TW201042116A - Method for producing a hydrophilic fibrous article - Google Patents

Abstract

A method of providing a durably hydrophilic coating to a substrate comprising contacting thermoplastic fibers with a coating composition comprising an aqueous dispersion of silica nanoparticles having average particle diameters of 100 nanometers or less, wherein the aqueous dispersion of silica nanoparticles has a pH of less than about 3 and drying to provide a silica nanoparticle coating. The silica nanoparticles may further comprise hydrophilic surface-modifying groups.

Description

201042116 VI. Description of the invention: [Technical field to which the invention pertains] This specification relates to a fibrous article having a nanoparticle coating, and more particularly to a paving article having a nanoparticle coating, and to a fibrous article A method of coating a nanoparticle coating. [Prior Art] Items having a hydrophilic or water wettable surface are desirable in many applications. For example, in a rainy environment, it is necessary to provide a door mat at the door of the building to quickly absorb the water in the shoes of the person entering the building or the water droplets falling from the umbrella or dripping from the outer garment of the person entering the building. Water droplets. In some places, cotton door mats are commonly used, which can quickly absorb water but have poor durability, often moldy and therefore require replacement of the door mat. Other types of door mats may be made of man-made fibers such as nylon or polypropylene, which may be less prone to mildew, but such materials may not absorb water very quickly. Known hydrophilic coatings of fibrous materials include those described in the following documents. U.S. Patent No. 6,136,215 (sil〇xane treatments for textiles), U.S. Patent No. 6, No. 436 855 (high-speed manufacturing of water-absorbing articles) and WO 2003097925 (treatment of synthetic fibers with polymers that contain Carboxyl gr0UpS)). The use of a nanoparticle system to functionalize soft surfaces has been described in U.S. Patent No. 7,112,621. 140083.doc 201042116 For example, the use of oxidative has been described in U.S. Patent Nos. 5,585,186, 5,723,175, 5,753,73, and 6, 6, 4, 〇53, and 1182, 4,237,833. The Shixi nanoparticle provides the hydrophilic nature of anti-fog applications. The use of nanoparticle as part of the surface treatment of carpets has been described in U.S. Patent Nos. 5,9,8,663, 7, 407, 899, and 7, 485, 588, the disclosure of which generally provides liquid repellency and stain resistance. SUMMARY OF THE INVENTION In some embodiments, a method of making a durable hydrophilic fibrous article is described, the method comprising: reacting a thermoplastic fiber with a silica dioxide particle comprising an average particle size of 100 nanometers or less and 100 millimeters or less. The coating of the aqueous dispersion is contacted with the aqueous dispersion of the dioxon nanoparticles having a positive value of less than about 3; and dried to provide a coating of the cerium oxide nanoparticles. In some embodiments of the method, the concentration of the coating composition particles is from 5 to 20 wt%. Non-wood thermoplastic fibers in the use of cerium oxide thermoplastic fibers comprising a hydrophobicity selected from the group consisting of polyfluorene prior to treatment of the rice particles in some embodiments of the process. In some embodiments of the method, the amine, the polyester, the polypropylene, the polyamidocarboxylic acid, the θ 气 θ Λ , ^ , θ ^ ethylene, the blend thereof, the ' 5, . Resin. In some embodiments of the method, the diameter of the dioxide is about 20 nm or less. The average granule oxidized nanoparticle of the kiln particles of the kiln particles comprises a surface having a diameter of about 10 nm or less in some embodiments of the method in some embodiments of the method. I40083.doc 201042116 Modified dioxycene nanoparticles. The surface modification f-cut cheonite particles may comprise a surface modifier having the formula: [(Z)c-R3]d-Si-(OR4)b(R4)4 ((iv)), wherein Z is hydrophilic a radical; R3 is a covalent bond or, optionally, a divalent or trivalent hydrocarbon bridging group having from about 丨 to 2 碳 carbon atoms, substituted by at least one oxygen atom and optionally substituted by a fluorenyl group; &

R 4 is independently hydrogen, or an alkyl, aryl or aralkyl group having 1 to 8 carbon atoms, optionally substituted by oxygen, nitrogen and/or sulfur atoms; c is 1 or 2 'b is 1 to 3 and d It is 1 or 2 and (b+d)$4. In some embodiments of the method, 2 may be selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, and salts thereof. In some embodiments of the method, z may be selected from the group consisting of hydroxyalkyl groups and polyhydroxyalkyl groups. In some embodiments of the β-Hai method, 'z may include a four-stage descriptive base. In some embodiments of the method, the coating composition of the method comprises from 8 to 95 wt% water and from 5 to 20 wt% of nitric oxide utah having an average particle size of 10 〇 nm or less. The particles, wherein the pH of the coating composition is less than about any of the above embodiments of the method, the coating composition can have a pH of less than about 2. In some embodiments, a hydrophilic article is described, wherein the hydrophilic article is prepared by any of the foregoing embodiments of the method. 140083.doc 201042116 In some embodiments, as measured by a Water 〇Plet Absorption Test after a water wash cycle according to a Laundering Test 6^1 5 J, 1 Λ 〇 〇 水 水The article has an average absorption time of less than about a spear y. Details of the water droplet absorption test and the water wash test are described in the Examples section. In some embodiments, the hydrophilic article has an average absorption time of less than about 5 seconds as measured by the water droplet absorption test after at least one wash cycle according to the water wash test. In some embodiments, the hydrophilic article has an average absorption time of less than about 5 seconds as measured by a water droplet absorption test after at least 2 washes of water wash cycle according to a water wash test. In some embodiments, the hydrophilic article is a floor mat. [Embodiment] For the terms defined below, the definitions should be applied unless the patent application states that a different definition is given elsewhere in %.

The term "polymer" is understood to include polymers, copolymers (eg, polymers formed from two or more different monomers), polymeric combinations, and can be exchanged, for example, by coextrusion or by vinegar exchange. Counter-banking: A polymer, oligomer or copolymer formed by the dissolution of a blend. Block copolymers and random copolymers are also included unless otherwise stated. The term "nanoparticle" as defined herein means a particle having a diameter of less than about 100. The term "chemically bonded to surface-modified nanoparticles" refers to particles including, for example, covalent bonds or moieties. Surface group changes 140083.doc 201042116 Physical or chemical properties of particles. The term "hydrophilic" as used herein describes a fiber or fiber surface that can be wetted by water droplets that are dripped onto an aqueous fluid (e.g., water, water). The hydrophilicity of the fibers is defined relative to the water droplet absorption test described in more detail in the examples, and the fibrous article having an average water droplet absorption time of less than about 1 second is considered hydrophilic. As used in the fibrous article of the present specification, the term "persistent hydrophilicity according to the water washing test (described herein) such as 2 cycles '5 times to ^ ❹ = more than one time or more than two times or more cycles of washing, etc. After repeated washings, 'maintains less than about 1G seconds (as measured by the water droplet absorption test, the average water droplet absorption time.) The range of values by endpoints includes all values included in the range (eg 1 to 5 including Bu Ruben) The singular forms "a" and "the" are used in the specification and the appended claims, unless otherwise specified. Including two or more mixtures of two or more compounds. As used in this specification and the accompanying application, unless otherwise specified, the term "or" is used to mean "and/or". Unless otherwise stated, all numerical values, qualitative qualities, etc. used in the scope of this specification and the scope of the claims are to be understood in all cases to be modified by the term "about". Unless otherwise stated, the numerical parameters recited in the foregoing specification and the appended claims are intended to be an approximation of the Equivalents For the application of the scope of the application of the scope of the application, the numerical parameters are to be interpreted at least in accordance with the number of significant figures reported and by the application of the general rounding technique, although the numerical scope of the broad scope of the invention is The parameters are approximate, but the values stated in the specific examples have been reported as accurately as possible. However, any numerical value inherently contains certain inevitable errors resulting from the standard deviations seen in the corresponding test measurements. Articles such as mats of hydrophilic fibers described herein may exhibit a permanent hydrophilicity of less than about ten seconds when subjected to a water droplet absorption test after at least one wash cycle according to a water wash test. In a preferred embodiment, the average absorption time is less than 5 seconds, 4 seconds, 3 seconds, 2 seconds, or 1 second. A method for producing a hydrophilic fibrous article, the method comprising contacting a polymeric fiber with an aqueous dispersion of hydrophilic dicex nanoparticles, wherein the cerium dioxide nanoparticles comprise, as the case may be, a surface-modified sulphur dioxide Nanoparticles and wherein the resulting coating renders the polymeric fibers hydrophilic. The hydrophilicity or lack of hydrophilicity of the fibers can be determined by subjecting a suitable sample of the fibers to a water drop absorption test as described below. The dimensional sample is defined as having the time required to absorb the i drip (about Q2 machine) = water droplet absorption time. The fiber having a water absorption time of > 9 leap seconds (4) = considered to have poor hydrophilicity, and 1 G seconds Or 5 seconds, 4 seconds, 3 seconds, ': The water absorption time indicates that the fiber sample is getting better and better hydrophilic. The persistence or lack of persistence of the bird root ^ hydrophilicity can be achieved by making the fiber sample 1 h in the chapter The repeated water wash cycle performed by the described water wash test subjects the fiber sample to water droplets (4) m to determine. Only after the 5 times of the water washing cycle of the water washing test s, it is shown that the fiber sample with reduced hydrophilicity can have poor durability, while in the water washing test, 1 〇, 15 times or Fiber samples that remain hydrophilic even after 20 wash cycles can have an increasingly longer hydrophilicity. Fibrous article substrate The polymeric fibrous substrate of the present disclosure can have any of the known knit constructions, knit constructions, non-woven constructions, and the like, or combinations thereof. The polymeric fibers ο 基材 substrate can have a weight of between about 1 and about 55 ounces per square yard. The polymeric fibrous substrate, such as a floor covering, may preferably have a weight of between about 5 ounces per square yard. In the present disclosure, suitable polymeric fibrous substrates can include floor mats, cloth, ping sheets, or various other types of mats. Any of the standard fibers and composite materials thereof used in the articles of the present invention are gathered. The fibers may comprise monofilament fibers, core-type fibers, etc. or may be in the form of a loop or any other type of carpet face. By way of example only, §, resistance, polyethylene, polypropylene, olefin, polyamine Missing *匕_ Λ - owe-a temple fibers can be tufted through the fabric (such as any fiber type of woven, non-original, ", or 'knit fabric, such as the fabrics listed previously) I #可0 S Any size of fiber or yarn, including micro-denier yarns: second-line (denier per filament) fibers less than 1? y,,, D-hai, etc. fibers or yarns may have j single 2000 filament deniers are flat to about a or less than less than about 1 denier to about 500 denier deniers of the number of deniers of III. 140083.doc 201042116 In some embodiments, untreated The polymeric fibrous substrate comprises a mat having poor hydrophilicity (i.e., having a water droplet absorption time of > 90 seconds). In some embodiments, the polymeric fibrous substrate can comprise a mat, wherein the fibers can be as US Patent No. No. 4,820,566 (Heine et al.) and U.S. Patent No. 5, No. 55,333 (Heine) Said in the form of a tufted loop in which a backing material A is inserted, both of which are incorporated herein by reference. In some embodiments, the mat may include, for example, a 3M company (Minnesota) Commercially available entrance mats such as St. Paul (MN) and Shanghai, China (Shanghai, 4, NOMAD 5000 and NOMAD 60〇〇 entrance mats. In some embodiments, combined with the polymeric fibers of this specification The fibrous article may additionally comprise natural fibers or fibers derived from natural fibers, including silk, wool and cotton fibers, or cellulose acetate fibers and related fibers or combinations thereof. However, the description is generally directed to polymeric fibers comprising the following Fibrous articles. Polymeric fiber 〇 Long-lasting hydrophilic fibers can be prepared from a typical hydrophobic (e.g., 'thermoplastic or thermosetting) polymeric resin that exhibits a water absorption time of > 9 sec. Suitable thermoplastic polymers can be included. Included such as poly(vinyl chloride), polyethylene (high density, low degree, very low temperature), commercial polymers such as polypropylene (commodity one window), such as poly (including, for example, poly(ethylene terephthalate) and poly(p-benzoic acid di(tetra)), polyamidoformic acid vinegar, and polyamidamine (for example, including terphenyl), and blends and mixtures thereof. In the crucible, the hydrophilic fibrous article comprises a group selected from the group consisting of an extruded material, a braid, a non-valued & non-, flat fabric, a foam, and combinations thereof, 140083.doc -10- 201042116 The material of the polymerized fiber coating consisting of dioxin, which contains dioxin-cut particles, is used in the case of w, _ ' has not been modified by surface modifiers, 'knife, and cerium dioxide nanoparticles' The bare "2" polymer fiber is "unmodified" or the presence of k-butyl and rice particles can make the surface of the polymer fiber hydrophilic, especially when the dioxide is too long. The particle system has been coated from a skin solution having a pH of less than about 3. ) in about 3 water

In some embodiments, the coating is applied to 6 people on the surface of the nanoparticle and the surface modification agent has a surface modification. Containing surface modification

The presence of a mass group as a hydrophilic agent allows the surface of the fiber to become hydrophilic. More specifically, the surface is modified to have an enveloping—the enamel group covalently attached to the surface of the granules in an amount sufficient to form a single layer or less than a single layer of ruthenium. It is hoped that the surface of the surface can be utilized (ie, 'Shixi burning alcohol group) 丄.; 卜 70 Wang modified to allow the nanoparticles to associate with the substrate through the residual unmodified hydroxy alcohol surface group . Other Fibrous Substrates In some aspects, the fibrous substrate can include Tian Qianwei and fibers derived from natural fibers. These fibers may already have a certain degree of hydrophilicity as measured by the water droplet absorption test. In some aspects, the fibrous substrate can comprise cellulose acetate, natural silk, wool, cotton, and combinations of such fibers. The surface modified cerium oxide nanoparticles and the acidified bare SiO2 granule coating of the present specification can be applied to the fibers, and the degree of hydrophilicity is increased as measured by a water absorbing absorption test. It may be desirable to adjust the pH of the coating composition to a range that does not damage the fibers. For example, it is possible that 140083.doc 201042116 needs to adjust the pH to a range of about 3 to about 5, and the nanoparticles are wheat & i + sub. Eight $ η inorganic nanoparticle having a surface-modified group of n. Suitable inorganic nanoparticles comprise dioxon nanoparticles. The cerium oxide non-rice particles are usually used in the form of a dispersion of submicron butyl-emulsified ceramsite particles in an aqueous solution = aqueous organic solvent mixture. The sulphur dioxide 夕 Ι Ι = Γ average granules can be 1 〇 ° nm or 1 〇. Below the nanometer, preferably 3. : Not more than below - and more preferably 10 nm or less. Average grain: can be greater than about 2 nanometers. The average particle size can be measured by transmission electron microscopy. If necessary, at least - part of the larger cerium oxide particles can be present in the coating.

In the composition, the amount does not lower the hydrophilicity of the substrate of the I yak low-selection ruthenium. The nanoparticles can be in the form of a colloidal dispersion. In some embodiments 'surface modified nanoparticles can provide improved dispersion stability. Without being bound by theory, it is believed that the surface modification can be seen as the nature of the modifier and the molecular size... increasing the space between the particles and/or the electrostatic stabilizing effect' thereby preventing them from binding together to form a large flaw.

Set aggregates. In such cases, the use of kneading modified nanoparticles may result in a lower solution enthalpy synergy, providing a more stable dispersion formulation or a range of stable pH values for the dispersion formulation. This allows the product to be used at near-neutral levels, thereby reducing (10) the potential for sputum or danger. ° Inorganic cerium oxide nanoparticles (sol) which are well known in the art and are commercially available from aqueous media. The cerium oxide sol in water or an aqueous alcohol solution may be, for example, LUDOX (by DuPont, Delaware, USA: I40083.doc -12, 201042116 (EI du Pont de Nemours and Co., Inc., Wilmington, Del·, US A), NYACOL (available from Nyacol Corporation of Ashland, MA) or NALCO (Nalco, Naperville, 111. USA) Trade name manufactured by Chemical Company). A suitable cerium oxide sol is NALCO 2326 available in the form of a cerium oxide sol having an average particle size of 5 nm, a pH of 10.5 and a solids content of 15% by weight. Other commercially available cerium oxide nanoparticles include "NALCO 1030TM", "NALCO 1034TM", "NALCO 1034A TM", "NALCO 1050TM", "NALCO 1115TM", and "NALCO 2326TM" available from NALCO Chemical. "NALCO 2327TM", "NALCO 2329TM", "NALCO 1130TM" and "NALCO 2359TM"; "Remasol SP30" available from Remet Corporation (Utica, NY, USA); Purchased from DuPont's "LUDOX SM". A non-aqueous cerium oxide sol (also known as cerium oxide organic sol) which is an organic solvent or an aqueous organic solvent cerium oxide sol dispersion may also be used. In the practice of the present invention, the cerium oxide sol is selected such that its liquid phase is compatible with an aqueous solvent or an aqueous organic solvent. However, it has been observed that sodium stabilized cerium oxide nanoparticles should be acidified prior to dilution with an organic solvent such as ethanol. Dilution prior to acidification may result in poor or uneven coatings. The ammonium stabilized cerium oxide nanoparticles can generally be diluted and acidified in any order. Surface Modifiers A variety of methods can be used to modify the surface of nanoparticles, including, for example, the addition of surface modifiers to nano-140083.doc •13· 201042116 particles (eg, in the form of powders or colloidal dispersions) and surface modification agents Reacts with nanoparticles. Other suitable surface modification treatments are described, for example, in U.S. Patent No. 2,801,185 (I.) and U.S. Patent No. 4,522,958 (Das et al.). The surface modifying group can be derived from a surface modifying agent. The surface modifying agent can be represented schematically by the formula RS-RL-Z, wherein Rs is a surface bonding group capable of linking to a stanol group (ie, a Si_〇H group) on the surface of the silica dioxide particle. Z represents a hydrophilic group which does not react with other components in the system (for example, a substrate) and R1 represents an organic linking group or a bond. Suitable surface-bonding groups Rs for the surface modifying agent may include decyl alcohol, alkoxy oxane or chlorodecane. In some embodiments, the hydrophilic group z can be a non-basic hydrophilic group, such as an acid group (including a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a salt thereof, or a combination thereof), an ammonium group, or a poly( Ethylene oxide) or hydroxyl group. These surface modifiers can be used to functionalize from 5% to 100% of the surface stanol groups (Si_〇H groups) of the cerium oxide nanoparticles. At least 60%, 70%, 80% or 90% of the surface of the SiO2 particles are typically functionalized. When dry, the remaining surface decane group can be adapted to produce a network of cerium oxide nanoparticles. The number of functional groups is determined experimentally by reacting the large amount of nanoparticle with an excess surface modifying agent such that all available reactive sites are functionalized by the surface modifying agent. A lower percentage of functionalization can then be calculated from the results. The amount of surface modifying agent is generally sufficient to provide a molar ratio of twice the surface modifying agent relative to the surface stanol groups on the inorganic nanoparticles. Excess alkoxy decane may be suitable for producing more than one layer of functionalized cerium oxide nanoparticles, and may also be suitable for forming a oxane chemical bond between particles when the coating is dried. In order to obtain a surface modifier of better high-temperature 140083.doc • 14· 201042116 oxidized granules on the cerium oxide nanoparticles, the important line is first to make the two-sided modification 'after the rest with the coating Combination of components. In some embodiments, the surface modifying agent has the formula: [(Z)c-R3]d-Si-(〇R4)b(R4)4(b+d), wherein z is a hydrophilic group;

R3 is a covalent bond or, optionally, substituted by at least one oxygen atom and, as the case may be, substituted by a group in the main chain, preferably has about (1). a divalent or trivalent hydrocarbon bridging group of one carbon atom; R4 is independently hydrogen or an alkyl group having from 丨 to 8 carbon atoms substituted by an oxygen, nitrogen and/or sulfur atom at a position where it may be utilized , aryl or aralkyl; side C is 1 or 2, b is 1 to 3 and d is 1 or 2 and (b+d)S4. In some embodiments, Z is a hydrophilic group selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, and salts thereof. Examples of suitable surface modifiers include the following: (H0)3SiCH2CH2CH2S03H, (HO)3SiCH2CH2CH2OCH2CH(OH)S03H, Na0Si(0H)2CH2CH2CH2S03Na, Na0Si(0H)2CH2CH2CH20CH2CH(0H)S03Na,

Na0Si(0H)2CH2CH2C02Na, and

Na0Si(0H)2CH2CH2P(0)(〇H)20Na and other known compounds. The reductive acid group-organic cerium compound can be prepared according to the procedure as seen in U.S. Patent No. 4,338,377 (Beck et al.). 140083.doc -15- 201042116 A carboxyl group-containing surface modifying group such as sodium carboxyethyl decane triol is commercially available from Gelest Corporation (M〇rrisvi Ue, pA). In another embodiment, the surface modifying agent can include, for example, a hydrophilic ether of 2-[methoxy(polyoxyethylene)propyl]trimethoxynonane available from Gdest Corporation (Mooreville, Pa.). . In another embodiment, the surface modifying agent can include, for example, N-(3-triethoxydecylpropyl)glucosamine which is commercially available as "" Company, Morrillville, Pa. Glycan. In another embodiment, the surface modifying agent can include a quaternary ammonium group. A non-limiting example of a surface modifying agent comprising an ammonium group is trisethoxyphosphonylpropyl-N,N,N- available from Geiest Corporation of M. Mirrisville, Pa. Trimethyl ammonium (TTMS, 500 / in decyl alcohol) and sense (trimethoxy decyl propyl) ethylene diamine triacetic acid (EDTAS). In another embodiment, the surface modifying agent may include a grafting group such as an epoxy alkoxydecane (eg, 3-glycidoxypropyltriethoxydecane) or such as an acrylate. Michael acceptor gr〇up. An example of an acrylate group-containing surface modifier is a mercapto propylene methoxy propyl trimethoxy decane available from GE Company. In another embodiment, the 'surface modifying agent can include an aromatic sulfonium chloride alkylate 5' such as 2_(4_chloro & decylphenyl) available from Gelest Corporation (Morville, Pa.) Ethyl-trimethoxydecane. While not being bound by any theory, it is believed that the sulfonyl chloride group (s〇2Cl) can be hydrolyzed to form a sulfonic acid group (so3h) under surface modification conditions including water. 140083.doc 16· 201042116 In another embodiment, the surface modified hydrophilic nanoparticle may be combined with bare cerium oxide nanoparticles, wherein the bare cerium oxide nanoparticles are preferably acidified with a mineral acid. We have found that these bare SiO2 particles are suitable for producing a durable hydrophilic coating when combined with the above surface modified bismuth nanoparticles. These combinations of bare cerium oxide nanoparticles and surface modified cerium oxide nanoparticles can result in a durable hydrophilic coating that is less expensive to manufacture than coatings comprising primarily surface modified cerium oxide nanoparticles. 〇 In some embodiments, the surface modified nanoparticles can be dried and readily dispersed in a solvent of the coating composition. Liquid Carriers These coating compositions comprise a liquid carrier. In a preferred embodiment, the liquid carrier comprises water. Although the coating composition does not require an organic solvent, it may contain a water-soluble or water-miscible organic solvent. The total v〇c content of the composition should be less than about 20% by weight, preferably less than about 15% by weight, and more preferably less than about 10% by weight based on the total weight of the formulation. The water-soluble or water-miscible organic solvent is preferably a low molecular weight sterol, preferably having a carbon atom content of less than about 6, including butyric acid, isopropanol, ethanol, and/or methanol, and a mixture of the alcohols or each other. A mixture of an alcohol and a VOC-free water-soluble or water-miscible organic solvent. The use of small amounts of such solvents (in accordance with existing US EPA regulations (see, for example, EPA 40 CFR 51.100(s) and continuous)) helps to reduce the surface tension of the coating formulation and to improve the wetting of the formulation on the hydrophobic surface. The ability to spread. In addition, the alcohol solvent can impart additional storage stability, inter alia, by participating in an equilibrium condensation reaction with the alkaloid. pH 140083.doc -17. 201042116 Before coating on the fiber, the cerium oxide nanoparticle (whether naked or not) can be used with an acid of pKa(H2〇) <5, preferably less than 2,5, optimally less than cerium. The aqueous dispersion of cerium oxide nanoparticles, surface modified cerium oxide nanoparticles or combinations thereof is acidified to the desired pH level. Suitable acids include organic and inorganic acids and may be, for example, oxalic acid, citric acid, benzoic acid 'acetic acid, citric acid, propionic acid, benzenesulfonic acid, H2S〇3, H3P04, CF3C02H, HC1 'HBr, HI, HBr〇3 , HN03, HC104, h2S04, CH3S03H, CF3S〇3H CF3C〇2H and CH3〇S〇2〇H. The best acids include hci, HNO3, HJO4 and HJO4. In some embodiments, it may be desirable to provide a mixture of an organic acid and an inorganic acid. In some embodiments, a mixture of an acid comprising pKaS5 (preferably < 2.5, optimally less than hydrazine) and a small amount of other acid of pKa>5 may be used. It has been found that a weaker acid utilizing pKa > 5 does not provide a uniform coating with desirable properties such as cleanability and/or durability. More specifically, a coating composition comprising a weaker acid or an alkaline coating composition typically forms a liquid bead on the surface of the polymeric substrate. In most embodiments, the coating composition typically contains sufficient acid to provide a pH of less than 5, preferably less than 4, more preferably less than 3, and most preferably less than about 2. In some embodiments, it appears that in order to obtain durability that can withstand 1 or more washes in a water wash test and still have less than 10 or 5 seconds, 4 seconds, 3 seconds, 2 seconds in the water drop absorption test. Or a 1 second water droplet absorption time such that the pH of the coating composition is less than about 2 is critical. Other Additives These fibers may further comprise other components as the case may be present in the coating. For example, the addition of a humectant, typically a surfactant, may have 140083.doc -18- 201042116. The term "surfactant" as used herein describes the inclusion of a hydrophilic (polar) region and hydrophobicity on the same molecule. The molecules of the (non-polar) region are sufficiently large in size to reduce the surface tension of the coating solution. Suitable surfactants may be included to aid in the wetting of the surface modifier on the surface of the cerium oxide nanoparticles. Examples of suitable surfactants are generally known to those skilled in the art and may include, for example, nonionic polyoxo surfactants. Coating Method 表面 Surface preparation of the substrate can be performed prior to coating. The effectiveness of the coating can be significantly affected by the ability to properly adhere to the substrate material. The presence of surface contaminants, oils, greases and oxides can physically weaken and reduce the adhesion of the coating to the substrate. The substrate can be surface treated or cleaned to improve the adhesion of the coating to the substrate. In an embodiment of the present disclosure, the mantle substrate can be surface treated. Methods of surface treatment include vacuum deposition, corona, laser, chemistry, heat, flame, electricity, ozone, and combinations thereof. It may be necessary to perform - or a plurality of such surface treatments when preparing non-polar fibers to accept the nano-ion coating of the Japanese. In the aspect, the present specification includes a hydrophilic fibrous article produced by a method comprising the steps of: coating with a coating solution comprising an aqueous dispersion of hydrophilic cerium oxide nanoparticles, the hydrophilicity of the towel The oxidized stone sulphide particles may be surface modified silica sand nanoparticles, bare SiO nanoparticles or a combination thereof. The coating process typically involves coating the polymeric fibers of the article with an excess of coating solution, including heating, drying and/or stripping steps as appropriate. Although 140083.doc -19- 201042116 has been found in some cases, it may be desirable to require at least about 0 42 g/m 2 of surface modification = cerium oxide nanoparticles to achieve the long-lasting hydrophilicity of the present specification, but it is desirable to utilize excess coating The layer solution provides a higher coating level. In some embodiments, the coating method can include applying a coating material and then allowing the coating to air dry at ambient temperature. In other embodiments the coating process can include heating to conveniently accelerate the coating process. In some embodiments, the coating method can include applying a coating material to the substrate and then at a temperature of from 9 °C to 120 °C. The substrate is heated in an environment within the range of 〇. The heating temperature is preferably selected so as not to cause degradation of the substrate. In the absence of heat, a typical drying time is about 20-24 hours; if it is at 9 Torr. (: to 12 〇. (: The heating of the coated substrate, the drying time can be shortened to about 丨 hours or even about 30 minutes. In some embodiments, the coating of ruthenium dioxide on the substrate The method of particles may further comprise a rinsing step of washing away excess coating material after drying. In a preferred embodiment, the rinsing liquid is water. The coating of the present disclosure may be applied to selected substrates by various coating techniques. These techniques include dip coating, spray coating, foam coating, roll coating, roll coating roll coating, pad coating, flood coating, and other coatings well known in the art. Technology. Washability test It is important for some coated fibers to maintain hydrophilic properties after multiple wash cycles. We use a water wash test (described below) to evaluate the durable hydrophilic coating on the fiber. The test model was tested using a whirlp〇〇1 111 top-loading washing machine. This test method can be applied to its 140083.doc -20· 201042116 washing machine of its type. The following examples describe this disclosure in more detail. Coating compositions and coated articles, such examples are intended to be illustrative only; as will be apparent to those skilled in the art, 5 many modifications and variations within the scope of the invention will be apparent. All parts, percentages, and ratios reported herein are by weight, and all reagents used in the examples are obtained or available from the chemical suppliers described below, or may be synthesized by conventional techniques. Nanoparticle dispersion, Nalco 2326TM (average particle size 5 nm), Nalco 2327TM (20 nm) and Nalco 2329TM (75 nm)

Nalco 1034ATM (average particle size 20 nm) was obtained from Nalco Chemical Company of Naperville, Ill.

NomadTM 0000 Mat: Nylon fiber mat, available from Shanghai, China (3). Q 2 —Hydroxy-3·[3_(trihydroxydecyl)propoxy]propane-1-sulfonic acid was prepared according to the procedure of U.S. Patent No. 4,338,377. Α-174: Mercaptopropoxypropyltrimethoxydecane, GE Company. SIM6492.7: 2-[Methoxy(polyvinyloxy)propyl]trimethoxy decane (MW=450-600), No. η, Donggang Road, Morrillville, PA [19067] (11 East Steel Road, Morrisville, PA 19067). SIC2263.0: 25% sodium carboxyethyl decane triol in water, Binxifa 140083.doc -21 . 201042116 Gelest Corporation, No. 11, Donggang Road, Morrillville, Ni. [19〇67]. SIC2417.0: 50% 2-(4-sulfonyl phenyl)ethyltrimethoxy decane in dichloromethane, Gelest, Inc., No. 11, Donggang Road, Morrillville, Pennsylvania [19067] . KH560 : (3-glycidoxypropyl) trimethoxy decane, Zhejiang Chem-Tech Group Co., Ltd., Hangzhou, China 〇 test sample unless otherwise stated Test samples of the specified type of floor mat were cut into squares having a size of 5 cm >< 5 cm. Wash test The coated test sample is tested in a standard top-loading household laundry. Place the sample and ballast load (90x90 0111 folded fabric, cotton or 5〇/5〇 cotton/polyester of unfinished plain fabric of about 25〇g/m) in the washing machine to produce 18:b() .2 kg (4 ± (). 5 stone side) total weight, which is not less than "kg (3 lbs) in the pressure interception. Add liquid detergent (75 Lu is also anti-fouling, Chen Shampoo (S〇 Il Retarding Carpet ShamP〇 (concentrated) 'purchased from 3M Company, St. Paul, Minnesota, and watered the washing machine to the (5) water mark, the water temperature was 41 ± 3. 6 degrees. At the price: in minutes, a total of 5 washing cycles, and in the forced ventilation cycle oven, the dry tester can change the situation according to the situation. 灭保口口h仪. Off the challenge. Change the heart of the ring Water absorption test to increase the durability of the coating 140083.doc 201042116 By applying a drop of 2 mL of deionized water from the dropper to the surface of the test sample and recording the time required for the water droplets to be completely absorbed (according to visual inspection) To perform the water drop absorption test. Unless otherwise stated, the value is the test. The average of three tests at different locations on the surface of the article. If the water absorption time is greater than 1 minute, the test is terminated and the absorption time is recorded as > 丨 minutes. The control example tests N〇mad 6〇〇〇 in the water absorption test. The untreated sample of the pad (5 emx5 cm). The results are shown in the table! 〇 Example 1 (5 nm surface modified SiO2 NR particles) by 5 nm cerium oxide nanoparticles (Nalc〇) 2326, 33.3 g, 15 wt% solids) of 2-(hydroxytrihydroxydecylalkyl)propoxy]propane-indolesulfonic acid (36 7 g, 9 加入) added to 3 〇g of deionized water in a stirred dispersion 7 wt /. Solid content) Preparation of surface modified cerium oxide nanoparticle dispersion, and after 1 hour at room temperature, a clear solution (pH = l 78 and decane coverage of 100 /.) was obtained. A N〇mad 6〇〇〇 floor mat test sample (5 CmX5 Cm) was applied to the pad dyeing machine under a pressure of 3 kg, followed by heating at 9 (TC for 1 hour, and then cooling the coated mat back to the surroundings Temperature. The results of the water drop absorption test performed after the repeated water wash cycle are shown in Table i. Example 2 ( 20 nm surface modified SiO2 NR particles) by adding 2 〇nm cerium oxide nanoparticles (Naic 〇 2327, 6·25 g, 40 Wt% solid content) to 40.6 g of water, followed by 2-Hydroxy-3·[3-(trihydroxydecyl)propoxy]propanesulfonic acid ^i3 g) was added with stirring, and then heated under 4 hours to obtain a pH of about 2 and a solid content of 15 wt. A transparent solution of cerium/lanthanum is used to prepare a surface-modified cerium oxide nanoparticle dispersion. 140083.doc -23- 201042116 This solution was applied to the test samples as described in Example 1, and the test results are shown in Table 1. Example 3 (75 nm surface modified cerium oxide nanoparticles) by adding 75 nm cerium oxide nanoparticles (Nalc 2329, 6.25 g, 40 wt% solids) to 42.9 g of water, followed by stirring 2_Phenyl-3-[3-(biguanide)-propoxy]propanone_丨_hemeic acid (〇·81 g) was added, followed by heating at 80 ° C for 4 hours. A transparent solution having a pH of about 2 〇 5 wt% solids was obtained to prepare a surface-modified cerium oxide nanoparticle dispersion. This solution was applied to the test sample as described in Example 1, and the test results are shown in Table 1. Included on the test sample, and Example 5 (2 经 modified with PEG-decane)

140083.doc Example 4 (2〇 particles modified with organostanol sulfonic acid and acrylate decane) by passing to 15 g of 2-hydroxy-3-yl-[3-(trihydroxydecyl)propoxy]propane-sulfonic acid (5.7 wt%) was added 2 〇nm cerium oxide nanoparticles (ΝΑ. 1034A, 29 g, 34 wt% solid content) and 71 g of deionized water, followed by stirring at room temperature for 30 minutes, and then 〇77 g Al74 was added, followed by stirring under the machine for 2 hours to obtain a translucent solution (1 〇% to 5% solids; coverage: organic smelting acid 50% and 875 55%; pH spit 56 ) to prepare = surface modified nitric oxide nanoparticle dispersion. This solution was applied as described in Example 1 and the results of the shouting are shown in Table 1. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A clear coating solution Ε was obtained; coverage: 100%; ρίί=7·02) to prepare a surface modified di-24- 201042116 oxidized stone smectite particle dispersion. Prior to coating, the solution was acidified to a positive value of 2 using H3p〇4. The dispersion was applied to the test sample as described in Example 1. Example 6 (5 nm particles modified with carboxy-decane) was added to a dispersion of 5 nm cerium oxide nanoparticles (Nak 〇Μ %, g, ' 15 wt % solids) with stirring. 35 g of deionized water, followed by addition of G.94 g SIC2263.G, and then mixing at room temperature for 3 hours, followed by overnight at 85 t to obtain a clear coating solution (1 () _ solid content; coverage Rate: 75%; PH = 10.64) to prepare a surface-modified cerium oxide cerium particle dispersion. Prior to coating, the solution was acidified to a positive value of 2-3 using H3p〇4. This solution was applied to the test samples as described in the Examples, and the test results are shown in Table 1. Example 7 (5 nm particles modified with phenyl-decane) By adding (3) g of deionized water to a dispersion of 5 nm of SiO2 sulphate particles (66.7 g, (6) g) under (iv) Add (g ethanol and 3.9 g SIC 2417 〇, then mix at room temperature for 1 minute, and then put O wc in the box for 1 hour to obtain a clear coating solution (10 Wt% solid content; cover ^ : 5表面%; ΡΗ=1·25) to prepare a surface-modified cerium oxide cerium particle dispersion. This solution was applied to the test sample as described in the example!, and the test results are shown in the table. (20 nm particles modified with stupid base-decane) By adding 75 g of deionized water to a dispersion of 20 nm cerium oxide nanoparticles (Naic 〇 MU, MG '40 wt%) with stirring, Then add! $ Ethanol and 2.0 g SIC 2417·〇' then at room temperature for _1 () minutes, and the receiver is placed in the machine for 1 hour to obtain a clear coating solution (10)_Solid 140083.doc -25 · 201042116 quantity; coverage: 50%; dance said) to prepare surface modification f dioxide stone nanoparticles dispersion. This solution was applied to the test sample as described in #11, and the test results are shown in Table 1. Example 9 (addition of (10) particles by organic phenolic acid and epoxy oxy-acid) The particle 1 〇 34A ' 29 g ' 34 wt % solid content was obtained by stirring to 2 〇 nm cerium oxide under stirring. To the dispersion, 16.5 g of 2-permeate [3 ("stone-based" propenyloxy]propan-1-ene acid (solid content: 5 〇 2 wt%) and 35 g of deionized water were added. a solution of the genus G 〇 6 〇 in 36 g of water, followed by stirring at room temperature for 24 hours to obtain a translucent coating / liquid (8. W 7 Wt% solid content; coverage: organic 50% of stanol sulfonic acid and KH560 1〇〇〇/0 sub-dispersion. For example, PH=2.29) to prepare surface-modified cerium oxide nano-particles, this solution is applied to the test sample as described in Example 1, and tested. The results are shown in the table. Example 1 〇 (5 nm particles modified with organic stanol sulfonic acid plus 5 nm bare cerium oxide nanoparticles) to 2-amino group 3-3_[3_(trihydroxy sulphate) propoxy] A small dispersion of oxidized cerium nanoparticles on a small acid surface (Nalco 2326, 16.9 g 5wt/o & solids coverage: 1〇〇〇/0; pH=l.94; for typical preparations > See Example 1) by adding 16 9 g of acidified 5 nm bare cerium oxide nanoparticles (NalC 〇 2326 ' 16.9 g, pH = 1.81 ' adjusted with Η 3 Ρ 04), and the mixture was allowed to stand at room temperature for 30 minutes to obtain The clear coating solution (5 wt% solids) was applied to the test samples as described in Example 1, and the test results are shown in Table 1. Example 11 (5 nm unmodified cerium oxide nanoparticles) 140083.doc •26- 201042116 by 5 nm dioxide cerium nanoparticles (Nalco 2326, 33.3 g, 15 wt% solids) A dispersion of cerium oxide nanoparticles was prepared by adding 67 g of deionized water to the stirred dispersion, and then adjusting the pH to 2.39 with nitric acid. This solution was applied to the test sample as described in Example 1, and the test results are shown in Table 1. Table 1

Water absorption time (s) Example number 5 times after the first 5 washes, 10 washes, 15 washes, 20 washes after the control >90s — -- — ~ 1 (5 nm) <ls 3s 3s 9s 2 (20 nm) Is 5s 6s 8s 6s 3(75 nm) Is 5s 10s 7s 6s 4(20 ran) <ls <ls <ls <ls <ls 5(20 nm) <ls 6s 7s 19s 5s 6(5 run ) <ls <ls <ls <ls <ls 7(5 nm) <ls <ls <ls <ls <ls 8(20 nm) <ls <ls <ls <ls <ls 9(20 nm) 15s 8s 4s 5s 5s 10(5 nm) <ls <ls <ls <ls <ls 11(5 nm) <ls 2s 4s 6s 8s And the test results are intended to be illustrative only and not predictive, and it is expected that changes in the test procedure will produce different results. The above detailed description and examples are given for purposes of clarity of understanding. It should not be construed as an unnecessary limitation. It will be apparent to those skilled in the art that in many embodiments, 140083.doc -27- 201042116 may be specifically exemplified herein; 5 /弋Μ人i features, slang, configuration, etc. Tampering and/or combination. The inventors presuppose that there are such variations and combinations that are in the limits of the invention. In the meantime, the scope of the invention is not to be construed as being limited to the details of the structure and the equivalents of the structure. In the event of any inconsistency or disagreement between the disclosures of any of the references incorporated by reference herein in the present specification, the present specification is hereby incorporated by reference.

140083.doc -28-

Claims (1)

201042116 VII. Patent Application Range: 1. A method of providing a durable hydrophilic coating to a fibrous substrate, the method comprising: contacting a thermoplastic fiber with a coating composition, the coating composition comprising: having an average particle size of 100 An aqueous dispersion of nanoparticles or less than 100 nm of cerium oxide nanoparticles, wherein the aqueous dispersion of the cerium oxide nanoparticles has a pH of less than about 3; and dried to provide cerium oxide on the thermoplastic fibers Nano particle coating. 2. The method of claim 1, wherein the concentration of the cerium oxide nanoparticles in the coating composition is from 5 to 20% by weight. 3. 4. 8. The method of claim 1, wherein the thermoplastic fiber is hydrophobic. The method of claim 1, wherein the thermoplastic fiber comprises a thermoplastic resin selected from the group consisting of polyfluorene, polystyrene, polypropylene, polyurethane, polyethylene, its holdings, and combinations. The method of claim 1, wherein the control is about 20 nm or less, as in the method of claim 1, wherein the method is about 1 〇 nanometer or less 〇 nanometer. Wherein the diameter is about 5 nm or less. The method of claim 1, wherein the change is known to 〜 矽 矽 矽 矽 nanoparticles. The average particle size of the cerium oxide nanoparticle particles, the average particle size of the cerium oxide nanoparticles, the average particle size of the oxidized cerium oxide particles, the surface of the cerium oxide nanoparticle containing 140083.doc 201042116 9. The method of claim 8 Wherein the surface modified cerium oxide nanoparticle comprises a surface modifying agent having the formula: [(z)c-R3]d-Si-(OR4)b(R4)4-(b+d), wherein 2 a hydrophilic group; R is a covalent bond or, optionally, substituted with at least one oxygen atom and optionally substituted with an -OH group, having from about 1 to 20; a divalent or trivalent hydrocarbon bridging group of the ε carbon atom And R is independently an alkyl group, an aryl group or an aralkyl group having 1 to 8 carbon atoms substituted by hydrogen or, optionally, an oxygen, nitrogen and/or sulfur atom; c is 1 or 2, and b is 1 to 3 And d is 1 or 2 and (b + d) $4. 10. The method of claim 9, wherein 2 is selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, and a salt thereof. 11. The method of claim 9, wherein the Z is selected from the group consisting of hydroxyalkyl groups and polyhydroxyalkyl groups. 12. The method of claim 9, wherein z comprises a quaternary ammonium group. The method of claim 1, wherein the coating composition comprises 80 to 95 wt% of water; and 5 to 20 wt% of the dioxide having an average particle diameter of 1 〇〇ηηι or 1 〇〇nm Nanoparticles; wherein the coating composition has a pH of less than about 3. The method of any one of claims 1 to 13, wherein the pH is less than about 1. 15. A hydrophilic article prepared by the method of claim ι. 140083.doc 201042116 The hydrophilic article of claim 15, wherein the article has an average absorption time of less than about ίο sec after being measured according to a water absorption test according to a water washing test. 1 7. If you ask for it! A hydrophilic article of 5, wherein the article has an average absorption time of less than about 5 seconds, as measured by a water droplet absorption test, after at least one wash cycle according to the water wash test. 18. The hydrophilic article of claim 15 wherein the article has an average absorption time of less than about 5 seconds as measured by a water droplet absorption test after at least 20 water wash cycles have been performed according to the water wash test. 19. The hydrophilic article of any one of claims 15 to 18 which is a floor mat. 140083.doc 201042116 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 140083.doc -2-