JP6783144B2 - Water-repellent and stain-proof non-fluorine composition - Google Patents

Description

The present invention relates to a fluorine-free composition that makes woven articles such as carpets and other textile floor coverings made from synthetic or natural fibers water repellent, stain resistant and dye resistant. The present invention further relates to methods of treating textile articles, as well as treated textile articles that are water repellent, stain resistant and resist dyeing, especially carpets.

Fluorine-containing chemicals and compositions are generally used to impart various beneficial properties to synthetic or naturally occurring textile fibers, especially to protect carpets and other textile floor coverings from wetting and dirt. Was known.

U.S. Pat. No. 6,824,854 combines a carpet treated with an antifouling agent containing a dispersion of a polyfluoroorganic compound having at least one urea, urethane, or ester bond in combination with an anionic surfactant. Is disclosed. According to this, the ratio of the polyfluoro compound to the surfactant is about 0.075: 1.0 to about 5: 1.

U.S. Pat. No. 4,264,484 is a water-insoluble polymer derived from a non-vinyl fluorine-free ethylenically unsaturated monomer that is antifouling and stain-proof and has one main transition temperature above about 25 ° C. And the carpet treated with a liquid containing a water-insoluble fluoroaliphatic radical having a main transition temperature higher than about 25 ° C. and an aliphatic chlorine-containing ester.

European Patent A 2 205 688 discloses a method of treating a substrate with a fluorinated water-soluble (meth) acrylate copolymer, and the fluorinated water-soluble (meth) acrylate copolymer is water-repellent and stain-resistant. And it certainly imparts resist dyeing to the substrate treated thereby.

European Patent A 2222 734 describes copolymers and methods of treating fibrous substrates with such copolymers to make them antifouling and impart minimal water repellency. The copolymer is prepared by polymerization of methacrylic acid with a fluorinated alkylated benzyl isocyanate having a linear or branched perfluoroalkyl group.

It is also known to impart non-fluorine properties and water repellency to woven fabrics and woven fabrics.

European Patent A 1 368 525 describes the composition and its use for treating woven fabrics, fibers and woven fabric substrates, thereby providing desired properties such as water repellency and durability. It will be enhanced. The composition comprises a compound having an epoxy functional group, a compound having an alkoxy functional group, a cross-linking component selected from a specific compound, and a metal salt of a mineral acid, for example, zinc chloride, magnesium chloride, metal soap, and anhydrous. It is a fairly complex mixture of various constituents, such as a compound-containing catalyst. When the compound having a particular functional group and the crosslinked constituents are reacted with the catalyst and cured, a condensation product suitable for imparting the desired properties to the fabric is formed.

International Publication Nos. 2013 059387 A1, 2013 059395 A1, 2013 059400 A1, and 2013 059416 A1 provide various combinations of surfactants, resist dyes, and any inorganic oxide species. A characteristic non-fluorinated antifouling composition is described. Preferred antifouling species are polymethylmethacrylate, methylmethacrylate / ethylmethacrylate copolymer, hydrolyzed styrene / maleic anhydride copolymer or hydrolyzed styrene / maleic anhydride / cumentapolymer alkali metal salt, styrene / anhydrous. It is provided as comprising a maleic acid copolymer or an ammonium salt of hydrolyzed styrene / maleic anhydride / cumenter polymer, amorphous silicon dioxide, colloidal silica, amorphous silica and the like.

However, related technologies include carpets or textile floor coverings treated with a non-fluorinated chemical composition that provides durable antifouling and water repellency, and fluorine-free and high quality properties carpet or fiber floor coverings. Not disclosed.

In addition, there is increasing interest in the carpet and textile bedding industry to replace the currently used C ₆ -fluorine chemicals with non-fluorinated antifouling and water repellent products. Ecolabels such as "Blue Angel" awarded by RAL gGmbH (St. Augustin, Germany) and others continue to reinforce this trend.
An object of the present invention

Therefore, it was an object of the present disclosure to provide a fluorine-free composition that reliably imparts durable surface protection to the fibrous floor covering substrate against the harmful effects of water and dirt. Such compositions must be easy to produce and easy to apply to synthetic or naturally derived fabrics, while at the same time being made of fluorine-containing chemicals such as those currently on the market. Must be given protection comparable to. In addition to this, treatment with such new compositions must provide reliable water repellency for carpets and textile floor coverings.

Therefore, the present invention
A) Nanoparticle silica clay (also called clay nanoparticles) and
B) Anionic acrylic copolymer binder and
C) With respect to the fluorine-free fiber protective composition X1 containing water.
The mixing ratio is 0.8 to 24 parts by volume for A, 1.3 to 23.8 parts by volume for B, and the rest is C. Composition X1 is useful in applications such as natural or synthetic fiber protection. In addition, following the evaporation of water, the fibers treated with composition X1 have improved water repellency and antifouling properties that are useful as substitutes and substitutes for the currently applied fluorinated fiber protective compositions. Present.

Another object of the present invention is the constituents A, B, C, and.
D) Fluorine-free woven fabric protective agent composition X2 containing a woven fabric softening agent.
The mixing ratio is 0.9 to 22.5 parts by volume for A, 1.3 to 19 parts by volume for B, 0.7 to 11 parts by volume D, and the rest is C. Composition X2 is also useful in applications such as natural or synthetic fiber protection.

In addition, other compositions effective in the present disclosure are effective and include only B, C, and D to produce a third composition, composition X3. Some compositions contain only A and D to produce a fourth composition, composition X4.

Another object of the present invention is a product, in particular a carpet or textile bedding, which is treated with the composition previously defined herein, for example by spraying or foaming, thereby this. The article is made water repellent and stain resistant.

Another object of the present invention is a composition as defined herein in an amount effective to make a synthetic or naturally occurring fabric or fiber water repellent, stain resistant and flexible. This is a method for non-fluorine treatment.

Another object of the present invention is a kit that provides one or more of the compositions X1, X2, X3, or X4 in separate containers that are then mixed and / or used at the carpet manufacturing site.

Fluorine-based chemicals are used as topical protective agent components in many industrial applications, including the carpet and textile industries. As a topical protective agent, certain fluorochemicals impart the desired water, oil repellency, and antifouling properties to the substrate as a surface coating. However, certain fluorochemicals, such as long-chain polymer perfluorocarbon species, can be used for unwanted bio-persistent species such as perfluoroalkylcarboxylic acid (PFCA) and perfluoroalkanesulfonic acid (PFSA). It has been shown to be a precursor. Examples of long-chain polymer perfluorocarbon species are those with C8, C10, or C10 all-fluorine-substituted side chains. There is a desire in the carpet and textile industry to reduce the overall use of fluorochemicals for environmental and cost reasons. Therefore, it can be understood that there is a demand for durable water repellent and antifouling fibers containing reduced amounts of fluorochemicals. Recent trends in this area have been directed towards the adoption of emulsified, shorter chain, all-fluorine-substituted polymer components for application on fibers, carpets, woven fabrics and the like. Examples of shorter chain total fluorine substituted polymers are those with C4 and / or C6 side chains. A prominent consideration of this topic is provided by Wang, Cousins, Scheringer, and Hungerbuehler of Environmental International. [[Fluorinetated alternates to long-chain perfluoroalkyl carboxylic acids (PFCSs), perfluoroalkane sulphonic acids (PFSAs) and thyre4r The solution is to remove the fluorochemical-containing treatment instead of using a non-fluorinated composition that imparts the desired water repellent and antifouling performance properties. Ecolabels such as "Blue Angel" awarded by RAL gGmbH (St. Augustin, Germany) and others continue to reinforce this trend.

In the carpet and textile industry, there is a need for solutions to provide durable water repellent and antifouling properties to fibrous substrates without the use of long chain polymeric perfluorocarbon species. Water repellency refers to the degree to which the substrate repels water and the water / isopropanol mixture and is determined using a method similar to that for oil repellency.

Unlike the antifouling or water repellent chemicals currently applied, the compositions of the present disclosure do not contain fluorine-containing components. The compositions X1, X2, and X3 contain two or more of the constituents A, B, C, and D and onto one or more carpets or textile floor coverings of X1, X2, or X3. The rate of application can be adjusted to achieve maximum water repellency and antifouling benefits. At the same time, such performance benefits are economically advantageous.

Typical nanoparticle silica clays useful as component A in the present invention include those described in US Patent Application Publication No. 2011/0311757 to Iverson et al., Which are incorporated herein by reference. These nanoparticulate silica clays can be selected from the group consisting of smectite, kaolin, illite, chlorite, attapulsite, and combinations thereof. More specific examples include montmorillonite, bentonite, pyrophyllite, hectrite, saponite, saponite, nontronite, talc, byderite, volconscoite, vermiculite, kaolinite, chlorite, antigolite, anakisite, Indellite, chrysotile, bravasite, muscovite, paragonite, black mica, corlens stone, chlorite, dombassite, sudoite, pennin, sepiolite, parigolskite, And combinations thereof.

The nanoparticle silica component A can be natural or synthetic. In one embodiment, the nanoparticle silica constituents include synthetic hectorite. Whether the clay nanoparticles are natural or synthetic, the clay nanoparticles constituents may be present in an amount of about 0.9 to about 24 parts by volume of the bound composition X1. Clay nanoparticles are typically present in an amount of about 7 to about 14 parts by volume of composition X1. An example of a suitable nanoparticle silica is one commercially available from BYK Adaptives GmbH under the trade 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% by weight solid aqueous dispersion. Laponite (R) Nanoparticles Silica found in the SL25 has a surface area of an average particle size of about 20nm~ about 90 nm, and about 120 m ² / g to about 500m ² / g.

Typical acrylic polymer components for use as component B in the present disclosure are anionic or nonionic, fluorine-free, water-dispersed acrylics known to act as binders. Mixtures comprising acrylic copolymer binders (“binders”) form clear or mostly clear coatings. In some examples, the acrylic copolymer binder is self-crosslinking. When used in accordance with the present disclosure, water-based non-fluorinated acrylic copolymers provide some tough water repellency to treated carpets and fibers.

Binders useful in accordance with the present disclosure are any non-fluorinated emulsifying acrylic polymers or woven fabrics, spun yarns, woven fabrics, carpets, rugs, mats and other flexible surfaces, or vinyl tiles, masonry, ceramic tiles, and firms. Contains copolymers suitable for use as a coating component on hard surfaces such as wood rugs. Many examples of such acrylic copolymers can be utilized as component B in the compositions described herein. Acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etacrylate, methyl etacrylate, ethyl etacrylate, propyl etacrylate, butyl ethanecrylate Acrylic copolymers having at least one of acrylic acids and ethylene monomers, and combinations and mixtures thereof, are good candidates for use in accordance with the present disclosure. The acrylic copolymer can be nonionic or anionic, but is preferably an acrylic copolymer having a net anionic charge association in the present disclosure. In addition, the preferred constituent is a self-crosslinking anionic acrylic copolymer, which can be crosslinked as described above by application of heat and / or photoinitiative stimuli. A number of non-fluorinated, emulsified acrylic copolymers suitable as constituent B, such as the self-crosslinked group of RHOPLEX ™ and the PRIMAL ™ emulsion manufactured by Rohm and Haas Company, are commercially available. One preferred binder is PRIMAL ™ ECO-36 (Rohm and Haas), which is anionic and can be applied onto the substrate as a 46.5-47.5% by weight solid substance aqueous emulsion. It is a self-crosslinked acrylic copolymer. Depending on the process requirements, PRIMAL ™ ECO-16 (self-crosslinked, nonionic, methylmethacrylate-ethylacrylate copolymer) and PRIRAL ™ ECO-8 (self-crosslinked, nonionic) may also be used. Corresponding polymer products from other manufacturers can also be used as MMA / EA copolymers.

Another possible aqueous acrylic copolymer could be ethylene acrylic acid copolymer (EAA). These dispersed polymers are also known by various trade names. For example, TECSEAL E-799 / 45 (Trub Emulations Chemie), an ethylene-acrylic acid dispersion (solid matter amount 45%, glass transition temperature 4 ° C.) can be used. Yet another possible type of aqueous acrylic copolymer can be a styrene-acrylic copolymer.

The present invention is not limited to the use of substances identified by a particular trade name, but it should be understood that other substances having properties similar to the purposes and effects of the present invention may be used.

Different types of acrylic copolymers with different mechanical properties can be mixed with each other to achieve the desired final properties of the treated fibers. The advantages of acrylic copolymers are
-Transparency,
-Thermosetting,
Can be summarized as-adhesive or durable, and-water repellency on fibers or carpets.

Textile softeners typically used as constituent D in the present disclosure include those known to act as textile softeners, and mixtures containing fabric softeners are smoother to the fabric. Provide a texture. The woven softening agent can act to improve the seizability of the yarn, or the softness or more satisfactory tactile sensation of the carpet and woven woven fabric. When woven softeners are used to treat spun yarns, woven fabrics, wovens, carpets, etc., they can act to enhance lubricity. Suitable examples of such agents are aminosilicone or aminosiloxane, various types of oils, polyalkylene glycols, polyalkylene waxes, partially oxidized polyalkylene waxes, lanolin, and lanolin derivatives, fatty acids, fatty acid esters, oxidized or functionalized polyolefins. , As well as stearic acid, described by Rudat in US Patent Application No. 2008/0287020. Rudat describes the use of aminosiloxanes as being effective when combined with fluorochemicals and silsesquioxane-containing sol. U.S. Patent Application No. 2008 0287020 is incorporated herein by reference. Polysiloxane compounds such as amino-functional polydimethylsiloxane, fatty acid condensates such as condensates of hydrated tallow with 2- [2-aminoethyl) -amino] ethanol, and acetate (CAS No. 68425-52-5). Alternatively, an acrylic compound such as bis [acrylic oxyethyl] -hydroxymethylammonium methyl sulfate (CAS No. 93334-15-7) is, in principle, suitable as a softening agent. Softeners from the compounds described above or mixtures thereof can be included in compositions according to the present invention. Suitable softeners have previously been described by Baumann in European Patent No. 1,746,199B1. Such woven and carpet softeners are commercially available, and examples of suitable products are Finistrol® AFN (Fatrite Condensation Product) from Thor (Speyer, Germany), and Huntsman Textile Effects (Langweid am Lech). , Germany) Megasoft® JET-LF, Rudolf GmbH & Co., Ltd. Perrustol (registered trademark) CCA 500 (fatty acid condensation product) manufactured by KG (Geretsried, Germany), Ranieft (registered trademark) TS 20 (fatty acid condensate product) manufactured by Rane Chemie (Wiehl, Germany), Textilcol Softicon N (fatty acid condensation product), CHT R. et al., Switzerland). Tabingal® OHS, manufactured by Beitrich GmbH (Tubingen, Germany), and Zschimmer & Schwarz Mohsdorf GmbH & Co., Ltd. Examples thereof include Cefasoft NI (fatty acid condensation product) manufactured by KG (Mohsdorf, Germany). European Patent No. 1,746,199 is incorporated herein by reference.

In general, the fiber treatment compositions disclosed herein are modifications of PFCA and PFSA fiber treatment techniques. The aqueous composition can be utilized directly only when used in conjunction with the addition of diluted water. In addition, the coating process is environmentally friendly and only results in the release of natural amounts of water vapor and harmless co-solvent vapors (dispersion aids) when the substrate dries.

Nanoparticles as a common type of chemical molecule are known to extend the stain protection properties provided by fluorine-containing chemicals. Nanoparticle treatment has previously been used as a fluorine extender for antifouling purposes, as disclosed in US Patent Application 2011/0311757 A1, which is incorporated herein by reference. WO 2013/116486, incorporated herein by reference, teach nanoparticles that have been shown to have antifouling properties when used with non-fluorinated chemicals that have water repellent properties. The nanoparticles disclosed in WO 2013/116486 demonstrate the effectiveness of non-fluorinated chemical treatments to produce softer hand fibers while maintaining the desired antifouling properties. To do.

Disclosed are antifouling fibers comprising a fluorine-free surface treatment containing at least one clay nanoparticle constituent and at least one acrylic copolymer constituent. Clay nanoparticles can refer to particles that substantially contain the following geological types of minerals: smectite, kaolin, illite, chlorite, and attapulsite. These types include montmorillonite, bentonite, pyrophyllite, hectorite, saponite, saponite, nontronite, talc, byderite, volchonskite, vermiculite, kaolinite, deckite, antigolite, anaukisite, Indellite, chrysotile, bravasite, suscovite, paragonite, black mica, corlens stone, bitter chlorite, donbassite, sudoite, pennin, sepiolite, and polygolskite ( Contains certain clays such as polygorskite). Clay nanoparticles can be either synthetic or natural and include synthetic hectorite and Laponite® from BYK Adaptive GmbH (Moosburg / Germany). The Laponite® clay nanoparticles can be Laponite® RD, Laponite® RDS, Laponite® JS, Laponite® S482, and Laponite® SL25. ..

Concentrates according to the invention typically contain stabilizing additives. Preferred concentrates according to the invention can contain surfactant or emulsifier species. Examples of suitable surfactants for the present disclosure are water-soluble salts of alkylbenzene sulfonic acids such as triethanolamine, C ₁₄ -alkylbenzene sulfonic acid, and / or isopropylamine salt of C ₁₄ aliphatic alcohol sulphonic acid, alkylsulfates, alkyls. Polyethoxyether sulphate, paraffin sulfonic acid, alpha olefin sulfonic acid and sulfosuccinate, alpha-sulfocarboxylate and their esters, alkyl glyceryl ether sulfonic acid, fatty acid monoglyceride sulphonic acid and sulfonic acid, alkylphenol polyethoxy ether sulphate, about 6 ~ Commonly used in the formulation of chemicals such as water-soluble salts or esters of alpha-sulfonated fatty acids containing about 20 carbon atoms in the fatty acid group and about 1 to about 10 carbon atoms in the ester group. It is either an anionic or nonionic surfactant to be used. Examples of preferred 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 emulsifier ensures that the fabric softening component is retained as a micronized emulsion in water. The choice of nonionic emulsifiers is advantageous because they act to inhibit unwanted foaming during coating and they also contribute to a uniform treatment on the substrate surface. If foaming is desired for application, a foaming agent may be provided. Other stabilizing additives include degluing agents. Glue-free agents improve the dispersibility of nanoparticles in dispersion media such as water. Examples of lytic agents suitable for the present disclosure include disodium etidronic acid, sodium carbonate, sodium metaphosphate, sodium polyacrylate, and sodium hydroxide. Disodium etidronic acid is a particularly preferred glutinating agent.

However, prior art has combined one or more of compositions X1, X2, X3, or X4 as a durable water repellent and stain protection fiber, spun yarn, woven fabric, woven fabric, and carpet treatment. Not disclosed. Applicants are surprised that topical application of composition X1 in an amount of nanoparticle silica of about 500 ppm to about 5,000 ppm can provide the desired end-use performance of durable water repellency and stain resistance. I found. In another aspect of the present disclosure, the compositions X3 and X4 can be applied simultaneously, providing the desired end-use performance of durable water repellency and antifouling properties. This is a significant finding to eliminate additional economic costs, treatment steps, and equipment needs, as well as environmental concerns associated with the use of fluorochemicals such as microcrystalline wax or other water repellent technologies.

The topical compositions X1, X2, X3, and X4 can be used in many applications such as gravure coating, silk screen printing, roll coating, size press coating, spray bar coating, rotary spray coating, bath coating, or foam wet treatment methods. It can be applied by different methods. In one non-limiting embodiment, the composition can be diluted prior to application. Suitable diluents include those known in the art. In one non-limiting embodiment, the diluent is water. In another non-limiting embodiment, the acidity of the formulation can be adjusted. In one non-limiting embodiment, the pH can be adjusted to 5-10. In another non-limiting embodiment, the pH can be adjusted to 5.5-6.5. Upon drying of the treated substrate and evaporation of water, the local compositions X1, X2, X3, and X4 during drying and evaporation of water form a coating on the substrate. Suitable substrates can be woven fabrics, spun yarns, fibers, woven fabrics, or carpets. Examples of preferred coating methods in the present disclosure include spray bar coating and rotary spray coating. Weightmann & Konrad GmbH & Co. A rotary coating system such as WEKO-FLOW having a WEKO-SIGMA liquid coating system manufactured by KG (Leinfelden-Echterdingen, Germany) is suitable. Similarly, rotary coater systems such as Wave and IQ spray coat systems from Consultex Systems (Spartanburg, South Carolina, USA) are suitable for coating the compositions of the present disclosure. Spray bar coater systems, or spray manifold systems, are well known in the art and any such system is suitable for applying the compositions described herein.
Definition

Mostly well known to those of skill in the art, the following definitions are provided for clarity purposes.

Approximate Weight% of Active Solids: Approximate amount of active constituents in the blended material, in weight%.

Formulation: For the purposes of the present disclosure, "blending" means, for example, one or more of the active constituents A, B, or C, eg, surfactants, cosolvents, emulsifiers, glutinates, or dispersions. Means that it is provided as a complex aqueous mixture in combination with such chemical aids such as agents. Thus, the anionic acrylic copolymer B can be provided as an aqueous formulation with a particular auxiliary agent present, and separately, the textile softener C is provided as an aqueous product with a specific auxiliary agent present. In this form, B and C can be combined and mixed with, for example, A and D.

Nanoparticles: Multidimensional particles, one of which is less than 100 nm in length.

owf: "per fiber weight". The amount of fiber protectant solids applied after evaporation of the solvent. The value of the applied solids per fiber weight is typically expressed as a percentage of the mass of fibers present in the article.

Liquid ppv: Volume by volume of the compounded (liquid-based) composition component.

Antifouling and anti-drying stains: As used herein, these terms are used interchangeably to describe the ability to prevent dry stains from adhering to the fibers. For example, dry stains can be filth brought in by walking.

tip: Number of twists per inch.

WPU (impregnation amount): The weight of solution applied to the fibers before the solvent is completely dried.

The present invention will be described in more detail with the help of the following examples which do not limit the scope of the invention. Further, it should be understood that the preparations in the present disclosure reflect specific utilizations for the constituents added as part of the preparations of the individual examples, but these preparations are shown. It should not be construed to be restricted for the purposes of the present disclosure so as not to cover a similarly effective range of utilization for the formulated components. For example, if component B is described as being used in a composition at 10.0 ppv, it is understood that B can also be used in compositions at 5, 7, 9, 11, 13, and 15 ppv. Should be.

The following are examples of mixtures of compositions X1, X2, X3, and X4 suitable for the present invention.

Antifouling property refers to the ability of the fibrous substrate to resist the adhesion of dry stains. Tests performed to assess antifouling levels include applying a standardized liquid-free dry stain composition to a fibrous substrate and further subjecting it to a moving load to simulate wear or movement. Accompanied by. The soiled substrate is subsequently subjected to a controlled stain removal process, such as with a vacuum cleaner. These tests may involve water extraction. The substrate is then compared to a control sample or established reference value.

Composition X1 is a combination of A, B, and C in the range of incorporation shown in Table 1. A suitable range for applying X1 over the area of the carpet fiber substrate is 0.1% to 8% owf. Application of X1 below 0.1% owf is not effective due to its tough antifouling properties and water repellency, application of X1 above 8% owf is industry preferred under current market conditions. It is understood that it is understood that it is not economical or practical enough to consider using the method of application. A more preferred range for applying X1 onto a fiber substrate such as a carpet is 0.3% to 2.5% owf.

Composition X2 is a combination of all four of A, B, C, and D in the range of incorporation shown in Table 2. A suitable range for applying X2 over the area of the carpet fiber substrate is 0.1% to 8% owf. A more preferable range of application of X2 on a fiber substrate such as a carpet is 0.4% to 2.5% owf.

The composition X3 is a combination of B, C, and D in the combination range shown in Table 3. A suitable range for applying X3 over the area of the carpet fiber substrate is 0.1% to 6% owf. It is understood that application of X3 below 0.1% owf is not effective for improving flexibility and application of X3 above 6% owf has a detrimental effect on the antifouling properties of the substrate. .. A more preferred range for applying X3 onto a fiber substrate such as a carpet is 0.3% to 2.0% owf.

Composition X4 is a combination of A and C within the range of incorporation shown in Table 4. A suitable range for applying X4 over the area of the carpet fiber substrate is 0.1% to 8% owf. While it is understood that application of X4 above 8% owf is not economical or practical enough to consider using the preferred application method in the industry under current market conditions. Application of X4 below 0.3% owf is not effective for antifouling properties. A more preferred range for applying X4 onto a fiber substrate such as a carpet is 0.5% to 4.0% owf.

In one embodiment, the composition X1, X2, X3, or X4 mixes, stirs, or sonicates the individual chemicals A, B, D in their required proportions in diluent C. Alternatively, it can be prepared by one or more of physical mixing.

In another embodiment, the compositions X1, X2, X3, or X4 are mixed, agitated, ultrasonically treated with the individual chemicals A, B, D in their required proportions in diluent C. Disperse, emulsify, ultrasonically treat, or dissolve each of A, B, and D in diluent C before binding the constituents by one or more of, or by physically mixing. Prepared by simmering or stirring.

In yet another embodiment, the composition X1 is applied to a spun yarn, fiber, woven fabric, woven fabric or carpet. The disclosed Nanoparticle Clay A, Acrylic Copolymer B, and Aqueous Diluent C are combined in one pot, a surprisingly stable composite liquid mixture, durable water repellent for fibers and A composition X1 effective for antifouling property was obtained. The composition X1 is then suitable for transport to a manufacturing facility where it can be optionally diluted with water and then applied onto spun yarns, fibers, fabrics, woven fabrics or carpets.

In another embodiment, the composition X2 is applied onto a spun yarn, fiber, woven fabric, woven fabric, or carpet. The disclosed nanoparticle clay A, acrylic copolymer B, aqueous diluent C, and textile softener D are combined in one pot and are a surprisingly stable composite liquid mixture for fibers. A composition X2 has been obtained that is effective for durable water repellency and antifouling properties and has the additional benefit of flexibility. The composition X2 is then suitable for transport to a manufacturing facility where it can be optionally diluted with water and then applied onto spun yarns, fibers, fabrics, woven fabrics, or carpets.

In yet another embodiment, one or more of the compositions X1, X2, X3, and X4 is applied over time to the spun yarn, fiber, woven fabric, woven fabric or carpet.

In yet another embodiment, one or more of the compositions X1, X2, X3, and X4 are applied simultaneously to the spun yarn, fiber, woven fabric, woven fabric or carpet.

In another embodiment, the compositions X1, X2, X3, and X4 of the present disclosure are foamed so that any foam produced by stirring X1, X2, X3, or X4 is temporary. Discover certain practicality in systems that apply little or no liquid. Coating methods in which a foam-free or low-foam composition is desired include methods using a spray bar and a rotary spray liquid coater.

In yet another aspect of the present disclosure, when foaming is proven necessary, any foaming agent used in the art is one or more of the compositions X1, X2, X3, or X4. Can be used to apply as foam. Examples of suitable blowing agents for use, alkylamine oxides, for example, Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox (R) CSL (Clariant, Switzerland), C 12 available from Clariant -C ₁₈ Coconut fatty acid alkyldimethylamine oxides, sodium alpha olefin sulfonates (eg Hansanyl® OS, Hansa Group AG, Germany), and sodium laureth sulfate (eg Hansanol® NS 242 cone, Hansa Group AG, Germany). ), But is not limited to these. However, when it proves necessary to apply foam, any of the standard foaming agents used in the industry is suitable. Examples of suitable blowing agents for use, alkylamine oxides, for example, Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox (R) CSL (Clariant, Switzerland), C 12 available from Clariant -C ₁₈ Coconut fatty acid alkyldimethylamine oxides, sodium alpha olefin sulfonates (eg Hansanyl® OS, Hansa Group AG, Germany), and sodium laureth sulfate (eg Hansanol® NS 242 cone, Hansa Group AG, Germany). ), But is not limited to these.

In another embodiment, one or more of the compositions X1, X2, X3, and X4 are transported to the manufacturer, appropriately diluted, and individually applied to spun yarn, fiber, woven fabric, woven fabric or carpet. Will be done.

In another embodiment, the acidity of the composition X1, X2, X3, or X4 is adjusted to pH 5.0 to pH 10 prior to application to spun yarns, fibers, fabrics, woven fabrics, or carpets. The preferred pH is pH 5.5-5 to pH 6.5.

In yet another embodiment, one or more of the compositions X1, X2, X3, and X4 are shipped together as a kit or package of chemicals to the manufacturer. In this embodiment, they are properly diluted and then co-applied to spun yarns, fibers, fabrics, woven fabrics, or carpets.

In yet another embodiment, one or more of the compositions X1, X2, X3, and X4 are shipped together as a kit or package of chemicals to the manufacturer. In this embodiment, they are combined in the factory, diluted appropriately and the resulting liquid is applied onto spun yarn, fibers, fabrics, woven fabrics or carpets.

Anti-Stain Agent The non-fluorine fiber protective composition contained herein may further contain one or more anti-stain chemicals to combine antifouling and water repellency with suitable stain protection, and stains. If a stop agent is used, it is also preferable to add a dispersant to support better application of the composition in aqueous form. When a stain inhibitor is used, it is also preferable to add a dispersant to support better application of the composition in aqueous form. Anti-stain components for use in the disclosed anti-staining compositions have components that carry acidic moieties that bind to polymer amine end groups and protect them from stains by acid dye dyes. A general category of chemicals suitable for the process of the present invention can include any chemical that blocks positively charged dye sites. Stain suppressants include cintan, novolac sulfonic acid, sulfonic acid aromatic aldehyde condensation product (SAC) and / or reactive phenol resin, olefin, formaldehyde product, phenol resin, substituted thiophenol resin, sulfone, substituted sulfone, branch. It is available in various forms such as polymers or copolymers of olefins, cyclic olefins, sulfonic acid olefins, acrylates, methacrylates, maleic acid dianhydrides, and organic sulfonic acids. These are usually made by reacting formaldehyde, phenol, polymethacrylic acid, maleic acid dianhydride, and sulfonic acid, depending on the particular chemical. In addition, stain inhibitors are usually water-soluble and generally penetrate the fibers, while the usual antifouling fluorochemicals are water-insoluble dispersions that coat the surface of the fibers.

Examples of stain inhibitors are CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton, Ga.), MESITOR (from Bayer Corporation, RockHill, NC.), ERINOAL (Cibor). (From C.), INTRATEX (from Crompton & Knowles Colors, Inc., Charlotte, NC), STAINKLEER (from Bayer, Inc., Dalton, Ga.), LANOSTAIN (from Lenmar Chemical Corporation, Galation) , And phenol formaldehyde polymers or copolymers such as SR-300, SR-400, and SR-500 (from EI du Pont de Nemours and Company, Wilmington, Del.); SCOTCHGARD FX Series Carpet Protective Agents (3M Company, 3M Company, Polymers of methacrylic acid such as (from St. Paul Minn.); Sulfated fatty acids (from Rockland React-Rite, Inc., Rockmart, Ga); ARROSHIELD ™ anti-staining product line (from ArrowStar LLC, Dalton, GA, U). S.), I-Protect® 2126 (INVISTA S. all., Company), and the Ultraguard SB-700 dye-resistant product line (Tri-Tex, Canda). Not limited.

The stain inhibitor is usually ionic in nature and can be applied equally well in both intermittent and continuous application in the carpet manufacturing process. In continuous application, the carpet travels through a normal dyeing and printing stage, while in intermittent application, various separate batches are used.

The procedure for applying the stain inhibitor to a woven fabric, such as a rug, can be a two-step or single application step. In the two-step procedure, the stain inhibitor is applied followed by a treatment with one or more of X1, X2, or X3. In a single coating step where a simultaneous coating system is used, the antifouling chemicals are applied using foam coating process techniques such as those practiced in the industry, and one or more of X1, X2, or X3 is applied. It is applied at the same time.

For stain inhibitors, an aqueous liquid input rate of 3.0-7.0% per fiber weight is recommended. For intermittent applications, a separate treatment batch is used for stain prevention after the carpet dyeing process. The carpet is processed at a temperature of 70-75 ° C. for a period of time of 20-30 minutes. The pH value depends on the type of stain inhibitor, but should be kept between 2.5 and 7.0. For continuous application, the carpet travels through a normal dyeing printing stage. The stain inhibitor is applied through a suitable application mechanism such as a dipping tank, a drop-in applicator, or a fluidizer. The stain remover must be applied at or around 60 ° C. ± 10 ° C., but the process will also work at lower temperatures. The stain inhibitor is immobilized in a steamer with a steam treatment time of 60 to 90 seconds. The carpet is then washed, evacuated and dried. Ideally, the antifouling as well as water repellent application by one or more of the constituents X1, X2, or X3 follows the stain inhibitor in the same process.

Suitable dispersants for this purpose include fatty alcohol polyglycol ethers (eg, Sera® Space M-DEW, DyStar Textilfarben GmbH & Co.), and alkylarylamine ethoxylates (eg, Avolan (registered)). Includes, but is not limited to, IW liquid, Tanatex® Chemicals, The Etherlands), both of which are essentially nonionic.

As already mentioned earlier, the woven fiber, carpet, or textile bedding for the substrate to be treated with the compositions of the present invention is of synthetic or natural origin. Suitable synthetic fabrics are polyamides such as polyamide 6.6 known as poly (hexamethylene adipamide), or polyamide 6 known as poly (caprolactam), or poly (ethylene terephthalate) and poly ( It is made from a polymer base such as polyester (propylene terephthalate), or poly (propylene), or a mixture or mixture of one or more of such suitable polymer bases. Suitable naturally derived fabrics are fibers made from wool or cotton.

Antifouling and water repellent chemicals are usually applied as the final step in carpet finishing after application of the resist chemicals and before drying or lining. Antifouling and water repellent chemicals may be applied to the carpet via spray coating or foam coating known in the art. The industry-recommended rate of application after dilution of the untreated formulation product corresponds to 1.0% to 1.6% by weight (500 ppm to 800 ppm fluorine atom content) based on the weight of the carpet fibers. To do). However, the coating range for non-fluorinated fiber protective compositions useful for the purposes of the present disclosure is typically 0.25 to 3.5% by weight.

Spray application is the easiest method for applying antifouling and water repellent chemicals. The spray equipment may be installed in front of the colored dryer or in front of the latex lined oven. A suction hood should be installed above the spray bar to prevent the spread of the spray. The aqueous solution of the composition is pumped into the carpet fluff through a spray nozzle placed above the moving carpet. For better distribution / penetration into the fluff, the solution must be applied to moistened carpet fibers. Alternatively, the aqueous liquid of the composition is pumped into the tank, which is measured for application by a spinning spinning plate. The rotating plate acts to apply tiny droplets of the aqueous composition in a uniform manner onto a moving fiber, spun yarn, woven fabric, woven fabric, or carpet substrate.

Foam application is a state-of-the-art method for the treatment of carpets with antifouling and water repellent chemicals. By using this minimal moisture application system, a highly concentrated liquid in the foam state is applied to the passing carpet. A further advantage of the foam coating method is its improved penetration. Foam coating equipment can be installed in front of a dryer or latex lined oven. If the foam is not stable enough, a foaming agent can be conveniently added. These foaming agents are formulated in such a way that they decompose under normal drying temperatures and do not adversely affect the antifouling and water repellent chemical performance.

Suitable foaming agents include alkyl amine oxides, e.g., Laviron 118 SK (Pulcra Chemicals, Germany) and Genaminox (R) CSL (Clariant, Switzerland), coconut fatty alkyl dimethyl available C ₁₂ -C ₁₈ from Clariant Amine oxides, sodium alpha olefin sulfonates (eg, Hansanyl® OS, Hansa Group AG, Germany), and sodium rasless sulfates (eg, Hansanol® NS 242 cone, Hansa Group AG, Germany) can be mentioned. , Not limited to these.

Both spray and foam applications require a subsequent drying process. Raising the fluffy surface of the carpet from 110 ° C to 130 ° C during the drying process is important for the complete binding of antifouling and water repellent chemicals to the fibers.



Intentionally blank

The examples of the present application below the experimental section are useful for exemplifying the present invention more concretely.

The following test methods were applied to determine the results of the present invention.

ISO Stain Test, EN ISO 11.378-2: 2001
Carpet samples are placed inside the drum and chrome alloy steel balls, nylon polymer pellets, and standard dry stains are added. The stains used are the following AATCC 122/123 standard stains.
38% by weight peat moss (dark color)
17% by weight Portland cement 17% by weight kaolin clay 17% by weight silica (200 mesh)
1.75% by weight carbon black (lamp or furnace black)
0.50% by weight red iron oxide 8.75% by weight mineral oil (medical use)
After filling the drum, it is sealed, spun at 1,000 revolutions, and then vacuumed. This test simulates initial smearing with a dirty sole (represented by a polymer pellet) in that the stain acts on both the carpet and the polymer pellets. 1,000 rotations in the drum. Carpets were then evaluated according to grayscale (level 1 = strong stains, level 5 = no stains, target = 2.5 or higher).

This test is hereafter abbreviated as "ISO".

Water repellency test AATCC 193, ISO 23232:
This test (modified from AATCC method 193) determines the resistance of the finished carpet to wetting with an aqueous liquid. Droplets of water-alcohol mixture of various surface tensions are placed on the fabric and the extent of surface wetting is visually determined. If, after 10 seconds, 4 of the 5 droplets are still visible as spherical to hemispherical, the carpet is given a passing score and the test is repeated with a higher rated liquid. The water repellency rating of the sample is the highest rating of the liquid used to pass the water repellency test. Carpets with a rating of 4 or higher have good antifouling properties. Without antifouling treatment, most nylon carpets have a rating of 1 for water repellency.

This test is hereinafter abbreviated as "WR".
The following liquids were used for the water repellency test.

Kool Aid test, AATCC method 175
Acid dye resist dyeing
Evaluate using a procedure modified from American Association of Textile Chemistry (AATCC) Method 175-2003 "Resist: Pile Floor Rug".
A 9 wt% aqueous dyeing solution is mixed with cherry-scented KOOL-AID® powder (Kraft / General Foods, White Plains, NY, especially a powdered beverage mix containing FD & C Red No. 40). By doing so, prepare according to the manufacturer's instructions.
Carpet samples (4 x 6 inches) are placed on a flat, non-absorbent surface. A hollow, plastic, 2 inch (5.1 cm) diameter cup is placed firmly on top of the carpet sample. Pour 20 ml of KOOL-AID® staining solution into the cup and allow the solution to be completely absorbed by the carpet sample. Remove the cup and leave the dyed carpet sample for 24 hours. After incubation, the dyed sample is thoroughly rinsed with cold tap water, centrifuged to remove excess water, and the sample is air dried. Carpet samples were visually inspected and FD & C Red No. 1 described in AATCC Method 175-2003. The stain was evaluated according to 40 Stein Scale. The resist dyeing property is measured using a scale of 1 to 10. The undetectable test stain is consistent with a value of 10.

Hot water extraction test Carpet test Samples are laid flat on a smooth, level surface without pre-cleaning. A wash solution of 1.0% Sapur® Duo (available under Ecolab®, pH = 7) is used to perform hot water extraction using a Kaercher spray extraction washer. The cleaning solution is added to the tank of the spray extraction unit and the cleaning is actually completed by moving the cleaning head above the surface of the carpet. The sample is washed for a maximum of 2 minutes or until the stain is completely removed (less than 2 minutes). The washed sample is air dried and evaluated as follows: 5.0 = complete removal, 4.0 = very good removal (> 75%), 3.0 = good removal (50%) Super), 2.0 = proper removal (less than 50%), and 1.0 = poor removal (less than 25%).

Example 1 was carried out to prove the antifouling performance and water repellency of the composition X2. The coating was manually applied in the laboratory to a standard velor carpet made from nylon 6 and 6 and dyed with "Baby Blue" with a fiber weight of 600 g / m2 using a portable sprayer. .. Following application of the chemicals, a curing process was performed in a laboratory oven at 130 ° C. for about 15 minutes.

As can be seen in Table 5, this combination exceeds / meets the test requirements.

Example 2 was carried out to demonstrate the antifouling performance and water repellency of the carpet treated by simultaneous application of the compositions X3 and X4. The coating was applied using a WEKO coating system onto carpet tiles in light gray with a deposition weight of 400 g / m ² , followed by a curing process in an oven at 130 ° C. for about 8 minutes.

As can be seen in Table 6, this process exceeds / meets the test requirements.

After hot water extraction (HWE) of the carpet treated by the indicated method, Example 3 was performed to demonstrate durability:
a. ) Using a portable spray device manually in the laboratory, apply the given liquids listed in Table 7 to a standard velor carpet of 600 g / m ² , "baby blue" color, followed by curing. The process was carried out in a laboratory oven at 130 ° C. for about 15 minutes.
b. ) Using the WEKO coating system, the liquids listed in Table 7 are applied in light gray to carpet tiles with a deposition weight of 400 g / m ² , followed by a curing process in an oven at 130 ° C. for about 8 minutes. It was.

Claims (21)

a. With at least one clay nanoparticle component,
b. With at least one acrylic copolymer component,
c. With at least one woven softening component,
d. Including water
Does not contain metal
The at least one textile softening component is selected from the group consisting of polyaminosiloxanes, hydroxy-terminated polyaminosiloxanes, alkoxy-terminated polyaminosiloxanes , alkoxy-modified polyaminosiloxanes, and combinations and mixtures thereof.
Fiber protection composition. a. The at least one clay nanoparticle component is present in a solid form of 0.8 to 24% by weight.
b. The fiber protection composition according to claim 1, wherein at least the acrylic copolymer constituent component is present in a solid substance of 1.4 to 23.8% by weight. The fiber protection composition according to claim 1, wherein the at least one clay nanoparticle component is selected from the group consisting of smectite, kaolin, illite, chlorite, and attapulsite. The at least one clay nanoparticle component is montmorillonite, bentonite, pyrophyllite, hectorite, saponite, saponite, nontronite, talc, byderite, volchonskite, vermiculite, kaolinite, dikite, antigo. Wright, Anaukisite, Indellite, Chrysotile, Bravasite, suskovite, Paragonite, Black mica, Correns stone, Bitter chlorite, Donbassite, Sudoite, Pennin The fiber protection composition according to claim 1, which is selected from the group consisting of, sepiolite, and polygorskite. The fiber protection composition according to claim 1 to 4, wherein the at least one clay nanoparticle component is a synthetic substance. The fiber protection composition according to claim 5, wherein the at least one clay nanoparticle component is synthetic hectorite. The at least one acrylic copolymer component is acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etacrilate, methyl etacrilate, ethyl etacrilate, The fiber protection composition according to claim 1, which comprises propyl ethanecrylate, butyl ethanecrylate, acrylic acid, and an ethylene monomer, and combinations and mixtures thereof. The fiber protection composition according to claim 1, wherein the at least one acrylic copolymer component is self-crosslinked. The fiber protection composition according to claim 1, wherein the at least one acrylic copolymer component is anionic or charge-neutral. The fiber protection composition according to claim 9, wherein the at least one acrylic copolymer component is anionic. a. The at least one clay nanoparticle component is present in a solid of 0.8-22.5% by weight.
b. The at least one acrylic copolymer component is present in 1.4-19% by weight solids.
c. The fiber protection composition according to claim 1, wherein the at least one woven fabric softening component is present in a solid substance of 0.7 to 11% by weight. The fiber protection composition according to claim 1, wherein the at least one woven fabric softening component is cationic or nonionic. The fiber protection composition according to claim 1, wherein the at least one woven fabric softening component is nonionic. The fiber protection composition according to claim 1, wherein the at least one woven fabric softening component is polyaminosiloxane. a. The at least one acrylic copolymer component is present in a solid form of 2.3-38% by weight.
b. The fiber protection composition according to claim 1, wherein the at least one woven fabric softening component is present in a solid substance of 1.8 to 14.8% by weight. The at least one acrylic copolymer component is acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etacrilate, methyl etacrilate, ethyl etacrilate, The fiber protection composition according to claim 15, which comprises propyl ethanecrylate, butyl ethanecrylate, acrylic acid, and an ethylene monomer, and combinations and mixtures thereof. A fiber treated with the composition according to claim 1. A manufactured product treated with the composition according to claim 1. The method for treating a synthetic or naturally occurring fabric or fiber with the composition of claim 1 in an amount effective to make the fabric or fiber water repellent and stain resistant. 19. The method of claim 19, wherein the treatment is by gravure coating, silk screen printing, roll coating, size press coating, spray bar coating, rotary spray coating, bath coating, or foam wet treatment method. 19. The method of claim 19, wherein the treatment is by a rotary spray applicator.