EP2313550B1 - Procédé de post-traitement ménagé de textiles teints - Google Patents

Procédé de post-traitement ménagé de textiles teints Download PDF

Info

Publication number
EP2313550B1
EP2313550B1 EP09781304A EP09781304A EP2313550B1 EP 2313550 B1 EP2313550 B1 EP 2313550B1 EP 09781304 A EP09781304 A EP 09781304A EP 09781304 A EP09781304 A EP 09781304A EP 2313550 B1 EP2313550 B1 EP 2313550B1
Authority
EP
European Patent Office
Prior art keywords
process according
mol
units
polypropylene
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP09781304A
Other languages
German (de)
English (en)
Other versions
EP2313550A1 (fr
Inventor
Pia Baum
Klaus Scheuermann
Dieter Boeckh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
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
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • D06P1/60—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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79—Polyolefins
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/79—Polyolefins
    • D06P3/794—Polyolefins using dispersed dyes
    • 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 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. For example, polyesters can be dyed in an exhaust process at 120 ° -130 ° C. with disperse dyestuffs.
  • the remaining on the surface excess dye can be removed, for example, by a reductive Nachmaschinesche with hydrosulfite and NaOH at 60-70 ° C. 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.
  • Polypropylene is a highly suitable polymer for the production of textile materials, but textiles made from polypropylene fibers are difficult to dye from aqueous baths due to the nonpolar nature of polypropylene. It is therefore known to improve the subsequent dyeability of polypropylene from aqueous dyebaths by adding suitable auxiliaries.
  • 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
  • maleic anhydride is preferably used.
  • WO 2006/128796 discloses a process for coloring polyolefins using polyolefins blended with a block copolymer of at least one nonpolar block consisting essentially of isobutene units and at least one polar block consisting essentially of oxyalkylene units.
  • polyesters and / or polyamides can also be incorporated as auxiliaries.
  • the object of the invention was therefore to provide a gentle process for after-washing, which avoids discoloration of the textiles.
  • the textile materials comprise polyester and / or polypropylene fibers and in which the said materials are treated with an aqueous formulation of at least one anionic and / or nonionic surfactant (A). at a temperature of 20 to 100 ° C, and wherein the aqueous solution further contains at least one graft copolymer (B) comprising a straight-chain or branched, hydrophilic backbone comprising N and / or O atoms and side chains grafted thereon
  • A anionic and / or nonionic surfactant
  • B graft copolymer
  • “Textile materials” may in principle 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 intermediates such as yarns, fabrics, knits, knitted fabrics, nonwovens or nonwovens. It may 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 yarn production, fibers of other polymers may be incorporated, or fiber blends may be made from 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. They are relatively high molecular weight, viscous products, which are characterized in the usual way by their melt flow index (determined according to ISO 1133). 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, 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.
  • polyesters can be used which have a melting point of 50 to 200 ° 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, 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.
  • dicarboxylic acid units X1 and (X2)
  • various dicarboxylic acid units may still be present therefrom.
  • Dicarboxylic acid units and / or cycloaliphatic dicarboxylic acid units are other aromatic ones 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, cycloliphatic and / or polyether diols, wherein 50 to 100 mol% of aliphatic 1, ⁇ -diols (Y1) are present, and the percentages are based on the total amount of all diols.
  • 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.
  • the polyesters may of course 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 ° C.
  • the melting point is 60 to 180 ° C, more preferably 80 to 160 ° C, most preferably 100 to 150 ° C and for example 110-130 ° 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 1133, 190 ° C., 2.16 kg).
  • a preferred bulk density is from 1.2 to 1.35 g / cm 3, more preferably 1.22 -1.30 g / cm 3.
  • the preferred Vicat softening temperature is 75 to 85 ° C, more preferably 78-82 ° C (VST A / 50, ISO 306).
  • 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 0.1 to 10 wt.% Of at least one block copolymer having at least one nonpolar block having a number average molecular weight 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 comprises included.
  • 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 units.
  • the polar blocks each have an average molar mass M n of 1000 to 20,000 g / mol.
  • 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.
  • 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.
  • the dyeing and / or printing of the textile materials can be carried out by methods known in principle to those skilled in the art.
  • disperse dyes may preferably be used.
  • the term "disperse dye” is known to the person skilled in the art. Disperse dyes are dyes with a low water solubility, which are used in disperse, colloidal form for dyeing, in particular for dyeing fibers and textile materials. Details of the dyeing and / or printing of textile materials are, for example, in WO 2006/128796 Page 15 to page 20 describe.
  • 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, for example, in WO 92/14808 .
  • 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 branching off (grafted) side chains, which may already be termed oligomers or polymers by their length.
  • the polymer backbone and the side chains are chemically different in 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 consisting 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 main chain generally comprises at least 90 mol% of alkylene oxide units. They are preferably ethylene oxide and / or propylene oxide units, which are 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. Particularly preferably, the main chain is polyethylene glycol.
  • the side chains consist essentially of ethylenically unsaturated monomers. These are preferably ethylenically unsaturated monomers having functional groups. Suitable monomers include vinyl derivatives or acrylic derivatives such as vinyl acetate, vinylamine, vinylpyrrolidone, vinylimidazole, vinyl esters, acrylic acid or acrylic esters. According to the 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, wherein the main chain has a number average molecular weight M n of 300 to 10,000 g / mol, preferably 300 up 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, such as, 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.
  • an aqueous formulation which additionally comprises at least one wetting agent (C2).
  • wetting aids include primary, secondary or tertiary phosphoric acid esters of alcohols, such as phosphoric acid esters of 2-ethylhexyl alcohol. Sulfosuccinates or other small-molecule surfactants can also be used for this purpose.
  • a formulation may comprise at least one sponge damper (C1) and at least one wetting aid (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 Formulltation is usually 0.01 g / l to 5 g / l. preferably 0.02 g / l to 2 g / l, more preferably 0.05 g / l to 1 g / l and most 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, more 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 most preferably 0 , 05 g / l to 0.6 g / l.
  • the process according to the invention for post-dying colored 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 being ruled out should, the procedure also until a later Time to perform.
  • the textile material is treated with the aqueous formulation ("liquor"), for example by simple immersion.
  • the weight ratio of textile materials to the aqueous formulation (“liquor ratio") is generally 1: 3 to 1:40, preferably 1: 5 to 1:10.
  • the treatment is usually carried out at 20 to 100 ° C, preferably 30 to 90 ° C and particularly preferably 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 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.
  • the fabric of additized polypropylene was prepared according to the WO 2006/128796 It was a polypropylene with a melt flow rate of 33 g / 10 min (230 ° C, 2.16 kg) used.
  • 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-polyethylene oxide-polyisobutene block copolymer (molecular weight M n of 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 used in a twin-screw extruder according to the WO 2006/128796 , Page 17 mixed together, 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 staining was carried out by methods known to the person skilled in the art in an A-HIBA® staining apparatus.
  • the dye used was weighed in, water was added and the bomb was heated for about 20 minutes in a 60 ° C hot water bath until the dye was dissolved.
  • the remaining additives for the dyebath were added (4.8 g of a 5% solution of a commercial wetting agent (Basojet ® XP) in water, 75 g of a 1% solution of a UV stabilizer in water (Cibafast® PEX)) and the pH of the dyeing liquor with a buffer solution (21 ml / l glacial acetic acid and 30 g / l Naacetat) to 4.5. Total amount of formulation 200 ml each.
  • a commercial wetting agent Basojet ® XP
  • a 1% solution of a UV stabilizer in water Cibafast® PEX
  • a buffer solution 21 ml / l glacial acetic acid and 30 g / l Naacetat
  • 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 ° 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, rinsed 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 the laboratory dryer for 2 min at 120 ° C and 700 rev / min.
  • 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).
  • Table 1 shows examples and comparative examples with three other dyes as well as textiles made 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 NaHSO 3 / NaOH. Nevertheless, the inventively post-treated polypropylene textiles do not stain more strongly in the wash fastness test.

Landscapes

  • 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)

Claims (15)

  1. Procédé de post-traitement de matériaux textiles teints et/ou imprimés, qui contiennent des fibres de polyester et/ou de polypropylène, dans lequel on traite lesdits matériaux par une formulation aqueuse d'au moins un agent tensioactif (A) anionique et/ou non ionique à une température de 20 à 100°C, caractérisé en ce que la solution aqueuse contient en outre au moins un copolymère greffé (B), le copolymère greffé (B) comprenant une chaîne principale linéaire ou ramifiée, hydrophile, comprenant des atomes de N et/ou de O ainsi que des chaînes latérales qui y sont greffées et où il s'agit, pour le copolymère greffé (B) d'au moins un copolymère choisi dans le groupe formé par
    (B1) les copolymères greffés présentant une chaîne principale essentiellement constituée d'unités d'oxyde d'alkylène ainsi que des chaînes latérales essentiellement constituées de monomères éthyléniquement insaturés, la chaîne principale présentant un poids moléculaire numérique moyen Mn de 300 à 60 000 g/mole et la chaîne principale étant constituée à raison d'au moins 90% en mole d'unités d'oxyde d'éthylène, par rapport à la quantité de toutes les unités d'oxyde d'alkylène et les chaînes latérales comprenant au moins 50% en mole d'unités d'acétate de vinyle, par rapport à la quantité de tous les monomères des chaînes latérales, et
    (B2) les copolymères greffés présentant une chaîne principale essentiellement constituée d'unités d'alkylène-imine ainsi que des chaînes latérales essentiellement constituées d'unités de polyéther, la chaîne principale présentant un poids moléculaire numérique moyen Mn de 300 à 10 000 g/mole et la chaîne principale étant constituée à raison d'au moins 90% en mole d'unités éthylène-imine, par rapport à la quantité de toutes les unités d'alkylène-imine, et où il s'agit, pour les chaînes latérales, de groupes de poly(oxyde d'alkylène), la proportion d'unités d'oxyde d'éthylène et/ou d'unités d'oxyde de propylène étant d'au moins 90% en mole par rapport à la quantité de toutes les unités d'oxyde d'alkylène.
  2. Procédé selon la revendication 1, caractérisé en ce que la formulation aqueuse comprend au moins un agent tensioactif non ionique (A1) de formule générale R1-O-(CH2-CH(R2)-O)n-H (I), les radicaux et les indices dans la formule (I) présentant la signification suivante :
    n : un nombre de 3 à 25,
    R1 : un radical hydrocarboné aliphatique et/ou aromatique, linéaire ou ramifié comprenant 8 à 20 atomes de carbone,
    R2 : indépendamment l'un de l'autre, hydrogène ou un radical alkyle comprenant 1 à 6 atomes de carbone, à condition qu'il s'agisse pour au moins 60% des radicaux R2, par rapport au nombre total des radicaux R2, d'hydrogène.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la formulation aqueuse comprend au moins un agent tensioactif (A2) pauvre en mousse, non ionique de formule générale R1-O-(CH2-CH(R3)-O)m-R4 (II), les radicaux et les indices dans la formule (II) présentant la signification suivante :
    m : un nombre de 3 à 30,
    R3 : hydrogène ou un radical alkyle comprenant 1 à 6 atomes de carbone, à condition qu'il s'agisse pour au moins 60% des radicaux R3, par rapport au nombre total des radicaux R2, d'hydrogène,
    R4 : un radical choisi dans le groupe formé par
    - les radicaux alkyle linéaires ou ramifiés comprenant 1 à 20 atomes de carbone,
    - les groupes de formule -CO-R6, où il s'agit, pour R6, d'un radical alkyle linéaire ou ramifié comprenant 1 à 20 atomes de carbone,
    - les groupes de formule -(CH2-CH(R5)-O)2-H, représentant un nombre de 1 à 15 et R5 représentant hydrogène ou un radical alkyle comprenant 1 à 6 atomes de carbone, à condition qu'il s'agisse, pour au moins 60% des groupes R5 par rapport au nombre total de tous les groupes R5 d'un radical alkyle comprenant 1 à 6 atomes de carbone.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la formulation aqueuse comprend au moins un antimousse (C1).
  5. Procédé selon la revendication 4, caractérisé en ce qu'il s'agit, pour l'antimousse (C1), de polypropylèneglycol ou d'un dérivé du polypropylèneglycol.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la concentration en agents tensioactifs (A) dans la formulation est de 0,01 g/l à 5 g/l.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la concentration en copolymères greffés (B) dans la formulation est de 0,5 g/l à 10 g/l.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le rapport pondéral des copolymères greffés (B) aux agents tensioactifs (A) est de 1:1 à 20:1.
  9. Procédé selon l'une quelconque des revendications 2 à 8, caractérisé en ce que la formulation comprend au moins un agent tensioactif (A1) et au moins un agent tensioactif (A2) pauvre en mousse, le rapport pondéral d'agents tensioactifs (A2) pauvres en mousse à la quantité totale de tous les agents tensioactifs valant au moins 1:1.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que les matériaux textiles comprennent des fibres de polypropylène.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que les matériaux textiles sont constitués de fibres de polypropylène.
  12. Procédé selon la revendication 10 ou 11, caractérisé en ce que les fibres de polypropylène comprennent comme additif 1 à 15% en poids d'au moins un polyester, l'indication pondérale se rapportant à la quantité de tous les composants des fibres de polypropylène.
  13. Procédé selon la revendication 12, caractérisé en ce qu'il s'agit d'un polyester présentant un point de fusion de 50 à 200°C.
  14. Procédé selon la revendication 12 ou 13, caractérisé en ce que les fibres de polypropylène comprennent, comme autre additif, 0,1 à 10% en poids d'au moins un copolymère à blocs, le copolymère à blocs comprenant au moins un bloc non polaire présentant une masse molaire numérique moyenne Mn d'au moins 200 g/mole, essentiellement constitué d'unités d'isobutène, et au moins un bloc polaire présentant une masse molaire numérique moyenne Mn d'au moins 500 g/mole, essentiellement constitué d'unités d'oxyalkylène.
  15. Procédé selon l'une quelconque des revendications 1 à 14, caractérisé en ce qu'on réalise le post-traitement à 30 jusqu'à 90°C.
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 EP2313550A1 (fr) 2011-04-27
EP2313550B1 true EP2313550B1 (fr) 2012-10-03

Family

ID=41170190

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09781304A Active EP2313550B1 (fr) 2008-08-11 2009-07-30 Procédé de post-traitement ménagé de textiles teints

Country Status (9)

Country Link
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
CA2767371A1 (fr) 2009-07-31 2011-02-03 Basf Se Procede de production de fibres de polyester aptes au filage et a la teinture
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
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
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

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
DE10321396A1 (de) 2003-05-12 2004-12-02 Basf Ag Verwendung von Copylymerisaten als Hilfsmittel für die Textilfärberei
DE10256618A1 (de) * 2002-12-03 2004-06-17 Basf Ag Verfahren zum Nachreinigen von gefärbtem Textil
ES2327114T3 (es) * 2002-12-03 2009-10-26 Basf Se Copolimerizados injertos como sustancias auxiliares para la tincion de textiles y la impresion de textiles.
CA2603865A1 (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
WO2006128796A2 (fr) 2005-05-30 2006-12-07 Basf Aktiengesellschaft Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges et procedes pour colorer de telles compositions ou realiser une impression sur ces dernieres
DE102006057221A1 (de) 2006-12-01 2008-06-05 Basf Se Verfahren zur Herstellung von gefärbten textilen Materialien umfassend Polypropylenfasern
EP2209836B1 (fr) 2007-11-09 2016-02-24 Basf Se Polyalcanolamines alcoxylés
CL2008003335A1 (es) 2007-11-09 2010-02-12 Basf Se Polialquileniminas alcoxiladas anfifilicas solubles en agua que tienen un bloque de oxido de polietileno interno y un bloque de oxido de polipropileno externo.
JP5431349B2 (ja) 2007-11-23 2014-03-05 ビーエーエスエフ ソシエタス・ヨーロピア アミノ基含有ポリマーのアルコキシ化方法
EP2310483B1 (fr) 2008-07-07 2016-03-16 Basf Se Composition enzymatique comprenant des particules de polymère renfermant une enzyme

Also Published As

Publication number Publication date
BRPI0917973A2 (pt) 2015-11-17
MY152745A (en) 2014-11-28
ES2397071T3 (es) 2013-03-04
WO2010018073A1 (fr) 2010-02-18
EP2313550A1 (fr) 2011-04-27
US20110154582A1 (en) 2011-06-30
CN102177291A (zh) 2011-09-07
MX2011001326A (es) 2011-03-21
CN102177291B (zh) 2013-07-17
US8475538B2 (en) 2013-07-02
PL2313550T3 (pl) 2013-03-29

Similar Documents

Publication Publication Date Title
DE102004002208B4 (de) Zubereitungen auf Basis von Organopolysiloxan-Polyammonium-Blockcopolymeren und deren Anwendung auf textilen Substraten
EP1891154A2 (fr) Compositions polymeres contenant des polyolefines et des copolymeres sequences amphiphiles ainsi qu'eventuellement d'autres polymeres et/ou des charges
EP2313550B1 (fr) Procédé de post-traitement ménagé de textiles teints
DE1945833A1 (de) Verfahren zur Herstellung eines Fadenverbandes
WO2008065185A2 (fr) Procédé de production de textiles colorés comprenant des fibres de polypropylène
EP2084321A1 (fr) Procédé de traitement de substrats
DE1290519B (de) Verfahren zum streifenfreien Faerben von Textilmaterialien aus Polyamiden
WO2008065133A2 (fr) Procédé pour produire des matériaux textiles colorés comprenant des fibres de polypropylène
DE69512766T2 (de) Verfahren zur verbesserung der fleckenbeständigkeit von fasern und faserprodukten
DE69521820T2 (de) Farbstoffzusammensetzung und Verfahren zum Färben von hydrophoben Fasern
DE2834413A1 (de) Verfahren zum nachbehandeln von gefaerbtem, polyesterfasern enthaltendem textilmaterial
DE3903926A1 (de) Faerbereihilfsmittel
DE1014962B (de) Verfahren zum Faerben und Bedrucken von geformten Gebilden aus hydrophoben, organischen Hochpolymeren, die Estergruppen enthalten
DE102005049015A1 (de) Kationisch ausgerüstetes Textilmaterial und seine Verwendung
DE102004058271A1 (de) Verwendung von wässrigen Dispersionen von wasserlöslichen (Co)polymerisaten von mindestens einem ethylenisch ungesättigten Monomer MON zur Herstellung von Textilhilfsmitteln
DE102005055078A1 (de) Polymerzusammensetzung umfassend Polyolefine und amphiphile Blockcopolymere sowie Verfahren zum Einfärben oder Bedrucken derartiger Zusammensetzungen
DE102005025018A1 (de) Polymerzusammensetzung umfassend Polyolefine und amphiphile Blockcopolymere sowie Verfahren zum Einfärben derartiger Zusammensetzungen
EP0965680A1 (fr) Dispersions aqueuses, leurs préparations et leurs utilisations
EP1611278B1 (fr) Agent auxilliaire pour le textile
DE1645328C (de) Verfahren zur Herstellung von PoIyolefin-Erzeugnissen
EP1659153B1 (fr) Utilisation de dispersions aqueuses à base des copolymères hydrosolubles d'au moins un monomère "MON" pour la préparation d'adjuvants textiles
EP0784117B1 (fr) Utilisation de homopolymere ou copolymere d'acrylamide comme agents ant-depot
DE1645328B2 (de) Verfahren zur herstellung von polyolefin erzeugnissen
EP1331302B1 (fr) Utilisation d'une composition comme agent anti-pli
DE102004012570A1 (de) Formulierungen und ihre Verwendung zur Behandlung von flexiblen Substraten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110311

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

AX Request for extension of the european patent

Extension state: AL BA RS

17Q First examination report despatched

Effective date: 20110714

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 578045

Country of ref document: AT

Kind code of ref document: T

Effective date: 20121015

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502009004991

Country of ref document: DE

Effective date: 20121129

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 13066

Country of ref document: SK

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2397071

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20130304

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130203

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130104

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20130103

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

26N No opposition filed

Effective date: 20130704

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E016583

Country of ref document: HU

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502009004991

Country of ref document: DE

Effective date: 20130704

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130730

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121003

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20160725

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20160726

Year of fee payment: 8

Ref country code: HU

Payment date: 20160725

Year of fee payment: 8

Ref country code: CZ

Payment date: 20160728

Year of fee payment: 8

Ref country code: PL

Payment date: 20160707

Year of fee payment: 8

Ref country code: SK

Payment date: 20160729

Year of fee payment: 8

Ref country code: AT

Payment date: 20160727

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20160725

Year of fee payment: 8

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20170801

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 578045

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170730

REG Reference to a national code

Ref country code: SK

Ref legal event code: MM4A

Ref document number: E 13066

Country of ref document: SK

Effective date: 20170730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170730

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170731

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170801

Ref country code: HU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170731

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170730

Ref country code: SK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170730

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170730

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20220725

Year of fee payment: 14

Ref country code: GB

Payment date: 20220719

Year of fee payment: 14

Ref country code: DE

Payment date: 20220527

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20220725

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20220726

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20230711

Year of fee payment: 15

Ref country code: ES

Payment date: 20230816

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502009004991

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20230730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240201

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230731

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230730