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
  • D06M15/21—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
• • 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

• Nylon fibres and other polyamide products can be dyed with acid dyes that are substantive to the dyeable dye sites of the polyamide structure, generally as a result of reaction between the acid dye and basic amino sites in the polyamide molecular structure.
• Syntans are sulphonated phenol formaldehyde condensation products.
• a polyamide product according to the invention has undyed dyeable dye sites and substantially all the undyed dyeable dye sites are blocked by a substantially non-colouring polymer that is chemically substantive to the said undyed sites, that is soluble in aqueous acid, that can be permeated through the molecular structure of the product when the product is swollen by heat and/or moisture, and that is an addition polymer of one or more vinyl addition monomers comprising 10 to 80 mole percent monomer containing sulphonic acid groups and 10 to 80 mole percent monomer containing at least one aromatic or cycloaliphatic or heterocyclic group.
• the sulphonic acid groups are essential in order that the polymer is chemically substantive to the said undyed sites.
• the aromatic, cycloaliphatic or heterocyclic groups are essential in order that the polymer has a relatively planar and bulky molecule in its structure since this seems necessary for good stain-resistance. Since the polymer is an addition polymer of one or more vinyl addition monomers it does not contain methylene groups condensed between phenol groups, as in U.S. 4,592,940. It appears that the presence of a methylene group between two adjacent phenyl groups provides a tendency to chromophore formation upon exposure to sunlight.
• any of the monomers used in the invention contains two rings, in particular two phenyl rings, it is preferred that these rings are not connected by a methylene bridge.
• the use of the addition polymers of the invention leads to an improved combination of stain-resist properties.
• it gives equivalent or better stain resistance to acid stains and better stain resistance to other stains such as coffee and tea and, especially mustard, and it gives less tendency to yellowing on exposure to sunlight.
• the product can be a synthetic polyamide film but is preferably a fibrous product. It can be in the form of filaments, yarn or staple fibres but is preferably in the form of a textile, most preferably a carpet.
• the textile has normally been dyed by one or more acid dyes either as a pale monocolour or, more usually, as a pattern.
• the invention is of value during the dyeing of the textile as a replacement for conventional Syntan treatment, so as to block undyed sites and prevent staining in unwanted areas by unfixed dye.
• the invention is, however, of particular value for rendering carpets and other textiles stain resistant to accidental staining.
• the polyamide is generally a synthetic polyamide, i.e., a nylon, but it can be a natural polyamide, for instance wool.
• the product can comprise a blend of nylon and wool or it can comprise a blend of the polyamide fibres, generally nylon, and other synthetic or natural fibres.
• the polymer must have a molecular size, hydrophobicity and structure such that it can be permeated into the fibres or film of polyamide in order that it can block substantially all the undyed dyeable sites, that is to say the sites that are liable to be dyed by migrating dye or accidental stain.
• the polymer should not easily be able to be permeated out of the molecular structure once it is substantive to the undyed sites.
• the molecular weight and the monomers used for forming the polymer are such that the polymer can be permeated through the polyamide fibres or other polyamide product when the product is swollen by heat and/or moisture (for instance by steaming or boiling water) but is much less able to permeate through the product when the product is unswollen, e.g., in normal use.
• the polymer can be applied while the product is swollen and will then tend to be trapped in the product when it is deswollen.
• the polymer In order that the polymer can permeate into the structure its molecular weight must usually be less than 100,000, generally below 50,000 and preferably below 30,000. In order that it can be trapped in the structure after deswelling the molecular weight must usually be at least 1,000, and generally at least 5,000 and preferably at least 10,000. Best results are generally obtained when the molecular weight is in the range 10,000 to 25,000. Throughout this specification all molecular weights are weight average molecular weight Mw as measured by Gel Permeation Chromatography using polystyrene sulphonates as molecular weight standards.
• the polymer must be substantially non-colouring to the polyamide product. Since some or all of this product normally includes pale areas, for instance white, the polymer should therefore be substantially colourless when applied to the polyamide product.
• the polymer is made by addition polymerisation of one or more vinyl-addition monomers.
• These can be ethylenically unsaturated monomers or they can be monomers that behave as ethylenically unsaturated monomers.
• a monomer may be used that includes an unsaturated ring structure which is capable of undergoing addition polymerisation with other ethylenically unsaturated monomer so that the ring is integral with the polymer backbone.
• Other vinyl addition monomers that may be used in the invention are ethylenically unsaturated monomers such as allyl and vinyl monomers, and the monomers generally include at least one acrylic monomer.
• the polymer must contain both sulphonic groups and aromatic, cycloaliphatic or heterocyclic groups. Both types of group can be supplied by a single monomer and thus the polymer may be formed of 10 to 80 mole percent of a monomer containing a sulphonic group and an aromatic, cycloaliphatic or heterocyclic group. Comonomer that is used with this type of monomer may contain or be free of sulphonic acid groups and may contain or be free of aromatic, cycloaliphatic or heterocyclic groups. Alternatively the polymer may be formed from 10 to 80 mole percent of a linear aliphatic sulphonate and 10 to 80 mole percent of a monomer providing aromatic, cycloaliphatic or heterocyclic groups, optionally with other monomer.
• the amount of sulphonic monomer is below 80 mole percent and preferably below about 50 mole percent but is normally above 10 mole percent and preferably above about 18 mole percent. Best results are generally obtained with 20 to 45 mole percent. This is based on the preferred monomers but, expressed as a weight percentage, the amount of sulphonic monomer is generally below 90 weight percent and preferably below 70 weight percent, and is generally above 15 weight percent and preferably above 30 weight percent. Best results are generally obtained when 20 to 45 mole percent, or 35 to 60 weight percent, of the monomers are sulphonic monomers.
• the sulphonic monomers may be linear aliphatic monomers such as 2-acrylamido-2-methyl propane sulphonate, allyl sulphonate, vinyl sulphonate or sulpho-ethyl acrylate but preferably the sulphonic monomer includes a cyclo aliphatic or aryl moiety.
• Preferred sulphonic monomers are styrene sulphonate (wherein the styrene may optionally be substituted with alkyl, generally methyl, groups, and, especially, cyclo aliphatic sulphonates, most preferably cyclo pentadiene sulphonate (i.e., the monomer of formula E at column 3 line 1 of U.S. 4,547,200) wherein the cyclo aliphatic group may additionally be substituted by alkyl or aryl groups.
• the copolymer should be a substantially random copolymer rather than a block copolymer, and the comonomer or comonomers must be stable to the polymerisation conditions and to the condition of use.
• non-sulphonated aromatic or cycloaliphatic monomers are cyclohexyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, N-cyclohexyl acrylamide, N-benzyl acrylamide, N-4-methyl phenyl methyl acrylamide, N-diphenyl methyl acrylamide and N,N-diphenyl methacrylamide.
• Aromatic, cycloaliphatic and heterocyclic monomers that are free of sulphonic acid groups are usually included in an amount of not more than 50 mole percent and usually not more than 30 weight percent.
• the polymer may contain no sulphonate-free groups of this type or may contain a low amount, for instance below 30 weight percent and often below 15 weight percent.
• higher amounts of sulphonate-free groups of this type may be suitable, for instance 18 to 50 mole percent or 15 to 90, usually 30 to 70, weight percent.
• Preferred monomers of this general type have at least one aromatic or cycloaliphatic group. This group may be distant from the ethylenic group through which copolymerisation occurs, being connected to the group by, for instance, a polyethoxy chain.
• the monomer is then an associative monomer, for instance as described in EP 172025, 172723 or 216479 and the prior art discussed in those.
• any monomer used in the invention that includes an aromatic, cycloaliphatic or heterocyclic ring has the ring either integral with the backbone of the polymer or pendant from the backbone by a linkage of zero, 1 or 2 atoms.
• cyclopentadiene sulphonate provides an aliphatic ring integral with the backbone
• styrene provides an aromatic ring connected to the backbone through a linkage containing zero atoms
• vinyl ethers would provide a linkage of 1 atom
• acrylic monomers would provide a linkage of two atoms.
• the acrylic monomer may be an ester with, for instance, (meth) acrylic acid where the esterifying group contains a cycloaliphatic or aromatic ring, or it may be an N-monosubstituted (meth) acrylamide or N,N-disubstituted (meth) acrylamide.
• Suitable monomers include cyclohexyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, N-cyclohexyl acrylamide, N-benzyl acrylamide, N-4-methyl phenyl methyl acrylamide, N-diphenyl methyl acrylamide and N,N-diphenyl methacrylamide. Analogs of these containing at least one sulphonic acid group in the ring may also be used.
• hydrophobic aliphatic monomers especially when the cyclic monomers are all substituted by sulphonic acid groups.
• the amount of hydrophobic aliphatic monomer is generally from 0 to 50 weight percent, often 0 to 30 weight percent. If such a monomer is present, it is generally present in an amount of at least 5%, for instance 5 to 15 weight percent.
• Suitable monomers of this type include alkyl (meth) acrylates and alkyl maleates where the alkyl group contains 1 to 22 carbon atoms, and associative monomers (as discussed above) wherein the hydrophobic group is a fatty aliphatic group. Vinyl esters can be used.
• the polymer is formed also from at least 10 mole percent, and usually at least 20 mole percent hydrophilic ethylenically unsaturated monomers.
• monomers are generally present in an amount of at least 30 to 40 weight percent and they can be present in amounts up to 80%, most usually 40 to 60 weight percent.
• Suitable monomers of this type include hydroxy alkyl (meth) acrylates where the alkyl generally has 1 to 4 carbon atoms and is preferably ethyl or propyl, N-vinyl formamide or acetamide, (meth) acrylamide, N-methylol- or N-alkoxy (usually n-butoxy)-­acrylamide or, preferably, an ethylenically unsaturated carboxylic monomer such as (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid or, preferably, maleic or (meth) acrylic acid.
• Some monomers are more able to form random copolymers than others and, for this reason, when using dicyclo pentadiene disulphonate it is particularly preferred to use maleic acid as a comonomer.
• the carboxylic and sulphonic monomers may initially be supplied in the form of salts, for instance with sodium or other alkali metal.
• Particularly preferred polymers for use in the invention are formed from 25 to 50 or 60 weight percent dicyclo pentadiene sulphonate, 0 to 15 or 20 weight percent dicyclo pentadiene or other hydrophobic monomer, with the balance being a randomly copolymerised monomer which is generally an carboxylic monomer, often maleic acid. Mw is preferably in the range 10 to 20,000.
• Other suitable monomers include monomers of substantially equal amounts of sodium styrene sulphonate and carboxylic monomer (often acrylic acid) often with from 0 to 20%, preferably 5 to 20%, styrene or other hydrophobic monomer.
• the polymer may be made by conventional polymerisation techniques that are suitable for forming susbtantially random copolymers of the monomers that are being used. They may be made by free radical polymerisation, for instance using acrylamide as comonomer, but it is often preferred to make them by cationic initiation under acidic conditions, in which event the comonomer must be stable to acid and so is preferably an anionic monomer such as (meth) acrylic acid.
• the polymer must be applied under pH conditions such that the sulphonate groups are substantive to dyeable sites and this generally necessitates application from acidic solution or from solution in the presence of an acid salt or an acid.
• the solution of polymer is generally applied to the entire polyamide product, for instance by exhaust, pad or spray impregnation of the fibre, yarn or carpet or other textile, and permeation of the polymer into the polymeric structure of the fibres or film is generally promoted by steaming the product or by conducting the impregnation with hot aqueous solution, often boiling aqueous solution.
• the product may then be dried.
• a 7cm2 circular area of carpet pile was tested for stain resistance by pushing a 3cm diameter section of polypropylene pipe into the pile and pouring into this 10ml of a solution containing 0.08 gm l ⁇ 1 of C.I. Food Red 17 (F.D. and C Red 40) and 0.4 gm. l ⁇ 1 of citric acid (just enough to saturate 7 cm2 of pile).
• the pipe section was removed and the wet stain left for 1 hour at 25°C then washed off in cold running water after which no red stain remained on the carpet which was assessed as 5 on the S.D.C. Grey Scale.
• the yellowing propensity of the treated carpet due to light was determined by exposing the carpet to 40 hours in a Microscal Light Fastness Tester equipped with a Mercury-Tungsten Lamp. Yellowing was very slight, no worse than untreated carpet.
• the padded carpet was steamed at 102°C for 10 minutes, washed in cold water and dried for 2 minutes at 130°C.
• the treated carpet was tested for stain resistance and yellowing properties as in Example 1. It was found to be stain resistance (4/5 on Grey Scale) and non-yellowing properties after 40 hours in the Light Fastness Tester.
• a copolymer of 45 weight percent sodium styrene sulphonate, 45 weight percent acrylic acid and 10 weight percent styrene was formed and was impregnated into a nylon carpet as described in Example 1. Although the stain resistance was not as good as in Example 1, it was better than for the untreated carpet.
• the padded carpet was then steamed at 102°C for 10 minutes, washed in cold water and dried for 2 minutes at 130°C.
• the treated carpet was tested for stain resistance and yellowing properties as in Example 1. It was found to have excellent stain resistance (4/5 on Grey Scale) but suffered from very severe yellowing after 40 hours in the Light Fastness Tester.

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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)

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Citations (1)

• 1988
  • 1988-03-17 GB GB888806348A patent/GB8806348D0/en active Pending
• 1989
  • 1989-03-17 EP EP19890302649 patent/EP0333500A3/fr not_active Withdrawn

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