EP0032637B1 - Apprêt textile - Google Patents

Apprêt textile Download PDF

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Publication number
EP0032637B1
EP0032637B1 EP19800304771 EP80304771A EP0032637B1 EP 0032637 B1 EP0032637 B1 EP 0032637B1 EP 19800304771 EP19800304771 EP 19800304771 EP 80304771 A EP80304771 A EP 80304771A EP 0032637 B1 EP0032637 B1 EP 0032637B1
Authority
EP
European Patent Office
Prior art keywords
polymer
articles
titanium
felt
chlorinated
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.)
Expired
Application number
EP19800304771
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German (de)
English (en)
Other versions
EP0032637A2 (fr
EP0032637A3 (en
Inventor
Ladislav Benisek
Penelope Christine Craven
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.)
Wool Development International Ltd
Original Assignee
Wool Development International Ltd
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Filing date
Publication date
Application filed by Wool Development International Ltd filed Critical Wool Development International Ltd
Priority to AT80304771T priority Critical patent/ATE13450T1/de
Publication of EP0032637A2 publication Critical patent/EP0032637A2/fr
Publication of EP0032637A3 publication Critical patent/EP0032637A3/en
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Publication of EP0032637B1 publication Critical patent/EP0032637B1/fr
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Classifications

    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
    • D06M13/262—Sulfated compounds thiosulfates
    • 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
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • 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
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof

Definitions

  • This invention relates to a method of finishing keratinous fibres to render textile articles made from such fibres resistant to area felting shrinkage and flame-retardant.
  • Keratinous fibres e.g. wool
  • Keratinous fibres are naturally flame retardant, but increasing stringency of regulations in various countries has meant that certain constructions of wool fabrics, or fabrics for certain end uses, e.g. in aeroplanes, and for clothing to provide protection against heat and flames, require an additional flame retardancy treatment.
  • the titanium and zirconium flame retardancy treatments described in our U.K. Patent Nos. 1,372,694 and 1,379,752 have proved eminently suitable for improving the flame retardancy of wool textiles to meet the standards imposed by various legislative bodies.
  • a method of finishing keratinous textile articles which comprises treating the articles with an anti-felt polymer and an anionic titanium or zirconium complex characterised in that the anti-felt polymer is applied with a polymer of chlorinated ethylenically unsaturated monomer, and thereafter the articles are treated with the anionic titanium or zirconium complex at pH 4 or less.
  • the process is generally applicable to water-soluble curable shrink-resist polymers and prepolymers and especially those having ionic charges.
  • Isocyanate functional polymers, and especially blocked isocyanate polymers are preferred particularly water-soluble blocked isocyanates such as polycarbamoyl sulphonates.
  • suitable polymers include polycarbamoyl sulphonates, Bunte salt polymers, the amphoteric polymers of our British Patent No. 1,547,958, and anionic acrylate emulsions.
  • Cationic polymers such as a polyamideephichlorhydrin polymer, or azetidinium polymers, may also be used provided they are compatible with the chlorinated polymer emulsion used, if a cationic emulsion is employed.
  • chlorinated polymer emulsions which are anionic, it is preferred to use anionic anti-felt polymers.
  • anionic anti-felt polymers Especially preferred are the polycarbamoyl sulphonates described in U.K. Patent No. 1,419,306. These may conveniently be prepared from polymeric di- or poly-isocyanates by treatment with sodium bisulphite.
  • Preferred polycarbamoyl sulphonates have polyoxyalkylene, e.g. polypropylene oxide, backbones and three carbamoyl sulphonate groups.
  • Particularly preferred compounds have the following structure: wherein
  • Preferred curable polymeric materials have a polymeric chain backbone and at least two thiosulphate groups per molecule.
  • the chain may advantageously be a polyoxyalkylene, e.g. polyoxypropylene, chain.
  • Particularly preferred materials of this type have the following structural formula: where n is about 13.
  • the polymer of a chlorinated ethylenically unsaturated monomer combines with the anti-felt polymer to give a shrink-resist effect, and thus allows less polymer to be used that would be necessary if it were used alone. Since the chlorinated polymers in general do not add to the fuel contribution of the textile and may even impart a degree of flame retardance, a net lowering of the fuel contribution of the shrink-resist treatment can be obtained.
  • the surprising properties of these polymers lie in their capacity both to enhance the shrink-resist qualities of other polymers, particularly polycarbamoyl sulphonates and Bunte salts, and enhance the flame retardant properties of the titanium and zirconium complexes.
  • the chlorinated polymers which may be used include in general, polyvinyl chloride, polyvinylidene chloride, polychloroprene, and dichlorobutadiene.
  • polyvinyl chloride polyvinylidene chloride
  • polychloroprene polychloroprene
  • dichlorobutadiene a polymer which may be used.
  • the higher the chlorine content of the polymer the better its flame retardancy characteristics, but this criterion is affected by other factors.
  • Most of these polymers are too hard alone and therefore are available as copolymers with such monomers as acrylonitrile or methacrylic acid. The latter add to the fuel contribution of the copolymer and in certain cases may render the polymer unsuitable.
  • most commercially available polyvinylchloride compositions are unsuitable.for this reason.
  • the preferred chlorinated polymers are Polidene 33-041 (a polyvinylidene chloride copolymer - trade mark of Scott Bader Co. Ltd.) and Neoprene 400 (a copolymer of polychloroprene and 2,3-dichloro-1,3-butadiene - Du Pont), especially the latter.
  • the treatment with titanium or zirconium may be carried as described in our above U.K. Patents.
  • the metals are applied, preferably by exhaustion as anionic complexes with flouride, citrato, or tartrato ions at a PH in the range 1 to 4.
  • the titanium treatment is more effective, weight for weight, than the zirconium treatment but leads to a slight yellow colouration and should generally be used only with dark shades or where colouration is immaterial.
  • the quantities of agents may vary within wide limits subject to the desired degree of shrink-resistance, the flame retardancy required, and such factors as the substrate, coreactants, and so on.
  • the anti-felt prepolymer may be applied in the range 0.1 to 10% oww, preferably 0.2 to 2%, the lowest amount compatible with adequate shrink-resistance being chosen.
  • the chlorinated polymer may be used in amounts of from 1 % to 10%, with 1. to 4% being preferred.
  • the titanium or zirconium treatments may be applied in the ranges of 0.5% to 2.5% or 1% to 5% respectively (calculated as oxide) again depending on the substrate and the level of flame retardancy required.
  • the keratinous fibres may be for example mohair, alpaca, vicuna, angora, or especially wool
  • the textile article may be in the form of loose stock, slivers, slubbings, rovings, yarns, fabrics, made-up garments or carpets, preferably fabrics.
  • the shrink-resist treatment may be carried out in any suitable manner e.g. exhaustion, dipping, spraying or padding, preferably the latter, and the flame retardancy treatment is preferably carried out by exhaustion from long liquor.
  • Lankrolan SHR3 and Neoprene 400 were padded onto a wool serge fabric. The fabric was dried and then cured at 150°C for 5 minutes. A titanium flame retardant treatment was applied by immersing the fabric at 1:20 liquor ratio in a bath containing 10% oww HCI (37%) 4% oww citric acid and 6% oww K 2 TiF 6 for 30 minutes at 60°C, liquor ratio 1:30, by rinsing and drying.
  • the Lankrolan SHR3 treatment is not compatible with the titanium flame-retardant treatments (Examples Nos. 1-3).
  • the addition of Neoprene 400to the Lankrolan SHR3 not only makes the shrink-resist treatment compatible with the flame retardant treatment but it also allows a lower concentration of Lankrolan SHR3 to be used to achieve adequate shrink-resistance (Examples Nos. 4-10).
  • the incorporation of Neoprene 400 imparts flame-resistance to Lankrolan SHR3 and it also acts as a shrink-resist agent.
  • Synthappret BAP (0.4% oww) NaHC0 3 (1 % oww) and Neoprene 400 (3%) were padded onto a wool serge fabric. The fabric was dried and then cured at 140°C for 5 minutes. Zirconium flame retardant treatment was applied by immersing the fabric at 1:20 liquor ratio in a bath containing 10% oww HCI (37%), 4% oww citric acid and 8% oww K 2 ZrF 6 for 30 minutes at 70°C, followed by rinsing and drying.
  • the area felting shrinkage of the fabric was zero after 1 hour and 2% after 3 hours test; and the fabric passed the FAR 25.853b test in both the warp and weft directions. It was also observed that the smooth drying properties of the fabric given this treatment was exceptionally good, and that the spray rating, according to B.S. 3702, was unchanged by the treatment. A similar fabric given a chlorination treatment showed a marked deterioration in spray rating.
  • An all-wool gaberdine fabric 270 g/m 2
  • the fabric was given a Zirpro treatment with 10% Hêl (37%), 4% citric acid, and 6% K 2 Ti F 6 for 30 minutes at 70°C at a fabric-to-liquor ratio of 1:25.
  • Example 20 was repeated with the inclusion of 3% FC214 (a fluorocarbon supplied by the 3M Company) in the Zirpro treatment.
  • FC214 a fluorocarbon supplied by the 3M Company
  • the process of the invention enables a shrink-resistant and flame retardant finish to be applied to wool fabrics by a simple route using commercially available chemicals, without adversely affecting properties such as water-repellency.

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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)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (11)

1. Procédé pour l'apprêtage d'articles textiles kératiniques qui consiste à traiter les articles avec un polymère anti-feutrage et un complexe anionique titane ou zirconium, caractérisé en ce qu'on applique le polymère anti-feutrage avec un polymère d'un monomère chloré éthyléniquement non saturé, après quoi, on traite les articles avec le complexe anionique titane ou zirconium à un pH de 4 ou moins.
2. Procédé selon la revendication 1, caractérisé en ce que le polymère anti-feutrage est un polymère fonctionnel d'isocyanate ou un polymère fonctionnel d'un sel de Bunte.
3. Procédé selon la revendication 2, caractérisé en ce que le polymère est un sulfonate de polycarbamoyle.
4. Procédé selon la revendication 2, caractérisé en ce que le polymère présente la structure suivante:
Figure imgb0008
ou
Figure imgb0009
où n est égal à environ 13.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le polymère chloré est du chlorure de polyvinyle, de polyvinylidène, du polychloroprène ou du dichlorobutadiène.
6. Procédé selon la revendication 5, caractérisé en ce que le polymère chloré est un copolymère de polychloroprène et de 2,3-dichloro-1,3-butadiène.
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le titane ou le zirconium est appliqué par épuisement sous forme de complexe anionique avec des ions de fluorure, citrate ou tartrate, à un pH de l'ordre de 1 à 4.
8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le polymère anti-feutrage est présent sur les articles à raison de 0,2 à 2% en poids, le polymère chloré est présent sur les articles à raison de 1 à 4% en poids et le titane ou le zirconium est présent à raison de 0,5 à 2,5% ou de 1 à 5% en poids, respectivement (calculé sous forme d'oxyde).
9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que les fibres kératiniques sont des fibres de laine.
10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'article textile est un tissu.
11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que les polymères sont appliqués par épuisement, trempage, aspersion ou tamponnage.
EP19800304771 1980-01-16 1980-12-31 Apprêt textile Expired EP0032637B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80304771T ATE13450T1 (de) 1980-01-16 1980-12-31 Textilveredlung.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8001470 1980-01-16
GB8001470 1980-01-16
GB8006507 1980-02-26
GB8006507 1980-02-26

Publications (3)

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EP0032637A2 EP0032637A2 (fr) 1981-07-29
EP0032637A3 EP0032637A3 (en) 1982-12-15
EP0032637B1 true EP0032637B1 (fr) 1985-05-22

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Family Applications (1)

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EP (1) EP0032637B1 (fr)
DE (1) DE3070684D1 (fr)
ES (1) ES8500363A1 (fr)
GB (1) GB2069019B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2415879A1 (fr) 2010-08-06 2012-02-08 LANXESS Deutschland GmbH Compositions comprenant au moins un composé contenant des groupes carbamoylsulfonates et leur utilisation comme agents de tannage

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1257107A (fr) * 1969-05-07 1971-12-15
GB1372694A (en) * 1970-10-22 1974-11-06 Iws Nominee Co Ltd Textile finishing
GB1379752A (en) * 1971-03-18 1975-01-08 Iws Nominee Co Ltd Zirconium flame-resist treatment
GB1423342A (en) * 1971-12-09 1976-02-04 Iws Nominee Co Ltd Polymeric compounds and process for their preparation
BE795575A (fr) * 1972-02-18 1973-06-18 Commw Scient Ind Res Org Procede de traitement de matieres keratiniques
GB1547958A (en) * 1975-03-06 1979-07-04 Iws Nominee Co Ltd Amphoteric polymers and process for their use

Also Published As

Publication number Publication date
GB2069019A (en) 1981-08-19
EP0032637A2 (fr) 1981-07-29
DE3070684D1 (en) 1985-06-27
ES498518A0 (es) 1984-10-01
EP0032637A3 (en) 1982-12-15
GB2069019B (en) 1983-03-16
ES8500363A1 (es) 1984-10-01

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