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
  • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
  • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
  • D06C29/00—Finishing or dressing, of textile fabrics, not provided for in the preceding groups
• • 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
  • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
  • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
  • D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
  • D06M14/24—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of animal origin, e.g. wool or silk
• • 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
  • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
  • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
  • D06M10/025—Corona discharge or low temperature plasma
• • 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
  • D06M11/77—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 silicon or compounds thereof
  • D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
• • 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
  • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
  • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
• • 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
  • D06M2101/10—Animal fibres
  • D06M2101/12—Keratin fibres or silk
• • 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
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
  • D06M2200/11—Oleophobic properties
• • 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
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
  • D06M2200/12—Hydrophobic properties
• • 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
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
• • 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
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/45—Shrinking resistance, anti-felting properties

Definitions

• the present invention relates to the treatment of wool and wool blend fabrics to improve laundering performance, in particular to reduce shrinkage due to felting during laundering.
• wool includes not only the fibres derived from the Caprinae family, such as sheep, but also the hair of certain other species of mammals, such as goats, llamas, alpacas and rabbits (e.g. cashmere, mohair or angora).
• Wool fibre is a popular material for making garments, due to its appearance and handling qualities, as well as its thermal insulating properties.
• the disadvantage of wool and wool blends is that it can shrink during laundering.
• the problem of shrinkage is due to felting caused by wool fibre's complex structure, consisting on an inner cortex and outer surface cuticle. It is this outer surface cuticle which is primarily responsible for felting shrinkage.
• the cuticle comprises an epicuticle which includes fatty lipids covalently bound to a protein surface, which provide some natural water repellency.
• the cuticle also comprises an exocuticle which has a rigid surface structure comprising of overlapping scales which protect the wool fibre from mechanical damage. This rigid surface structure of the exocuticle is responsible for a ‘directional frictional effect’ (DFE) which leads to wool felting during laundering.
• DFE directional frictional effect
• fibres When the fibres are being laundered, they are subject to water, heat and mechanical agitation, causing the fibres to interlock. Due to the nature of the exocuticle, fibres can slide more easily in one direction than the other leading to preferential unidirectional movement which causes felting.
• the coefficient of friction in the ‘with’ scale direction is less than in the ‘against’ scale direction due to the hardness of the scale edge and its lack of deformability when it comes into contact with other fibres.
• the result of the DFE is that the fibres progressively lock together, the yarns closes up and the fabric shrinks irreversibly.
• the major method of treating wool to make it machine washable is the chlorine Hercosett process, which aims to “mask and smooth” the surface scales hence eliminating the DFE.
• the process involves a series of aqueous baths; starting with acid chlorination to modify the epicuticle and thereby impart wettability, create reactive functionality for the reactive polymer bonding and raise surface energy to allow the polymer coating to spread.
• a subsequent step is antichlorination/neutralisation which creates further reactive functionality for the reactive polymer bonding and removes residual chlorine from the fibre. This step is followed by application of the polymer, softening and drying.
• Hercosett polymer is a soft, cationic reactive epichlorohydrin polyamide which exhausts onto the negatively charged wool fibre and covalently bonds to the fibre surface. It masks the scale edges so eliminating the DFE.
• Chlorine Hercosett process is described in more detail in T. Shaw & M. A. White, Chapter 5, P. 346 (1984), Handbook of Fiber Science & Fiber Technology, Vol. II, Chemical Processing of Fibers & Fabrics, Functional Finishes, Part B, Edited by M. Lewin & S. B. Sello. Marcel Dekker Inc., New York. ISBN 0-8247-7118.
• the Chlorine Hercosett process is also described in both J. Lewis, Wool Science Review, 54, 2 (1977) and also H. J. Katz, G. F. Wood & M. T. Goldsmith, Textile Manufacturer, 95, 84 (1969).
• the Chlorine Hercosett process has the disadvantage that adsorbable organohalogens (AOX) are produced in the chlorination stage, causing other solutions to be sought.
• AOX adsorbable organohalogens
• Durable water repellent coatings are often added to fabrics to make them water resistant, for example Fluoropel and Olephobol are two typical fluoropolymers coatings applied by wet chemistry techniques to give water repellency. Durable water repellent coatings are discussed in E. Kissa, Chapter 2, P. 143 (1984), Handbook of Fiber Science & Fiber Technology, Vol. II, Chemical Processing of Fibers & Fabrics, Functional Finishes, Part B, Edited by M. Lewin & S. B. Sello. Marcel Dekker Inc., New York. ISBN 0-8247-7118 and also F. Audenaert, H. Lens, D. Rolly and P. Van der Elst, Fluorochemical Textile Repellents—Synthesis, and Applications: A 3M Perspective, J. Text. Inst., 90, 3, 76 (1999).
• Plasma deposition techniques have been used for the deposition of polymeric coatings onto a range of surfaces, and in particular onto fabric surfaces. This technique is recognised as being a clean, dry technique that generates little waste compared to conventional wet chemical methods. Using this method, plasmas are generated from organic molecules, which are subjected to an electrical field. When this is done in the presence of a substrate, the radicals of the compound in the plasma polymerise on the substrate. Conventional polymer synthesis tends to produce structures containing repeat units that bear a strong resemblance to the monomer species, whereas a polymer network generated using a plasma can be extremely complex. The properties of the resultant coating can depend upon the nature of the substrate as well as the nature of the monomer used and conditions under which it is deposited.
• a first aspect of the present invention provides a method of treating wool in the form of fibre, sliver, yarn, fabric or garment comprising said fibre or yarn, to prevent shrinkage due to felting during laundering, the method comprising applying a polymer coating by plasma polymerisation.
• a sliver is carded and combed wool formed into a tube of fibres.
• the Textile Institute define a sliver as an assemblage of fibres in continuous form without twist.
• the fibre, yarn, sliver, fabric or garment may comprise pure wool or a wool/polymer blend.
• any monomer that undergoes plasma polymerisation or modification of the surface to form a suitable polymeric coating layer may suitably be used.
• monomers include those known in the art to be capable of producing hydrophobic polymeric coatings on substrates by plasma polymerisation including, for example, carbonaceous compounds having reactive functional groups, particularly substantially —CF 3 dominated perfluoro compounds (see WO 97/38801), perfluorinated alkenes (Wang et al., Chem Mater 1996, 2212-2214), hydrogen containing unsaturated compounds optionally containing halogen atoms or perhalogenated organic compounds of at least 10 carbon atoms (see WO 98/58117), organic compounds comprising two double bonds (WO 99/64662), saturated organic compounds having an optionally substituted alky chain of at least 5 carbon atoms optionally interposed with a heteroatom (WO 00/05000), optionally substituted alkynes (WO 00/20130), polyether substituted alkenes (U.S. Pat. No. 6,482,
• a particular group of monomers which may be used to produce the coating of the present invention include compounds of formula (I)
• R 1 , R 2 and R 3 are independently selected from hydrogen, halo, alkyl, haloalkyl or aryl optionally substituted by halo; and R 4 is a group —X—R 5 where R 5 is an alkyl or haloalkyl group and X is a bond; a group of formula —C(O)O—, a group of formula —C(O)O(CH 2 ) n Y— where n is an integer of from 1 to 10 and Y is a sulphonamide group; or a group —(O) p R 6 (O) q (CH 2 ) t — where R 6 is aryl optionally substituted by halo, p is 0 or 1, q is 0 or 1 and t is 0 or an integer of from 1 to 10, provided that where q is 1, t is other than 0.
• halo or “halogen” refers to fluorine, chlorine, bromine and iodine. Particularly preferred halo groups are fluoro.
• aryl refers to aromatic cyclic groups such as phenyl or naphthyl, in particular phenyl.
• alkyl refers to straight or branched chains of carbon atoms, suitably of up to 20 carbon atoms in length.
• alkenyl refers to straight or branched unsaturated chains suitably having from 2 to 20 carbon atoms.
• Haloalkyl refers to alkyl chains as defined above which include at least one halo substituent.
• Suitable haloalkyl groups for R 1 , R 2 , R 3 and R 5 are fluoroalkyl groups.
• the alkyl chains may be straight or branched and may include cyclic moieties.
• the alkyl chains suitably comprise 2 or more carbon atoms, suitably from 2-20 carbon atoms and preferably from 4 to 12 carbon atoms.
• alkyl chains are generally preferred to have from 1 to 6 carbon atoms.
• R 5 is a haloalkyl, and more preferably a perhaloalkyl group, particularly a perfluoroalkyl group of formula C m F 2m+1 where m is an integer of 1 or more, suitably from 1-20, and preferably from 4-12 such as 4, 6 or 8.
• Suitable alkyl groups for R 1 , R 2 and R 3 have from 1 to 6 carbon atoms.
• R 1 , R 2 and R 3 are hydrogen. In a particular embodiment R 1 , R 2 , R 3 are all hydrogen. In yet a further embodiment however R 3 is an alkyl group such as methyl or propyl.
• n is an integer which provides a suitable spacer group.
• n is from 1 to 5, preferably about 2.
• Suitable sulphonamide groups for Y include those of formula —N(R 7 )SO 2 ⁇ where R 7 is hydrogen or alkyl such as C 1-4 alkyl, in particular methyl or ethyl.
• the compound of formula (I) is a compound of formula (II)
• R 5 is as defined above in relation to formula (I).
• the compound of formula (I) is an acrylate of formula (III)
• n and R 5 as defined above in relation to formula (I) and R 7a is hydrogen, C 1-10 alkyl, or C 1-10 haloalkyl.
• R 7a is hydrogen or C 1-6 alkyl such as methyl.
• a particular example of a compound of formula (III) is a compound of formula (IV)
• R 7a is as defined above, and in particular is hydrogen and x is an integer of from 1 to 9, for instance from 4 to 9, and preferably 7.
• the compound of formula (IV) is 1H,1H,2H,2H-heptadecafluorodecylacrylate.
• the polymeric coating is formed by exposing the fibre, yarn, sliver, fabric or garment to plasma comprising one or more organic monomeric compounds, at least one of which comprises two carbon-carbon double bonds for a sufficient period of time to allow a polymeric layer to form on the surface.
• the compound with more than one double bond comprises a compound of formula (V)
• R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are all independently selected from hydrogen, halo, alkyl, haloalkyl or aryl optionally substituted by halo; and Z is a bridging group.
• Suitable bridging groups Z for use in the compound of formula (V) are those known in the polymer art. In particular they include optionally substituted alkyl groups which may be interposed with oxygen atoms. Suitable optional substituents for bridging groups Z include perhaloalkyl groups, in particular perfluoroalkyl groups.
• the bridging group Z includes one or more acyloxy or ester groups.
• the bridging group of formula Z is a group of sub-formula (VI)
• n is an integer of from 1 to 10, suitably from 1 to 3
• each R 14 and R 15 is independently selected from hydrogen, halo, alkyl or haloalkyl.
• R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are haloalkyl such as fluoroalkyl, or hydrogen. In particular they are all hydrogen.
• the compound of formula (V) contains at least one haloalkyl group, preferably a perhaloalkyl group.
• R 14 and R 15 are as defined above and at least one of R 14 or R 15 is other than hydrogen.
• a particular example of such a compound is the compound of formula B.
• the polymeric coating is formed by exposing the fibre, yarn, sliver, fabric or garment to plasma comprising a monomeric saturated organic compound, said compound comprising an optionally substituted alkyl chain of at least 5 carbon atoms optionally interposed with a heteroatom for a sufficient period of time to allow a polymeric layer to form on the surface.
• saturated means that the monomer does not contain multiple bonds (i.e. double or triple bonds) between two carbon atoms which are not part of an aromatic ring.
• heteroatom includes oxygen, sulphur, silicon or nitrogen atoms. Where the alkyl chain is interposed by a nitrogen atom, it will be substituted so as to form a secondary or tertiary amine. Similarly, silicons will be substituted appropriately, for example with two alkoxy groups.
• Particularly suitable monomeric organic compounds are those of formula (VII)
• R 16 , R 17 , R 18 , R 19 and R 20 are independently selected from hydrogen, halogen, alkyl, haloalkyl or aryl optionally substituted by halo; and R 21 is a group X—R 22 where R 22 is an alkyl or haloalkyl group and X is a bond or a group of formula C(O)O(CH 2 ) x Y— where x is an integer of from 1 to 10 and Y is a bond or a sulphonamide group; or a group —(O) p R 23 (O) s (CH 2 ) t — where R 23 is aryl optionally substituted by halo, p is 0 or 1, s is 0 or 1 and t is 0 or an integer of from 1 to 10, provided that where s is 1, t is other than 0.
• Suitable haloalkyl groups for R 16 , R 17 , R 18 , R 19 , and R 20 are fluoroalkyl groups.
• the alkyl chains may be straight or branched and may include cyclic moieties and have, for example from 1 to 6 carbon atoms.
• the alkyl chains suitably comprise 1 or more carbon atoms, suitably from 1-20 carbon atoms and preferably from 6 to 12 carbon atoms.
• R 22 is a haloalkyl, and more preferably a perhaloalkyl group, particularly a perfluoroalkyl group of formula C z F 2z+1 where z is an integer of 1 or more, suitably from 1-20, and preferably from 6-12 such as 8 or 10.
• y is an integer which provides a suitable spacer group.
• y is from 1 to 5, preferably about 2.
• Suitable sulphonamide groups for Y include those of formula —N(R 23 )SO 2 — where R 23 is hydrogen, alkyl or haloalkyl such as C 1-4 alkyl, in particular methyl or ethyl.
• the monomeric compounds used preferably comprises a C 6-25 alkane optionally substituted by halogen, in particular a perhaloalkane, and especially a perfluoroalkane.
• the polymeric coating is formed by exposing the fibres, yarn, sliver, fabric or garment to plasma comprising an optionally substituted alkyne for a sufficient period to allow a polymeric layer to form on the surface.
• the alkyne compounds used comprise chains of carbon atoms, including one or more carbon-carbon triple bonds.
• the chains may be optionally interposed with a heteroatom and may carry substituents including rings and other functional groups.
• Suitable chains which may be straight or branched, have from 2 to 50 carbon atoms, more suitably from 6 to 18 carbon atoms. They may be present either in the monomer used as a starting material, or may be created in the monomer on application of the plasma, for example by the ring opening
• Particularly suitable monomeric organic compounds are those of formula (VIII)
• R 24 is hydrogen, alkyl, cycloalkyl, haloalkyl or aryl optionally substituted by halo
• X 1 is a bond or a bridging group
• R 25 is an alkyl, cycloalkyl or aryl group optionally substituted by halogen.
• Suitable bridging groups X 1 include groups of formulae —(CH 2 ) s —, —CO 2 (CH 2 ) p —, —(CH 2 ) p O(CH 2 ) q —, —(CH 2 ) p N(R 26 )CH 2 ) q —, —(CH 2 ) p N(R 26 )SO 2 —, where s is 0 or an integer of from 1 to 20, p and q are independently selected from integers of from 1 to 20; and R 26 is hydrogen, alkyl, cycloalkyl or aryl. Particular alkyl groups for R 26 include C 1-6 alkyl, in particular, methyl or ethyl.
• R 24 is alkyl or haloalkyl, it is generally preferred to have from 1 to 6 carbon atoms.
• Suitable haloalkyl groups for R 24 include fluoroalkyl groups.
• the alkyl chains may be straight or branched and may include cyclic moieties.
• R 24 is hydrogen.
• R 25 is a haloalkyl, and more preferably a perhaloalkyl group, particularly a perfluoroalkyl group of formula C r F 2r+1 where r is an integer of 1 or more, suitably from 1-20, and preferably from 6-12 such as 8 or 10.
• the compound of formula (VIII) is a compound of formula (IX)
• R 27 is haloalkyl, in particular a perhaloalkyl such as a C 6-12 perfluoro group like C 6 F 13 .
• the compound of formula (VIII) is a compound of formula (X)
• p is an integer of from 1 to 20, and R 27 is as defined above in relation to formula (IX) above, in particular, a group C 8 F 17 .
• p is an integer of from 1 to 6, most preferably about 2.
• R 26 is as defined above an in particular is ethyl
• R 27 is as defined in relation to formula (IX), in particular a group C 8 F 17 .
• the alkyne monomer used in the process is a compound of formula (XIV)
• R 28 is hydrogen, alkyl, cycloalkyl, haloalkyl or aryl optionally substituted by halo
• R 29 , R 30 and R 31 are independently selected from alkyl or alkoxy, in particular C 1-6 alkyl or alkoxy.
• Preferred groups R 28 are hydrogen or alkyl, in particular C 1-6 alkyl.
• R 29 , R 30 and R 31 are C 1-6 alkoxy in particular ethoxy.
• the fibres, yarn, sliver, fabric or garment to be treated is placed within a plasma chamber together with the material to be deposited in a gaseous state, a glow discharge is ignited within the chamber and a suitable voltage is applied, which may be pulsed.
• the polymeric coating may be produced under both pulsed and continuous-wave plasma deposition conditions but pulsed plasma may be preferred as this allows closer control of the coating, and so the formation of a more uniform polymeric structure.
• the expression “in a gaseous state” refers to gases or vapours, either alone or in mixture, as well as aerosols.
• Precise conditions under which the plasma polymerization takes place in an effective manner will vary depending upon factors such as the nature of the polymer, the fibres, yarn, sliver, fabric or garment treated and will be determined using routine methods and/or the techniques.
• Suitable plasmas for use in the method of the invention include non-equilibrium plasmas such as those generated by radiofrequencies (RF), microwaves or direct current (DC). They may operate at atmospheric or sub-atmospheric pressures as are known in the art. In particular however, they are generated by radiofrequencies (RF).
• RF radiofrequencies
• Various forms of equipment may be used to generate gaseous plasmas. Generally these comprise containers or plasma chambers in which plasmas may be generated. Particular examples of such equipment are described for instance in WO2005/089961 and WO02/28548, but many other conventional plasma generating apparatus are available.
• the gas present within the plasma chamber may comprise a vapour of the monomer alone, but it may be combined with a carrier gas, in particular, an inert gas such as helium or argon, if required.
• a carrier gas in particular, an inert gas such as helium or argon, if required.
• helium is a preferred carrier gas as this can minimise fragmentation of the monomer.
• the relative amounts of the monomer vapour to carrier gas are suitably determined in accordance with procedures which are conventional in the art.
• the amount of monomer added will depend to some extent on the nature of the particular monomer being used, the nature of the substrate being treated, the size of the plasma chamber etc.
• monomer is delivered in an amount of from 50-250 mg/minute, for example at a rate of from 100-150 mg/minute. It will be appreciated however, that the rate will vary depending on the reactor size chosen and the number of substrates required to be processed at once; this in turn depends on considerations such as the annual through-put required and the capital outlay.
• Carrier gas such as helium is suitably administered at a constant rate for example at a rate of from 5-90 standard cubic centimetres per minute (sccm), for example from 15-30 sccm.
• sccm standard cubic centimetres per minute
• the ratio of monomer to carrier gas will be in the range of from 100:0 to 1:100, for instance in the range of from 10:0 to 1:100, and in particular about 1:0 to 1:10. The precise ratio selected will be so as to ensure that the flow rate required by the process is achieved.
• a preliminary continuous power plasma may be struck for example for from 15 seconds to 10 minutes, for example from 2-10 minutes within the chamber.
• This may act as a surface pre-treatment step, ensuring that the monomer attaches itself readily to the surface, so that as polymerisation occurs, the coating “grows” on the surface.
• the pre-treatment step may be conducted before monomer is introduced into the chamber, in the presence of only an inert gas.
• the inert gas comprises argon.
• the plasma is then suitably switched to a pulsed plasma to allow polymerisation to proceed, at least when the monomer is present.
• a glow discharge is suitably ignited by applying a high frequency voltage, for example at 13.56 MHz. This is applied using electrodes, which may be internal or external to the chamber, but in the case of larger chambers are generally internal.
• the gas, vapour or gas mixture is supplied at a rate of at least 1 standard cubic centimetre per minute (sccm) and preferably in the range of from 1 to 100 sccm.
• sccm standard cubic centimetre per minute
• this is suitably supplied at a rate of from 80-300 mg/minute, for example at about 120 mg/minute depending upon the nature of the monomer, the size of the chamber and the surface area of the product during a particular run whilst the pulsed voltage is applied. It may however, be more appropriate for industrial scale use to have a fixed total monomer delivery that will vary with respect to the defined process time and will also depend on the nature of the monomer and the technical effect required.
• Gases or vapours may be delivered into the plasma chamber using any conventional method. For example, they may be drawn, injected or pumped into the plasma region. In particular, where a plasma chamber is used, gases or vapours may be drawn into the chamber as a result of a reduction in the pressure within the chamber, caused by use of an evacuating pump, or they may be pumped, sprayed, dripped, electrostatically ionised or injected into the chamber as is common in liquid handling.
• Polymerisation is suitably effected using vapours of compounds for example of formula (I), which are maintained at pressures of from 0.1 to 400 mtorr, suitably at about 10-100 mtorr.
• the applied fields are suitably of power of from 5 to 500 W for example from 20 to 500 W, suitably at about 100 W peak power, applied as a continuous or pulsed field.
• pulses are suitably applied in a sequence which yields very low average powers, for example in a sequence in which the ratio of the time on:time off is in the range of from 1:100 to 1:1500, for example at about 1:650.
• Particular examples of such sequence are sequences where power is on for 20-50 ⁇ s, for example about 30 ⁇ s, and off for from 1000 ⁇ s to 30000 ⁇ s, in particular about 20000 ⁇ s.
• Typical average powers obtained in this way are 0.1-0.2 W.
• the fields are suitably applied from 30 seconds to 90 minutes, preferably from 5 to 60 minutes, depending upon the nature of the compound of formula (I) and the fibres, yarn, sliver, fabric or garment being treated.
• a plasma chamber used is of sufficient volume to accommodate multiple fibres, yarn, slivers, fabrics or garments.
• the plasma is created with a voltage as a pulsed field, at an average power of from 0.001 to 500 W/m 3 , for example at from 0.001 to 100 W/m 3 and suitably at from 0.005 to 0.5 W/m 3 .
• These conditions are particularly suitable for depositing good quality uniform coatings, in large chambers, for example in chambers where the plasma zone has a volume of greater than 500 cm 3 , for instance 0.1 m 3 or more, such as from 0.5 m 3 -10 m 3 and suitably at about 1 m 3 .
• the layers formed in this way have good mechanical strength.
• the dimensions of the chamber will be selected so as to accommodate the particular fibres, yarn, sliver, fabric or garment being treated.
• generally cuboid chambers may be suitable for a wide range of applications, but if necessary, elongate or rectangular chambers may be constructed or indeed cylindrical, or of any other suitable shape.
• the chamber may be a sealable container, to allow for batch processes, or it may comprise inlets and outlets for the fibre, yarn, sliver, fabric or garment, to allow it to be utilised in a continuous process as an in-line system.
• the pressure conditions necessary for creating a plasma discharge within the chamber are maintained using high volume pumps, as is conventional for example in a device with a “whistling leak”.
• high volume pumps as is conventional for example in a device with a “whistling leak”.
• a second aspect of the present invention provides use of a polymer coating obtained by plasma polymerisation on a wool containing fibre, yarn, sliver, fabric or garment made from said fibre or yarn to reduce shrinkage due to felting during laundering.
• a third aspect of the present invention provides a wool containing fibre, yarn, sliver, fabric or garment made from said fibre or yarn, wherein the fibre, yarn, sliver, fabric or garment has been treated according to the method as described above to prevent shrinkage due to felting during laundering.
• a fifth aspect of the present invention provides use of a polymer coating obtained by plasma polymerisation on a wool containing fibre, yarn, sliver, fabric or garment made from said fibre or yarn as a water and/or oil repellent coating which does not require post laundering refreshing.
• any feature disclosed herein may be replaced by an alternative feature serving the same or a similar purpose.
• the fabrics samples tested were untreated wool, Chlorine-Hercosett treated wool and polyester/wool blend fabrics, containing hollow and solid polyester filaments. These samples were treated with “traditional” fluorocarbon technology and with a plasma polymerisation system. The resulting coated samples were then evaluated for liquid repellency after washing, dry cleaning and flat abrasion and the results of the different fluorocarbon coating compared.
• the three different wool containing fabrics were: 100% wool botany serge (190 g/m 2 , supplied by Whaleys, Bradford), plain weave chlorine-Hercosett treated wool (100% wool, 210 g/m 2 ) supplied by Bulmer & Lumb, Bradford and undyed wool/polyester (60/4) blend fabrics (yarn count 60/2, 160 g/m 2 ) also supplied by Bulmer & Lumb, Bradford.
• the SDC ECE phosphate-based reference detergent without optical brightening agents, was used during the wash fastness tests. It was used as the washing powder addition because it is the standard detergent in the ISO C06 wash fastness tests to simulate domestic laundering.
• the wool fabrics Prior to finishing, the wool fabrics were washed with an aqueous non-ionic detergent solution to remove any possible impurities which could potentially interfere with the subsequent surface treatment; and then air dried.
• the “traditional” fluorocarbons were applied to the samples by the following method. Fabric samples were treated using a pad-dry-cure method with either 50 g/l Oleophobol SL-A or 50 g/l Fluorepel OWS. The pad bath was set at pH 6-7 and the wet pick-up was 70%. The padded fabrics were dried at 100° C. for 2 minutes (100% wool fabrics) or 1 minute (blend fabrics), and then cured for 5 minutes at 150° C. or 1 minute at 170° C. for the wool and blend fabrics, respectively.
• the plasma polymerisation coating was applied by the following method.
• the plasma polymerization experiments were performed in an inductively coupled glow discharge reactor with a base pressure of 6.13 ⁇ 10 ⁇ 3 mbar, a leak rate of better than 6 ⁇ 10 ⁇ 9 mol s ⁇ 1 and a monomer flow rate 4 mg/min or 3.2 mol s ⁇ 1 .
• This was connected to a two stage Edwards rotary pump via a liquid nitrogen cold trap, a thermocouple pressure gauge, and a monomer tube containing the 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate monomer. All connections were grease free.
• An L-C matching unit was used to minimize the standing wave ratio (SWR) of the transmitted power between a 13.56 MHz radio frequency (RF) generator and the electrical discharge.
• the RF source was triggered by a signal generator, and an oscilloscope was used to monitor the pulse width and amplitude.
• the substrate to be coated was placed into the centre of the reactor, followed by evacuation back down to the base pressure.
• the fluoro-monomer vapour was then introduced at a constant pressure of ⁇ 0.2 mbar and allowed to purge through the system for 5 minute, followed by ignition of the glow discharge.
• the pressure on the reactor outlet was found to be steady, which is consistent with sufficient monomer flow rate.
• Deposition was terminated after enough time to form a film, based on the previous trials, on the substrates surface.
• the monomer vapour was allowed to continue to pass over the substrate for a further 5 minute and subsequently the plasma chamber was evacuated back down to the base pressure and then vented to the atmosphere.
• the optimum pulsing conditions were determined using factorial experimental design, followed by simplex optimization.
• the abrasion resistance of finished fabrics was measured according to BS 12947-2: 1999, on a Martindale Wear & Abrasion Tester and the repellency properties evaluated after 3,000 rubs.
• the water repellency of the fabrics samples was determined using the 3M water repellency test using a series of water/isopropyl alcohol solutions.
• Table 1 below shows the results for the 3M water repellency analysis of fluorocarbon treated Chlorine/Hercosett Wool Fabrics.
• Table 1 indicates the effectiveness of the plasma polymerisation of the fluoro-monomer on the Chlorine Hercosett treated wool fabric in imparting water repellency relative to the traditional wet chemical fluorocarbon applications.
• the table shows the different results when an argon plasma pre-treatment is applied for 1, 2 or 3 minutes respectively. It is apparent that the argon plasma pre-treatment prior to plasma polymerisation system has introduced much better polymer re-orientation behaviour at room temperature, hence not requiring a hot press for restoring the water repellency performance after laundering.
• Pre-treating the wool with an argon plasma has a beneficial effect in eliminating/reducing the need for a post-heat treatment but the abraded plasma treated wool fabrics appear to have lost some repellency performance probably due to the thinner PP coating layer relative to the traditional fluorocarbon finishes.
• the oil repellency of the fabric was determined using the AATCC 118-2007 oil repellency test using a series of eight standard hydrocarbon solutions.
• the oil repellency grade is the highest numbered test liquid which does not wet the fabric surface.
• Table 2 below shows the results of the 3M Oil Repellency Analysis of Fluorocarbon Treated Chlorine/Hercosett Wool Fabrics.
• Table 2 indicates the effectiveness of the plasma polymerisation of the fluoro-monomer on the Chlorine Hercosett treated wool fabric in imparting oil repellency relative to the traditional wet chemical fluorocarbon applications.
• Samples of Chlorine Hercosett treated fabrics with different fluorocarbon treatments underwent surface analysis using both X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF-SIMS).
• XPS X-ray photoelectron spectroscopy
• TOF-SIMS time of flight secondary ion mass spectrometry
• ToF-SIMS analyses were carried out using a PHI 7000 instrument operating at a base pressure of less than 4.0 ⁇ 10 ⁇ 8 Torr.
• the instrument was equipped with a reflectron analyser, a Cs + ion source (8 keV; pulsed length 1.25 ns) and a pulsed electron flood source (50-70 eV) for charge compensation.
• Both positive and negative secondary ion mass spectra were acquired from areas measuring 250 ⁇ m ⁇ 250 ⁇ m over the mass range 0-2000.
• the total primary ion dose was less than 1 ⁇ 10 12 ions/cm 2 , which lies below the threshold value for static SIMS of 1 ⁇ 10 13 ions/cm 2 .
• XP spectra were obtained using a Kratos Axis Ultra XPS instrument with an Al K ⁇ -alpha x-ray source. The samples (300 ⁇ 800 ⁇ m) were attached to sample bar with double sided adhesive. Wide scan spectra were recorded at a 80 eV pass energy. High resolution spectra in the S(2p), C(1s), N(1s), O(1s), and F(1s) regions were obtained at a 20 eV pass energy. To overcome the insulation problems of textile fibres during the analyses, the charge neutraliser flood gun provided a constant stream of electrons in order to neutralize the charge build up. Binding energy values were calculated relative to the C(1s) photoelectron peak at 285.0 eV. The samples surface elemental composition and atomic ratios were obtained by Casa XPS software and Wagner's sensitivity factors.
• the XPS (X-ray photoelectron spectroscopy) data of the plasma treated sample indicates obvious incorporation of fluorocarbon into the surface of the fibre with the fluorine content increasing up to 47%, when an argon pretreatment is used.
• the tensile properties of the fabrics were determined according to the BS 13934-1:1999 test method on an Instron model 5564, with gauge length of 100 mm, crosshead speed of 50 mm/min, and each value presented is the average of 10 measurements.
• the influence of the treatments on the fabric's mechanical (handle) properties both before and after treatment was objectively assessed using the Kawabata Evaluation System (KES).
• Kawabata Evaluation System The 20 ⁇ 20 cm samples were conditioned at 20° C. and 65% R.H. (Relative Humidity) prior to testing the tensile, shear, and bending properties.
• Table 4 shows the tensile strength of wool fabrics treated with plasma and fluorocarbons, whilst table 5 shows the results for KES-F analysis of the selected mechanical properties of the Chlorine Hercosett treated wool fabrics.
• the felting shrinkage of the wool fabrics was determined using a Wascator FOM 71P, with a standard 5A wash programme. Fabric shrinkage was determined after each wash cycle by measuring the new fabric area and comparing it with the initial area value. The fabric samples were dry cleaned in accordance with the BS EN ISO 3175:1998 test method, by PPT Company, Ambergate, and their repellency properties were determined after 1 and 3 cycles. The results are shown in table 6.
• Chlorine/Hercosett treated wool fabric is machine washable and will not shrink
• untreated wool will shrink extensively depending on fabric structure and processing. Examination of Table 6 indicates the untreated wool fabric shrinks progressively up to 63.4% area shrinkage after 5 ⁇ 5A wash cycles.
• the traditional fluorocarbon coatings have no beneficial effect in reducing felting but in contrast the fluoro-monomer plasma polymerised wool sample has much lower felting shrinkage. The reduction in felting is very encouraging and potentially creates an opportunity to achieve a dual effect of combined liquid repellency and machine washability.
• the Chlorine Hercosett treated wool is machine washable and the PP treatment does not affect this vital performance criteria.
• the untreated wool fabric shrinks by 63% in area with repeated launderings and the Oleophobol and Fluorepel coatings do not affect this level of felting shrinkage.
• the fluoropolymer PP treatment significantly reduces the felting shrinkage.
• the effect of the fluorocarbon treatments on the tensile strength of the fabrics is marginal, while the KES-F analysis of the fabrics indicated the Oleophobol and Fluorepel finishes impart some fabric stiffening, in contrast the PP treatment appears to have a beneficial effect on fabric handle on the blend fabrics.
• silica nanoparticles were applied to a wool sample before a fluoropolymers coating was added. The shrinkage, water and oil repellency, colour of the wool samples and KES-F analysis were then tested.
• the wool sample was 100% wool botany serge (190 g/m2) was supplied by Whaleys, Bradford.
• the ‘traditional’ fluorochemical used was Oleophobol SL-A 0, Ciba and the shrink proofing polymer Synthapret BAP was supplied by Bayer.
• the fabric samples were padded with a bath containing 0.3% on weight of fabric, o.w.f., nanoparticles and 5 ml/l iso-propanol, at 70% wet pick up.
• the different sized nanoparticles are shown in table 11.
• the padded fabrics were dried at 100° C. for 2 minutes and then cured for 4 minutes at 140° C.
• Fabric samples were treated with the ‘traditional’ fluorochemicals using a pad-dry-cure method with 18 g/l Synthapret BAP, 24 g/l Oleophobol SL-A, 0.3% on weight of fabric, o.w.f., nanoparticles and 5 ml/l iso-propanol.
• the pad bath was set at pH6-7, using acetic acid, and the wet pick-up was 70%.
• the padded fabrics were dried at 100° C. for 2 minutes and then cured for 4 minutes at 140° C.
• Nano-particle Tradename (Nissan) Particle Size (nm) Snowtex OS (OS) 4-6 Snowtex O (O) 10-20 Snowtex OL (OL) 40-50 MP-1040 100 MP-4540 430
• the felting shrinkage of the wool fabrics was determined using a Wascoator FOM 71P, with a standard 5A wash programme as described above.
• Table 12 shows the fabric shrinkage for the wool coated with silica nanoparticles with different fluoropolymers coatings. The tests have been repeated for both dyed and undyed samples.
• the fluoropolymers plasma polymerisation has the beneficial effect in reduction of felting shrinkage.
• Table 12 shows the effect of silica nanoparticles on felting shrinkage in combination with different treatments.
• This effect may be due to the fluoropolymer plasma coating lubricating the surface protrusions. Similarly on plasma polymerising the fluorocarbon over the nanoparticles there is a significant reduction in felting shrinkage. Surprisingly in general it appears the larger nanoparticles have the better effect and it may be related to the particles providing a stand off protective mechanism.
• the fabric colour was measured using a Datacolor Reflectance Spectrophotometer.
• the samples were triple folded and an average of four valued used to provide the mean. The results are illustrated in tables 17 and 18.
• the effect of the nanoparticles on the mechanical properties of the treated fabric is variable. If applied alone or alone followed by a plasma polymerisation process the 2HG5 value (the indicator of interyarn friction and softness) increases; probably due to the protruding particles causing increased frictional interaction. In contrast, if the nanoparticles are incorporated with the shrinkproofing or water/oil repellent finish, the mechanical properties are similar to the control fabric.

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