred embodiment of The invention relates to the ethylenically unsaturated monomers of the side chains at least 50 mol% vinyl acetate, preferably at least 80 mol% of vinyl acetate and particularly preferably exclusively vinyl acetate.
  • the graft copolymers (B1) can be prepared in a manner known in principle by carrying out the polymerization of the ethylenically unsaturated monomers of the side chains in the presence of polyalkylene oxides, in particular polyethylene glycol.
  • the quantitative ratio of polyalkylene oxides to ethylenically unsaturated monomers is preferably selected such that the graft copolymer comprises 30 to 80% by weight of polyalkylene oxide, preferably 30 to 50% by weight of polyalkylene oxide.
  • (B1) is a graft copolymer of polyethylene glycol and vinyl acetate with 30 to 50 wt.% Polyethylene glycol, wherein the main chain has a number average molecular weight M n of 4000 to 8000 g / mol.
  • the graft copolymer (B) is a graft copolymer (B2) having a main chain consisting essentially of alkyleneimine units, the main chain having a number average molecular weight M n of from 300 to 10,000 g / mol 300 to 1000 g / mol.
  • the backbone is preferably polyethyleneimine, more preferably hyperbranched polyethylenimine typically obtained in the polymerization of ethyleneimine.
  • the side chains are polyether units.
  • Such graft copolymers (B2) can be obtained in a manner known in principle by alkoxylation of polyethyleneimine, in particular with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, preferably ethylene oxide and / or propylene oxide. If different alkylene oxides are used, they may be present statically or else as block copolymers.
  • the number of grafted Alkylenoxidiseren is usually at 5 to 100 per side group preferably 5 to 50.
  • the aqueous formulation may optionally comprise further components (C) as auxiliary agents.
  • components include foam suppressants, wetting and deaerating agents or dispersants.
  • the aqueous formulation additionally comprises at least one foam damper (C1).
  • foam damper may, for example, be foam silencers based on polysiloxanes, for example polydimethylsiloxanes.
  • silicon-free foam suppressants such as fatty alcohol derivatives, disperse silicic acid or polyethers such as polypropylene glycol, poly (propylene glycol-ethylene glycol) copolymers or polypropylene glycol derivatives.
  • the aqueous formulation additionally comprises at least one wetting aid (C2).
  • wetting aids include primary, secondary or tertiary phosphoric acid esters of alcohols, such as phosphoric acid esters of 2-ethylhexyl alcohol. It is also possible to use sulfosuccinates or other small-molecule surfactants for this purpose.
  • the formulation comprises at least one foam damper (C1) and at least one wetting assistant (C2).
  • concentrations of the components of the formulation are determined by those skilled in the art according to the desired properties of the formulation.
  • the concentration of the surfactants (A) in the formulation is generally 0.01 g / l to 5 g / l, preferably 0.02 g / l to 2 g / l, particularly preferably 0.05 g / l to 1 g / l and very particularly preferably 0.1 g / l to 0.5 g / l.
  • the weight ratio of low-foaming surfactants (A2) to the total amount of all surfactants should as a rule be at least 1: 1.
  • the concentration of the graft copolymers (B) in the formulation is generally 0.5 g / l to 10 g / l, preferably 0.1 g / l to 5 g / l, particularly preferably 0.2 g / l to 2 g / l and most preferably 0.3 g / l to 1 g / l.
  • the weight ratio of graft copolymers (B) to surfactants (A) in the formulation is at least 1: 1.
  • the weight ratio (B) / (A) is 1: 1 to 20: 1, more preferably 2 : 1 to 10: 1 and for example 3: 1 to 8: 1.
  • the concentration of auxiliaries (C), if present, is generally up to 5 g / l, preferably 0.01 g / l to 2 g / l, more preferably 0.02 g / l to 1 g / l, and very particularly preferably 0.05 g / l to 0.5 g / l.
  • the process according to the invention for after-treatment of dyed and / or printed textile materials is a partial step in the course of the production process of textile materials and is generally carried out immediately after the dyeing and / or printing of the textile materials, typically with the textile dye itself, without it should be ruled out, the procedure only time to perform.
  • the textile material is treated with the aqueous formulation ("liquor"), for example by simple dipping
  • the weight ratio of textile materials to aqueous formulation (“liquor ratio”) is generally from 1: 3 to 1:40, preferably 1: 5 to 1:10.
  • the treatment is generally at 20 to 100 0 C, preferably 30 to 90 0 C and particularly preferably from 40 to 70 ° C.
  • the duration of the aftertreatment is generally 5 to 60 minutes, preferably 10 to 30 minutes and particularly preferably 15 to 25 minutes.
  • the textile material is usually rinsed once or several times with water.
  • the process according to the invention has several advantages over the reductive after-cleaning, in particular in the after-treatment of textile materials containing polypropylene:
  • the excess color is removed from the surface of the fabric without significantly worsening the color depth of the dyeing. So it only works on the surface and does not penetrate into the interior of the fiber material.
  • This is not only an advantage over the reductive process, but also over the post-cleaning with surfactants. Since these are low molecular weight surfactants can be incorporated into the interior of polymeric materials such as e.g. Polypropylene penetrate, and migrate together with dyes back out.
  • hydrosulfite and NaOH there are also ecological advantages, since neither hydrosulfite nor NaOH can reach the wastewater.
  • formulations with hydrosulfite / NaOH inevitably have an alkaline pH, so that it must be neutralized again after the aftertreatment.
  • the formulations used according to the invention are at most slightly alkaline, so that the neutralization can be dispensed with.
  • test fabrics made of commercially available PET and additized polypropylene were used.
  • the polypropylene adducted fabric was prepared according to the method described in WO 2006/128796.
  • the polypropylene contains as an additive about 5 wt.% Of a polyester having a melting point of 94 ° C, prepared according to WO 2006/128796, page 33 and about 1 wt.% Of a polyisobutene-poly ethylene oxide polyisobutene block copolymer (molecular weight M n of the blocks: about 1000 - about 6000 - about 1000), prepared according to WO 2006/128796, page 21 (example block copolymer 2).
  • the polypropylene and the additives were mixed together in a twin-screw extruder according to the procedure described in WO 2006/128796, page 17, spun into threads and processed into a textile fabric.
  • the textile fabric of PET and polypropylene were washed before the dyeing tests with a commercial industrial detergent.
  • the dye used was weighed in, water was added and the bomb was heated for about 20 minutes in a 60 0 C hot water bath until the dye was dissolved. After cooling to about 40 0 C the remaining additions to the dyebath was added (4.8 g of a 5% solution of a commercially available wetting agent (Basojet ® XP) in water, 75 g of a 1% solution of a UV stabilizer were in water (Cibafast PEX ®)) and the pH of the dye liquor with a buffer solution (21 ml / l glacial acetic acid and 30 g / l sodium acetate) adjusted to 4.5. Total amount of formulation 200 ml each.
  • Basojet ® XP commercially available wetting agent
  • 75 g of a 1% solution of a UV stabilizer were in water (Cibafast PEX ®)
  • a buffer solution 21 ml / l glacial acetic acid and 30 g / l sodium acetate
  • the textile was removed well rinsed with hot water and rinsed with cold water. Then it was spun and dried in a drying oven at 60 0 C circulating air.
  • the polyester and polypropylene fabrics were each stained with commercially available dyes, namely a black disperse dye (Panacron ® Black AM-B, 3 wt.% In dye liquor), a red disperse dye (Dianix ® Deep Red SF, 2 wt.% In dyeing liquor) and a yellow disperse dye (Dianix ® flavins, 1 wt.% in dye liquor).
  • a black disperse dye Panacron ® Black AM-B, 3 wt.% In dye liquor
  • a red disperse dye Dianix ® Deep Red SF, 2 wt.% In dyeing liquor
  • a yellow disperse dye Dianix ® flavins, 1 wt.% in dye liquor
  • Water is first heated without additives to the desired temperature for after-treatment. After reaching the temperature, the additives are added as a concentrate in aqueous solution so that the desired concentration is established, and at the same time the textile sample is added. The textile sample is agitated for the desired treatment time in the formulation, after which the formulation is decanted, followed by rinsing with warm and then cold water.
  • the textile sample is then in a solution of 0.5 l of water with 2 ml conc. Briefly rinsed acetic acid, centrifuged and dried in a laboratory dryer for 2 min at 120 0 C and 700 rev / min.
  • Nonionic surfactant based on a Ci3-oxo-alcohol the alcohol was ethoxylated with 5 units of ethylene oxide
  • the particular formulation, temperature and duration of the treatment are summarized in Table 1 below.
  • the color depth of the dye before and after the aftertreatment was assessed.
  • the color change of the material is determined via the gray scale for assessing the change of color (ISO 105-A02: 1993 DIN-EN 20105-A02 1994).
  • the change of color is indicated in notes 1-5 (5: lowest change, 1: highest change).
  • the wash fastness of the aftertreated samples was carried out with a wash fastness test according to DIN ISO 105-C06-A1S without using steel balls.
  • the aftertreated fabric is washed at 40 ° C.
  • the dyed textile is used to wash white fabrics made of other textile materials (wool, cotton, polyamide). It is judged how strongly the white tissues discolour.
  • the evaluation is carried out according to gray scale for the evaluation of the Anblutens ISO105-A03: 1993 DIN EN 20105-A03: 1994). The color intensity is given in grades 1-5 (5: lowest color pickup foreign tissue, 1: highest color pickup foreign tissue).
  • Formulation 1 according to the invention, V1: 2 g / l NaHSO 3 /0.5 g / l NaOH; V2: 4 g / l NaHSO 3/2 g / l NaOH
  • Table 1 lists examples and comparative examples with three other dyes and textiles of both polypropylene and PET fibers.
  • the aftertreatment was carried out under the same conditions either with NaHSO 3 / NaOH or the formulation to be used according to the invention.
  • the tests show that the decolorization of the polypropylene textiles in the case of after-treatment with the formulation according to the invention is lower in each case than in the after-treatment with NaHSOs / NaOH. Nevertheless, the inventively post-treated polypropylene textiles do not stain more strongly in the wash fastness test.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Coloring (AREA)

Abstract

L'invention porte sur un procédé pour le post-traitement de textiles teints et/ou imprimés, pour éliminer les fractions en excès de colorants, procédé suivant lequel on utilise une formulation aqueuse, qui comprend au moins un copolymère greffé ayant une chaîne principale hydrophile, ainsi que des tensio-actifs.
EP09781304A 2008-08-11 2009-07-30 Procédé de post-traitement ménagé de textiles teints Active EP2313550B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP09781304A EP2313550B1 (fr) 2008-08-11 2009-07-30 Procédé de post-traitement ménagé de textiles teints
PL09781304T PL2313550T3 (pl) 2008-08-11 2009-07-30 Sposób łagodnej obróbki wykańczającej barwionych wyrobów tekstylnych

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08162153 2008-08-11
EP09781304A EP2313550B1 (fr) 2008-08-11 2009-07-30 Procédé de post-traitement ménagé de textiles teints
PCT/EP2009/059893 WO2010018073A1 (fr) 2008-08-11 2009-07-30 Procédé de post-traitement ménagé de textiles teints

Publications (2)

Publication Number Publication Date
EP2313550A1 true EP2313550A1 (fr) 2011-04-27
EP2313550B1 EP2313550B1 (fr) 2012-10-03

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US (1) US8475538B2 (fr)
EP (1) EP2313550B1 (fr)
CN (1) CN102177291B (fr)
BR (1) BRPI0917973A2 (fr)
ES (1) ES2397071T3 (fr)
MX (1) MX2011001326A (fr)
MY (1) MY152745A (fr)
PL (1) PL2313550T3 (fr)
WO (1) WO2010018073A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10202712B2 (en) 2009-07-31 2019-02-12 Basf Se Producing spinnable and dyeable polyester fibers
DE102013113656A1 (de) * 2013-12-06 2015-06-11 Schill + Seilacher Gmbh Verwendung einer Tensidzusammensetzung zur hydrophilen Ausrüstung von Textilfasern und daraus hergestellten Textilerzeugnissen
GB201600098D0 (en) * 2016-01-04 2016-02-17 Nikwax Ltd Ascorbic acid dye clearing process patent
CN107828533A (zh) * 2017-11-13 2018-03-23 东莞市古川纺织助剂有限公司 一种织物分散染料清洗剂
CN107815898A (zh) * 2017-11-13 2018-03-20 东莞市古川纺织助剂有限公司 一种织物涤棉一浴免还原清洗剂

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287514A1 (fr) 1987-04-15 1988-10-19 Ciba-Geigy Ag Détergent pour le postlavage de teintures réactives, son procédé de préparation et son emploi
DE4105602A1 (de) 1991-02-22 1992-08-27 Basf Ag Verwendung einer mischung aus mindestens zwei alkoxylierten alkoholen als schaumdaempfender tensidzusatz in reinigungsmitteln fuer maschinell ablaufende reinigungsprozesse
EP0918089A1 (fr) * 1997-11-24 1999-05-26 The Procter & Gamble Company Compositions d'entretien du tissu
US6447696B1 (en) 1999-07-30 2002-09-10 Nippon Shokubai Co., Ltd. Grafted polymer and its production process and use
DE10017197A1 (de) 2000-04-07 2001-10-11 Basf Ag Alkoholalkoxylate als schaumarme oder schaumdämpfende Tenside
PT1570123E (pt) 2002-12-03 2009-07-23 Basf Se Aplicação de copolímeros como auxiliares para tingimento e impressão de têxteis
DE10256618A1 (de) * 2002-12-03 2004-06-17 Basf Ag Verfahren zum Nachreinigen von gefärbtem Textil
DE10321396A1 (de) 2003-05-12 2004-12-02 Basf Ag Verwendung von Copylymerisaten als Hilfsmittel für die Textilfärberei
WO2006098730A1 (fr) 2005-03-11 2006-09-21 Aquadye Fibers, Inc. Fil teint a base d’olefine et tissus textiles utilisant de tels fils
DE102005011608A1 (de) 2005-03-14 2006-09-21 Basf Ag Veresterte Alkylalkoxylate als schaumarme Tenside
US20090039543A1 (en) 2005-05-30 2009-02-12 Basf Aktiengesellschaft Polymer Composition Comprising Polyolefins And Amphiphilic Block Copolymers And Optionally Other Polymers And/Or Fillers And Method For Dying Compositions Of That Type Or Printing Thereon
DE102006057221A1 (de) 2006-12-01 2008-06-05 Basf Se Verfahren zur Herstellung von gefärbten textilen Materialien umfassend Polypropylenfasern
AU2008324178A1 (en) 2007-11-09 2009-05-14 Basf Se Amphiphilic water-soluble alkoxylated polyalkyleneimines having an inner polyethylene oxide block and an outer polypropylene oxide block
ES2567256T3 (es) 2007-11-09 2016-04-21 Basf Se Polialcanolaminas alcoxiladas
US8507613B2 (en) 2007-11-23 2013-08-13 Basf Se Process for the alkoxylation of amino group containing polymers
ES2569913T3 (es) 2008-07-07 2016-05-13 Basf Se Composición de enzima que comprende partículas poliméricas que contienen enzima

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010018073A1 *

Also Published As

Publication number Publication date
CN102177291A (zh) 2011-09-07
PL2313550T3 (pl) 2013-03-29
US20110154582A1 (en) 2011-06-30
US8475538B2 (en) 2013-07-02
ES2397071T3 (es) 2013-03-04
CN102177291B (zh) 2013-07-17
BRPI0917973A2 (pt) 2015-11-17
MY152745A (en) 2014-11-28
EP2313550B1 (fr) 2012-10-03
WO2010018073A1 (fr) 2010-02-18
MX2011001326A (es) 2011-03-21

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