EP0129322B1 - Verfahren zum Behandeln von Wolle - Google Patents

Verfahren zum Behandeln von Wolle Download PDF

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Publication number
EP0129322B1
EP0129322B1 EP84303233A EP84303233A EP0129322B1 EP 0129322 B1 EP0129322 B1 EP 0129322B1 EP 84303233 A EP84303233 A EP 84303233A EP 84303233 A EP84303233 A EP 84303233A EP 0129322 B1 EP0129322 B1 EP 0129322B1
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EP
European Patent Office
Prior art keywords
wool
polymer
weight
amino
dry
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Expired - Lifetime
Application number
EP84303233A
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English (en)
French (fr)
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EP0129322A3 (en
EP0129322A2 (de
Inventor
Ronald James Haslam
Kenneth Michael Huddlestone
Herbert Martin Longbottom
Anthony Szpala
Petrus Theodorus Cornelia De Waal
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Precision Processes Textiles Ltd
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Precision Processes Textiles Ltd
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Priority to AT84303233T priority Critical patent/ATE57546T1/de
Publication of EP0129322A2 publication Critical patent/EP0129322A2/de
Publication of EP0129322A3 publication Critical patent/EP0129322A3/en
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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
    • 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
    • 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
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups

Definitions

  • This invention relates to improvements in the treatment of wool to impart shrink resistance thereto and is more especially concerned with the treatment of materials consisting of or containing wool which are available in continuous lengths, or which can readily be joined together into a continuous form to enable the same to be subjected to substantially uniform treatment.
  • Woollen materials which are available in continuous lengths include yarns, tops and woven and knitted fabrics consisting of or containing wool. Such lengths may also be formed by sewing together knitted garments such as socks: these are then separated after completion of the treatment.
  • the invention can also be applied to loose wool.
  • means are required for transporting loose wool in a continuous fashion.
  • Such means are known in the field and include conveyor belts and rotating rake systems.
  • Amino-acrylic polymers are well known and are described, for example, in British Patent Nos. 1318781 and 1393273. The use of such polymers for the shrink-proofing of wool has been suggested, for example in U.S. Patent Nos. 3678098 and 3842054, although not it is believed in a two-stage continuous process.
  • FR-A-2156036 describes a shrink-resist process which comprises treating wool fibres with an oxidizing agent and then with an aqueous composition comprising a minor proportion of a water-soluble cationic resin and a major proportion of a dispersed acrylic copolymer capable of reaction with the cationic resin.
  • the present invention results from our discovery that certain polymers containing quaternized amino groups confer surprisingly good shrink-resistance and other advantages when used in a two-stage treatment of the conventional kind.
  • Preferred forms of the invention overcome each of the three disadvantages noted above.
  • a major advantage of the present process is that it requires significantly less energy than other conventional shrink-proofing processes, in order to achieve a comparable degree of drying of the wool. Indeed, it is estimated that there is at least a 20% saving in energy over such processes.
  • wool treated by the present process requires less heat treatment than wool treated by known processes.
  • the wool is preferably dried to a moisture level of 12-15% (by weight), whereas conventional processes involve drying to a lower moisture content. A low moisture level may lead to handling difficulties during subsequent processing of the wool.
  • the temperature of the drier can be reduced, thus saving power.
  • the drying time can be reduced, thus increasing throughput.
  • chlorinating pretreatment is a conventional procedure and a number of suitable treatments are already well known.
  • Chlorinating agents such as hypochlorite or sodium dichloroisocyanurate may be employed, (optionally together with potassium permanganate or permonosulphate) at levels of 0.25-2.0% active chlorine, by weight on the weight of the dry wool (O.W.W.), most preferably 0.5-1.2%.
  • active chlorine by weight on the weight of the dry wool (O.W.W.), most preferably 0.5-1.2%.
  • the pretreatment wii by itself, produce a small degree of shrink-resistance in the wool.
  • the wool is subjected to antichlorination treatment with sulphite and rinsed and is then ready for the polymer application stage.
  • the polymer used contains quaternized amino groups in sufficient proportion to cause the polymer to exhaust from aqueous solution on to the (anionic) wool fibres.
  • the polymer is derived from a monomer or polymer containing tertiary amino groups, some or preferably all of these are quaternized, sufficient to confer the desired cationic character on the polymer.
  • the polymers may be homopolymers or copolymers. Two classes of such polymers are described, of which B) is preferred:-A) Polymers derived from at least one acrylic monomer and one or more monomers at least one of which is a heterocyclic compound carrying an ethylenically unsaturated group.
  • Heterocyclic compounds with tertiary nitrogen atoms which can be quaternized include pyridine and imidazole.
  • Monomers from which the polymers can be derived include 2- and 4-vinyl pyridines and 2- and 4-vinyl imidazoles.
  • Tertiary nitrogen atoms may be quaternized before or after polymerisation of the monomers. Quaternisation techniques are well known in the art and will not be described here. Quaternizing agents may be monofunctional or polyfunctional, and it may be useful to use a polyfunctional agent either alone or in admixture with a monofunctional one, in order to achieve some degree of cross-linking of the polymers after application to the wool fibres.
  • Suitable quaternizing agents include:
  • Monomers containing tertiary nitrogen atoms may be homopolymerized, or alternatively may be copolymerized with one or more other monomers such as:-
  • this other monomer may be chosen to impart desired properties to the copolymer.
  • acrylamide may give rise to a copolymer having greater water-solubility than does methyl methacrylate.
  • the molar proportion of the amino-group-containing monomer in the polymer (100% in homopolymers, less than 100% in copolymers) is chosen with various factors in mind. The proportion must be sufficiently large for the polymer to be soluble in water at the required concentration and to exhaust on to wool fibres. at a satisfactory rate. If the proportion is too high, then the shrink-resist properties of the polymer on the wool may not be realised immediately or may be affected by subsequent dyeing or washing treatments, or dye uptake and fastness may be adversely affected.
  • the polymers may be prepared by solution polymerisation in a water-miscible organic solvent.
  • the proportion of amino-group-containing monomer(s) needs to be chosen bearing in mind the need to perform the polymerisation and subsequent quaternization reactions in solution.
  • a chain transfer agent may be included. Isopropanol is a suitable solvent and has the advantage of acting also as a chain transfer agent.
  • Polymerization conditions are well known in the art and not critical. Preferred conditions result in a concentrated solution of polymer in 50:50 isopropanol:water. This is diluted with water to 5% solids for eventual use as make-up for the treatment bath. In continuous operation, the polymer concentration in the bath reaches an equilibrium value generally in the range 0.1 % to 1% by weight.
  • polymers are water-soluble under acid conditions, and are preferably stored and transported at a pH of from 3 to 6. Under alkaline conditions, cross-linking may occur, particularly when quaternization has been effected using a difunctional agent such as epichlorhydrin.
  • a feature of the present process is that very low levels of polymer may be used and still produce acceptable shrink-resist properties.
  • the precise level of polymer employed will depend on the concentration of chlorine used in the pretreatment, i.e. use of a high level of chlorine will generally mean that a lower level of polymer is required and vice-versa.
  • the polymer should be applied to the wool at a level of 0.4-2.0% (o.w.w.), preferably 0.5-0.8%.
  • the aqueous polymer solution should be acid stabilised (preferably pH 3.5-4.0) and diluted to approximately 5% solids before being fed to the application bowl.
  • the application bowl itself should be previously set at an alkaline pH (in the range pH 7-10 preferably pH 8.5-9.5) and maintained at this value by the addition of an agent such as sodium carbonate.
  • a preferred solution to the problem comprises the use of a water-soluble cationic material which may be either monomeric or polymeric. This material should react preferentially with the proteinaceous material and keep it in solution or suspension. It should be used in an amount small enough as not to substantially affect the exhaustion of the polymer on to the wool fibres; an amount of from 2% to 20% by weight on the weight of the polymer is suitable.
  • the material may be added to the polymer concentrate followed by dilution of the mixture to the desired concentration for addition to the treatment bath.
  • Suitable materials are available commercially; their chemical constitutions are often not published in detail, but it is believed that they generally contain tertiary or quaternary nitrogen atoms:-
  • the wool is dried.
  • the drying stage requires significantly less energy than that required by other comparable shrink-proofing processes, in order to achieve the same degree of drying of the wool. Indeed, care must be taken to avoid over drying the wool since this may cause handling problems due to the development of static electricity.
  • Example 1 demonstrates the effectiveness of various polymers according to the present invention in imparting shrink-resistance to wool.
  • Examples 2 and 3 are comparative Examples serving to demonstrate the advantages of the present process over various other commercially available shrink-proofing processes.
  • Example 4 relates to a number of industrial trials which have been carried out to illustrate the improved drying properties exhibited by the process of the invention.
  • Example 5 is a comparative Example illustrating the effectiveness of the additive in reducing turbidity and precipitation in the polymer bowl.
  • Wool tops were oxidatively treated by the chlorination process ii) of Example 1 and spun and knitted into fabric.
  • Polymer was then applied to the fabric by exhaustion from a bath at pH 9.0.
  • Wool tops were treated according to the process of the invention on a commercial backwasher range and dried by passing through a 3 drum dryer operating deliberately at a high temperature of 90°C. A quantity of tops were removed before entering the dryer and allowed to dry at room temperature. Samples were then immediately spun to 2/24's worsted count, knitted and tested according to the TM 185 test.
  • Example 1 ii) using polymer b The treatment substantially as described in Example 1 ii) using polymer b), has been applied in a series of trials on three industrial plants which normally operate the same oxidative process as that being used for the pretreatment in these experiments. In each case the trials were run for approximately 1 hour with the machine speed and the initial dryer temperature being the same as for normal production.
  • This plant has a 3 drum dryer, normal temperature being 100,90 and 85°C. Using these conditions the emerging wool was excessively over-dried.
  • Dryer temperature were reduced to 75-80°C on all drums, the wool being well dried throughout.
  • Normal dryer temperature is 60-70°C.
  • the wool was over-dry and gave problems on leaving the dryer due to electrostatic charge. Rapid cooling of the dryer by opening the side doors improved the running, the wool still being dry.
  • Dryer temperature was at 50-60°C. Problems were still encountered at the beginning of the run. Steam was turned off entirely and the run was completed with the wool satisfactorily dry.
  • the wool was dried to a moisture content below 18% using at least 20% less energy than had been required to dry to the same moisture content the wool routinely shrink-resist treated in that plant.
  • the pre-treated sliver then passed through a four bowl backwasher where they were successively given an antichlorination treatment, a water rinse, application of a polymer, and finally, application of a cationic softener.
  • the sulphite bowl was maintained at a concentration of 1% and pH 8.5-9.0 by appropriate addition of sulphite solution and alkali.
  • the polymer bowl was fed with a 5% solution of polymer type (b) at a rate to give 0.75% polymer solids on weight of wool passing through the bowl.
  • the pH of the bath was maintained at pH 8.5-9.0 by addition of alkali.

Claims (10)

1. Kontinuierliches Verfahren zur Herstellung von einlauffester Wolle, welches die folgenden Schritte umfaßt:
(i) die Wolle wird durch oxidierendes Chlorieren vorbehandelt;
(ii) danach wird die Wolle in einer wäßrigen Polymerlösung behandelt, sodaß sich das Polymer auf den Wollfasern festsetzt; und
(iii) die Wolle wird bis zu einem gewählten Feuchtigkeitsgrad getrocknet; dadurch gekennzeichnet, daß in Schritt ii) ein wasserlösliches Acrylpolymer, das quaternisierte Aminogruppen enthält, verwendet wird, und daß die Wolle in Schritt iii) bis zu einer Feuchtigkeit von 12 bis 18 Gewichts % vom Gewicht der trockenen Wolle getrocknet wird.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Vorbehandlung durch Chlorieren auf einem Pegel von 0.25-2.0 Gewichts % aktivem Chlor (bezogen auf das Gewicht der trockenen Wolle) durchgeführt wird.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Polymer ein Copolymer von mindestens einem Monomer, das eine Aminogruppe enthält, und mindestens einem anderen Monomer ist, in welchem das Molverhältnis des Monomers, das die Aminogruppe enthält (der Monomere, die die Aminogruppe enthalten) zu dem(den) anderen Monomer(en) von 1:1 bis 1:10 beträgt.
4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Polymer von mindestens einem Amino-Acrylmonomer abgeleitet ist.
5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Grad des auf die Wolle aufgebrachten Polymers 0.4-2.0 Gewichts % (bezogen auf das Gewicht der trockenen Wolle) beträgt.
6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Polymer Aminogruppen enthält, die durch Epichlorhydrin quaternisiert wurden.
7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Polymer in Gegenwart eines wasserlöslichen kationaktiven Materials auf die Wolle aufgebracht wird.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß das wasserlösliche kationaktive Material die Formel
Figure imgb0008
 hat, wo
R: C1-C22-Alkyl oder -Alkenyl ist,
R1: H oder CH3, und
x+y=2-40 ist.
9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß das Material in einem Ausmaß von 2-20 Gewichts % vom Gewicht des Polymer vorhanden ist.
10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Wolle bis zu einem Feuchtigkeitsgrad von 12-15 Gewichts% getrocknet wird.
EP84303233A 1983-05-13 1984-05-11 Verfahren zum Behandeln von Wolle Expired - Lifetime EP0129322B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84303233T ATE57546T1 (de) 1983-05-13 1984-05-11 Verfahren zum behandeln von wolle.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB838313262A GB8313262D0 (en) 1983-05-13 1983-05-13 Method of treating wool
GB8313262 1983-05-13

Publications (3)

Publication Number Publication Date
EP0129322A2 EP0129322A2 (de) 1984-12-27
EP0129322A3 EP0129322A3 (en) 1987-08-05
EP0129322B1 true EP0129322B1 (de) 1990-10-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP84303233A Expired - Lifetime EP0129322B1 (de) 1983-05-13 1984-05-11 Verfahren zum Behandeln von Wolle

Country Status (8)

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EP (1) EP0129322B1 (de)
JP (1) JPS59228082A (de)
AT (1) ATE57546T1 (de)
BE (1) BE899657A (de)
DE (1) DE3483407D1 (de)
GB (1) GB8313262D0 (de)
IT (1) IT1173633B (de)
ZA (1) ZA843625B (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3544958A1 (de) * 1985-12-19 1987-06-25 Hansa Textilchemie Gmbh Verfahren zum ausruesten von maschenware
GB8725921D0 (en) * 1987-11-05 1987-12-09 Precision Proc Textiles Ltd Treatment of wool
FR2708943B1 (fr) * 1993-08-09 1995-09-29 Protex Manuf Prod Chimiq Procédé d'amélioration de la stabilité des fibres de laine.
FR2827314B1 (fr) * 2001-07-13 2004-07-23 Protex Additif exempt de formaldehyde pour une composition de traitement destinee a ameliorer l'infroissabilite et/ou la stabilite dimensionnelle d'un support textile
DE102005062164A1 (de) * 2005-12-22 2007-06-28 Lanxess Deutschland Gmbh Verfahren zur Antifilzausrüstung von Wolle

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3678098A (en) * 1969-04-04 1972-07-18 Rohm & Haas Unsaturated quaternary monomers and polymers
US3842054A (en) * 1971-04-05 1974-10-15 Hercules Inc Vinyl-type addition polymers containing a plurality of tertiary nitrogens quaternized with an epihalohydrin
BE789701A (fr) * 1971-10-06 1973-02-01 Iws Nominee Co Ltd Procede en vue de rendre la laine irretrecissable

Also Published As

Publication number Publication date
EP0129322A3 (en) 1987-08-05
JPS633077B2 (de) 1988-01-21
JPS59228082A (ja) 1984-12-21
EP0129322A2 (de) 1984-12-27
IT8420894A0 (it) 1984-05-11
ATE57546T1 (de) 1990-11-15
IT8420894A1 (it) 1985-11-11
ZA843625B (en) 1985-04-24
IT1173633B (it) 1987-06-24
DE3483407D1 (de) 1990-11-22
GB8313262D0 (en) 1983-06-22
BE899657A (fr) 1984-08-31

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