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EP1828451B1 - Verfahren zum vernetzen und färben von cellulosefasern - Google Patents

Verfahren zum vernetzen und färben von cellulosefasern Download PDF

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Publication number
EP1828451B1
EP1828451B1 EP05794754A EP05794754A EP1828451B1 EP 1828451 B1 EP1828451 B1 EP 1828451B1 EP 05794754 A EP05794754 A EP 05794754A EP 05794754 A EP05794754 A EP 05794754A EP 1828451 B1 EP1828451 B1 EP 1828451B1
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EP
European Patent Office
Prior art keywords
fibres
cross
man
fabric
cellulose fibres
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EP05794754A
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English (en)
French (fr)
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EP1828451A2 (de
Inventor
Patrick Arthur White
Malcolm Hayhurst
James Martin Taylor
Alan Owens
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Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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Publication of EP1828451A2 publication Critical patent/EP1828451A2/de
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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
    • 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
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/828—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl groups
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—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
    • 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
    • D06P1/613—Polyethers without 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
    • 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
    • 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
    • D06P3/82—Textiles which contain different kinds of fibres
    • 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
    • D06P5/22—Effecting variation of dye affinity on textile material by chemical means that react with the fibre

Definitions

  • This invention relates to a process involving the cross-linking of man-made cellulose fibres and the subsequent dyeing of fabrics made from such fibres.
  • Man-made cellulose fibres are produced by taking a naturally occurring source of cellulose, such as wood pulp, converting it into a spinnable solution and spinning fibres from that solution.
  • Lyocell fibres are man-made cellulose fibres produced by extrusion of a solution of cellulose through a spinning jet into a coagulation bath by a process known as solvent spinning. Such a process is described in US-A-4,246,221 and uses as the solvent an aqueous tertiary amine N-oxide, particularly N-methylmorpholine N-oxide.
  • Lyocell fibres are distinguished from other man-made cellulose fibres, which are produced by forming the cellulose into a soluble chemical derivative and then extruding a solution of this derivative into a bath to regenerate the extrudate as cellulose fibres.
  • Viscose fibres including the high strength modal types, are made by forming a soluble derivative in this way.
  • Cross-linking treatments of cellulose fabrics are well known for imparting crease-resistance, durable-press or wash-wear qualities to such fabrics. A general description of such treatments is found in Kirk-Othmer's Encyclopaedia of Chemical Technology, third edition, Volume 22 (1983), Wiley-Interscience, in an article entitled “Textiles (Finishing)" at pages 769-790 , and by H. Petersen in Rev. Prog. Coloration, Vol 17 (1987), pages 7-22 .
  • Crosslinking agents may sometimes be referred to by other names, for example crosslinking resins, chemical finishing agents and resin finishing agents.
  • Crosslinking agents are small molecules containing a plurality of functional groups capable of reacting with the hydroxyl groups in cellulose to form crosslinks.
  • N-methylol resins that is to say small molecules containing two or more N-hydroxymethyl or N-alkoxymethyl, in particular N-methoxymethyl, groups.
  • N-methylol resins are generally used in conjunction with acid catalysts chosen to improve crosslinking performance.
  • acid catalysts chosen to improve crosslinking performance.
  • a solution containing about 5-9% by weight N-methylol resin crosslinking agent and 0.4-3.5% by weight acid catalyst is padded onto dry cellulosic fabric to give 60-100% by weight wet pickup, after which the wetted fabric is dried and heated to cure and fix the crosslinking agent.
  • US-A-4,780,102 describes a process for cross-linking cotton fabrics to impart wash-wear qualities by padding the fabrics with an N- methylol cross-linking agent, an acid catalyst for the cross-linking reaction and polyethylene glycol.
  • the fabric is dried and heated to effect cross-linking before being dyed.
  • the inclusion of the polyethylene glycol allows the cross-linked fabric to be post-dyed with a dye normally used to dye cellulose whilst achieving the desired wash-wear quality imparted by the cross-linking treatment.
  • the level of dyeing achieved in this process is still reduced compared with non-cross-linked cotton fabrics.
  • This is put to advantage by applying the cross-linking chemicals as a print formulation to achieve differential dyeing between the printed and unprinted areas of the fabric when it is post-dyed.
  • cross-linking is carried out to reduce the fibrillation tendency of lyocell fibres.
  • a flexible linear polymer for example polyethylene glycol, is included with the cross-linking agent in order to impart dye affinity to the cross-linked lyocell fibres in a post-dyeing operation.
  • the present invention is also concerned with using a cross-linking process of the type described but for the purpose of overcoming a problem caused by the reduced dye uptake of cotton compared with man-made cellulose fibres such as lyocell and viscose fibres.
  • the present invention provides a process for producing an evenly-dyed fabric comprising both cotton fibres and man-made cellulose fibres, in which a fabric is manufactured from both said fibres and is dyed, characterised by impregnating the man-made cellulose fibres, prior to manufacture of the fabric, with a water-soluble, flexible linear polymer and a cross-linking agent reactive with cellulose, and, at a stage of the process prior to dyeing of the fabric, effecting a cross-linking reaction between the man-made cellulose fibres and the cross-linking agent, thereby producing a reduction in the dye affinity of the man-made cellulose fibres to a level more proximate to the dye affinity of the cotton fibres.
  • the process enables the even dyeing of the fabric to a solid shade of colour, in contrast to the skittery, marl or speckled effects that are usually obtained when fabrics made from such fibre blends are dyed.
  • the dye affinity of a fibre is a relative value, which is measured by a test in which a weighed sample of fabric is dyed using a standardised dyebath and procedure.
  • the colour strength obtained is measured by a spectrophotometer and compared with the value obtained when a control fabric of identical construction and weight is dyed and measured by the same procedure.
  • the value given to the control is usually expressed as 100 per cent and the value given to the fabric being compared to the control is expressed as the ratio of the measured colour strengths times 100 per cent.
  • the dye affinity test specified for use to determine the dye affinity of the fibres for compliance with the process of the present invention is described later in this specification.
  • the evenness of dyeing required to obtain a solid shade of colour is usually judged by eye.
  • the standard of evenness required will vary according to the proposed end-use of the dyed fabric and according to the dye colour used. In the latter case, for example, yellow dyes disguise skittery dyeing more easily than dark blue dyes.
  • even-dyeing to a solid shade of colour may be obtained using the process of the invention if the dye affinity of the man-made cellulose fibres is reduced to within about 15 per cent of (either side of but, more usually, above), the dye affinity of the cotton fibres, taking the latter at the 100 per cent value.
  • the dye affinity of cotton fibres varies according to type, source and treatment but, in general, taking the cotton fibres at the control value of 100 per cent, standard viscose fibres have a dye affinity of about 130 per cent and standard lyocell fibres have a dye affinity of about 140 per cent. Despite this original disparity in dye affinity between man-made cellulose fibres and cotton fibres, evenly dyed blend fabrics can be obtained using the process of the invention.
  • the man-made cellulose fibres preferably are lyocell fibres, but the process is also effective using other man-made cellulose fibres such as viscose fibres.
  • the impregnation of the man-made cellulose fibres with the cross-linking chemicals may be carried out on the fibres in fibre form or in yarn form. It is preferably carried out on the fibres before they are spun into a yarn and, more preferably, by applying the flexible linear polymer and the cross-linking agent as a solution to the man-made cellulose fibres whilst they are in the form of a never-dried tow, i.e. just after the fibres have been wet-spun but before they have been dried for the first time.
  • the cross-linking agent may in general be any of those known in the art for crease-resistant finishing of cellulose but is preferably an agent classed as a zero-formaldehyde or low-formaldehyde cross-linking agent, preferably used in conjunction with a cross-linking catalyst.
  • the cross-linking agent is preferably a zero-formaldehyde cross-linking agent when the method of the invention is carried out on fabric.
  • One class of low-formaldehyde cross-linking agents consists of the N-methylol resins.
  • suitable N-methylol resins are those described in the abovementioned articles in Kirk-Othmer and by Petersen.
  • suitable N-methylol resins include 1,3-dimethylolethyleneurea (DMeEU), 1,3-dimethylolpropyleneurea (DMePU) and 4,5-dihydroxy-1,3-dimethylolethyleneurea (DHDMeEU).
  • DMeEU 1,3-dimethylolethyleneurea
  • DMePU 1,3-dimethylolpropyleneurea
  • DHDMeEU 4,5-dihydroxy-1,3-dimethylolethyleneurea
  • Other examples include compounds based on urones, triazinones and carbamates.
  • Another example of a suitable cross-linking agent is melamine.
  • a preferred class consists of compounds based on 1,3-dialkyl-4,5-dihydroxy(alkoxy)ethyleneurea, for example 1,3-dimethyl-4,5-dihydroxyethyleneurea (DMDHEU).
  • DMDHEU 1,3-dimethyl-4,5-dihydroxyethyleneurea
  • BTCA butanetetracarboxylic acid
  • Cross-linking agents for crease-resistant finishing of cellulose are generally used in conjunction with a catalyst for the cross-linking reaction, commonly an acid catalyst. The method of the invention preferably utilises such a catalyst when recommended for use with the chosen cross-linking agent.
  • N-methylol resins and 1,3-dialkyl-4,5-dihydroxy(alkoxy)ethyleneureas are preferably used in conjunction with an acid catalyst, for example an organic acid such as acetic acid or a latent acid such as an ammonium salt, amine salt or metal salt, e.g. zinc nitrate or magnesium chloride.
  • an acid catalyst for example an organic acid such as acetic acid or a latent acid such as an ammonium salt, amine salt or metal salt, e.g. zinc nitrate or magnesium chloride.
  • an acid catalyst for example an organic acid such as acetic acid or a latent acid such as an ammonium salt, amine salt or metal salt, e.g. zinc nitrate or magnesium chloride.
  • an acid catalyst for example an organic acid such as acetic acid or a latent acid such as an ammonium salt, amine salt or metal salt, e.g. zinc nitrate or magnesium chloride.
  • the water-soluble, flexible linear polymer is preferably a wholly aliphatic polymer, preferably unbranched. It may have terminal functional groups, for example hydroxyl or amino groups, and it is possible that these take part in the reaction with the cross-linking agent.
  • the effect of the flexible linear polymer is to moderate the depression of the dye affinity of the man-made cellulose fibres by the cross-linking resin so that the dye affinity becomes more proximate to that of cotton. It appears to achieve this effect by preventing excessive collapse of the cellulose fibre structure during the cross-linking reaction, so that the structure retains a degree of openness which allows ingress of sufficient dye to produce the desired level of dyeing. After dyeing, the flexible linear polymer has no further function and will tend to be washed out of the fibres to the extent that it is not held in place by any involvement of its functional groups in the cross-linking reaction.
  • Preferred types of flexible linear polymer include polymerised glycols such as polypropylene glycol (PPG) and in particular polyethylene glycol (PEG). Amine-tipped derivatives of such polymerised glycols may be used. It will be understood that such flexible linear polymers are generally mixtures of molecules having a range of chain lengths and are characterised in terms of their average molecular weight and chain length. For example, chain lengths may range from about 5 to 150 atoms.
  • a preferred example of a flexible linear polymer is PEG having an average molecular weight in the range 200 to 2000.
  • the cross-linking agent, flexible linear polymer and any catalyst are preferably applied to the man-made cellulose fibres from solution, preferably an aqueous solution.
  • Polymerised glycols such as PEG and PPG are generally soluble in water.
  • the solution may be applied to the fibres by known methods, for example the solution may be padded onto a tow of the fibres, preferably a never-dried tow, or a tow of fibres may be passed through a treatment bath of the solution. It is also possible to treat the fibres in staple form.
  • a tow of never-dried fibres may have a moisture content of about 45-65%, often around 50%, by weight, after application of the solution.
  • the treatment solution may contain 0.5 to 15%, preferably 1.5 to 5%, by weight cross-linking agent (expressed on a 100% activity basis).
  • the solution preferably contains 0.1 to 5% by weight flexible linear polymer.
  • the solution may contain 0.1 to 5%, preferably 0.25 to 2.5%, by weight catalyst.
  • the solution may contain one or more additional substances, for example a soft finish for the fibre.
  • the treated man-made cellulose fibres preferably contain 0.2 to 5%, more preferably 1 to 4%, by weight cross-linking agent calculated owc (on weight of cellulose) and 0.1 to 3% by weight flexible linear polymer calculated owc.
  • the fabric made from the impregnated man-made cellulose fibres and the cotton fibres may be a knitted, woven or non-woven fabric. In the case of knitted and woven fabrics, the fibres are first spun into yarns. A preferred method is to blend the impregnated man-made cellulose fibres and the cotton fibres and to spin yarns from the blend. An alternative method is to make yarns individually from the respective fibres and to combine the yarns in making the fabric. Any blend ratio suitable for the desired end-use may be used, common blend ratios with cotton being in the range 70:30 to 30:70 by weight, with a 50:50 blend being most common.
  • cross-linking or curing, step is carried out before dyeing. If there is any other wet treatment to be carried out before dyeing, then cross-linking should be effected before that other wet treatment in order to avoid loss of the cross-linking chemicals from the treated yarns during that wet treatment step.
  • cross-linking is carried out on the fabric or on the yarn.
  • cross-linking preferably is carried out on the fabric.
  • the intended fabric is a woven fabric, however, it is preferred to carry out the cross-linking on the yarn, because the warp sizing operation that is usually preliminary to weaving can lead to loss of the cross-linking chemicals from the yarns, if they are not already cross-linked.
  • Cross-linking at the fibre stage is also a possibility but is not preferred because the cross-linked fibres can become hairy and difficult to process through the yarn-spinning and fabric-making stages.
  • a preferred process comprises impregnating the man-made cellulose fibres with the flexible linear polymer and the cross-linking agent, blending the impregnated fibres with the cotton fibres, making a yarn from the blended fibres, manufacturing a fabric from the yarn, and effecting the cross-linking reaction on the yarn or on the fabric, preferably on the yarn in the case of a woven fabric.
  • Cross-linking may be effected by a heating step at a temperature and for a time appropriate to the cross-linking agent and any catalyst employed.
  • the fabric When cross-linking is carried out on the fabric, the fabric may be passed through a hot air oven on a stenter.
  • Suitable cross-linking conditions comprise a temperature in the range 140°C to 200°C for a period in the range 30 seconds to 5 minutes, with higher temperatures as a rule involving appropriately shorter times than lower temperatures.
  • Previously drying treatments for example the drying of the tow after the application of the cross-linking chemicals, should be carried out under conditions, mainly lower temperatures, at which premature cross-linking does not occur.
  • the temperature of the fibres themselves is preferably kept below 110°C during drying.
  • the fibres preferably are not dried to a moisture level below about 7 per cent by weight on weight of fibres.
  • Dyeing of the fabric may be carried out using dyes and methods conventionally used for dyeing cellulose fabrics. Suitable dyes include direct dyes, vat dyes, sulphur dyes and reactive dyes. Commercial dyeing machines may be used, including water-driven jet dyeing machines, for example the machines known as Thies Ecosoft, Gaston County Futura and Hisaka Circular CUT-SL, and air jet dyeing machines, for example the machines known as Thies Airstream, Thies Lucas Roto, Hisaka AJ-1, Krantz Aerodye and Then AFS.
  • water-driven jet dyeing machines for example the machines known as Thies Ecosoft, Gaston County Futura and Hisaka Circular CUT-SL
  • air jet dyeing machines for example the machines known as Thies Airstream, Thies Heil Roto, Hisaka AJ-1, Krantz Aerodye and Then AFS.
  • the invention includes a first embodiment of undyed fibrous product, comprising both cotton fibres and man-made cellulose fibres, in which the man-made cellulose fibres are impregnated with a water-soluble, flexible linear polymer and a cross-linking agent reactive with cellulose, the impregnated man-made cellulose fibres not yet being cross-linked but having the potential of a reduced dye affinity more proximate to the dye affinity of the cotton fibres upon the effecting of a cross-linking reaction between the man-made cellulose fibres and the cross-linking agent prior to dyeing of the fibrous product.
  • This first embodiment of undyed fibrous product may be an undyed fibre blend of the cotton fibres and the impregnated man-made cellulose fibres, yarn made from such a fibre blend, or a fabric made from such yarn. It may also be a fabric made from cotton yarn and yarn comprising the impregnated but non-cross-linked man-made cellulose fibres.
  • the invention further includes a second embodiment of undyed fibrous product, comprising both cotton fibres and man-made cellulose fibres, in which the man-made cellulose fibres are impregnated with a water-soluble, flexible linear polymer and with a cross-linking agent which has reacted with the cellulose of the man-made cellulose fibres in a cross-linking reaction which has reduced the dye affinity of the man-made cellulose fibres to a level more proximate to the dye affinity of the cotton fibres.
  • This second embodiment of undyed fibrous product preferably is a yarn or a fabric. It may also be a fabric made from cotton yarn and yarn of the cross-linked man-made cellulose fibres.
  • the dye affinity of the cross-linked cellulose fibres is at a level within about 15 per cent of the dye affinity of the cotton fibres as measured by the test specified herein, using cotton as the 100 per cent control value.
  • the invention further includes the cross-linked fibrous product of the second embodiment in the form of a fabric which is evenly dyed to a solid shade of colour.
  • the dye affinity test specified for employment to determine compliance with the process of this invention uses an aqueous dyebath incorporating 0.05 per cent Solophenyl Green 27 (a direct dye) and 10 g/l (grams per litre) sodium chloride.
  • Test fabric samples of 5 g (grams) weight are dyed at a liquor-to-fabric weight ratio of 20:1, with dyeing being carried out at a dyebath temperature of 95°C for 45 minutes, before the dyebath is cooled and the fabric sample is rinsed and dried.
  • the colour strength of each dyed sample is measured using a Minolta CM-3300D spectrophotometer, and all readings are made relative to a sample of dyed control fabric, which is rated at the 100 per cent figure.
  • the control fabric is taken as a cotton fabric because it is the dye affinity of cotton that is being matched in order to obtain even dyeing of blend fabrics.
  • Parity between the tested fabrics is maintained by making them all from the same count of yarn (20 Tex), the same fabric (plain knit) and the same sample weight (5g). Before dyeing, all fabric samples are scoured in an aqueous scour bath containing 2 g/l soda ash and 2 g/l Zetex HPLFN for 30 minutes at a temperature of 70°C.
  • Lyocell fibres were spun by a process based on a commercial process for spinning lyocell fibres of 1.4 dtex by spinning a solution of cellulose in an aqueous solvent of N-methylmorpholine N-oxide through a spinning jet into an aqueous coagulating bath to form fibres in the form of a tow of filaments, followed by washing of the tow.
  • Example 1 the specified concentration of PEG in the pad bath was 5 g/l, and for Example 2 it was 10 g/l.
  • the levels of PEG on the fibres were 0.5 per cent by weight owf for the fibres of Example 1 and 1.0 per cent by weight owf for the fibres of Example 2.
  • samples were made up for testing by the specified method.
  • staple fibres of 38 mm staple length were cut from each of the respective dried, impregnated tows and spun into respective yarns of count 20 Tex.
  • Plain knit fabrics were made from these respective yarns and cross-linking of the resin and polymer on each of the fabrics was effected by heating the fabrics at a temperature of 140°C for 10 minutes. In fact, cross-linking would be effected in a shorter time than this but an excess time was used to be certain of full curing.
  • the dried, impregnated tows produced according to Examples 1 and 2 were then tested for evenness of dyeing of the fibres in blends with cotton.
  • staple fibres of 38 mm staple length were cut from the respective tows, and, in each case, these were blended with combed cotton fibres in a 50:50 weight blend.
  • the respective blends of fibres were each spun into yarn of count 30s Ne, and these respective yarns were knitted into respective fabrics of a double jersey interlock construction of basis weight 200 gsm (grams per square metre).
  • Cross-linking of the resin on the respective fabrics was effected by heating the fabrics in a stenter oven at a temperature of 170°C for 1 minute.
  • a fabric of the same construction was made from yarn of the same count spun from a 50:50 weight blend of combed cotton fibres and lyocell staple fibres which had not been treated with the cross-linking resin and PEG.
  • Each of the fabrics was slit and pre-set at a temperature of 170°C for 1 minute before being re-sewn into tubular form and loaded into a jet dyeing machine.
  • the fabrics were first scoured in an aqueous bath containing 2 g/l A-lube P60 (a lubricant), 2 g/l Sandoclean PCT (a detergent) and 2g/l soda ash for 30 minutes at a temperature of 80°C.
  • the scoured fabrics were then successively rinsed in hot and then cold water before being dyed brown using hot-dyeing reactive dyes by the hot migration method.
  • the aqueous dyebath comprised (percentages by weight):
  • the bath was set with the dyeing auxiliaries at a temperature of 50°C.
  • the dyes were then added to the bath whilst raising the bath temperature to 95°C at a rate of 2°C per minute.
  • the dyebath was held at this temperature for 30 minutes before being cooled to a temperature of 80°C.
  • the soda ash was then added to the dyebath in two successive portions (one third and then two thirds) over 15 minutes, after which the machine continued to run for a further 60 minutes.
  • the dyebath was then cooled to a temperature of 50°C before being dropped from the machine.
  • the dyed fabrics were then rinsed and boiled off in the machine.
  • the fabrics were given a softening treatment for 20 minutes using an aqueous soft-finish bath at a temperature of 40°C and comprising (percentages by weight):
  • Both of the fabrics made according to Examples 1 and 2 became evenly dyed to a solid shade of brown, being free from any skittery or marl appearance.
  • the control fabric became dyed to a shade of brown having an uneven mottled appearance arising from the differential dyeing of the lyocell and cotton components.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Coloring (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (19)

  1. Prozess zum Herstellen eines sowohl Baumwollfasern als auch künstliche Zellulosefasern enthaltenden, gleichmäßig gefärbten Stoffs, in dem ein Stoff aus diesen Fasern hergestellt und gefärbt wird, gekennzeichnet durch Imprägnieren der künstlichen Zellulosefasern vor der Herstellung des Stoffs mit einem wasserlöslichen, flexiblen linearen Polymer und einem Vernetzungsmittel, das mit Zellulose reagiert, und auf einer Stufe des Prozesses vor dem Färben des Stoffes Ausführen einer Vernetzungsreaktion zwischen den künstlichen Zellulosefasern und dem Vernetzungsmittel, um dadurch eine Reduzierung der Farbstoffaffinität der künstlichen Zellulosefasern auf ein Niveau, das näher bei der Farbstoffaffinität der Baumwollfasern liegt, hervorzurufen.
  2. Prozess nach Anspruch 1, dadurch gekennzeichnet, dass die Farbstoffaffinität der künstlichen Zellulosefasern durch die Vernetzungsreaktion auf ein Niveau innerhalb von 15 Prozent der Farbstoffaffinität der Baumwollfasern, gemessen durch den hier spezifizierten Farbstoffaffinitätstest, reduziert wird.
  3. Prozess nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass die künstlichen Zellulosefasern Lyozellenfasern sind.
  4. Prozess nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die künstlichen Zellulosefasern imprägniert werden durch Anwenden einer Lösung des wasserlöslichen, flexiblen linearen Polymers und des Vernetzungsmittels auf die künstlichen Zellulosefasern, während sie in Form eines niemals trockenen Taus sind.
  5. Prozess nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass nach dem Imprägnieren der künstlichen Zellulosefasern mit dem wasserlöslichen, flexiblen linearen Polymer und dem Vernetzungsmittel die künstlichen Zellulosefasern mit den Baumwollfasern gemischt werden, aus den gemischten Fasern Garn hergestellt wird, aus dem Garn Stoff hergestellt wird und die Vernetzungsreaktion an dem Garn oder an dem Stoff ausgeführt wird.
  6. Prozess nach Anspruch 5, dadurch gekennzeichnet, dass der aus dem Garn hergestellte Stoff ein gewebter Stoff ist und die Vernetzungsreaktion an dem Garn ausgeführt wird.
  7. Prozess nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Vernetzungsmittel ein Vernetzungsmittel ohne oder mit niedrigem Formaldehydgehalt ist, das zusammen mit einem Vernetzungskatalysator verwendet wird.
  8. Prozess nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das flexible lineare Polymer funktionale Endgruppen besitzt.
  9. Prozess nach Anspruch 8, dadurch gekennzeichnet, dass das flexible lineare Polymer ein polymerisiertes Glycol ist.
  10. Prozess nach Anspruch 9, dadurch gekennzeichnet, dass das flexible lineare Polymer Polyethylenglycol (PEG) ist.
  11. Prozess nach Anspruch 10, dadurch gekennzeichnet, dass das PEG ein durchschnittliches Molekulargewicht im Bereich von 200 bis 2000 besitzt.
  12. Prozess nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die Menge des flexiblen linearen Polymers, die auf die künstlichen Zellulosefasern aufgebracht wird, im Bereich von 0,1 bis 3 Gewichtsprozent bezogen auf das Zellulosegewicht liegt.
  13. Prozess nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Menge des Vernetzungsmittels, das auf die künstlichen Zellulosefasern aufgebracht wird, im Bereich von 0,2 bis 5, vorzugsweise im Bereich von 1 bis 4 Gewichtsprozent bezogen auf das Zellulosegewicht liegt.
  14. Ungefärbtes faserartiges Produkt, das sowohl Baumwollfasern als auch künstliche Zellulosefasern enthält, dadurch gekennzeichnet, dass nur die künstlichen Zellulosefasern mit einem wasserlöslichen, flexiblen linearen Polymer und mit einem Vernetzungsmittel, das mit Zellulose reagiert, imprägniert sind, wobei die imprägnierten künstlichen Zellulosefasern noch nicht vernetzt sind, jedoch das Potential einer reduzierten Farbstoffaffinität, die näher bei der Farbstoffaffinität der Baumwollfasern liegt, haben, wenn eine Vernetzungsreaktion zwischen den künstlichen Zellulosefasern und dem Vernetzungsmittel vor dem Färben des faserartigen Produkts vorgenommen wird.
  15. Ungefärbtes faserartiges Produkt nach Anspruch 14, gekennzeichnet durch ein ungefärbtes Fasergemisch aus den Baumwollfasern und den imprägnierten künstlichen Zellulosefasern oder ein aus einem solchen Fasergemisch hergestelltes Garn oder einen aus einem solchen Garn hergestellten Stoff.
  16. Ungefärbtes faserartiges Produkt, das Baumwollfasern und künstliche Zellulosefasern enthält, dadurch gekennzeichnet, dass nur die künstlichen Zellulosefasern mit einem wasserlöslichen, flexiblen linearen Polymer und mit einem Vernetzungsmittel, das mit der Zellulose der künstlichen Zellulosefasern in einer Vernetzungsreaktion reagiert hat, imprägniert sind, wobei die Vernetzung die Farbstoffaffinität der künstlichen Zellulosefasern auf ein Niveau reduziert hat, das näher bei jenem der Farbstoffaffinität der Baumwollfasern liegt.
  17. Ungefärbtes faserartiges Produkt nach Anspruch 16, dadurch gekennzeichnet, dass die Farbstoffaffinität der vernetzten künstlichen Zellulosefasern ein Niveau innerhalb von 15 Prozent der Farbstoffaffinität der Baumwollfasern, gemessen durch den hier spezifizierten Farbstoffaffinitätstest, hat, wobei als 100-Prozent-Kontrollwert Baumwolle verwendet wird.
  18. Ungefärbtes faserartiges Produkt nach Anspruch 16 oder Anspruch 17, dadurch gekennzeichnet, dass das faserartige Produkt ein ungefärbtes Garn oder ein ungefärbter Stoff ist.
  19. Faserartiges Produkt, dadurch gekennzeichnet, dass es einen Stoff ansonsten nach einem der Ansprüche 16 bis 18 enthält, der nicht mehr ungefärbt ist, sondern gleichmäßig in einen kräftigen Farbton gefärbt ist.
EP05794754A 2004-10-20 2005-10-20 Verfahren zum vernetzen und färben von cellulosefasern Active EP1828451B1 (de)

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GBGB0423296.3A GB0423296D0 (en) 2004-10-20 2004-10-20 Cross-linking and dyeing cellulose fibres
PCT/GB2005/004052 WO2006043070A2 (en) 2004-10-20 2005-10-20 Cross-linking and dyeing cellulose fibres

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CN102747569B (zh) * 2012-06-21 2014-02-05 广东德美精细化工股份有限公司 活性染料轧染染色方法
CN103510383B (zh) * 2013-09-10 2016-04-27 上海工程技术大学 一种提高Lyocell竹纤维抗皱防缩性能的方法
CN110172754B (zh) * 2019-02-26 2021-10-08 东华大学 一种抗原纤化纤维素类纤维的制备方法
CN115627632A (zh) * 2022-10-12 2023-01-20 中国纺织科学研究院有限公司 一种莱赛尔短纤维的制备方法及莱赛尔短纤维

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US3824172A (en) * 1972-07-18 1974-07-16 Penn Olin Chem Co Electrolytic cell for alkali metal chlorates
DE2836609A1 (de) * 1977-08-26 1979-03-08 Ciba Geigy Ag Verfahren zum ton-in-ton klotzfaerben oder bedrucken von textilmaterial aus mischfasern aus cellulose und synthetischem material
US4780102A (en) * 1985-10-18 1988-10-25 The United States Of America As Represented By The Secretary Of Agriculture Process for dyeing smooth-dry cellulosic fabric
GB9304887D0 (en) * 1993-03-10 1993-04-28 Courtaulds Plc Fibre treatment
WO2001073186A2 (en) * 2000-03-29 2001-10-04 The Procter & Gamble Company Methods for improving fibrillation or pill resistance of fabrics and fabrics with improved properties
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WO2006043070A3 (en) 2006-07-20
WO2006043070A2 (en) 2006-04-27
TW200615427A (en) 2006-05-16
PT1828451E (pt) 2011-03-16
GB0423296D0 (en) 2004-11-24
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KR20080084561A (ko) 2008-09-19
KR101245390B1 (ko) 2013-03-19
CN101076623A (zh) 2007-11-21

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