EP1670986A1 - Method for the preliminary treatment of cellulose-containing textile - Google Patents

Method for the preliminary treatment of cellulose-containing textile

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Publication number
EP1670986A1
EP1670986A1 EP04787002A EP04787002A EP1670986A1 EP 1670986 A1 EP1670986 A1 EP 1670986A1 EP 04787002 A EP04787002 A EP 04787002A EP 04787002 A EP04787002 A EP 04787002A EP 1670986 A1 EP1670986 A1 EP 1670986A1
Authority
EP
European Patent Office
Prior art keywords
textile
copolymer
general formula
dyeing
dyed
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.)
Granted
Application number
EP04787002A
Other languages
German (de)
French (fr)
Other versions
EP1670986B1 (en
Inventor
Karl Siemensmeyer
Steffen Gibs
Frank Funke
Andreas Bastian
Michael Gotsche
Heinz Heissler
James David Carnahan
Tanja Schneider
Holger SCHÖPKE
Stefan Frenzel
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
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Filing date
Publication date
Priority claimed from DE2003145797 external-priority patent/DE10345797A1/en
Priority claimed from DE200410026096 external-priority patent/DE102004026096A1/en
Application filed by BASF SE filed Critical BASF SE
Publication of EP1670986A1 publication Critical patent/EP1670986A1/en
Application granted granted Critical
Publication of EP1670986B1 publication Critical patent/EP1670986B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • 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
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/6025—Natural or regenerated cellulose using vat or sulfur 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
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/62—Natural or regenerated cellulose using direct 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
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes

Definitions

  • the present invention relates to a process for the pretreatment of cellulosic textile, comprising the following steps:
  • R is selected from hydrogen and -CC 0 alkyl, and (a2) optionally partial hydrolysis,
  • the dyeing of cellulosic textile can be done by various methods. Usual today are dyeings with reactive, vat or direct dyes. In many cases, however, it is observed that exhaustion, i. the proportion of dye that can be applied from the dyeing liquor to the textile, as well as the fastness level of the dyeing to be desired.
  • a further object of the present invention is to provide a process by which textile can be dyed without high salt loads of the dyeing liquors to be disposed of being obtained.
  • cellulosic textile or textiles are cellulose-containing textile fibers, cellulosic textile semifinished and finished products and finished articles produced therefrom which, in addition to textiles for the clothing industry, also include, for example, carpets and other home textiles as well as textile structures serving technical purposes. These include unshaped structures such as flakes, linear structures such as twine, threads, yarns, linen, cords, ropes, threads and body structures such as felts, fabrics, nonwovens and wadding.
  • Cellulose-containing textiles may be of natural origin, for example cotton or flax, or blended fabrics, for example cotton / polyester, cotton / polyamide, the size of the cellulose being uncritical.
  • cellulose-containing textile is treated in a step (a) with a
  • R is selected from C 1 -C 10 -alkyl, branched or preferably unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isobutyl, Pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably straight-chain CC 4 alkyl such as methyl, ethyl, n-propyl, n-butyl; and especially hydrogen
  • copolymers obtainable by copolymerization of N-vinylamide of the general formula I with at least one suitable comonomer are possible, which copolymers may be random copolymers, block copolymers and especially graft copolymers.
  • suitable comonomers are (meth) acrylates such as, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, N-vinylpyrrolidone, N-vinylimidazole, ethyl methacrylate, ethylene, propylene, 1-butene or 1,3-butadiene.
  • copolymers obtainable by copolymerization of N-vinylamide of general formula I with at least one suitable comonomer contain at least 20% by weight, preferably at least 30% by weight, based on copolymer, of N-vinylamide the general formula I.
  • a solution of copolymer obtainable by copolymerizing from 20 to 90% by weight of N-vinylamide of general formula I and from 10 to 80% by weight of comonomer selected from N-vinylpyrrolidone and N-vinylimidazole, and optionally subsequent partial hydrolysis, wherein in wt .-% are each based on the copolymer used.
  • a solution of copolymer obtainable by copolymerization of 20 to 80% by weight of N-vinylamide of the general formula I, 10 to 70% by weight of N-vinylimidazole and 10 to 70% by weight is used .-% N-vinylpyrrolidone and optionally subsequent partial hydrolysis, wherein in wt .-% are each based on the copolymer used.
  • a solution of copolymer of at least two different monomers of the general formula I is used, where copolymers may be random copolymers, block copolymers and especially graft copolymers.
  • a solution of homopolymer of N-vinylformamide is employed.
  • the polymers or copolymers used in step (a) have a molecular weight M w in the range of 10,000 to 1,000,000 g / mol, preferably 30,000 to 400,000 g / mol, determined for example by gel permeation chromatography.
  • step (a) use is made of a polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide of the general formula I and subsequent partial hydrolysis of the amide groups, for example with dilute aqueous alkali or dilute aqueous Alkalicarbonatties or dilute aqueous acid such as phosphoric acid or sulfuric acid, for example, 60 moI% or 30 mol or 10 mol% of all amide groups can be hydrolyzed.
  • aqueous solution of the polymer or tfopolymer obtainable by polymerization or copolymerization of N-vinylamide c ⁇ general formula I, in a concentration of 0.1 to 20 wt .-%, preferably 0.5 to 5 wt. -% used.
  • step (a) can be carried out one or more times.
  • Various polymers or copolymers can be used, of which at least one is obtainable by polymerization or copolymerization of N-vinylamide.
  • step (a) can be carried out, for example, according to an exhaustion process or a padding process. If it is desired to carry out step (a) in the manner of an exhaustion process, the cellulosic textile to be pretreated can be drawn through a preferably aqueous liquor containing a solution of polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide of general formula I. , contains. Then you pull vorzubehandelndes cellulosic textile by rolling and squeezes off excess solution.
  • step (a) in the manner of a padding method, one can use common machines. Preference is given to foulards which contain, as an essential element, two rollers pressed onto one another, through which the cellulosic textile to be pretreated is guided. Above the rollers, liquid containing solution of polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide of general formula I is filled in and wets the textile. The pressure squeezes off the textile and ensures a constant application. In another embodiment of the padding, one or more impregnating baths are used, through which the cellulosic textile to be treated is drawn. After that, the fabric passes through a padder and excess solution is squeezed off.
  • the pretreatment in step (a) is carried out in the presence of at least one fixing agent.
  • Suitable fixing agents are, for example:
  • Urea-forrna-dehyd- and melamine-formaldehyde addition products optionally in combination with inorganic salts such as MgCl 2 -6H 2 O or NH 4 Cl, in particular urea-formaldehyde-glyoxal condensation products, their hydroxyl groups partially or quantitatively
  • inorganic salts such as MgCl 2 -6H 2 O or NH 4 Cl
  • urea-formaldehyde-glyoxal condensation products their hydroxyl groups partially or quantitatively
  • methanol can be etherified
  • Isocyanates or their dimers or trimers such as, for example, 4,4'-methylene (diphenyl isocyanate) MDI, hexamethylene diisocyanate HDI, isophorone diisocyanate, in each case free or blocked with, for example, 3,5-dimethylpyrazole, acetone oxime or sec.-butanone oxime, in particular trimeric hexamethylene diisocyanate and trimeric isophorone diisocyanate, each free or blocked.
  • 4,4'-methylene (diphenyl isocyanate) MDI hexamethylene diisocyanate HDI
  • isophorone diisocyanate in each case free or blocked with, for example, 3,5-dimethylpyrazole, acetone oxime or sec.-butanone oxime, in particular trimeric hexamethylene diisocyanate and trimeric isophorone diisocyanate, each free or blocked.
  • Examples can be found in EP-B 0206
  • Di-, tri- and polyepoxides selected from, for example, epichlorohydrin-reacted diols, polyols, diamines, polyamines,
  • oligomeric carbodiimines Di- and trialdehydes such as, for example, glutaraldehyde, glyoxal, dextran polyaldehydes, and starch aldehydes, prepared, for example, according to US 2001-0025102 A1;
  • Epoxysiiane produced for example according to DE 3528006 and DE 41 28894,
  • aziridine compounds such as e.g. Trimethylolpropane (betaaziridino) propionate.
  • each z is an integer in the range of 0 to 10.
  • drying (b) can be carried out in common apparatus, such as drying cabinets, or in the fresh air. Temperatures in the range of 30 ° C to 120 ° C are useful, preferably 70 to 110 ° C. The drying time is usually dependent on the drying temperature and the desired residual moisture content and may be in the range of 30 seconds to 3 hours, but longer or shorter periods are possible.
  • step (a) If it is desired to carry out step (a) several times, it is possible to dry after each individual treatment step (a) or preferably only after the last treatment step (a).
  • step (c) of the process according to the invention at least a portion of the amide groups are saponified.
  • amide groups of the polymer or copolymers applied to the textile according to step (a) which are obtainable by polymerization or copolymerization of N-vinylamide of the general formula.
  • steps (a2) and (c) are carried out, i.
  • cellulose-containing textile is treated with a solution of polymer or copolymer which is obtainable by polymerization or copolymerization of N-vinylamide of general formula I and which has been partially hydrolyzed according to step (a2). b) and then hydrolyzed at least a portion of the amide groups according to step (c).
  • step (c) is carried out by treating treated and optionally dried textile with dilute aqueous solution.
  • ger alkali hydroxide solution or dilute aqueous alkali carbonate solution preferably with sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution or potassium carbonate solution.
  • concentrations for example, 0.5 to 10 wt .-%, preferably 2 to 5 wt .-% are suitable.
  • the temperature at which step (c) is carried out is in the range of room temperature to 90 ° C, preferably in the range of 70 to 90 ° C.
  • step (c) The pressure conditions of step (c) are not critical, you can, for example, operate at atmospheric pressure, but pressures of, for example, 1, 1 bar to 10 bar are also conceivable.
  • Step (c) may be carried out in the form of a continuous or batch process.
  • step (c) at least a portion of the amide groups is usually saponified.
  • At least one third of the amide groups of the one or more polymers or copolymers from step (a) are saponified, preferably at least 90 mol% and particularly preferably at least 95 mol%.
  • the amide groups of the one or more polymers or copolymers from step (a) are hydrolyzed quantitatively.
  • step (c) neutralization steps, preferably with organic acids such as, for example, citric acid, tartaric acid, adipic acid or succinic acid, can be carried out.
  • rinsing and drying steps can be carried out following step (c).
  • a thermal fixing step (d) it is preferable, following the pretreatment, to attach an example of a thermal fixing step (d).
  • a thermal fixing step for example, you can fix at temperatures of 150 ° C to 190 ° C over a period of 30 seconds to 5 minutes.
  • the fixing step (d) is suitable on all fixing and drying units customary in the textile industry, for example on tenter frames and drying cabinets, for example with circulating air.
  • Another aspect of the present invention is cellulosic textile, as defined by the process of the invention. It is particularly suitable for the production of dyed textile. Another aspect of the present invention is Therefore, the use of pretreated cellulose-containing textile according to the invention for the production of dyed textile.
  • Another aspect of the present invention is a process for the production of dyed textile, hereinafter also called dyeing process according to the invention.
  • the dyeing process according to the invention is based on cellulosic textile pretreated according to the invention and comprises at least one dyeing step using at least one reactive, vat or direct dye, the choice of reactive or vat dyes or direct dyes being uncritical.
  • the dyeing process according to the invention can be carried out, for example, at normal pressure or at pressures of 1.1 to 20 bar. It is preferred to carry out the dyeing process according to the invention at atmospheric pressure.
  • the dyeing process according to the invention can be carried out, for example, at temperatures in the range from room temperature to 100 ° C., temperatures in the range from 50 to 90 ° C. are preferred. If it is desired to carry out the dyeing process according to the invention at pressures of 1.1 to 20 bar, temperatures in the range from 100 to 130 ° C. are conceivable.
  • the dyeing process according to the invention can be carried out in an aqueous dyeing liquor, the liquor ratio and concentration of the reactive or vat dyes or direct dyestuffs being able to be of the usual dyeing order.
  • inorganic salts for example alkali metal or alkaline earth metal salts such as halides, carbonates or sulfates, preferably NaCl or Na 2 SO.
  • Typical amounts of inorganic salts may be, for example, 60 to 80 g / l dyeing liquor.
  • the dyeing liquor in the range of 0 to 20 g / l contains inorganic salts such as NaCl or Na 2 SO 4 , in particular up to 15 g / l.
  • Dyed cellulose-containing textile according to the invention is very well suited for the production of brilliantly colored, hardwearing substrates, for example for trousers, which have a brilliant coloration even after mechanical stress and repeated washing.
  • the invention will be explained by working examples. Examples 1 to 16 and Comparative Example C1
  • the hydrolysis or partial hydrolysis is then carried out at 80 ° C with 25 wt .-% sodium hydroxide solution.
  • the molecular weight was determined by gel permeation chromatography (GPC) using polystyrene as standard. The determination of the degree of hydrolysis was carried out by titration.
  • Table 1 Overview of the poly-N-vinylformamides used by way of example in step (a) of the pretreatment process according to the invention
  • Each is a random copolymer.
  • Table 1 a Overview of the poly-N-vinyl-formamide copolymers used by way of example in step (a) of the pretreatment process according to the invention
  • Dye 1 Hexasodium salt of the dye shown below:
  • Dye mixture 2 33.3% by weight each Color Index Reactive Yellow 208 Color Index Reactive Red 268 Color Index Reactive Blue 263
  • Dye mixture 3 33.3% by weight each Color Index Reactive Orange 84 Color Index Reactive Red 141 Color Index Reactive Blue 160
  • Dye 4 Color Index Reactive Blue 71
  • Fixing agent F1 methylpolyethylene glycol-modified trimeric hexamethylene diisocyanate prepared according to EP-B 0206059, Examples 1 and 2, as a 70% by weight solution in propylene carbonate. Amounts are always based on the entire solution.
  • Fixative F2 trimethylopropane tris (betaaziridino) propionate
  • the textile pretreated according to the invention was then treated with 3 g / l sodium hydroxide in a liquor ratio of 1:20 at 70 ° C., then rinsed twice with water (25 ° C.) and then with an aqueous solution containing 1.5 g / l citric acid contained, neutralized (each liquor ratio 1: 20, treatment time 10 min at 30 ° C).
  • the textile pretreated according to the invention was dried at 95 ° C. in a circulating air drying cabinet.
  • An aqueous dyeing liquor was prepared from 1 g / l of reactive dye, 1 g / l of 1-hydroxymethylidenebisphosphonic acid, 1 g / l of para-nitrobenzenesulfonic acid sodium salt and 60 g / l of common salt and water.
  • 100 ml of dyeing liquor were mixed with 10 g of fabric pretreated according to the invention and transferred to a staining bomb.
  • the staining bomb was sealed and placed in a staining apparatus (Ahiba Labomat) preheated to 50 ° C. The mixture was then heated to 82 ° C. in the course of 15 minutes and dyed at 82 ° C. for a further 30 minutes.
  • the staining bomb was removed from the dyebath, opened and the dye liquor 1, 5 g Na 2 CO 3 , dissolved in 10 ml of water, added and homogenized.
  • the staining bomb was then sealed, placed in the dyeing apparatus and held at 82 ° C for a further 60 min to fix the dye.
  • the mixture was then cooled within 5 minutes to about 30 ° C, opened the dyeing bomb and removed the dyed textile according to the invention, which was then rinsed for 5 min at 60 to 70 ° C under running water.
  • the dyed textile according to the invention was in a liquor ratio of 1:10 with a solution of 2 g / l polyacrylic acid Na salt (M w 70,000 g / mol) at a pH of 8.5 over a period of Soaped at 98 ° C for 15 minutes. It was then rinsed once for 5 min at 60 to 70 ° C and then for 5 min at 20 to 35 ° C under running water and then dried at 80 ° C in a convection oven for 20 minutes.
  • 2 g / l polyacrylic acid Na salt M w 70,000 g / mol
  • An aqueous dyeing liquor prepared from 2 g / l of dye No. 4, 1 g / l of 1-hydroxymethylidenebisphosphonic acid, 1 g / l of para-nitrobenzenesulfonic acid sodium salt, Table salt according to Table 3 and water.
  • 100 ml of dyeing liquor were mixed with 10 g of fabric pretreated according to the invention and transferred to a staining bomb.
  • the staining bomb was sealed and placed in a staining apparatus (Ahiba Labomat) preheated to 50 ° C. The mixture was then heated to 82 ° C. in the course of 15 minutes and dyed at 82 ° C. for a further 30 minutes.
  • the staining bomb was removed from the dyebath, opened and the dye liquor 1, 5 g Na 2 CO 3 , dissolved in 10 ml of water, added and homogenized.
  • the staining bomb was then sealed, placed in the dyeing apparatus and held at 82 ° C for a further 60 min to fix the dye.
  • the mixture was then cooled within 5 minutes to about 30 ° C, opened the dyeing bomb and removed the dyed textile according to the invention, which was then rinsed for 5 min at 60 to 70 ° C under running water.
  • the dyed textile according to the invention was in a liquor ratio of 1:10 with a solution of 2 g / l polyacrylic acid Na salt (M w 70,000 g / mol) at a pH of 8.5 over a period of 15 soaped at 98 ° C min. It was then rinsed once for 5 min at 60 to 70 ° C and then for 5 min at 20 to 35 ° C under running water and then dried at 80 ° C in a convection oven for 20 minutes.
  • the starting materials were each non-pretreated textile.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Coloring (AREA)

Abstract

Disclosed is a method for the preliminary treatment of cellulose-containing textile, comprising the following steps: a) cellulose-containing textile is treated with a polymer or copolymer solution obtained by (a1) polymerizing or copolymerizing N-vinylamide of general formula (I), wherein R is selected among hydrogen and C1-C10 alkyl, and (a2) optional partial hydrolysis, b) the treated textile is optionally dried, and c) at least some of the amide groups are saponified. At least one of steps (a2) and (c) is carried out.

Description

Verfahren zur Vorbehandlung von zellulosehaltigem TextilProcess for the pretreatment of cellulosic textile
Die vorliegende Erfindung betrifft ein Verfahren zum Vorbehandlung von zellulosehaltigem Textil, umfassend die folgenden Schritte:The present invention relates to a process for the pretreatment of cellulosic textile, comprising the following steps:
(a) Behandlung von zellulosehaltigem Textil mit einer Lösung von Polymer oder Copolymer, das erhältlich ist durch (a1 ) Polymerisation oder Copolymerisation von N-Vinylamid der allgemeinen Formel I,(a) treatment of cellulosic textile with a solution of polymer or copolymer obtainable by (a1) polymerization or copolymerization of N-vinylamide of general formula I,
wobei R gewählt wird aus Wasserstoff und Cι-Cι0-Alkyl, und (a2) gegebenenfalls partielle Hydrolyse, wherein R is selected from hydrogen and -CC 0 alkyl, and (a2) optionally partial hydrolysis,
(b) optional Trocknung des behandelten Textils, und(b) optionally drying the treated textile, and
(c) optional Verseifung zumindest eines Anteils der Amidgruppen, wobei man mindestens einen der Schritte (a2) und (c) durchführt.(c) optionally saponification of at least a portion of the amide groups, by carrying out at least one of the steps (a2) and (c).
Das Färben von zellulosehaltigem Textil kann nach verschiedenen Verfahren erfolgen. Üblich sind heute Färbungen mit Reaktiv-, Küpen- oder Direktfarbstoffen. In vielen Fällen beobachtet man jedoch, dass Ausziehgrad, d.h. der Anteil an Farbstoff, der aus dt Färbeflotte auf das Textil aufgebracht werden kann, sowie Echtheitsniveau der Färbung zu wünschen übrig lassen.The dyeing of cellulosic textile can be done by various methods. Usual today are dyeings with reactive, vat or direct dyes. In many cases, however, it is observed that exhaustion, i. the proportion of dye that can be applied from the dyeing liquor to the textile, as well as the fastness level of the dyeing to be desired.
Insbesondere bei Reaktivfärbungen wird häufig nur ein Ausziehgrad erhalten, der deutlich unterhalb von 80 % liegt. Hervorgerufen ist dieses beispielsweise dadurch, dass es in vielen Fällen nicht gelingt, eine vollständige Reaktion des Reaktivankers mit den OH-Gruppen der Zellulose zu erreichen. Der restliche Farbstoff wird in der Regel über die Kläranlage entsorgt.In particular, in reactive dyeing often only a degree of exhaustion is obtained, which is well below 80%. This is caused, for example, by the fact that in many cases it is not possible to achieve a complete reaction of the reactive anchor with the OH groups of the cellulose. The remaining dye is usually disposed of via the treatment plant.
Das in vielen Fällen unbefriedigende Echtheitsniveau der Färbung wird insbesondere dadurch verursacht, dass nicht sämtlicher Farbstoff ausreichend fixiert wird. Man beobachtet bei dem Gebrauch von Textil, dass nicht fixierter Farbstoff während der vom Endverbraucher durchgeführten Waschvorgänge ausgewaschen wird. Selbst scheinbar ausreichend fixierter Reaktivfarbstoff kann ausgewaschen werden, wenn die chemische Bindung zwischen Reaktivfarbstoff und Faser während der üblichen Waschpro- zesse gespalten wird, was neben dem Anbluten der Begleitgewebe auch ein Ausbleichen des gewaschenen Textils zur Folge hat. Um das Echtheitsniveau von Färbungen mit insbesondere Reaktivfarbstoffen zu verbessern, werden heute oft kationische Nachbehandlungsmittel für gefärbtes Textil eingesetzt, was aber mit zusätzlichen Prozessschritten im Färbeprozess bzw. in der Ausrüstung verbunden ist und dementsprechend höhere Kosten verursacht.The in many cases unsatisfactory level of authenticity of the coloration is caused in particular by the fact that not all the dye is sufficiently fixed. It is observed in the use of textile, that unfixed dye is washed out during the washing by the end user. Even apparently sufficiently fixed reactive dye can be washed out if the chemical bond between reactive dye and fiber is split during the customary washing processes, which, in addition to the bleeding of the accompanying fabrics, also results in bleaching of the washed textile. In order to improve the fastness level of dyeings with reactive dyes in particular, cationic aftertreatment agents for dyed textile are often used today, but this is associated with additional process steps in the dyeing process or in the equipment and accordingly causes higher costs.
Weiterhin wurde vorgeschlagen, kationische Nachbehandlungsmittel und auch Polye- thylenamine vor dem eigentlichen Färbeprozess auf zellulosehaltiges Textil aufzubringen. Dieses Aufbringen bewirkt eine deutlich intensivere Färbung (Bunt-Denim, Tl/T 240 d, Juli 1993, BASF Aktiengesellschaft), jedoch kann man in vielen Fällen eine un- erwünschte Ringfärbung beobachten, das heißt, einige oder alle Fasern sind nicht gleichmäßig über den Querschnitt, sondern nur an der Oberfläche gefärbt. Bei starker mechanischer Beanspruchung von derartig gefärbten Fasern wird die Färbung leicht mechanisch entfernt, und die Fasern erhalten innerhalb kurzer Zeit ein unerwünschtes Aussehen.It has also been proposed to apply cationic aftertreatment agents and also polyethyleneamines to cellulosic textile before the actual dyeing process. This application causes a much more intense coloration (colored denim, Tl / T 240 d, July 1993, BASF Aktiengesellschaft), but in many cases an undesirable ring dyeing can be observed, that is, some or all of the fibers are not uniform over the Cross-section, but only colored on the surface. Under heavy mechanical stress of such dyed fibers, the dyeing is easily removed mechanically, and the fibers get an undesirable appearance in a short time.
Aufgabe der vorliegenden Erfindung war-es-daher, ein Verfahren zur Vorbehandlung von Textil bereit zu stellen, das die Nachteile des Stands der Technik vermeidet und insbesondere gleichmäßig durchgefärbtes Textil verfügbar macht. Weiterhin war es Aufgabe der vorliegenden Erfindung, ein Verfahren bereit zu stellen, durch das Textil gefärbt werden kann, ohne dass es zu hohen Salzfrachten der zu entsorgenden Färbeflotten kommt.It was therefore an object of the present invention to provide a process for the pretreatment of textile which avoids the disadvantages of the prior art and, in particular, makes uniform dyed fabric available. A further object of the present invention is to provide a process by which textile can be dyed without high salt loads of the dyeing liquors to be disposed of being obtained.
Demgemäß wurde das eingangs definierte Verfahren gefunden.Accordingly, the method defined above was found.
! *nter zellulosehaltigem Textil bzw. Textilien sind im Rahmen der vorliegenden Erfindung zellulosehaltige Textilfasem, zellulosehaltige textile Halb- und Fertigfabrikate und daraus hergestellte Fertigwaren zu verstehen, die neben Textilien für die Bekleidungsindustrie beispielsweise auch Teppiche und andere Heimtextilien sowie technischen Zwecken dienende textile Gebilde umfassen. Dazu gehören auch ungeformte Gebilde wie beispielsweise Flocken, linienförmige Gebilde wie Bindfäden, Fäden, Garne, Leinen, Schnüre, Seile, Zwirne sowie Körpergebilde wie beispielsweise Filze, Gewebe, Vliesstoffe und Watten. Zellulosehaltige Textilien können natürlichen Ursprungs sein, beispielsweise Baumwolle oder Flachs, oder Mischgewebe, beispielsweise mit Baumwolle/Polyester, Baumwolle/Polyamid, wobei die Größe des Anteils an Zellulose unkri- tisch ist.! In the context of the present invention, cellulosic textile or textiles are cellulose-containing textile fibers, cellulosic textile semifinished and finished products and finished articles produced therefrom which, in addition to textiles for the clothing industry, also include, for example, carpets and other home textiles as well as textile structures serving technical purposes. These include unshaped structures such as flakes, linear structures such as twine, threads, yarns, linen, cords, ropes, threads and body structures such as felts, fabrics, nonwovens and wadding. Cellulose-containing textiles may be of natural origin, for example cotton or flax, or blended fabrics, for example cotton / polyester, cotton / polyamide, the size of the cellulose being uncritical.
Erfindungsgemäß behandelt man zellulosehaltiges Textil in einem Schritt (a) mit einerAccording to the invention, cellulose-containing textile is treated in a step (a) with a
Lösung von Polymer oder Copolymer, das erhältlich ist durchSolution of polymer or copolymer obtainable by
(a1) Polymerisation oder Copolymerisation von N-Vinylamid der allgemeinen Formel I, wobei(a1) polymerization or copolymerization of N-vinylamide of the general formula I, in which
R gewählt wird aus CrCio-Alkyl, verzweigt oder bevorzugt unverzweigt, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n- Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1 ,2-Dimethylpropyl, iso-Amyl, n- Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl; besonders bevorzugt unverzweigtes C C4-Alkyl wie Methyl, Ethyl, n-Propyl, n- Butyl; und insbesondere WasserstoffR is selected from C 1 -C 10 -alkyl, branched or preferably unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isobutyl, Pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl; more preferably straight-chain CC 4 alkyl such as methyl, ethyl, n-propyl, n-butyl; and especially hydrogen
und (a2) gegebenenfalls partielle Hydrolyse.and (a2) optionally partial hydrolysis.
In einer Ausführungsform der vorliegenden Erfindung setzt man Copolymere ein, die durch Copolymerisation von N-Vinylamid der allgemeinen Formel I mit mindestens ei- nem geeignetem Comonomer erhältlich sind, wobei es sich bei Copolymeren um statistische Copolymere, Blockcopolymere und speziell Pfropfcopolymere handeln kann. Geeignete Comonomere sind beispielsweise (Meth)acrylate wie beispielsweise Acryl- säuremethylester, Methylmethacrylat, Ethylacrylat, N-Vinylpyrrolidon, N-Vinylimidazol, Ethylmethacrylat, Ethylen, Propylen, 1 -Buten oder 1 ,3-Butadien.In one embodiment of the present invention, copolymers obtainable by copolymerization of N-vinylamide of the general formula I with at least one suitable comonomer are possible, which copolymers may be random copolymers, block copolymers and especially graft copolymers. Examples of suitable comonomers are (meth) acrylates such as, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, N-vinylpyrrolidone, N-vinylimidazole, ethyl methacrylate, ethylene, propylene, 1-butene or 1,3-butadiene.
In e' x Ausführungsform enthalten Copolymere, die durch Copolymerisation von N- Vinyla&iid der allgemeinen Formel I mit mindestens einem geeignetem Comonomer erhältlich sind, mindestens 20 Gew.-%, bevorzugt mindestens 30 Gew.-%, bezogen auf Copolymer, an N-Vinylamid der allgemeinen Formel I.In e ' x embodiment, copolymers obtainable by copolymerization of N-vinylamide of general formula I with at least one suitable comonomer contain at least 20% by weight, preferably at least 30% by weight, based on copolymer, of N-vinylamide the general formula I.
In einer Ausführungsform der vorliegenden Erfindung setzt man eine Lösung von Copolymer ein, das erhältlich ist durch Copolymerisation von 20 bis 90 Gew.-% N-Vinylamid der allgemeinen Formel I und 10 bis 80 Gew.-% Comonomer, gewählt aus N-Vinylpyrrolidon und N-Vinylimidazol, und gegebenenfalls anschließende partielle Hydrolyse, wobei Angaben in Gew.-% jeweils auf eingesetztes Copolymer bezogen sind.In one embodiment of the present invention, a solution of copolymer obtainable by copolymerizing from 20 to 90% by weight of N-vinylamide of general formula I and from 10 to 80% by weight of comonomer selected from N-vinylpyrrolidone and N-vinylimidazole, and optionally subsequent partial hydrolysis, wherein in wt .-% are each based on the copolymer used.
In einer Ausführungsform der vorliegenden Erfindung setzt man eine Lösung von Copolymer ein, das erhältlich ist durch Copolymerisation von 20 bis 80 Gew.-% N-Vinylamid der allgemeinen Formel I, 10 bis 70 Gew.-% N-Vinylimidazol und 10 bis 70 Gew.-% N-Vinylpyrrolidon und gegebenenfalls anschließende partielle Hydrolyse, wobei Angaben in Gew.-% jeweils auf eingesetztes Copolymer bezogen sind. In einer anderen Ausführungsform der vorliegenden Erfindung setzt man eine Lösung von Copolymer aus mindestens zwei verschiedenen Monomeren der allgemeinen Formel I ein, wobei es sich bei Copolymeren um statistische Copolymere, Blockcopo- lymere und speziell Pfropfcopolymere handeln kann.In one embodiment of the present invention, a solution of copolymer obtainable by copolymerization of 20 to 80% by weight of N-vinylamide of the general formula I, 10 to 70% by weight of N-vinylimidazole and 10 to 70% by weight is used .-% N-vinylpyrrolidone and optionally subsequent partial hydrolysis, wherein in wt .-% are each based on the copolymer used. In another embodiment of the present invention, a solution of copolymer of at least two different monomers of the general formula I is used, where copolymers may be random copolymers, block copolymers and especially graft copolymers.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung setzt man eine Lösung von Homopolymer von N-Vinylformamid ein.In a preferred embodiment of the present invention, a solution of homopolymer of N-vinylformamide is employed.
In einer Ausführungsform der vorliegenden Erfindung haben die in Schritt (a) eingesetzten Polymere oder Copolymere ein Molekulargewicht Mw im Bereich von 10.000 bis 1.000.000 g/mol, bevorzugt 30.000 bis 400.000 g/mol, bestimmt beispielsweise durch Gelpermeationschromatographie.In one embodiment of the present invention, the polymers or copolymers used in step (a) have a molecular weight M w in the range of 10,000 to 1,000,000 g / mol, preferably 30,000 to 400,000 g / mol, determined for example by gel permeation chromatography.
In einer Ausführungsform der vorliegenden Erfindung setzt man in Schritt (a) solches Polymer oder Copolymer ein, das erhältlich ist durch Polymerisation oderCopolymeri- sation von N-Vinylamid der allgemeinen Formel I und anschließende partielle Hydrolyse der Amidgruppen, beispielsweise mit verdünnter wässriger Alkalilauge oder verdünnter wässriger Alkalicarbonatlösung oder verdünnter wässriger Säure wie bei- spielsweise Phosphorsäure oder Schwefelsäure, wobei beispielsweise 60 moI-% oder 30 mol- oder 10 mol-% aller Amidgruppen hydrolysiert sein können.In one embodiment of the present invention, in step (a), use is made of a polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide of the general formula I and subsequent partial hydrolysis of the amide groups, for example with dilute aqueous alkali or dilute aqueous Alkalicarbonatlösung or dilute aqueous acid such as phosphoric acid or sulfuric acid, for example, 60 moI% or 30 mol or 10 mol% of all amide groups can be hydrolyzed.
In einer Ausführungsform der vorliegenden Erfindung wird wässrige Lösung des Polymers oder tfopolymers, erhältlich durch Polymerisation oder Copolymerisation von N- Vinylamid cϊ allgemeinen Formel I, in einer Konzentration von 0,1 bis 20 Gew.-%, bevorzugt 0,5 bis 5 Gew.-% eingesetzt.In one embodiment of the present invention, aqueous solution of the polymer or tfopolymer obtainable by polymerization or copolymerization of N-vinylamide cϊ general formula I, in a concentration of 0.1 to 20 wt .-%, preferably 0.5 to 5 wt. -% used.
In einer Ausführungsform der vorliegenden Erfindung setzt man im Bereich von 0,1 bis 10 Gew.-%, bevorzugt 2 bis 8 Gew.-% , bezogen auf zellulosehaltiges Textil, an gege- benenfalls partiell hydrolysiertem Polymer oder Copolymer ein, erhältlich durch Polymerisation oder Copolymerisation von N-Vinylamid der allgemeinen Formel I.In one embodiment of the present invention, in the range from 0.1 to 10% by weight, preferably from 2 to 8% by weight, based on cellulosic textile, of optionally partially hydrolyzed polymer or copolymer obtainable by polymerization or Copolymerization of N-vinylamide of the general formula I.
Im Rahmen der vorliegenden Erfindung kann man Schritt (a) ein oder mehrfach durchführen. Dabei können verschiedene Polymere bzw. Copolymere zum Einsatz kommen, von denen mindestens eines durch Polymerisation oder Copolymerisation von N- Vinylamid erhältlich ist. Man kann aber auch jeweils das gleiche Polymer bzw. Copolymer einsetzen, das durch Polymerisation oder Copolymerisation von N-Vinylamid und gegebenenfalls partieller Hydrolyse erhältlich ist.In the context of the present invention, step (a) can be carried out one or more times. Various polymers or copolymers can be used, of which at least one is obtainable by polymerization or copolymerization of N-vinylamide. However, it is also possible in each case to use the same polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide and optionally partial hydrolysis.
Die Behandlung in Schritt (a) kann beispielsweise gemäß einem Ausziehverfahren o- der einem Klotzverfahren erfolgen. Wünscht man Schritt (a) in der Art eines Ausziehverfahrens durchzuführen, so kann man das vorzubehandelnde zellulosehaltige Textil durch eine vorzugsweise wässrige Flotte ziehen, welches eine Lösung von Polymer bzw. Copolymer, erhältlich durch Polymerisation bzw. Copolymerisation von N-Vinylamid der allgemeinen Formel I, enthält. Anschließend zieht man vorzubehandelndes zellulosehaltiges Textil durch Rollen und quetscht überschüssige Lösung ab.The treatment in step (a) can be carried out, for example, according to an exhaustion process or a padding process. If it is desired to carry out step (a) in the manner of an exhaustion process, the cellulosic textile to be pretreated can be drawn through a preferably aqueous liquor containing a solution of polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide of general formula I. , contains. Then you pull vorzubehandelndes cellulosic textile by rolling and squeezes off excess solution.
Wünscht man Schritt (a) in der Art eines Klotzverfahrens durchzuführen, so kann man gängige Maschinen verwenden. Bevorzugt sind Foulards, die als wesentliches Element zwei aufeinandergepresste Rollen enthalten, durch die das vorzubehandelnde zellulosehaltige Textil geführt wird. Oberhalb der Rollen ist Flüssigkeit, enthaltend Lösung von Polymer bzw. Copolymer, erhältlich durch Polymerisation bzw. Copolymerisation von N-Vinylamid der allgemeinen Formel I, eingefüllt und benetzt das Textil. Durch den Druck wird das Textil abgequetscht und ein konstanter Auftrag gewährleistet. In einer anderen Ausführungsform des Klotzens arbeitet man mit einem oder mehreren Imprägnierbädern, durch die das zu behandelnde zellulosehaltige Textil gezogen wird. Anschließend daran läuft das Textil durch einen Foulard, und überschüssige Lösung wird abgequetscht.If one wishes to carry out step (a) in the manner of a padding method, one can use common machines. Preference is given to foulards which contain, as an essential element, two rollers pressed onto one another, through which the cellulosic textile to be pretreated is guided. Above the rollers, liquid containing solution of polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide of general formula I is filled in and wets the textile. The pressure squeezes off the textile and ensures a constant application. In another embodiment of the padding, one or more impregnating baths are used, through which the cellulosic textile to be treated is drawn. After that, the fabric passes through a padder and excess solution is squeezed off.
In einer Ausführungsform der vorliegenden Erfindung führt man die Vorbehandlung in Schritt (a) in Gegenwart mindestens eines Fixiermittels durch. Als Fixiermittel sind beispielsweise geeignet:In one embodiment of the present invention, the pretreatment in step (a) is carried out in the presence of at least one fixing agent. Suitable fixing agents are, for example:
Harnstoff-Forrna?dehyd- und Melamin-Formaldehyd-Additionsprodukte, gegebenenfalls in Kombination i?t anorganischen Salzen wie beispielsweise MgCI2-6 H2O oder NH4CI, insbesondere Harnstoff-Formaldehyd-Glyoxal-Kondensationsprodukte, deren Hydroxylgruppen partiell oder quantitativ mit beispielsweise Methanol verethert sein können,Urea-forrna-dehyd- and melamine-formaldehyde addition products, optionally in combination with inorganic salts such as MgCl 2 -6H 2 O or NH 4 Cl, in particular urea-formaldehyde-glyoxal condensation products, their hydroxyl groups partially or quantitatively For example, methanol can be etherified,
Kondensationsprodukte von N,N'-Dimethylharnstoff mit Glyoxal,Condensation products of N, N'-dimethylurea with glyoxal,
Isocyanate bzw. ihre Dimere oder Trimere, wie beispielsweise 4,4'- Methylen(diphenylisocyanat) MDI, Hexamethylendiisocyanat HDI, Isophorondiisocya- nat, jeweils frei oder blockiert mit beispielsweise 3,5-Dimethylpyrazol, Acetonoxim o- der sec.-Butanonoxim, insbesondere trimeres Hexamethylendiisocyanat und trimeres Isophorondiisocyanat, jeweils frei oder blockiert. Beispiele finden sich in EP-B 0206 059,Isocyanates or their dimers or trimers, such as, for example, 4,4'-methylene (diphenyl isocyanate) MDI, hexamethylene diisocyanate HDI, isophorone diisocyanate, in each case free or blocked with, for example, 3,5-dimethylpyrazole, acetone oxime or sec.-butanone oxime, in particular trimeric hexamethylene diisocyanate and trimeric isophorone diisocyanate, each free or blocked. Examples can be found in EP-B 0206 059,
Di-, Tri- und Polyepoxide, gewählt aus beispielsweise mit Epichlorhydrin umgesetzten Diolen, Polyolen, Diaminen, Polyaminen,Di-, tri- and polyepoxides selected from, for example, epichlorohydrin-reacted diols, polyols, diamines, polyamines,
oligomere Carbodiimine, Di- und Trialdehyde wie beispielsweise Glutardialdehyd, Glyoxal, Dextranpolyaldehyde, sowie Stärkealdehyde, hergestellt beispielsweise nach US 2001-0025102 A1 ;oligomeric carbodiimines, Di- and trialdehydes such as, for example, glutaraldehyde, glyoxal, dextran polyaldehydes, and starch aldehydes, prepared, for example, according to US 2001-0025102 A1;
Epoxysiiane, hergestellt beispielsweise nach DE 3528006 und DE 41 28894,Epoxysiiane, produced for example according to DE 3528006 and DE 41 28894,
Poly-Al koxycarbonyl-Ami noderivatePoly-Al koxycarbonyl-Ami noderivate
sowie Aziridinverbindungen wie z.B. Trimethylolpropantris-(betaaziridino)-propionat.and aziridine compounds such as e.g. Trimethylolpropane (betaaziridino) propionate.
Ganz besonders bevorzugte Di-, Tri- und Polyepoxide sindVery particularly preferred di-, tri- and polyepoxides are
wobei z jeweils eine ganze Zahl im Bereich von 0 bis 10 ist. where each z is an integer in the range of 0 to 10.
Im Anschluss an Schritt (a) kann man gemäß Schritt (a) behandeltes Textil trocknen (b). Diese optional durchzuführende Trocknung (b) kann man in gängigen Apparaturen, beispielsweise Trockenschränken, oder auch an der frischen Luft durchführen. Temperaturen im Bereich von 30°C bis 120°C sind sinnvoll, bevorzugt sind 70 bis 110°C. Die Trockendauer ist üblicherweise abhängig von der Trockentemperatur und vom gewünschten Restfeuchtegehalt und kann im Bereich von 30 Sekunden bis 3 Stunden liegen, jedoch sind auch längere oder kürzere Zeitdauern möglich.Following step (a), it is possible to dry treated textile according to step (a) (b). This optionally carried out drying (b) can be carried out in common apparatus, such as drying cabinets, or in the fresh air. Temperatures in the range of 30 ° C to 120 ° C are useful, preferably 70 to 110 ° C. The drying time is usually dependent on the drying temperature and the desired residual moisture content and may be in the range of 30 seconds to 3 hours, but longer or shorter periods are possible.
Wünscht man Schritt (a) mehrfach durchzuführen, so kann man nach jedem einzelnen Behandlungsschritt (a) trocknen oder bevorzugt nur nach dem letzten Behandlungs- schritt (a).If it is desired to carry out step (a) several times, it is possible to dry after each individual treatment step (a) or preferably only after the last treatment step (a).
Im optionalen Schritt (c) des erfindungsgemäßen Verfahrens verseift man zumindest einen Anteil der Amidgruppen. Darunter sind die Amidgruppen des oder der gemäß Schritt (a) auf das Textil aufgebrachten Polymere bzw. Copolymere zu verstehen, die durch Polymerisation oder Copolymerisation von N-Vinylamid der allgemeinen Formel erhältlich sind.In optional step (c) of the process according to the invention, at least a portion of the amide groups are saponified. These are understood as meaning the amide groups of the polymer or copolymers applied to the textile according to step (a), which are obtainable by polymerization or copolymerization of N-vinylamide of the general formula.
Man führt im Rahmen der vorliegenden Erfindung mindestens einen der Schritte (a2) und (c) durch, d.h. man kann zellulosehaltiges Textil mit partiell hydrolysiertem Polymer oder Copolymer von N-Vinylamid der allgemeinen Formel I behandeln und auf Schritt (c) verzichten, oder man kann Schritt (c) durchführen und auf eine partielle Hydrolyse nach (a2) verzichten.In the context of the present invention, at least one of steps (a2) and (c) is carried out, i. One can treat cellulosic textile with partially hydrolyzed polymer or copolymer of N-vinyl amide of general formula I and waive step (c), or you can perform step (c) and dispense with a partial hydrolysis of (a2).
In einer Ausführungsform der vorliegenden Erfindung behandelt man zellulosehaltiges Textil mit einer Lösung von Polymer oder Copolymer, das erhältlich ist durch Polymerisation oder Copolymerisation von N-Vinylamid der allgemeinen Formel I und das man gemäß Schritt (a2) partiell hydrolysiert hat, trocknet optional nach Schritt (b) und verseift anschließend zumindest einen Anteil der Amidgruppen gemäß Schritt (c).In one embodiment of the present invention, cellulose-containing textile is treated with a solution of polymer or copolymer which is obtainable by polymerization or copolymerization of N-vinylamide of general formula I and which has been partially hydrolyzed according to step (a2). b) and then hydrolyzed at least a portion of the amide groups according to step (c).
In einer Ausführungsform der vorliegenden Erfindung führt man Schritt (c) so durch, dass man behandeltes und gegebenenfalls getrocknetes Textil mit verdünnter wässri- ger Alkalihydroxidlösung oder verdünnter wässriger Alkalicarbonatlösung behandelt, bevorzugt mit Natronlauge, Kalilauge, Natriumcarbonatlösung oder Kaliumcarbonatlö- sung. Als Konzentrationen sind beispielsweise 0,5 bis 10 Gew.-%, bevorzugt 2 bis 5 Gew.-% geeignet.In one embodiment of the present invention, step (c) is carried out by treating treated and optionally dried textile with dilute aqueous solution. ger alkali hydroxide solution or dilute aqueous alkali carbonate solution, preferably with sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution or potassium carbonate solution. As concentrations, for example, 0.5 to 10 wt .-%, preferably 2 to 5 wt .-% are suitable.
In einer Ausführungsform liegt die Temperatur, bei der Schritt (c) durchgeführt wird, im Bereich von Zimmertemperatur bis 90°C, bevorzugt im Bereich von 70 bis 90°C.In one embodiment, the temperature at which step (c) is carried out is in the range of room temperature to 90 ° C, preferably in the range of 70 to 90 ° C.
Die Druckbedingungen von Schritt (c) sind unkritisch, man kann beispielsweise bei Normaldruck arbeiten, aber Drücke von beispielsweise 1 ,1 bar bis 10 bar sind ebenfalls denkbar.The pressure conditions of step (c) are not critical, you can, for example, operate at atmospheric pressure, but pressures of, for example, 1, 1 bar to 10 bar are also conceivable.
Schritt (c) kann man in Form eines kontinuierlichen oder diskontinuierlichen Verfahrens ausgeführen.Step (c) may be carried out in the form of a continuous or batch process.
In Schritt (c) wird üblicherweise zumindest ein Anteil der Amidgruppen verseift.In step (c), at least a portion of the amide groups is usually saponified.
In einer Ausführungsform der vorliegenden Erfindung verseift man mindestens ein Drittel der Amidgruppen des oder der Polymere bzw. Copolymere aus Schritt (a), bevor- zugt mindestens 90 mol-% und besonders bevorzugt mindestens 95 mol-%.In one embodiment of the present invention, at least one third of the amide groups of the one or more polymers or copolymers from step (a) are saponified, preferably at least 90 mol% and particularly preferably at least 95 mol%.
In einer Ausführungsform der vorliegenden Erfindung verseift man die Amidgruppen des oder der Polymere bzw. Copolymere aus Schritt (a) quantitativ.In one embodiment of the present invention, the amide groups of the one or more polymers or copolymers from step (a) are hydrolyzed quantitatively.
Natürlich kann man im Rahmen der vorliegenden Erfindung im Anschluss an Schritt (c) Neutralisationsschritte, vorzugsweise mit organischen Säuren wie beispielsweise Citronensäure, Weinsäure, Adipinsäure oder Bernsteinsäure, durchführen. Auch kann man im Rahmen der vorliegenden Erfindung im Anschluss an Schritt (c) Spül- und Trockenschritte durchführen.Of course, in the context of the present invention, following step (c), neutralization steps, preferably with organic acids such as, for example, citric acid, tartaric acid, adipic acid or succinic acid, can be carried out. Also, in the context of the present invention, rinsing and drying steps can be carried out following step (c).
Wenn man die erfindungsgemäße Vorbehandlung in Gegenwart von einem oder mehreren Fixiermitteln durchgeführt hat, so ist es bevorzugt, im Anschluss an die Vorbehandlung einen beispielsweise thermischen Fixierschritt (d) anzuschließen. Beispielsweise kann man bei Temperaturen von 150°C bis 190°C über einen Zeitraum von 30 Sekunden bis 5 Minuten fixieren. Der Fixierschritt (d) ist auf allen in der Textilindustrie üblichen Fixier- und Trocknungsaggregaten, beispielsweise auf Spannrahmen und Trockenschränke, beispielsweise mit Umluft, geeignet.If the pretreatment according to the invention has been carried out in the presence of one or more fixing agents, then it is preferable, following the pretreatment, to attach an example of a thermal fixing step (d). For example, you can fix at temperatures of 150 ° C to 190 ° C over a period of 30 seconds to 5 minutes. The fixing step (d) is suitable on all fixing and drying units customary in the textile industry, for example on tenter frames and drying cabinets, for example with circulating air.
Ein weiterer Aspekt der vorliegenden Erfindung ist zellulosehaltiges Textil, vorbehan- delt nach dem erfindungsgemäßen Verfahren. Es eignet sich in besonderer Weise zur Herstellung von gefärbtem Textil. Ein weiterer Aspekt der vorliegenden Erfindung ist daher die Verwendung von erfindungsgemäß vorbehandeltem zellulosehaltigen Textil zur Herstellung von gefärbtem Textil.Another aspect of the present invention is cellulosic textile, as defined by the process of the invention. It is particularly suitable for the production of dyed textile. Another aspect of the present invention is Therefore, the use of pretreated cellulose-containing textile according to the invention for the production of dyed textile.
Ein weiterer Aspekt der vorliegenden Erfindung ist ein Verfahren zur Herstellung von gefärbtem Textil, im Folgenden auch erfindungsgemäßes Färbeverfahren genannt. Das erfindungsgemäße Färbeverfahren geht aus von erfindungsgemäß vorbehandeltem zellulosehaltigem Textil und umfasst mindestens einen Färbeschritt unter Verwendung von mindestens einem Reaktiv-, Küpen- oder Direktfarbstoff, wobei die Auswahl des oder der Reaktiv-, Küpen- oder Direktfarbstoffe unkritisch ist.Another aspect of the present invention is a process for the production of dyed textile, hereinafter also called dyeing process according to the invention. The dyeing process according to the invention is based on cellulosic textile pretreated according to the invention and comprises at least one dyeing step using at least one reactive, vat or direct dye, the choice of reactive or vat dyes or direct dyes being uncritical.
Das erfindungsgemäße Färbeverfahren kann beispielsweise bei Normaldruck oder bei Drücken von 1 ,1 bis 20 bar durchgeführt werden. Bevorzugt ist es, das erfindungsgemäße Färbeverfahren bei Normaldruck durchzuführen.The dyeing process according to the invention can be carried out, for example, at normal pressure or at pressures of 1.1 to 20 bar. It is preferred to carry out the dyeing process according to the invention at atmospheric pressure.
Das erfindungsgemäße Färbeverfahren kann beispielsweise bei Temperaturen im Bereich von Zimmertemperatur bis 100°C durchgeführt werden, bevorzugt-sind Temperaturen im Bereich von 50 bis 90°C. Wünscht man das erfindungsgemäße Färbeverfahren bei Drücken von 1 ,1 bis 20 bar durchzuführen, sind Temperaturen im Bereich von 100 bis 130°C denkbar.The dyeing process according to the invention can be carried out, for example, at temperatures in the range from room temperature to 100 ° C., temperatures in the range from 50 to 90 ° C. are preferred. If it is desired to carry out the dyeing process according to the invention at pressures of 1.1 to 20 bar, temperatures in the range from 100 to 130 ° C. are conceivable.
Das erfindungsgemäße Färbeverfahren kann man in wässriger Färbeflotte durchführen, wobei Flottenverhältnis und Konzentration des oder der Reaktiv-, Küpen- oder Direktfarbstoffe in Färberei-üblichen Größenordnungen liegen kann.The dyeing process according to the invention can be carried out in an aqueous dyeing liquor, the liquor ratio and concentration of the reactive or vat dyes or direct dyestuffs being able to be of the usual dyeing order.
In einer Ausführungsform des erfirat cιngsgemäßen Färbeverfahrens kann man der Färbeflotte übliche Mengen an anorganischen Salzen zusetzen, beispielsweise Alkalimetall- oder Erdalkalimetallsalze wie Halogenide, Carbonate oder Sulfate, bevorzugt NaCI oder Na2SO . Übliche Mengen an anorganischen Salzen können beispielsweise 60 bis 80 g/l Färbeflotte sein.In one embodiment of the dyeing process according to the invention, it is possible to add customary amounts of inorganic salts to the dyeing liquor, for example alkali metal or alkaline earth metal salts such as halides, carbonates or sulfates, preferably NaCl or Na 2 SO. Typical amounts of inorganic salts may be, for example, 60 to 80 g / l dyeing liquor.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung enthält die Färbeflotte im Bereich von 0 bis 20 g/l anorganische Salze wie beispielsweise NaCI oder Na2SO4, insbesondere bis 15 g/l.In a preferred embodiment of the present invention, the dyeing liquor in the range of 0 to 20 g / l contains inorganic salts such as NaCl or Na 2 SO 4 , in particular up to 15 g / l.
Man beobachtet eine verbesserte Auszehrung der Färbeflotte. Führt man Schnitte an erfindungsgemäß gefärbtem Textil durch, so beobachtet man eine gleichmäßige Durchfärbung und praktisch keine Ringfärbung. Auch nach längerer mechanischer Strapazierung und mehreren Wäschen behält erfindungsgemäß gefärbtes Textil eine brillante Färbung. Außerdem ist es möglich, auf den Gebrauch stark Salz-haltiger Fär- beflotten zu verzichten und dennoch gute Färbeergebnisse zu erhalten. Natürlich kann man im Rahmen der vorliegenden Erfindung an den eigentlichen Färbungsschritt noch Färberei-übliche Nachbehandlungsschritte anschließen; beispielhaft seien Nachseifschritte, Spülschritte, Trockenschritte und auch Ausrüstungsschritte genannt.One observes an improved emaciation of the dyeing liquor. If cuts are made on textile dyed according to the invention, uniform dyeing and practically no ring dyeing are observed. Even after prolonged mechanical stress and several washes dyed textile according to the invention retains a brilliant color. In addition, it is possible to dispense with the use of strongly salt-containing dye liquors and still obtain good staining results. Of course, in the context of the present invention, the actual dyeing step can be followed by dyeing-customary aftertreatment steps; Examples are Nachseifschritte, rinsing steps, drying steps and equipment steps called.
Durch Ausübung des erfindungsgemäßen Färbeverfahrens erhält man erfindungsgemäßes gefärbtes zellulosehaltiges Textil, das ebenfalls ein Aspekt der vorliegenden Erfindung ist. Erfindungsgemäßes gefärbtes zellulosehaltiges Textil ist sehr gut geeignet zur Herstellung von brillant gefärbten strapazierfähigen Substraten, beispielsweise für Hosen, die auch nach mechanischer Beanspruchung und wiederholter Wäsche eine brillante Färbung aufweisen. Die Erfindung wird durch Arbeitsbeispiele erläutert. Beispiele 1 bis 16 und Vergleichsbeispiel V1By carrying out the dyeing process according to the invention one obtains dyed cellulosic textile according to the invention, which is also an aspect of the present invention. Dyed cellulose-containing textile according to the invention is very well suited for the production of brilliantly colored, hardwearing substrates, for example for trousers, which have a brilliant coloration even after mechanical stress and repeated washing. The invention will be explained by working examples. Examples 1 to 16 and Comparative Example C1
I. Verwendete Substanzen 1.1. Herstellung von Poly-N-vinylformamid (Homopolymere) Die Herstellung von Poly-N-vinylformamid erfolgte durch radikalische Polymerisation, vgl. „Kinetics and modelling of free radical polymerization of N-vinylformamide", L Gu, S. Zhu, A.N. Hrymak, R.H. Pelton, Polymer 2001 , 42, 3077.I. Substances used 1.1. Preparation of poly-N-vinylformamide (homopolymers) The preparation of poly-N-vinylformamide was carried out by free-radical polymerization, cf. "Kinetics and modeling of free radical polymerization of N-vinylformamide", L Gu, S. Zhu, A.N. Hrymak, R.H. Pelton, Polymer 2001, 42, 3077.
Die Hydrolyse bzw. partielle Hydrolyse erfolgt anschließend bei 80°C mit 25 Gew.-% Natronlauge. iThe hydrolysis or partial hydrolysis is then carried out at 80 ° C with 25 wt .-% sodium hydroxide solution. i
Die Bestimmung des Molekulargewichtes erfolgte mittels Gelpermeationschroma- tographie (GPC) mit Polystyrol als Standard. Die Bestimmung des Hydrolysegrades erfolgte titrimetrisch.The molecular weight was determined by gel permeation chromatography (GPC) using polystyrene as standard. The determination of the degree of hydrolysis was carried out by titration.
Tabelle 1 : Übersicht über die in Schritt (a) des erfindungsgemäßen Vorbehandlungsverfahrens beispielhaft eingesetzten Poly-N-vinylformamideTable 1: Overview of the poly-N-vinylformamides used by way of example in step (a) of the pretreatment process according to the invention
I.2. Herstellung von Copolymeren des N-Vinylformamids I.2. Preparation of copolymers of N-vinylformamide
Herstellung P7Production P7
In einem 2-Liter-Dreihalskolben wurden 550 g destilliertes Wasser und 34 g N-Vinylimidazol vorgelegt und auf 75°C erwärmt. Man gab unter Rühren über einen Zeitraum von 2 Stunden eine Mischung von 138,8 g N-Vinylformamid und 170 g N-Vinylpyrrolidon tropfenweise zu. Gleichzeitig begann man, tropfenweise eine Lösung von 1 ,7 g Azobisisobutyronitnl in 100 g destilliertem Wasser zuzugeben. Nach 3 Stunden war die Zugabe der wässrigen Lösung von Azobisisobutyronitril sowie der Mischung von N-Vinylformamid und N-Vinylpyrrolidon beendet. Man rührte weitere zwei Stunden bei 75°C und erhielt eine farblose, klare viskose Lösung. Mw (GPC): 620.000 g/mol, Feststoffgehalt: 20,1 Gew.-%.In a 2-liter three-necked flask, 550 g of distilled water and 34 g of N-vinylimidazole were introduced and heated to 75 ° C. A mixture of 138.8 g of N-vinylformamide and 170 g of N-vinylpyrrolidone was added dropwise with stirring over a period of 2 hours. At the same time, a solution of 1.7 g of azobisisobutyronitrile in 100 g of distilled water was added dropwise. After 3 hours, the addition of the aqueous solution of azobisisobutyronitrile and the mixture of N-vinylformamide and N-vinylpyrrolidone was completed. The mixture was stirred at 75 ° C. for a further 2 hours to obtain a colorless, clear, viscous solution. M w (GPC): 620,000 g / mol, solid content: 20.1 wt%.
Zur Herstellung von P6, P8 und P9 wurde jeweils wie oben beschrieben vorgegangen, wobei stets die Gesamtmenge an Comonomeren 342,8 g betrug und stets N- Vinylimidazol vorgelegt und das oder die Comonomeren N-Vinylformamid bzw. N- Vinylpyrrolidon zugegeben wurden. Die Molekulargewichte findet man in Tabelle 1a.The procedure for preparing P6, P8 and P9 was in each case as described above, the total amount of comonomers always being 342.8 g and N-vinylimidazole always being charged and the comonomer (s) N-vinylformamide or N-vinylpyrrolidone being added. The molecular weights are found in Table 1a.
Es handelt sich jeweils um statistische Copolymere.Each is a random copolymer.
Tabelle 1 a: Übersicht über die in Schritt (a) des erfindungsgemäßen Vorbehandlungsverfahrens beispielhaft eingesetzten Poly-N-viny'formamid-CopolymereTable 1 a: Overview of the poly-N-vinyl-formamide copolymers used by way of example in step (a) of the pretreatment process according to the invention
Angaben in Gew.-% beziehen sich jeweils auf die Gesamtmasse an Poly-N- Vinylformamid-Copolymer P8 wurde als wässrige Lösung mit einem Feststoffgehalt 19,7 Gew.-%, P9 als wässrige Lösung mit Feststoff gehalt 25,1 Gew.-% eingesetzt. Verwendete Farbstoffe: Data in% by weight relate in each case to the total mass of poly-N-vinylformamide copolymer P8 was used as an aqueous solution having a solids content of 19.7% by weight, P9 as an aqueous solution having a solids content of 25.1% by weight. used. Dyes used:
Farbstoff 1 : Hexanatriumsalz des unten abgebildeten Farbstoffs:Dye 1: Hexasodium salt of the dye shown below:
Farbstoffmischung 2: je 33,3 Gew.-% Colour Index Reaktiv Gelb 208 Colour Index Reaktiv Rot 268 Colour Index Reaktiv Blau 263Dye mixture 2: 33.3% by weight each Color Index Reactive Yellow 208 Color Index Reactive Red 268 Color Index Reactive Blue 263
Farbstoffmischung 3: je 33,3 Gew.-% Colour Index Reaktiv Orange 84 Colour Index Reaktiv Rot 141 Colour Index Reaktiv Blau 160Dye mixture 3: 33.3% by weight each Color Index Reactive Orange 84 Color Index Reactive Red 141 Color Index Reactive Blue 160
Farbstoff 4: Colour Index Reaktiv Blau 71Dye 4: Color Index Reactive Blue 71
Farbstoff 5: Octanatriumsalz vonDye 5: octa sodium salt of
Farbstoff 6: Pentanatriumsalz von Dye 6: Pentasodium salt of
I.4. Verwendete FixiermittelI.4. Used fixatives
Fixiermittel F1 : Methylpolyethylenglykol-modif iziertes trimeres Hexamethylendiisocyanat, hergestellt nach EP-B 0206059, Beispiele 1 und 2, als 70 Gew.-% Lösung in Pro- pylencarbonat. Einsatzmengen sind stets auf gesamte Lösung bezogen. Fixiermittel F2: TrimethyloIpropantris-(betaaziridino)-propionatFixing agent F1: methylpolyethylene glycol-modified trimeric hexamethylene diisocyanate prepared according to EP-B 0206059, Examples 1 and 2, as a 70% by weight solution in propylene carbonate. Amounts are always based on the entire solution. Fixative F2: trimethylopropane tris (betaaziridino) propionate
II. Allgemeine Vorschriften zur erfindungsgemäßen Vorbehandlung von zellulosehaltigem Gewebe mit Poly-N-Vinylformamid und zum FärbenII. General provisions for the pretreatment of cellulosic tissue according to the invention with poly-N-vinylformamide and for dyeing
11.1. Allgemeine Vorschrift zur erfindungsgemäßen Vorbehandlung von zellulosehaltigem Gewebe mit Poly-N-Vinylformamid11.1. General procedure for the pretreatment of cellulosic tissue according to the invention with poly-N-vinylformamide
X g Poly-N-Vinylformamid gemäß den Tabellen 1 und 2 wurde in 100 ml Wasser gelöst. Anschließend wurde mittels eines Foulards (Hersteller Fa. Mathis, Typ Nr. HVF12085) ein zellulosehaltiges Textil (100 % Baumwollwebware, Flächengewicht 160 g/m2 gebleicht, färbefertig) mit der so erhaltenen Polymer-Lösung getränkt. Die Flottenaufnahme betrug zwischen 50 und 85 Gew.-%, bezogen auf das Warengewicht. Anschließend wurde das Gewebe bei 80°C 5 Minuten lang getrocknet.X g of poly-N-vinylformamide according to Tables 1 and 2 was dissolved in 100 ml of water. Subsequently, using a foulard (manufacturer Mathis, type no. HVF12085), a cellulosic textile (100% cotton weave, basis weight 160 g / m 2 bleached, ready for dyeing) was impregnated with the polymer solution obtained in this way. The liquor pickup was between 50 and 85 wt .-%, based on the weight of the product. Subsequently, the fabric was dried at 80 ° C for 5 minutes.
Das erfindungsgemäß vorbehandelte Textil wurde dann mit 3 g/l Natronlauge im Flottenverhältnis von 1 :20 bei 70°C behandelt, anschließend wurde zweimal mit Wasser (25°C) gespült und anschließend mit einer wässrigen Lösung, die 1,5 g/l Citronensäure enthielt, neutralisiert (jeweils Flottenverhältnis 1 :20, Behandlungsdauer 10 min bei 30°C). Das erfindungsgemäß vorbehandelte Textil wurde bei 95°C im Umlufttrocken- schrank getrocknet.The textile pretreated according to the invention was then treated with 3 g / l sodium hydroxide in a liquor ratio of 1:20 at 70 ° C., then rinsed twice with water (25 ° C.) and then with an aqueous solution containing 1.5 g / l citric acid contained, neutralized (each liquor ratio 1: 20, treatment time 10 min at 30 ° C). The textile pretreated according to the invention was dried at 95 ° C. in a circulating air drying cabinet.
Zur Durchführung des Vergleichsbeispiels wurde wie oben beschrieben vorgegangen, jedoch Poly-N-Vinylformamid weggelassen.To carry out the comparative example, the procedure was as described above, but omitted poly-N-vinylformamide.
II.2 Allgemeine Vorschrift zur Färbung des vorbehandelten zellulosehaltigen Gewebes aus 11.1II.2 General procedure for coloring the pretreated cellulosic tissue from 11.1
Es wurde eine wässrige Färbeflotte hergestellt aus 1 g/l Reaktivfarbstoff, 1 g/l 1- Hydroxymethylidenbisphosphonsäure, 1 g/l para-Nitrobenzolsulfonsäurenatriumsalz und 60 g/l Kochsalz Sowie Wasser. 100 ml Färbeflotte wurden mit 10 g erfindungsgemäß vorbehandelten Textils versetzt und in eine Färbebombe überführt. Die Färbebombe wurde verschlossen und in einen Färbeapparat (Ahiba Labomat) eingesetzt, der auf 50°C vorgewärmt war. Anschließend wurde innerhalb von 15 min auf 82°C aufgeheizt und weitere 30 min bei 82°C gefärbt. Dann wurde die Färbebombe aus dem Färbebad entnommen, geöffnet und der Färbeflotte 1 ,5 g Na2CO3, gelöst in 10 ml Wasser, zugesetzt und homogenisiert. Die Färbebombe wurde dann verschlossen, in den Färbeapparat eingesetzt und zur Fixierung des Farbstoffs weitere 60 min bei 82°C gehalten. Anschließend wurde innerhalb von 5 Minuten auf ca. 30°C abgekühlt, die Färbebombe geöffnet und das erfindungsgemäß gefärbte Textil entnommen, welches dann 5 min bei 60 bis 70°C unter fließendem Wasser gespült wurde. Nach dem Spülen wurde das erfindungsgemäß gefärbte Textil -jn einem Flottenverhältnis von 1 :10 mit einer Lösung von 2 g/l Polyacrylsäure-Na-Salz (Mw 70.000 g/mol) bei einem pH-Wert von 8,5 über eine Dauer von 15 min bei 98°C geseift. Im Anschluss daran wurde einmal 5 min bei 60 bis 70°C und anschließend 5 min bei 20 bis 35°C unter fließendem Wasser gespült und danach bei 80°C im Umlufttrockenschrank 20 Minuten lang getrocknet.An aqueous dyeing liquor was prepared from 1 g / l of reactive dye, 1 g / l of 1-hydroxymethylidenebisphosphonic acid, 1 g / l of para-nitrobenzenesulfonic acid sodium salt and 60 g / l of common salt and water. 100 ml of dyeing liquor were mixed with 10 g of fabric pretreated according to the invention and transferred to a staining bomb. The staining bomb was sealed and placed in a staining apparatus (Ahiba Labomat) preheated to 50 ° C. The mixture was then heated to 82 ° C. in the course of 15 minutes and dyed at 82 ° C. for a further 30 minutes. Then the staining bomb was removed from the dyebath, opened and the dye liquor 1, 5 g Na 2 CO 3 , dissolved in 10 ml of water, added and homogenized. The staining bomb was then sealed, placed in the dyeing apparatus and held at 82 ° C for a further 60 min to fix the dye. The mixture was then cooled within 5 minutes to about 30 ° C, opened the dyeing bomb and removed the dyed textile according to the invention, which was then rinsed for 5 min at 60 to 70 ° C under running water. After rinsing, the dyed textile according to the invention was in a liquor ratio of 1:10 with a solution of 2 g / l polyacrylic acid Na salt (M w 70,000 g / mol) at a pH of 8.5 over a period of Soaped at 98 ° C for 15 minutes. It was then rinsed once for 5 min at 60 to 70 ° C and then for 5 min at 20 to 35 ° C under running water and then dried at 80 ° C in a convection oven for 20 minutes.
Man erhielt erfindungsgemäß gefärbtes Textil gemäß Beispiel 1 bis 16 (Tabelle 2) und ein Vergleichstextil gemäß Vergleichsbeispiel V1. Die erfindungsgemäßen Textilien gemäß Beispiel 1 bis 16 zeigten eine brillante Färbung. Schnitte zeigten, dass die Fasern - anders als bei Vergleichstextil gemäß Vergleichsbeispiel V1 - gleichmäßig durchgefärbt war und keine Ringfärbung aufwies. Tabelle 2: Ergebnisse des erfindungemäßen Vorbehandlungsverfahrens, des erfindungsgemäßen Färbeverfahrens und von Vergleichsexperimenten (V1 ) mit Farbstoff 1According to the invention, dyed textile according to Examples 1 to 16 (Table 2) and a comparison textile according to Comparative Example C1 were obtained. The textiles of the invention according to Example 1 to 16 showed a brilliant color. Sections showed that the fibers were dyed uniformly and had no ring dyeing, unlike the comparison textile according to Comparative Example C1. Table 2: Results of the pretreatment process according to the invention, the dyeing process according to the invention and of comparative experiments (V1) with dye 1
Tabelle 2 (Fortsetzung) Table 2 (continued)
Tabelle 2 (Fortsetzung) Table 2 (continued)
Tabelle 2 (Fortsetzung) Table 2 (continued)
n.b.: nicht bestimmt Tabelle 2 (Fortsetzung) nb: not determined Table 2 (continued)
als 100% bezeichnet. referred to as 100%.
III. Allgemeine Vorschriften zur erfindungsgemäßen Vorbehandlung von zellulosehaltigem Textil unter Verwendung von Poly-N-Vinylformamid-Copolymer 111.1. Erfindungsgemäße Vorbehandlung ohne Fixiermittel 50 g Poly-N-vinylformamid-Copolymer bzw. 50 g wässrige Lösung von Poly-N- vinylformamid-Copolymer gemäß Tabelle 1 a wurden mit Wasser auf 1000 ml Färbeflotte aufgefüllt. Anschließend wurde mittels eines Foulards (Hersteller Fa. Mathis, Typ Nr. HVF12085) ein zellulosehaltiges Textil (100 % Baumwollwebware, Flächengewicht 160 g/m2, gebleicht, färbefertig) mit der so erhaltenen Färbeflotte getränkt. Die Flottenauf- nähme betrug zwischen 50 und 85 Gew.-%, bezogen auf das Warengewi^ht. Anschließend wurde das vorbehandelte Textil bei 80°C 5 Minuten lang getrocknet.III. General rules for the pretreatment of cellulosic textile according to the invention using poly-N-vinylformamide copolymer 111.1. 50 g of poly-N-vinylformamide copolymer or 50 g of aqueous solution of poly-N-vinylformamide copolymer according to Table 1 a were made up to 1000 ml of dyeing liquor with water. Subsequently, using a foulard (manufacturer Mathis, type no. HVF12085), a cellulosic textile (100% cotton weave, basis weight 160 g / m 2 , bleached, ready-to-dye) was impregnated with the dyeing liquor obtained in this way. The fleet absorption was between 50 and 85% by weight, based on the goods weight. Subsequently, the pretreated textile was dried at 80 ° C for 5 minutes.
III.2 Erfindungsgemäße Vorbehandlung mit Fixiermittel 50 g Poly-N-vinylformamid-Copolymer bzw. 50 g wässrige Lösung von Poly-N- vinylformamid-Copolymer gemäß Tabelle 1 a und 1 ,5 g Fixiermittel gemäß Tabelle 3 wurden mit Wasser auf 1000 ml Färbeflotte aufgefüllt. Anschließend wurde mittels eines Foulards (Hersteller Fa. Mathis, Typ Nr. HVF12085) ein zellulosehaltiges Textil (100 % Baumwollwebware, Flächengewicht 160 g/m2, gebleicht, färbefertig) mit der so erhaltenen Färbeflotte getränkt. Die Flottenaufnahme betrug 80 Gew.-%, bezogen auf das Warengewicht. Anschließend wurde das vorbehandelte Textil bei 160°C 3 Minuten lang getrocknet und dadurch thermisch fixiert.III.2 Pretreatment with Fixative According to the Invention 50 g of poly-N-vinylformamide copolymer or 50 g of aqueous solution of poly-N-vinylformamide copolymer according to Table 1 a and 1, 5 g of fixative according to Table 3 were mixed with water to 1000 ml of dyeing liquor refilled. Subsequently, using a foulard (manufacturer Mathis, type no. HVF12085), a cellulosic textile (100% cotton weave, basis weight 160 g / m 2 , bleached, ready-to-dye) was impregnated with the dyeing liquor obtained in this way. The liquor pickup was 80% by weight, based on the weight of the product. Subsequently, the pretreated textile was dried at 160 ° C for 3 minutes and thereby thermally fixed.
III.3 Färbung von vorbehandeltem Textil gemäß 11.1 bzw. II.2III.3 Staining of pretreated textile according to 11.1 or II.2
Es wurde eine wässrige Färbeflotte hergestellt aus 2 g/l Farbstoff Nr. 4, 1 g/l 1 - Hydroxymethylidenbisphosphonsäure, 1 g/l para-Nitrobenzolsulfonsäurenatriumsalz, Kochsalz gemäß Tabelle 3 sowie Wasser. 100 ml Färbeflotte wurden mit 10 g erfindungsgemäß vorbehandelten Textils versetzt und in eine Färbebombe überführt. Die Färbebombe wurde verschlossen und in einen Färbeapparat (Ahiba Labomat) eingesetzt, der auf 50°C vorgewärmt war. Anschließend wurde innerhalb von 15 min auf 82°C aufgeheizt und weitere 30 min bei 82°C gefärbt. Dann wurde die Färbebombe aus dem Färbebad entnommen, geöffnet und der Färbeflotte 1 ,5 g Na2CO3, gelöst in 10 ml Wasser, zugesetzt und homogenisiert. Die Färbebombe wurde dann verschlossen, in den Färbeapparat eingesetzt und zur Fixierung des Farbstoffs weitere 60 min bei 82°C gehalten. Anschließend wurde innerhalb von 5 Minuten auf ca. 30°C abgekühlt, die Färbebombe geöffnet und das erfindungsgemäß gefärbte Textil entnommen, welches dann 5 min bei 60 bis 70°C unter fließendem Wasser gespült wurde.An aqueous dyeing liquor prepared from 2 g / l of dye No. 4, 1 g / l of 1-hydroxymethylidenebisphosphonic acid, 1 g / l of para-nitrobenzenesulfonic acid sodium salt, Table salt according to Table 3 and water. 100 ml of dyeing liquor were mixed with 10 g of fabric pretreated according to the invention and transferred to a staining bomb. The staining bomb was sealed and placed in a staining apparatus (Ahiba Labomat) preheated to 50 ° C. The mixture was then heated to 82 ° C. in the course of 15 minutes and dyed at 82 ° C. for a further 30 minutes. Then the staining bomb was removed from the dyebath, opened and the dye liquor 1, 5 g Na 2 CO 3 , dissolved in 10 ml of water, added and homogenized. The staining bomb was then sealed, placed in the dyeing apparatus and held at 82 ° C for a further 60 min to fix the dye. The mixture was then cooled within 5 minutes to about 30 ° C, opened the dyeing bomb and removed the dyed textile according to the invention, which was then rinsed for 5 min at 60 to 70 ° C under running water.
Nach dem Spülen wurde das erfindungsgemäß gefärbte Textil in einem Flottenverhältnis von 1 :10 mit einer Lösung von 2 g/l Polyacrylsäure-Na-Salz (Mw 70.000 g/mol) bei einem pH-Wert von 8,5 über eine Dauer von 15 min bei 98°C geseift. Im Anschluss daran wurde einmal 5 min bei 60 bis 70°C und anschließend 5 min bei 20 bis 35°C unter fließendem Wasser gespült und danach bei 80°C im Umlufttrockenschrank 20 Minuten lang getrocknet. Zur Durchführung der Vergleichsbeispiele ging man jeweils von nicht vorbehandeltem Textil aus.After rinsing, the dyed textile according to the invention was in a liquor ratio of 1:10 with a solution of 2 g / l polyacrylic acid Na salt (M w 70,000 g / mol) at a pH of 8.5 over a period of 15 soaped at 98 ° C min. It was then rinsed once for 5 min at 60 to 70 ° C and then for 5 min at 20 to 35 ° C under running water and then dried at 80 ° C in a convection oven for 20 minutes. For carrying out the comparative examples, the starting materials were each non-pretreated textile.
Man erhielt erfindungsgemäß gefärbtes Textil gemäß Beispiel 17 bis 24 (Tabelle 3) und Vergleichstextilien gemäß Vergleichsbeispielen V2 bis V6 (Tabelle 4). Die e.^ndungs- gemäßen Textilien gemäß Beispiel 17 bis 24 zeigten eine brillante Färbung; Schnitte zeigten, dass die Fasern - anders als bei Vergleichstextil gemäß den Vergleichsbeispielen V2 bis V6 - gleichmäßig durchgefärbt war und keine Ringfärbung aufwies.Inventively dyed textile according to Example 17 to 24 (Table 3) and comparative textiles according to Comparative Examples V2 to V6 were obtained (Table 4). The e.Andungs- proper textiles according to Example 17 to 24 showed a brilliant color; Sections showed that the fibers - in contrast to the comparison textile according to Comparative Examples V2 to V6 - was uniformly colored and had no ring dyeing.
Die Werte für L, A, B und Delta E wurden nach CIELAB bestimmt.The values for L, A, B and Delta E were determined according to CIELAB.
Tabelle 3: Färbung von vorbehandeltem TextilTable 3: Staining of pretreated textile
Tabelle 3 (Fortsetzung) Table 3 (continued)
Tabelle 4: Vergleichsbeispiele: Färbung von nicht vorbehandeltem Textil Table 4: Comparative Examples: Dyeing of non-pretreated textile

Claims

Patentansprüche claims
1. Verfahren zur Vorbehandlung von zellulosehaltigem Textil, umfassend die folgenden Schritte: (a) Behandlung von zellulosehaltigem Textil mit einer Lösung von Polymer oder Copolymer, das erhältlich ist durch (a1 ) Polymerisation oder Copolymerisation von N-Vinylamid der allgemeinen Formel I,A process for pretreating cellulosic textile comprising the steps of: (a) treating cellulosic textile with a solution of polymer or copolymer obtainable by (a1) polymerizing or copolymerizing N-vinyl amide of general formula I,
10 wobei R gewählt wird aus Wasserstoff und CrC10-Alkyl, und (a2) gegebenenfalls partielle Hydrolyse, (b) optional Trocknung des behandelten Textils, und (c) optional Verseifung zumindest eines Anteils der Amidgruppen, 15 wobei man mindestens einen der Schritte (a2) und (c) durchführt. 10 where R is selected from hydrogen and C 1 -C 10 -alkyl, and (a2) optionally partial hydrolysis, (b) optionally drying of the treated textile, and (c) optionally saponification of at least a portion of the amide groups, at least one of the steps ( a2) and (c).
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man wässrige Lösung von Polymer oder Copolymer einsetzt.2. The method according to claim 1, characterized in that one uses aqueous solution of polymer or copolymer.
" 20 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass in der allge- meinen Formel I R für Wasserstoff steht. "20 3. The method of claim 1 or 2, characterized in that in the general formula IR my is hydrogen.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Polymer oder Copolymer, erhältlich durch Polymerisation oder Copolymerisation 25 von N-Vinylamid der allgemeinen Formel I, ein Mw im Bereich von 10.000 bis 1.000.000 g/mol aufweist.4. The method according to any one of claims 1 to 3, characterized in that the polymer or copolymer obtainable by polymerization or copolymerization of N-vinylamide of the general formula I, an M w in the range of 10,000 to 1,000,000 g / mol ,
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Copolymer erhältlich ist 30 durch (a1 ) Copolymerisation von N-Vinylamid der allgemeinen Formel I mit mindestens einem weiteren Comonomer, gewählt aus N-Vinylpyrrolidon und N-Vinylimidazol. 5. The method according to any one of claims 1 to 4, characterized in that the copolymer is obtainable by 30 (a1) copolymerization of N-vinylamide of the general formula I with at least one further comonomer selected from N-vinylpyrrolidone and N-vinylimidazole.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man Polymer oder Copolymer einsetzt, das erhältlich ist durch (a1) Polymerisation oder Copolymerisation von N-Vinylamid der allgemeinen Formel I und (a2) anschließende partielle Hydrolyse.6. The method according to any one of claims 1 to 5, characterized in that one uses polymer or copolymer which is obtainable by (a1) polymerization or copolymerization of N-vinylamide of the general formula I and (a2) subsequent partial hydrolysis.
7. Zellulosehaltiges Textil, vorbehandelt nach einem Verfahren nach einem der Ansprüche 1 bis 6.7. Cellulose-containing textile, pretreated by a process according to one of claims 1 to 6.
8. Verwendung von zellulosehaltigem Textil, vorbehandelt nach einem Verfahren nach mindestens einem der Ansprüche 1 bis 6, zur Herstellung von gefärbtem Textil.8. Use of cellulosic textile, pretreated by a process according to any one of claims 1 to 6, for the production of dyed textile.
9. Verfahren zur Herstellung von gefärbtem zellulosehaltigem Textil, dadurch gekennzeichnet, dass man vorbehandeltes zellulosehaltiges Textil nach Anspruch 7 mit Reaktiv-, Küpen- oder Direktfarbstoff färbt.9. A process for the preparation of dyed cellulosic textile, characterized in that pretreated cellulosic textile according to claim 7 dyed with reactive, vat or direct dye.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die Färbeflotte im Bereich von 0 bis 20 g/l eines oder mehrerer anorganischer Salze enthält.10. The method according to claim 9, characterized in that the dyeing liquor in the range of 0 to 20 g / l of one or more inorganic salts.
11. Gefärbtes zellulosehaltiges Textil, erhältlich nach einem Verfahren nach Anspruch 9 oder 10. 11. A dyed cellulosic textile obtainable by a process according to claim 9 or 10.
EP04787002A 2003-09-30 2004-09-24 Method for the preliminary treatment of cellulose-containing textile Not-in-force EP1670986B1 (en)

Applications Claiming Priority (3)

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DE2003145797 DE10345797A1 (en) 2003-09-30 2003-09-30 Pretreatment of cellulose-containing textiles before dyeing, e.g. for production of colored hard-wearing fabrics, involves treatment with a vinylamide polymer which is at least partly hydrolysed before and-or after drying
DE200410026096 DE102004026096A1 (en) 2004-05-25 2004-05-25 Treatment of cellulose-containing textiles especially prior to dyeing involves treatment with vinyl amide (co)polymer optionally followed by hydrolysis and or saponifying
PCT/EP2004/010721 WO2005033402A1 (en) 2003-09-30 2004-09-24 Method for the preliminary treatment of cellulose-containing textile

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CN115151235A (en) * 2020-01-21 2022-10-04 纽泰克温图斯公司 Continuous production of keratin fibers

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ES2663483T3 (en) * 2013-03-19 2018-04-12 Mitsubishi Rayon Co., Ltd. Use of a cationizing agent, method for firmly fixing water insoluble particles and method for producing dyed material

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CH690401A5 (en) * 1996-06-11 2000-08-31 Ciba Sc Holding Ag A method for the treatment of dyed cellulose fiber material.
DE10124387A1 (en) * 2001-05-18 2002-11-28 Basf Ag Hydrophobically modified polyethyleneimine and polyvinylamine as anticrease agents for treatment of cellulose containing textiles, useful as textile finishing agents in both solid and liquid formulations

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Publication number Priority date Publication date Assignee Title
EP3421583A1 (en) * 2017-06-26 2019-01-02 Basf Se Use of cationic vinylcarboxamide/vinylamine copolymers as a color care agent for laundering formulations
CN115151235A (en) * 2020-01-21 2022-10-04 纽泰克温图斯公司 Continuous production of keratin fibers

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PE20050740A1 (en) 2005-09-29
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JP2007507620A (en) 2007-03-29
EP1670986B1 (en) 2011-08-10
TW200521287A (en) 2005-07-01
ATE519887T1 (en) 2011-08-15
WO2005033402A1 (en) 2005-04-14

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