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
  • 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
  • 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
  • D06M15/19—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
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
  • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino 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
  • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
  • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

• the present invention pertains to fluorine-free compositions rendering textile articles, such as carpets and other textile floor coverings made from synthetic fibres or natural fibres water repellent, soil resistant and stain resistant.
• US-6,824,854 discloses a carpet treated with a soil resistant agent comprising a dispersion of polyfluoro organic compounds having at least one urea, urethane or ester linkage in combination with an anionic surfactant.
• the ratio of polyfluoro compound to surfactant is thereby from about 0.075 : 1.0 to about 5 : 1.
• US-4,264,484 relates to a carpet which is soil resistant and stain resistant and which has been treated with a composition
• a composition comprising a liquid containing a water-insoluble polymer derived from ethylenically unsaturated monomer free of nonvinylic fluorine having one major transition temperature higher than about 25 °C and a water insoluble fluoroaliphatic radical- and aliphatic chlorine-containing ester having a major transition temperature higher than about 25 °C.
• EP-A 2 205 688 discloses a method of treating substrates with fluorinated water-soluble (meth)acrylate copolymers which do impart water repellancy, soil resistance and stain resistance to the treated substrates thereby
• EP-A 2 222 734 describes a copolymer and a method for treatment of fibrous substrates with such copolymer to render them soil resistant and to impart minimal water repellency.
• the copolymer is prepared by polymerization of methacrylic acid with certain fluorinated alkylated benzyl isocyanates having straight chain or branched perfluoroalkyl groups.
• EP-A 1 368 525 describes a composition and its use for treating textiles, fibres and fabric substrates, whereby desirable properties like water repellency and durability are enhanced.
• Said composition is a quite complex mixture of various components such as a compound having an epoxy functionality, a compound having an alkoxy functionality, a crosslinking component selected from specific compounds and a catalyst comprising metal salts of mineral acids, e.g. zinc chloride, magnesium chloride, metal soaps and anhydrides.
• a condensation product is formed that is suitable to impart the desired properties to textiles when the compounds having the particular functionalities and the crosslinking component is reacted with the catalyst and cured.
• WO 2013 059387 A1 WO 2013 059395 A1 , WO 2013 059400 A1 , and WO 2013 059416 A1 describe non-fluorinated soil resist compositions featuring various combinations of surfactant, stain resist, and optional inorganic oxide species.
• the preferred soil resistant species are given as including polymethylmethacrylate, methyl methacrylate/ethyl methacrylate copolymer, an alkali metal salt of a hydrolysed styrene/maleic anhydride copolymer or of a hydrolyzed styrene/maleic anhydride/cumene terpolymer, an ammonium salt of a styrene/maleic anhydride copolymer or of a hydrolyzed styrene/maleic anhydride/cumene terpolymer, amorphous silicon dioxide, colloidal silica, and amorphous silica.
• the related art fails to disclose a carpet or a textile floor covering treated with fluorine-free chemical compositions providing durable soil resistance and water repellency, and a carpet or textile floor covering free of fluorine and having these high quality properties.
• compositions are inter alia described in US 2013/102215 and WO 2013/116486 .
• compositions that reliably impart durable surface protection to textile flooring substrates against the detrimental influences of water and soil.
• Such compositions should be easy to manufacture and easy to apply to textiles of synthetic or natural origin, while at the same time imparting a comparable protection as with fluorine containing chemicals as they are currently available on the market.
• reliable water repellency should be provided to carpets and textile floor coverings by treatment with such new compositions.
• the present invention pertains to a fluorine-free fiber protectant according to claim 1.
• composition X1 comprising:
• Another object of the invention is a fluorine-free fiber protectant Composition X2 comprising components A, B, C and:
• compositions effective under this disclosure are effective and include only B, C and D to yield a third composition, composition X3, which is not part of the present invention. And some compositions include only A and D, to yield a fourth composition, composition X4, which is not part of the present invention.
• Fluorochemicals are used as topical protectant ingredients in many industrial applications, including carpets and textiles industries. As topical protectants, certain fluorochemicals impart desirable water repellency, oil repellency and soil repellency attributes to substrates as surface coatings.
• certain fluorochemicals such as long chain polymeric perfluorocarbon species, have been shown to be precursors to undesirably bio-persistent species, such as perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs). Examples of long chain polymeric perfluorocarbon species are those having C8, C10 or C10 perfluorinated side chains.
• Water repellency refers to the degree to which a substrate repels water and water/isopropanol mixtures and is determined using a similar method to that for oil repellency.
• compositions in this disclosure are free of fluorine-containing ingredients.
• the compositions X1, X2 and X3 comprise two or more of components A, B, C and D, and the application rates of one or more of X1, X2 or X3 onto the carpet or textile floor covering may be adjusted to achieve maximum water and soil repellency benefit. Such performance benefits are, at the same time, economically advantageous.
• Typical nanoparticulate silicate clays useful in the invention as component A include those described in U.S. Patent Application Publication No. 2011/0311757 to Iverson et al. , which is incorporated herein by reference. These nanoparticulate silicate clays can be selected from the group consisting of smectites, kaolins, illites, chlorites, attapulgites, and combinations thereof.
• More specific examples include montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volkonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, muscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, palygorskite and combinations thereof.
• the nanoparticulate silicate component, A may be natural or synthetic.
• the nanoparticulate silicate component includes synthetic hectorite. Regardless of whether the clay nanoparticle is natural or synthetic, the clay nanoparticle component may be present in an amount from about 0.9 to about 24 volume parts of the combined composition X1. Typically, the clay nanoparticle is present in an amount of about 7 to about 14 parts by volume of the composition X1.
• suitable nanoparticulate silicates are those commercially available from BYK Additives GmbH under the brand name Laponite®. These include Laponite® RD, Laponite® RDS, Laponite® JS, Laponite® SL25, and Laponite® S482.
• Laponite® SL-25 is a basic (pH 8-10), 21.5--25 wt% solids aqueous dispersion.
• the nanoparticulate silicate found in Laponite® SL25 has an average particle size of from about 20 nm to about 90 nm, and a surface area of from about 120 m 2 /g to about 500 m 2 /g;
• Typical acrylic polymer components for use in the present disclosure as component B include those anionic or non-ionic, fluorine-free, water-dispersed acrylics that are known to act as binding agents, wherein the mixture including the acrylic copolymer binding agent ("binder") forms a transparent or largely transparent coating.
• the acrylic copolymer binder is self-crosslinking.
• the water-based non-fluorinated acrylic copolymer provides a certain degree of durable water repellency to the treated carpets and fibers.
• Binding agents useful according to this disclosure include any non-fluorinated emulsifiable acrylic polymer or copolymer suitable for use as a coating ingredient for soft surfaces, such as textiles, yarn, fabric, carpets, rugs, mats, or hard surfaces, such as vinyl tile, stone masonry, ceramic tile, and hardwood flooring. Many examples of such acrylic co-polymers can be utilized as component B in the compositions described by this disclosure.
• Acrylic-based copolymers having at least one of acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethacrylate, methyl ethacrylate, ethyl ethacrylate, propyl ethacrylate, butyl ethacrylate, acrylic acid, and ethylene monomers, and combinations and blends thereof, are suitable candidates for use according to this disclosure.
• the acrylic-based copolymers can be non-ionic, or anionic, but the preferred acrylic-based copolymers in this disclosure have a net anionic charge association. Further, preferred components are those anionic acrylic-based copolymers that are self-crosslinking, and can thus crosslink by application of thermal and/or photoinitiated stimuli. Numerous non-fluorinated, emulsified acrylic copolymers suitable as component B are commercially available, such as the self-crosslinking families of RHOPLEXTM and PRIMALTM emulsions, manufactured by Rohm and Haas Company.
• PRIMALTM ECO-36 (Rohm and Haas), which is an anionic, self- crosslinking acrylic based copolymer that can be applied on a substrate as a 46.5-47.5 wt% solids aqueous emulsion.
• PRIMALTM ECO-16 self-crosslinking, non-ionic, methyl methacrylate - ethyl acrylate copolymer
• PRIMALTM ECO-8 silicasel- crossiinking, nonionic
• MMA/EA copolymers corresponding polymer products from other manufacturers may also be used.
• Another possible water-based acrylic copolymer may be ethylene acrylic acid copolymer (EAA). These dispersion polymers are also known under various tradenames. For example TECSEAL E-799/45 (Trub Emulsions Chemie), an ethylene-acrylic acid dispersion (solids content 45%, Tg 4°C), may be used. Still another possible water-based acrylic copolymer class may be styrene-acrylic copolymers.
• Acrylic copolymers of different types with differing mechanical properties may be blended with each other to achieve the desired final properties of the treated fiber.
• the advantages of the acrylic copolymers can be summarized as
• Typical textile softening agents for use in the present disclosure as component D include those that are known to act as textile softening agents, wherein the mixture including the textile softening agent provides a smoother handle to the textile.
• Textile softening agents can act to improve the sewability of threads, or the softness or more pleasing tactile sensation of carpets and knitted fabrics. Textile softening agents can act to enhance lubricity when used to treat yarns, fabrics, textiles, carpets, and the like. Examples of softening agents are described by Rudat in U.S. Patent Appl. No.
• 2008 0287020 as being aminosilicones or aminosiloxanes, oils of various types, polyalkylene glycols, polyalkylene waxes, partially-oxidized polyalkylene waxes, lanolin and lanolin derivatives, fatty acids, fatty acid esters, oxidized or functionalized polyolefins, and stearates.
• Rudat describes the use of aminosiloxanes as efficacious when combined with fluorochemicals and silsesquioxane-containing sols.
• Polysiloxane compounds such as amino functional polydimethylsiloxane; fatty acid condensation products, such as condensation products of hydrated tallow with 2-[2-aminoethyl)-amino] ethanol; and acetate salt ( CAS No. 68425-52-5 ) or acryl compounds such as bis [acryloxyethyl]-hydroxymethyl ammonium methyl sulfate ( CAS No. 93334-15-7 ) are suitable in principle as softeners. Softeners suitable for the present invention are defined in claim 1. Softeners have also been described previously by Baumann in EP 1,746,199 B1 .
• Such textile and carpeting softeners are commercially available, and examples are Finistrol® AFN (fatty acid condensation product) of Thor, Speyer, Germany, and Megasoft® JET-LF of Huntsman Textile Effects, Langweid am Lech, Germany; Perrustol® CCA 500 (fatty acid condensation product) of Rudolf GmbH & Co. KG, Geretsried, Germany; Raniesoft® TS 20 (fatty acid condensation product) of Ranie Chemie, Wiehl, Germany; Softycon N (fatty acid condensation product) Textilcolor AG, Sevelen, Switzerland; Tubingal® OHS of CHT R. Beitlich GmbH, Tübingen, Germany; and Cefasoft Nl (fatty acid condensation product) of Zschimmer & Schwarz Mohsdorf GmbH & Co. KG, Mohsdorf, Germany.
• the textile softening is selected from the group consisting of a polyaminosiloxane, hydroxyterminated polyaminosiloxane, an alkoxyterminated polyaminosiloxane, alkyl modified polyaminosiloxane, alkoxy modified polyaminosiloxane, and combinations and blends thereof.
• the fiber treatment compositions disclosed herein are improvements over PFCA and PFSA fiber treatment technology.
• the aqueous compositions can be utilized directly, only with the addition of water of dilution. Further, the application process is environmentally friendly, resulting only in release of water vapor and negligent amounts of nonhazardous cosolvent vapors (dispersion aids) when the substrate is dried.
• Nanoparticles as a general class of chemical molecules, are known to extend the soiling protection properties provided by fluorine containing chemicals. As disclosed in U.S. patent application No. 2011/0311757 A1 , nanoparticle treatments have been used previously as a fluorine extender for anti-soiling purposes.
• WO2013/116486 teaches nanoparticles shown to have anti-soiling properties when used in conjunction with non-fluorinated chemicals having water repellent properties. The nanoparticles disclosed in WO2013/116486 demonstrate efficacy of non-fluorochemical treatments to produce a softer hand fiber, while retaining desirable soil-resistant attributes.
• a soil repellent fiber comprising a fluorine-free surface treatment comprising at least one clay nanoparticle component and at least one acrylic copolymer component.
• the clay nanoparticle can refer to particles substantially comprising minerals of the following geological classes: smectites, kaolins, illites, chlorites, and attapulgites.
• These classes include specific clays such as montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, muscovite paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, and palygorskite.
• specific clays such as montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravaisite, mus
• the clay nanoparticles can be either synthetic or natural, including synthetic hectorite, and Laponite® from BYK Additive GmbH, Moosburg/Germany.
• the Laponite® clay nanoparticles can be Laponite® RD, Laponite® RDS, Laponite® JS, Laponite® S482 and Laponite® SL25.
• the concentrates according to the disclosure typically contain stabilizing additives.
• Preferred concentrates according to the disclosure cany contain surfactant or emulsifier species.
• surfactants suitable for the present disclosure are any of the anionic or non-ionic surfactants commonly used in formulating chemicals, such as triethanolamine, water-soluble salts of alkylbenzene sulfonates such as the isopropylamine salt of a C 14 -alkyl benzene sulfonic acid, and/or a C 14 fatty alcohol sulfate, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates and sulfosuccinates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alky
• non-surfactant emulsifier species are diethylene glycol monobutyl ether (butyl diglycol) and ethylene glycol monohexyl ether (hexyl glycol). Glycols and glycol ethers are particularly preferred emulsifiers.
• the preferred emulsifiers ensure the textile softening constituents are kept as a finely divided emulsion in water.
• the choice of non-ionic emulsifiers is advantageous as they act to inhibit unwanted foaming during application, and they contribute to uniform treatment on the substrate surface. Should foaming be desired for application, a foaming agent can be provided.
• Other stabilizing additives include peptizing agents.
• Peptizing agents improve dispersability of nanoparticulates in a dispersion medium such as water.
• examples of peptizing agents suitable for this disclosure are disodium etidronate, sodium carbonates, sodium metaphosphates, sodium polyacrylates, and sodium hydroxide.
• Disodium etidronate is an especially preferred peptizing agent.
• compositions X1, X2, X3 or X4 as fiber, yarn, fabric, textile and carpet treatments for durable water repellency and soiling protection.
• the topical application of composition X1 in an amount from about 500 ppm to about 5,000 ppm nanoparticulate silicate can result in the desired end use performance of durable water repellency and soil resistance.
• Compositions X3 and X4 can be applied simultaneously and can also result in the desired end use performance of durable water repellency and soil resistance.
• Topical compositions X1, X2, X3 and X4 can be applied by many different methods, such as gravure coating, silk screen printing, roll coating, size press coating, spray bar application, rotary spray applicator, bath application, or foam wet processing methods.
• the compositions can be diluted prior to application. Suitable dilutents include those known in the art.
• the diluent is water.
• the acidity of the formulation may be adjusted.
• the pH may be adjusted to be between 5 and 10. In another nonlimiting embodiment, the pH may be adjusted to be between 5.5 and 6.5.
• the topical compositions X1, X2, X3, and X4 that on drying and evaporation of the water, form a coating on the substrate.
• Suitable substrates may be textile, yarn, fiber, fabric or carpeting. Examples of preferred methods of application in this disclosure are spray bar application and rotary spray applicator.
• Rotary applicator systems such the WEKO-FLOW with WEKO-SIGMA liquid application system, manufactured by Weitmann & Konrad GmbH & Co. KG of Leinfelden-Echterdingen, Germany are suitable.
• rotary applicator systems such as The Wave and The IQ Spray Application Systems, manufactured by Consultex Systems of Spartanburg, South Carolina, USA are suitable for application of compositions of this disclosure.
• Spray bar applicator systems, or spray manifold systems, are well known in the trade, and any such system is suitable for applying the compositions described herein.
• active solids the approximate amount, in terms of weight percent, of the active component in the formulated material.
• Formulated it is meant that, for example, one or more of the active components A, B, or C, are provided as complex water-borne mixtures, in combination with such chemical adjuncts as surfactants, cosolvents, emulsifying agents, peptizing agents, or dispersing agents, for example.
• the anionic acrylic-based copolymer, B can therefore be provided as a water-borne formulation having certain adjuncts present, and, separately, the textile softening agent, C, can be provided as a water-borne product having certain adjuncts present, and in this form B and C can, for example, be combined and mixed with A and D.
• Nanoparticulate A multidimensional particle in which one of its dimensions is less than 100 nm in length.
• owf "on weight of fiber.”
• the amount of solids of fiber protectant applied after evaporation of solvent.
• the value of solids applied owf is typically expressed as a percentage of the mass of fiber present in the article.
• fluid ppv parts per volume of a formulated (fluid-based) composition component.
• Soil repellency and dry soil resistance Terms used herein interchangeably to describe the ability to prevent dry soils from sticking to a fiber.
• the dry soil may be dirt tracked in by foot traffic.
• tpi twists per 2.54 cm.
• Weight Pick-up The amount of solution weight that was applied to the fiber before drying off the solvent.
• compositions X1, X2, X3 and X4 or mixtures thereof are not part of the present invention.
• composition X1 Composition X1:
• Table 1a Exemplary ranges for ingredients in Composition X1.
• the parts per volume refer to ranges of component Identifier approx. wt. %, active ingredient fluid ppv A Laponite ® SL25 21.5 - 25 4 - 96 B Primal TM ECO-36 46.5 - 47.5 3 - 50 C Water, any auxiliary stabilizers balance Total 100 Table 1b.
• composition X2 Composition X2:
• Table 2a Exemplary ranges for ingredients in Composition X2.
• component Identifier fluid ppv A Laponite ® SL25 80,0 B Primal TM ECO-36 10,0 D Tubingal OHS 5,0 C Water, any auxiliary stabilizers balance Total 100
• composition X3 is a composition having the following properties:
• Table 3a Exemplary ranges for ingredients in Composition X2.
• Table 3b An example recipe for Composition X3.
• composition X4
• Table 4a Exemplary ranges for ingredients in Composition X4.
• Soil repellency refers to the ability of a fibrous substrate to resist the adhesion of dry soils.
• the tests performed to evaluate soiling performance levels generally involve applying standardized, non-liquid-containing dry soil compositions to a fibrous substrate, and further subjecting the substrate to a moving load to simulate wear or trafficking.
• the soiled substrate is subsequently subjected to a controlled soil removal process, such as by vacuum cleaner. These tests may also involve water extraction.
• the substrate is then compared to a control sample, or a standard of established value.
• Composition X1 is the combination of A, B, and C at a range of incorporation indicated in Table 1.
• a suitable range of application of X1 onto an area of carpet fiber substrate is 0.1% - 8% owf.
• Application of X1 at less than 0.1 % owf is ineffective for durable soil and water repellency, and application of X1 at greater than 8% owf is understood to understood to not be economical under current market conditions, or practical as would be considered using the preferred methods of application in industry.
• a more preferable range of application of X1 on a fiber substrate such as carpet is 0.3% - 2.5% owf.
• Composition X2 is the combination of all four of A, B, C, and D, at a range of incorporation indicated in Table 2.
• a suitable range of application of X2 onto an area of carpet fiber substrate is 0.1% - 8% owf.
• a more preferable range of application of X2 on a fiber substrate such as carpet is 0.4% - 2.5% owf.
• Composition X3 is the combination of B, C, and D at a range of incorporation indicated in Table 3.
• a suitable range of application of X3 onto an area of carpet fiber substrate is 0.1% - 6% owf.
• Application of X3 at less than 0.1 % owf is ineffective for softness improvement, and application of X3 at greater than 6% owf is understood to have a detrimental effect on the soil resistance of the substrate.
• a more preferable range of application of X3 on a fiber substrate such as carpet is 0.3% - 2.0% owf.
• Composition X4 is the combination of A, and C at a range of incorporation indicated in Table 4.
• a suitable range of application of X4 onto an area of carpet fiber substrate is 0.1% - 8% owf.
• Application of X4 at less than 0.3 % owf is ineffective for soil resistance, while application of X4 at greater than 8% owf is understood to not be economical under current market conditions, or practical as would be considered using the preferred methods of application in industry.
• a more preferable range of application of X4 on a fiber substrate such as carpet is 0.5% - 4.0% owf.
• Compositions X1, X2, X3, or X4 are prepared by one or more of mixing, agitating, sonicating, or physically blending the individual chemistries A, B, D, in their requisite proportions, in diluent C.
• compositions X1, X2, X3, or X4 are prepared by taking each of A, B, D, and dispersing, emulsifying, sonicating, dissolving, or agitating each in diluent C, prior to combining the components by one or more of: mixing, agitating, sonicating, or physically blending the individual chemistries A, B, D, in their requisite proportions, in diluent C.
• a Composition X1 is applied to yarns, fibers, textiles, fabrics or carpets.
• the disclosed nanoparticle clays, A, acrylic-based copolymers, B, and aqueous diluent, C, are combined, in one pot, to yield a composition, X1, that is a surprisingly stable complex liquid mixture and is effective for durable water and soil repellency for fibers.
• Composition X1 is thereafter suitable for transport to a manufacturing facility, where it can optionally be diluted with water, then applied onto yarns, fibers, textiles, fabrics or carpets.
• a Composition X2 is applied to yarns, fibers, textiles, fabrics or carpets.
• the disclosed nanoparticle clays, A, acrylic-based copolymers, B, aqueous diluent, C, and textile softening agents, D, are combined, in one pot, to yield a composition, X2, that is a surprisingly stable complex liquid mixture and is effective for durable water and soil repellency for fibers, with additional softness benefit.
• Composition X2 is thereafter suitable for transport to a manufacturing facility, where it can optionally be diluted with water, then applied onto yarns, fibers, textiles, fabrics or carpets.
• compositions X1, X2, X3 and X4 are sequentially applied to yarns, fibers, textiles, fabrics or carpets.
• compositions X1, X2, X3 and X4 are applied simultaneously to yarns, fibers, textiles, fabrics or carpets.
• compositions X1, X2, X3, and X4 of the present disclosure find particular utility in systems that apply liquids under low- or no-foam conditions.
• Application methods wherein no- or low-foam compositions are desired include spray bar and rotary spray liquid applicator methods.
• any foaming agent used in the trade may be employed for applying one or more of a-Composition X1, X2, X3 or X4 as a foam.
• foaming agents suitable for use include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g.
• foaming agents suitable for use include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g. Hansanol® NS 242 conc, Hansa Group AG, Germany).
• alkyl amine oxides for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland)
• C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides available from Clariant
• sodium alpha olefin sulphonates e.g. Hansanyl® OS, Hansa Group AG, Germany
• sodium laureth sulfate
• compositions X1, X2, X3 and X4 are transported to manufacturers, diluted accordingly, and applied individually to yarns, fibers, textiles, fabrics or carpets.
• the acidity of Compositions X1, X2, X3, or X4 is adjusted to be between pH 5.0 and pH 10, prior to application to yarns, fibers, textiles, fabrics or carpets.
• a preferable pH is between pH 5.5 and pH 6.5.
• the fluorine-free fiber protection compositions included herein may additionally contain one or more stain-block chemistries, in order to combine soil protection and water repellency with suitable stain protection. If a stain-blocker is used, it is preferred to also add a dispersing agent in order to support better application of the composition in aqueous form.
• Anti-stain components for use in the disclosed stain blocker compositions have a component bearing an acidic moiety which associates with polymer amine end groups and protects them from staining by acidic dye stains.
• the general category of chemicals suitable to the process of the instant invention can comprise any chemical that blocks positively charged dye sites.
• Stain blockers are available in various forms such as syntans, sulfonated novolacs, sulfonated aromatic aldehyde condensation products (SACs) and/or reaction phenolics, olefins, products of formaldehyde, phenolics, substituted thiophenolics, sulfones, substituted sulfones, polymers or copolymers of branched olefins, cyclic olefins, sulfonated olefins, acrylates, methacrylates, maleic dianyhydride, and organosulfonic acids.
• SACs sulfonated aromatic aldehyde condensation products
• the stain blocker is typically water soluble and generally penetrates the fiber while the anti-soil, usually a fluorochemical, is a non-water soluble dispersion that coats the surface of fiber.
• stain blockers include, but are not limited to: phenol formaldehyde polymers or copolymers such as CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton, Ga.), MESITOL (from Bayer Corporation, Rock Hill, N.C.), ERIONAL (from Ciba Corporation, Greensboro, N.C.), INTRATEX (from Crompton & Knowles Colors, Inc., Charlotte, N.C.), STAINKLEER (from Dyetech, Inc., Dalton, Ga.), LANOSTAIN (from Lenmar Chemical Corporation, Dalton, Ga.), and SR-300, SR-400, and SR-500 (from E. I.
• SCOTCHGARD FX series carpet protectors from 3M Company, St. Paul Minn.
• sulfonated fatty acids from Rockland React-Rite, Inc., Rockmart, Ga
• the ARROSHIELDTM stain resist product line ArrowStar LLC, Dalton, GA, U.S.
• I-Protect® 2126 IVISTA S. a r. I., Germany
• Stain-blockers are usually ionic in nature and can be equally well applied in both discontinuous and continuous application in the carpet manufacturing process. In the continuous application, the carpet runs through the usual dyeing and printing stages, whereas in the discontinuous application various separate baths are used.
• the procedure to apply the stain-blocker to the textile can be in two steps or in a single application step.
• the stain-blocker application is followed by a treatment with one or more of X1, X2 or X3.
• stain-block chemistry is applied and one or more of X1, X2 or X3 are applied simultaneously, using foam application process technology such as is practiced in the trade.
• a dosage rate of 3.0 to 7.0% aqueous liquor on weight of fiber is recommended for the stain blocker.
• a separate treatment bath for the stain-blocking is used after the carpet dyeing process.
• the carpet is treated for a time period of from 20 to 30 minutes at a temperature of from 70 to 75 °C.
• the pH-value depends on the type of stain-blocker and should be held between 2.5 and 7.0.
• the carpet runs through the usual dyeing and printing stages.
• the stain-blocker is applied through a suitable application mechanism such as a dip trough, waterfall applicator or fluidyer.
• the stain block liquor should be applied at or around 60 °C ⁇ 10 °C, although the process will also work at colder temperatures.
• the stain-blocker is fixed in the steamer with a steaming time of 60 to 90 seconds.
• the carpet is then washed, vacuumed and dried.
• a soil resistant and water repellent application with one or more of components X1, X2, or X3 follows the stain-blocker, in the same process.
• Suitable dispersing agents for this purpose include, but are not limited to, fatty alcohol polyglycolethers (e.g. Sera® Sperse M-DEW; DyStar Textilmaschine GmbH & Co.) and alkyl aryl aminethoxylate (e.g. Avolan® IW liquid, Tanatex® Chemicals, The Netherlands), both of which are nonionic in nature.
• fatty alcohol polyglycolethers e.g. Sera® Sperse M-DEW; DyStar Textilmaschine GmbH & Co.
• alkyl aryl aminethoxylate e.g. Avolan® IW liquid, Tanatex® Chemicals, The Netherlands
• the textile fibers for the substrate, the carpet or the floor covering which is subjected to treatment with the compositions of the invention is of synthetic or natural origin.
• Suitable synthetic textiles are made from polymer bases such as polyamide like polyamide 6.6, which is known as poly(hexamethylene adipamide), or polyamide 6, which is known as poly(caprolactam), or polyesters like poly(ethylene terephthalate) and poly(propylene terephthalate), or poly(propylene), or mixtures or blends of one or more of such suitable polymer bases.
• Suitable textiles of natural origin are fibres made from wool or cotton.
• Soil resistant and water repellent chemicals are usually applied as the last step in carpet finishing, after application of stain resist chemistry, and prior to drying or backing. Soil resistant and water repellent chemicals may be applied to the carpet via spray application or foam application, which is known in the art. Following dilution of as-received formulated products, industry-recommended rates for application are from 1.0 wt% to 1.6 wt% on weight of carpet fiber (corresponding to 500 ppm to 800 ppm elemental fluorine content). However, application ranges for the fluorine-free fiber protection compositions useful for purpose of this disclosure are usually from 0,25 to 3,5 wt%.
• Spray application is the easiest method of applying soil resistant and water repellent chemicals.
• a spray facility may be installed in front of a dryer after coloration or in front of a latex backing oven.
• a suction hood should be installed above the spray bar.
• An aqueous solution of the composition is pumped through spray nozzles, installed above the running carpet, onto the carpet pile. For better distribution/penetration into the pile the solution should be applied to moistened carpet fiber.
• an aqueous liquor of the composition is pumped into a tank where it is metered for application by a spinning rotary plate. The rotary plate acts to apply microscopic droplets of the aqueous composition in uniform fashion onto the moving fiber, yarn, fabric, textile or carpet substrate.
• Foam application is the most advanced method for the treatment of carpets with soil resistant and water repellent chemicals. By using this minimum moisture application system, highly concentrated liquors in a foam state are applied to carpets running past. A further advantage of the foam application method is its improved penetration. Foam application facilities can be installed in front of a dryer or a latex backing oven. In case of insufficient foam stability a foaming agent can be added advantageously. These foaming agents are formulated in such a way that they decompose under common drying temperatures and do not negatively impact the performance of the soil resistant and water repellent chemicals.
• Suitable foaming agents include, but are not limited to alkyl amine oxides, for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland), C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides, available from Clariant, sodium alpha olefin sulphonates (e.g. Hansanyl® OS, Hansa Group AG, Germany) and sodium laureth sulfate (e.g. Hansanol® NS 242 conc, Hansa Group AG, Germany).
• alkyl amine oxides for example Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox® CSL (Clariant, Switzerland)
• C 12 to C 18 coconut fatty acid alkyl dimethyl amine oxides available from Clariant
• sodium alpha olefin sulphonates e.g. Hansanyl® OS, Hansa Group AG, Germany
• sodium laureth sulfate
• carpet samples are mounted on the interior of a drum, and chrome alloy steel balls, nylon polymer pellets, and a standard dry soil are added.
• the soil used is AATCC 122/123 standard soil:
• the test simulates initial soiling by dirty shoe soles (represented by the polymer pellets) in that the soil acts on both the carpet, and on the polymer pellets. 1.000 revolutions in a drum.
• This test determines a finished carpet's resistance to wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the fabric and the extent of surface wetting is determined visually. If after 10 seconds, four out of the five drops are still visible as spherical to hemispherical, the carpet is given a passing rating and the test is repeated with a higher rating number liquid.
• the repellency rating of the sample is the highest rating number liquid used to pass the repellency test. Carpets with a rating of 4 or higher have good anti-soiling properties. Without anti-soil treatment, most nylon carpets have a rating of 1 for water repellency.
• the test is later abbreviated as: "WR".
• the following liquids were used for water repellency tests: Rating Number Liquid Composition % Isopropanol % Water 1 2 98 2 5 95 3 10 90 4 20 80 5 30 70 6 40 60
• Acid dye stain resistance is evaluated using a procedure modified from the American Association of Textile Chemists and Colorists (AATCC) Method 175-2003, "Stain Resistance: Pile Floor Coverings.”
• 9 wt % of aqueous staining solution is prepared, according to the manufacturer's directions, by mixing cherry-flavored KOOL-AID® powder (Kraft/General Foods, White Plains, N.Y., a powdered drink mix containing, inter alia, FD&C Red No. 40).
• a carpet sample (4 x 6-inch or 10.16 x 15.24 cm) is placed on a flat non-absorbent surface.
• a hollow plastic 2-inch (5.1cm) diameter cup is placed tightly over the carpet sample.
• KOOL-AID® staining solution Twenty ml of the KOOL-AID® staining solution is poured into the cup and the solution is allowed to absorb completely into the carpet sample. The cup is removed and the stained carpet sample is allowed to sit undisturbed for 24 hours. Following incubation, the stained sample is rinsed thoroughly under cold tap water, excess water is removed by centrifugation, and the sample is dried in air. The carpet sample was visually inspected and rated for staining according to the FD&C Red No. 40 Stain Scale described in AATCC Method 175-2003. Stain resistance is measured using a 1-10 scale. An undetectable test staining is accorded a value of 10.
• the carpet test sample is not pre-cleaned and is placed flat on a smooth, horizontal surface.
• the cleaning solution is added into the tank of the spray-extraction unit, whereas cleaning is accomplished by moving the cleaning head over the carpet's surface.
• Samples are cleaned over a maximum time period of 2 minutes or until the stain is completely removed (less than 2 min).
• Example 1 (not part of the invention) was performed to demonstrate the soiling performance and water repellency of a Composition X2.
• the application liquor was applied manually in the lab using a hand-held spray device to a standard velour carpet dyed "baby blue" made from nylon 6,6, and having a fibre weight of 600 g/m 2 .
• the chemical application was followed by a curing process in a laboratory oven at 130 °C for about 15 minutes.
• Example 2 (not part of the invention) was performed to demonstrate the soiling performance and water repellency of a carpet treated by co-application of a Composition X3 and X4.
• the application liquor was applied using a WEKO application system onto a carpet tile, light grey in colour and having pile weight 400 g/m 2 , followed by a curing process in an oven at 130°C for about 8 minutes.
• Example 3 (not part of the invention) was performed to demonstrate the durability after hot water extraction (HWE) of carpets treated thusly:

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