TW201042117A - Hydrophilic fibrous article - Google Patents

Abstract

A fibrous article, comprising polymeric fibers comprising a coupling agent and surface-modified silica nanoparticles, wherein the surface-modified silica nanoparticles comprise an acidic surface modifying agent and render the polymeric fibers hydrophilic.

Description

201042117 VI. Description of the invention: [Technical field to which the invention pertains] The coated fibrous article, and the more special layer of the paving article, and the fiber to the specification are related to the nanoparticle-coated "with respect to having nanoparticle coating" Method for coating nano-particle coating on dimensional articles [Prior Art] Ο

Articles having a hydrophilic or water wettable surface are desirable in many applications. For example, 'in a rainy environment' needs to provide a doorway at the door of the building to quickly absorb the water in the shoes of the person entering the building or the water droplets that are shaking off the umbrella or dripping from the outerwear of the person entering the building. Water droplets. In the lifetime, cotton door mats are often 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 the coatings described in the following documents: U.S. Patent No. 6,136,215 ( siloxane treatments for textiles), U.S. Patent No. 6,436,855 (two Fiber Hnishing prior to high speed manufacture of water-absorbing articles and WO 2003097925 (treatment of synthetic fibers with polymers that contain carb〇xyl groups) ). The use of a nanoparticle system to functionalize soft surfaces has been described in U.S. Patent No. 7,112,621. The use of cerium oxide nanoparticles to provide hydrophilic properties for anti-fog applications has been described, for example, in U.S. Patent Nos. 5,585,186, 5,723,175, 5,753,373 and 6,040,053, and US 20040237833. The use of nanoparticles as part of the surface treatment of carpets has been described in U.S. Patent Nos. 5,908,663, 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 fibrous article comprising a polymeric fiber having a coupling agent and surface modified cerium oxide nanoparticles is described, wherein the surface modified cerium oxide nanoparticles comprise a hydrophilic surface modification The granules and the hydrophilic fibers are rendered hydrophilic. In some embodiments, a floor mat comprising a polymeric fiber having a coupling agent and surface modified cerium oxide nanoparticles, wherein the surface modified cerium oxide nanoparticles comprise a hydrophilic surface modifying agent and The polymeric fibers become hydrophilic. In some embodiments, a mantle comprising a polymeric fiber having a coupling agent and surface modified-emulsified Myna particles is described, wherein the surface modified dioxynamin particles comprise a hydrophilic surface modifying agent and the The dimension becomes permanently hydrophilic. In some embodiments, a method of making a fibrous article is described, the method comprising (4) coating a polymeric fiber with a coupling agent, and (b) coating the polymeric dispersion with an aqueous dispersion of hydrophilic = surface modified cerium oxide nanoparticles. Fibers: (4) Dry the coated fibers, wherein the surface-modified dioxycene nanoparticles render the dried polymeric fibers hydrophilic. In 139995.doc 201042117, in some embodiments, the coupling agent may comprise an aminodecane. In other embodiments, the coupling sword may comprise polyethylenimine. Some of the coupling agents are covalently bonded to the surface of the polymeric fibers. Glycosyl (including hydrazine) In some embodiments, the surface modified cerium oxide nanoparticles may comprise a hydrophilic surface modifying group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, and a salt thereof. In some embodiments, the hydrophilic surface modifying group can comprise a hydrophilic ether group (including polyoxyethylene oxime groups), an aliphatic group thereof or a glycodecane). In each of these embodiments, the fibrous article can further comprise any of the attributes or combinations thereof as described herein. Fiber items are permanently hydrophilic. The polymeric fibers can be hydrophobic (prior to coating with surface modified cerium oxide nanoparticles). The polymeric fibers may comprise a thermoplastic resin selected from the group consisting of polyamidamine, polyester, propylene, polyurethane urethane, polyethylene oxide, blends thereof, and combinations thereof. The fiber article is tested in water droplet absorption after v 1 G_human or even 2G water washing cycles according to the Laundering Test.

Abs〇_onTest) may have an average absorption time of less than about (7) seconds or 5 seconds, 4 seconds, 3 seconds, 2 seconds, or 1 second. [Embodiment] For the following definitions, the definitions should be applied unless the scope of the patent application or the rest of the specification is different. The term polymer! Kang Shenchu a TM ^ ^ 匕 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚(d) Exchange reactions with turbid, terpolymer or copolymer. Unless otherwise stated 139995.doc 201042117 Month's otherwise block copolymers and money copolymers are included. The term "nanoparticle" as used herein means a particle having a diameter of about 1 such as a primary particle or an associated primary particle. (7) Faceted modified nanoparticle" means a particle comprising, for example, a chemical group or moiety attached to the surface of a particle by a covalent bond. Surface groups alter the physical or chemical properties of the particles. The term "hydrophilic" as used herein describes a fiber or fiber surface that can be wetted by an aqueous fluid (e.g., water droplets) dropped thereon. The hydrophilicity and leakage of the continuous coated surface can be used with a contact angle of less than 90. To define it. However, in the case of fibrous articles, the contact angle is difficult to measure, so the hydrophilicity as used herein is defined relative to the water droplet absorption test described in more detail in the examples, and the average water droplet absorption time is less than about 1 Torr. The fiber item of the second is considered to be hydrophilic. The term "persistently hydrophilic" as used in the fibrous article of this specification means

Depending on the water wash test (described herein), such as 2 cycles, 5 times or more, W times or more, 15 times or more, or more than 20 times or more, the washing cycle is maintained for less than about 1 second (eg, The average water droplet absorption time as determined by the water drop absorption test. The term "coupler" as used herein, refers to a compound having at least two reactive functional groups. A reactive functional group can be covalently bonded to the Si-fluorene group on the surface of the ceria nanoparticles. Second reactive functional: capable of reacting with organic functional groups on the surface of the polymeric fibers. The recitation of numerical ranges by endpoints includes all values included in the range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3 8 〇, 4 and . 139995.doc 201042117 as described in this specification and accompanying application As used in the claims, the singular forms "a" The use of the term "or" is used in the meaning of "and/or" unless otherwise specified, unless otherwise stated. And 0 (4) used in the scope of patent application, the numerical value of the quantity of the component, the quality of the quality, etc. shall be construed as being modified by the term "about" in all cases. Therefore, unless stated to the contrary, the description and accompanying The numerical parameters recited in the scope of the patent application are approximations of the changes in the desired properties that the skilled artisan seeks to obtain using the teachings of the present invention. Limitation Equivalence For the application of the patent application, the numerical parameters should be interpreted at least according to the number of valid figures reported and by applying the general rounding technique. Although the numerical range and parameters of the extensive _ For approximations, # has reported as accurately as possible the values stated in the particular examples. However, any numerical value inherently also has some inevitable error, which is due to the standard deviation of the corresponding test measurements. • Article 3, such as a mat of hydrophilic fibers described herein, may exhibit less than about 1 second when tested according to the water drop absorption test after at least 1 G wash cycle performed by the root #wash test. Long-lasting hydrophilicity. In the preferred embodiment, the average absorption time is less than 5 seconds, 4 seconds, 3 seconds, 2 seconds or i seconds. In 1 mesh, the hydrophilicity of the coupling agent and the surface-modified nai particles is described. Fibrous articles such as ruthenium may be produced by first contacting the polymeric fibers with a coupling agent 139995.doc 201042117 and then contacting the polymeric fibers with an aqueous dispersion of surface modified cerium oxide nanoparticles. The surface modified cerium oxide cerium nanoparticles render the polymeric fibers hydrophilic. The hydrophilicity or lack of hydrophilicity of the hydrophilic fibers can be determined by subjecting a suitable sample of the fibers to a water drop absorption test as described below. For the sake of simplicity, the fiber sample is defined as having a "water droplet absorption time" equal to the time required to absorb i drip (about 2 mL). A fiber having a water absorption time of > 90 seconds can be regarded as having poor hydrophilicity. And the water absorption time of 1 sec or 5 sec, 4 sec, 3 sec, 2 sec, or 1 sec indicates that the fiber sample is getting better hydrophilicity. Fiber, hydrazine, hydrophilicity, durability or lack of persistence can be borrowed The fiber sample was subjected to a repeated water wash cycle according to the water wash described in the real money towel, and then the fiber sample was subjected to a water drop absorption test. The reduced hydrophilicity of the fiber was shown only after 5 wash cycles according to the water wash test. π can have poor durability, and fiber samples that remain hydrophilic after 1 〇 : 1 5 \ or even 20 wash cycles according to the water wash test can have an increasingly longer hydrophilicity. Fibrous Article The I-fibrous substrate of the present disclosure may have any known configuration, including a knit construction, a woven construction, a non-woven construction, and the like, or a combination thereof. The polymeric fiber substrate can have a weight of between about 1 and about 55 ounces per square yard. The polymeric fibrous substrate, such as floor coverings σσ, may preferably have a weight of between about 20 and about 5 ounces per square yard. In the present disclosure, suitable polymeric fibrous substrates can include floor mats, cloth, 139995.doc 201042117 wiping sheets, and various other types of mats. The polymeric fibers of the present disclosure encompass any of the standard fibers and composite materials used therein for the flooring σ /=t m σσ. The polymeric fibers can be said to be Μ 早 3 early silk fibers, core sheath fibers, etc. or can be looped, cut pile or any other type of carpet face. By way of example only, nylon, polyethylene, polypropylene, polyester, polyvinyl chloride, #, polyaminocarboxylic acid, etc. fibers may be used to penetrate the fabric (such as woven, non-woven or knitted fabrics of any fiber type, Fabrics such as those previously listed are tufted. The polymeric fiber substrate can comprise fibers or yarns of any size, including microdenier fibers or yarns (fibers or yarns having a denier per filament less than i). The fibers or yarns can have a denier of from less than about 10,000 filaments to about 2000 denier per filament, or more preferably less than about! Denier in the range from single denier to about _ monofilament denier. In some embodiments, the untreated 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 described in U.S. Patent No. 4,820,566 (Heine et al.) and U.S. Patent No. 5,554,333 (Heine et al.). In the form of a velvet ring inserted into a backing material, both of which are incorporated herein by reference. In some embodiments, the floor mat may include, for example, a 3M company (St. Paul, Minnesota (st.)

Paul, MN) and Shanghai, China, N〇MAD 4〇 (10), NOMAD 5000 and NOMAD 6000 entrance maps are marketed in σ. In some embodiments, in combination with the polymeric fibers of the present specification, the fibrous article may additionally comprise natural fibers or weaves derived from natural fibers, including rim, 139995.doc 201042117 wool and cotton fibers, or cellulose acetate fibers and related Fiber or a combination thereof. However, the present specification is generally directed to fibrous articles comprising polymeric fibers as described below. Polymeric Fibers The durable hydrophilic fibers can be prepared from a generally hydrophobic (e.g., thermoplastic or thermoset) polymeric resin that exhibits a water absorption time of >90 seconds. Suitable thermoplastic polymers may include commercial polymers such as poly(ethylene), polyethylene (high density, low density 'very low density), polypropylene, etc. (c〇mm〇dity polymer) such as polyester (for example including poly( Engineering plastics such as polyethylene terephthalate) and poly(butylene terephthalate)), & amine phthalates and polyamines (for example, including nylon); and blends of such materials And a mixture. In the aspect, the 'hydrophilic fibrous article comprises a substrate selected from the group consisting of extruded materials, dazzling materials, woven fabrics, non-woven fabrics, foams, and combinations thereof. The article comprises a coating. A polymeric fibrous substrate. The coating comprises a surface modified dioxon nanoparticle electrical component having a surface modifying agent on the surface of the nanoparticle and a coupling agent for coupling the surface modified nanoparticle to the polymeric fiber. Containing a surface modifying group as a hydrophilic surface becomes hydrophilic. Moreover, the body m exists such that the fiber table ", m is more octagonal and the 5 surface modifying group is covalently formed in an amount sufficient to form a single 曰 or less than a single layer. Lian Wen Wang does not wood particle surface. The surface of the surface of Weixi' surface s (that is, the Shixi smelting alcohol group) is not completely modified to allow the nanoparticle to associate with the ginseng. ^ by the unrepaired (tetra) alcohol surface group And base # coupling agent I39995.doc 201042117 In some embodiments, the fibers of the mat substrate may be modified with a suitable coupling agent to introduce reactive functional groups on at least a portion of the surface of certain fibers. Suitable coupling agents are described below. Described in detail in these embodiments, the surface modified cerium oxide nanoparticles can be associated with a reactive functional group introduced by the coupling agent. Examples of suitable reactive functional groups to which the coupling agent can be introduced can include amines. a base, a decyl group, an epoxy group, and a hydroxyl group or a combination thereof.

In some embodiments, the coupling agent comprises a decane coupling agent. For example, the decane coupling agent may have the formula: [(Y)c-R3]d-Si-(〇R4)b(R4)4 (b+d) wherein Y is compatible with a predetermined substrate (including polymeric fibers) The surface of the substrate) is bonded or associated with a functional group, and may, for example, be selected from an organofunctional group; r3 is a covalent bond or a divalent or tri(tetra) bridging group® 4R4 is independently reduced or, as the case may be, available An alkyl, aryl or aralkyl group having from 1 to 8 carbon atoms substituted by oxygen, nitrogen and 'or a sulfur atom; ... or 2, ... to... or 2. In some embodiments, b is 3, c is 1 and ..., and (b+d)s4. The group of the formula may be bonded or associated with the substrate by forming a /, 6 bond by condensation, addition or displacement reaction, or by association with the substrate by ionic bonding or van der Waals force. And t, R3 is a covalent bond, or a divalent or trivalent hydrocarbon bridging group having about i^20 rabbit atoms, including a stretching base, an exfoliating earth, and an octagonal and argon, optionally in the main chain Including 1 to 5 groups selected from the group consisting of thiol 2, -s〇2_, and _nr2- (and combinations thereof, such as -C(O)-O-) (wherein R3 is a gas or a Ci_c) In another embodiment: = is a poly (a gasification knife) having a formula of _(〇CH2CH2_)n(〇cH2CH(Ri))m_ wherein η is at least 5, m may be 〇 and preferably at least丨, and _ 139995.doc 201042117 has a molar ratio of at least 2:1 (preferably at least 3:1), and an alkyl group. It should be understood that when "c" of formula II is !, then r3 is a covalent bond. Or a divalent smoke bridging group, and when "c" is 2, then R3 is a trivalent bridging group. R3 is preferably a divalent alkylene group and c is 1 ^ R4 is preferably a Ci_C4 alkyl group and 1> is 1 to 3. In some embodiments, Y is selected from an amine group, an epoxy group (including a glycidyl group), The organic functional group γ1 of a group, an ester group, a hydroxyl group and a thiol group. Preferred amine functional decane coupling agents include 3-aminopropyltrimethoxysilane and N-3-(2-aminoethyl)-amine group Propyltrimethoxydecane. Suitable epoxy functional decane coupling agents include 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 2-(3,4-epoxycyclohexyl) Ethyltrimethoxydecane, 5,6-epoxyhexyltriethoxydecane, (3·glycidoxypropyl)triethoxysulfonate and (3-glycidoxypropyl)trimethyl Oxygen stone burning). The decane coupling agent can be prepared, for example, by conventional techniques, or it can be from, for example, Gelest Corporation (Morrisville, Pa., USA), Momentive Performance Materials, Inc. (Wilton, CT, USA). Conn., USA)) and United Chemical Technologies (H〇rsham, Pa, 113 8) and other suppliers. Further reference to £1> ?11^£1£^11^11,

"Ultra Co., Ltd. And U.S. Patent No. 5, 372, 756 A2 to Bilkadii and European Patent Application No. 0,372,756 A2. In some embodiments, a coupling agent other than the above-mentioned decane couple 139995.doc 12· 201042117 mixture may be coated on the substrate. To provide a surface with enhanced compatibility to facilitate coating of the cerium oxide nanoparticles. Examples of other suitable coupling agents may include polyethyleneimine, branched polyethyleneimine, ethoxylated polyethyleneimine, Ethyleneimine, ethyleneimine oligomer, tetraethyl ortho-decanoate, 3-(triethoxyphosphonium-16)propyl isophthalic acid vinegar, di-ethyltriamine or any suitable base A compatible mixture of any such coupling agents. Polyamines useful as coupling agents are polyamines, known as polyimines, such as polyethyleneimine, which can have a wide range of molecular weights and The degree of branching is utilized. Polyethyleneimine includes a large family of water-soluble polyamines of the same molecular weight. It is generally known that the polymerization of ethyleneimine does not produce a polymer that completely contains units having a linear structure, but the degree of branching of polyethylenimine depends on the acid concentration during polymerization and The degree of branching can vary, for example, between 12% and 38%. The formula of polyethyleneimine can be expressed in the form of units A, B or c where: " A is a -r6_n(R5)2 unit and B is R5 -N(R6-)2 unit, and c is 〇(_r6)3N_unit' wherein R5 is hydrogen and R6 is a -CH2CH2- group. Unit A: Unit B: Unit ratio of c unit can be about 1: 〇5 From 0 5 to about 1:2:1, but preferably from about 1:1:1 to about 1:2:1. Other groups can be grafted onto the polyethyleneimine by methods well known in the art. 'In order to change the affinity of the coating to the substrate or to change the adhesion properties, such as the reaction of the polyethyleneimine with the ethylene oxide structure (ethylene oxide, glycidol) to introduce a hydroxyl group. The preferred molecular weight of the polyethyleneimine is about 600 to Approximately 80,000. The optimum molecular weight of polycarbimine is from about 6 〇〇 to about 25,000. 139995.doc -13- 201042117 Others of polyamine coupling agents Examples may include the combination of a primary amine group and/or a secondary amine group typically present in the molecule and may have the following amines that allow sufficient water solubility from the aqueous system: di-ethyltriamine, n-(2-amino Ethyl)-1,3-propanediamine, 33, a face 苴\tm 甘^ a fe-based-N-mercaptodipropylamine, tri-extension ethyltetramine, n, n, _ double (3_ Aminopropyl)-extended ethyldiamine, n,n,_diaminopropyl)-1,3-propylenediamine, penta-ethylhexamine, group trioxa-u3-dodecane Monoamine and 4,9-trioxa-M2-tridecanediamine. Nanoparticles: Nanoparticles are inorganic nanoparticles with surface modifying groups on the surface. Suitable inorganic nanoparticles comprise 7 nm nanoparticles. Cerium dioxide = is usually used in the form of a dispersion of submicron sized titanium dioxide nanoparticles in an aqueous dissolved organic solvent mixture. The average particle diameter of the dioxide may be (10) nanometers or less, preferably 3 nanometers or 3 nanometers, preferably 10 nanometers or less. The average particle size can be greater than about 2 nanometers. Flat ten uniforms. If necessary, at least m/transmission electron microscopy of the composition, t-larger larger dioxide dioxide particles may be present in the coating 'eight without reducing the hydrophilicity of the selected substrate. Take the rice & + $g colloidal dispersion form. The non-aqueous particles may be in some embodiments, surface modified nanoparticle stability. In the case that it is not limited to the decoration, it is considered that the surface modification can be determined by the nature and molecular size of the modifier:: Space and / set aggregates. In the case of 兮 .. In the formation of a large unstable lower pH value ^ brother's surface modification of the use of nano particles can synergize with the night to provide a more stable dispersion of the formulation or expansion I39995.doc « 14- 201042117 Stable pH range for large dispersion formulations. This allows the product to be used at near neutral pH levels, thereby reducing the likelihood of irritation or hazard to the user. Inorganic cerium oxide nanoparticle (sol) commercially available in an aqueous medium. The cerium oxide sol can be used in water or an aqueous alcohol solution such as LUDOX (EI Du Pont, Wilmington, DE) Made by De Nemours and Co., Inc., Wilmington, Del., USA), NYACOL (available from Nyacol Corporation of Ashland, MA) or NALCO (by Naper, Illinois, USA) A trade name is available from Nalco Chemical Co., of Naperville, 111. USA. A suitable cerium oxide sol is a oxidizing agent having an average particle size of 5 nm, a pH of 10.5 and a solids content of 15% by weight.矽Sol NALCO 23 26 is commercially available. Other commercially available cerium oxide nanoparticles include "NALCO 1030TM", "NALCO 1034TM", "NALCO 1050TM", and "NALCO 1115" available from NALCO Chemical. TM", "NALCO 2326TM", "NALCO 2327TM", "NALCO 1130TM" and "NALCO 2359TM"; "Remasol SP30" available from Remet Corporation (Utica, NY, USA) And "LUDOX SM" available from DuPont. It is also possible to use a non-aqueous cerium oxide sol (also known as cerium oxide organosol) which is a cerium oxide sol dispersed in an organic solvent or an aqueous organic solvent. 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 used, such as ethanol. Acidification 139995.doc •15· 201042117 The agent is acidified prior to dilution. Dilution prior to acidification may result in poor or uneven coating. Stabilized silica dioxide nanoparticles can usually be ordered in any order. Release and Acidification. Surface Modifiers A variety of methods can be used to modify the surface of nanoparticles, including, for example, adding surface modifiers to the rice particles (eg, in the form of powders or colloidal dispersions) and allowing surface modifiers to be used. The reaction of the rice particles. Other suitable surface modification treatments are described, for example, in U.S. Patent No. 2,801,185 (1) er) 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 schematically represented by the formula Rs_rL_z, wherein rS is a surface bonding group capable of being bonded to a stanol group (ie, a group) on the surface of the ceria particle, and the z represents a system (for example, The other component of the substrate ^ reacts with a hydrophilic group, and rL represents an organic linking group or a bond: a suitable surface bonding group RS of the surface modifying agent may include a stone sulphate, an alkoxy smelting or 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), Ammonium-based or poly(oxyethylene)-based or trans-base. The amount of the surface modifier can be used to make the surface of the SiO2 particles to 100% of the surface functional groups (Si_〇H group. Typically, at least 嶋, 7G%, or 9G% of the surface of the cerium oxide nanoparticles are functionalized. By experimenting with the number of functional groups, a large number of nanoparticles are reacted with an excess of surface modifying agent. All available reactive sites are functionalized with surface modifiers and can then be calculated from the results A lower percentage of functionalization. The amount of surface modifier is generally sufficient to provide a surface modification agent that is twice the molar ratio of the surface stanol group on the inorganic nanoparticle 139995.doc 16 201042117. A particularly high concentration of surface modifier is obtained on the cerium oxide nanoparticles, the important one being to first modify the surface of the cerium oxide nanoparticles and then combine with the remaining components of the coating. - In some embodiments The surface modifier has the following formula: . [(Z)c-R7]d-Si-(OR8)b(R«)4.(b+d), wherein Α is a hydrophilic group; ❹ R7 is a total a valence bond or a divalent or trivalent hydrocarbon bridging group having from about 1 to 20 carbon atoms, optionally substituted with at least one oxygen atom and optionally substituted with a fluorenyl group; R8 is independently hydrogen or optionally An alkyl, aryl or aryl group having 1 to 8 carbon atoms substituted by an oxygen, nitrogen and/or sulfur atom at the position; c is 1 or 2, b is 1 to 3 and d is 1 or 2 And (b+d)$4. 0 In a preferred embodiment 'Z is a hydrophilic group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a phosphonium group, and a salt thereof. Suitable surface modifiers Examples thereof include the following: - (H0) 3SiCH2CH2CH2S03H, (H〇) 3SiCH2CH2CH20CH2CH (0H) CH2S03H, NaOSi (OH) 2CH2CH2CH2S03Na, Na0Si (0H) 2CH2CH2CH20CH2CH (0H) CH2S03Na, Na0Si (0H) 2CH2CH2C02Na, and

Na0Si(0H)2CH2CH2P(0)(0H)20Na 139995.doc • 17· 201042117 and other known compounds. The sulfonate-organodecane compound can be prepared according to the procedure as seen in U.S. Patent No. 4,33,377 (Beck et al.). In another example, the surface modifying agent may include, for example, a hydrophilic mystery of 2-[methoxy(polyoxyethylene)propyl]trimethoxy-stone. In another embodiment, the surface modification The agent may include, for example, N_(3_triethoxy oxacillinyl) glucosamine, in some embodiments, the surface modified nanoparticles may be dried and easily dispersed in the coating. The solvent of the layer composition. Liquid carrier The coating composition comprises 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 water soluble or A water-miscible organic solvent. The total v〇c content of the composition should be less than about 20% by weight of the total weight of the formulation, preferably less than about 15% by weight, and more preferably less than about 10% by weight. Water-soluble or water-miscible organic The solvent is preferably a low molecular weight alcohol, preferably having a carbon atom content of less than about 6 'including butanol, isopropanol, ethanol and/or methanol and mixtures of such alcohols with each other or with no VOCs. Or a mixture of water-miscible organic solvents. Use a small amount of these solvents (in accordance with the amount There are US EPA regulations (see, for example, EpA 4〇CFR·5 1·1〇〇(1) and continuous cases) to help reduce the surface tension of coating formulations and to improve the wetting and spreading of such formulations on hydrophobic surfaces. In addition, the alcohol solvent can impart additional storage stability, inter alia, by participating in an equilibrium condensation reaction with an alkoxy decane and/or a decane coupling agent. The pH can be applied to the fiber before pKa(H2〇)< 5, preferably less than 139995.doc -18- 201042117 2.5, the acid of preferably less than 1 acidifies the aqueous dispersion of surface modified nano particles to the desired pH level. Suitable acids include organic and inorganic acids and For example, oxalic acid, citric acid, benzoic acid, acetic acid, formic acid, propionic acid, benzenesulfonic acid, H2S〇3, H3P〇4, CF3C02H, HC1, HBr, HI, HBr〇3, hno3, HC104, H2S04, CH3S03H, CF3S03H , cf3c 〇 2h and CH3OS 〇 2 〇 H. The most preferred acids include HCl, hno3, h2S04 and H3P 〇 4. In some embodiments, it may be desirable to provide a mixture of an organic acid and a mineral acid. In some embodiments, it may be used. Containing ρκγ5 (preferably < 2 5, optimally less than 1) A mixture of acid and other acid acids of a small amount of pKa > 5. It has been found that a weaker acid utilizing PK lun 5 does not provide a uniform coating with desirable properties such as cleanability and/or durability. In particular, it contains a weaker acid. The coating composition or alkaline coating composition typically forms a bead on the surface of the polymeric substrate. In many embodiments, the coating composition typically contains sufficient acid to provide less than 5, preferably less than 4, optimal. A pH of less than 3. Other additives, such 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 the term "surfactant" as used herein to describe a molecule comprising a hydrophilic (polar) region and a hydrophobic (non-polar) region on the same molecule. It is large enough to reduce the surface tension of the coating solution. When water is a liquid carrier in the preferred embodiment, the inclusion of a surfactant may be particularly advantageous for coating the coupling agent on the polymeric fibers. Suitable surfactants for use in the present invention include anionic, cationic, nonionic or amphoteric surfactants. Example package 139995.doc •19· 201042117 Includes the following: surfactant type---- surfactant name product name source anion type^_ sodium dodecylbenzene sulfonate DS-10 Rhone-Poulenc sex-- - Ν-cocoa-aminopropionic acid MIRATAINE AP-C Rhone-Poulenc Non-ionic lauryl dimethyl amine oxide RRODAMOX LO Rhone-Poulenc non-isolated type ------ PEG/PPG/PEG block Copolymer PLURONIC F38 BASF Non-ionic - Organic Polyoxic Oxygen Surfactant ΒΥΚ-333 BYK Non-ionic----- Organic Poly-Oxygen Surfactant Q2-5211 Dow-Coming Non-ionic--- - Fluorochemical surfactant FC-4430 3M Nonionic---,, Fluorine-containing surfactant FC-4432 3M Non-ionic - Polyethylene oxide (7) Lauryl ether AE07-24S Sasol (China) Chemical Co. , Ltd. Nonionic Polyoxyethylene (9) Lauryl Ether AE07-24S Sasol (China) Chemical Co., Ltd. Nonionic Polyoxyethylene (18) Lauryl Ether AE07-24S Sasol (China) Chemical Co., Ltd . Cationic Dioleate Triethanolamine Tetra-Ammonium Salt PRAEPAGEN 4317 Clariant Chemical s (China) Ltd. Cationic chlorinated ditallow decyl ammonium PRAEPAGEN 3345 Clariant Chemicals (China) Ltd. Cationic chlorinated alkyl dimethyl sulphate DODIGEN 226 Clariant Chemicals (China) Ltd. 139995.doc -20- 201042117

Ο Waidian active agent type and class of surfactant name product name source anion type succinyl sulfosulfate sodium octyl AEROSOL OT Cytec Industries anionic succinate succinyl sulfonate ( C10-C16) POLYSTEP A-13 Stepan Company Benzobenzenesulfonate and Sulfate ~7ΓΖ—~~~~__ Branched Alkyl (C12) Sodium Benzene Sulfonate POLYSTEP A-16 Stepan Company 13⁄4 Ion Based Studate and Sulfate - Dodecylbenzenesulfonate RHODOCAL DS-10 Rhone-Poulenc Anionic linear or branched aliphatic sulfate polyethoxylated derivative polyethoxylated alkyl (C12) Ammonium Sulfate Sulfate STEOL CA-460 Stepan Company Anionic Linear or Branched Aliphatic Sulfate and Sustained Salts Fatty Sulfate HOSTASTAT HS-1 Hoechst Celanese Corp. Anionic Alkyl Benzate and Sulfuric Acid Salt linear alkyl (C12) benzoic acid sodium POLYSTEP A-15 Stepan Company Anionic alkyl carboxylate sodium stearate Witco amphoteric alkyl carboxylate Ν-coco quinone-aminopropionic acid MIRATAINE AP-C Rhone-Poulenc Anionic Burning Acid Filling S Or diester ethoxylated dodecanol sulphate S sodium salt RRODAFAC MC-470 Rhone-Poulenc nonionic polyethylidene succinyl alcohol polyoxyethylene (23) lauryl ether BRIJ35 ICI Americas Inc. 139995.doc •21 · 201042117 Non-ionic polyethoxylated alkyl alcohol polyoxyethylene (4) Lauryl ether BRIJ30 ICI Americas Inc. Non-ionic polyethoxylated alkyl alcohol polyethylene oxide (7) Laurel key AE07-24S Sasol (China) Chemical Co., Ltd. Nonionic Polyethoxylated Alkyl Alcohol Polyoxyethylene (9) Lauryl Ether AE09-24S Sasol (China) Chemical Co., Ltd. Nonionic Polyethoxylated Alkyl alcohol polyoxyethylene (18) Laurel bond AE018-24S Sasol (China) Chemical Co., Ltd. Block copolymer of nonionic polyethylene oxide and polypropylene oxide. Block copolymer of ethylene oxide and propylene oxide TETRONIC 1502 BASF Corp. Block copolymer of nonionic polyethylene oxide and polyoxypropylene PEG-PPG-PEG block copolymer PLUROMC F38 BASF Corp. Block copolymer of nonionic polyethylene oxide and polypropylene oxide PEG-PPG-PEG block copolymer TETRONIC 908 BASF Corp. Nonionic amine oxide lauryl dimethyl amine oxide RHODAMOX LO Rhone-Poulenc Nonionic polyethoxylated alkyl alcohol ethoxylated triterpene sterol TERGITOL TMN-6 Union Carbide Chemical & Plastics Co. Right using a surfactant, the surfactant concentration in the coating composition of the present specification is preferably at least 〇丨 wt% (wt%), more preferably at least 0.4 wt%, and even at least 0.4 wt% of the coating composition. More preferably at least 1 wt%. If the interface activity 139995.doc •22· 201042117 is used, the concentration of the surfactant preferably does not exceed 涂层 of the coating composition, and does not exceed 5 wt% of the coating composition. The interface activity 1 includes a polysulfide 1 nonionic surfactant. A preferred surfactant is Q2-5211, a nonionic polyoxo-copolymer copolymer surfactant available from D0W Corning Company of Mdland, MI. It has been observed that although surfactants and coupling agents are included to impart a certain level of hydrophilicity to the polymeric fibers of the Japanese, the hydrophilicity of the surfactants as observed in Control 2 in the examples may be observed. Can not withstand the washing process. Instead, the polymeric fibers are first coated with a coupling agent, followed by coating the polymeric fibers with surface modified cerium oxide nanoparticles to produce a more durable hydrophilicity. If necessary, the surface-modified cerium oxide nanoparticle coating mixture may optionally contain a binder in which the nanoparticles are dispersed. Depending on the case, the adhesive solution is tetramethyl 〇rth〇Sj丨jcate (TEOS), which is compatible with the permanent hydrophilic coating of this specification (see examples). 5). Coating Method 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. Surface contamination The presence of oils, oils and oxides physically weakens and reduces 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 one embodiment of the present invention, the mat substrate can be surface treated. Surface treatment 139995.doc •23· 201042117 Methods include vacuum deposition, pulp, ozone and electro-acoustic lasers, chemistry, heat, flame, and electricity. In preparing non-polar fibers to accept this specification: Agents: It may be necessary to perform - or a plurality of such surface treatments. Raw Hydrophilic 1 This specification includes at least partial drying using a method comprising the steps of first coating a polymeric fiber 'preferably Tai' stagrant' with a coupling agent and then modifying the cerium oxide with a hydrophilic surface. The aqueous dispersion is coated with a polymeric fiber. The coating method generally comprises the use of π-denier fibers, followed by the use of the agent solution to coat the articles of the polymerization vapor: the modified dioxon nanoparticle solution coating: two fibers, quasi-including heating, drying and/or depending on the situation Or sudden. Although it has been found that at least about 0 to the surface-modified dioxins may be required to achieve the long-lasting hydrophilicity of the present specification, it is desirable to provide a more coating by the use of an excess of the coupling agent and the surface-modified dioxonide particles. Level. In some embodiments, the coating method can comprise applying a coating material and the coating is allowed to air dry at ambient temperature. In other embodiments the coating method may 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 heating the substrate in a temperature range of 90C to (4) (d). 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 between 9 and 12 inches. . By heating the coated substrate within the range, the drying time can be shortened to about ι hours or even about 30 minutes. In some embodiments, the coating of the cerium dioxide nanoparticles on the substrate 139995.doc -24 - 201042117 may be followed by a rinsing step comprising washing away excess coating material after drying. In a preferred embodiment, the rinsing liquid is water. The coating of the present invention can be applied to selected substrates by various coating techniques, including dip coating, spray coating, foam coating, roll coating, roll-box, flexible roll coating, and coating. (pad c〇ating), overcoating (fl〇〇dc〇ating) and other coating techniques well known in the art. Washability test 0 For some coated fibers, remain hydrophilic after multiple wash cycles

Features may be important. We used a water wash test (described below) to evaluate the durable hydrophilic coating on the weave. We used the Whirlp〇〇l 1U top-loading washing machine to perform the test method in the test model. This test method is considered to be applicable to other models of washing machines. The coating compositions and coated articles of the present disclosure are described in more detail in the following examples, which are intended to be illustrative only, as many modifications and variations within the scope of the invention will be apparent to those skilled in the art. Variety. Unless otherwise stated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are obtained or available from the chemical suppliers described below. Or can be synthesized by conventional techniques. Example material Sodium oxide nanoparticle dispersion, available from Nalco 2326TM (average particle size 5 nm) and Nalco 2327 (20 nm) from Nalco Chemical Company 内Z-6020: N Naperville, Ill. -(2-Aminoethyl)-3-aminopropyltrimethoxy sylvestre, 139995.doc -25- 201042117 available from Dow Corning Company of Midland, Michigan. KH5 50 : 3-Aminopropyltriethoxy Shi Xi Xuan, available from Zhejiang Chem-Tech Group Co., Ltd. Hangzhou, China °

NomadTM 6000 Mat: Resistant to the fiber mat, available from 3M (China), Shanghai, China. Q2-5211: Super Wetter: Nonionic Polyoxodiol Copolymer Interface Active Agents are available from D〇w Corning Company of Midland, Michigan. Polyethylenimine (50% in water), polyethyleneimine (8% ethoxylated, 30% in water), polyethyleneimine (branches, Mn i〇〇〇〇 (GPS), Mw 25000 ( LS)) and ethyleneimine oligomer mixture (viscosity 2〇〇, 〇〇〇cps) available from 3050 St. Louis Bruce Street, Missouri, USA (3〇5〇)

Spruce Street, St. Louis, MO 63103 USA) Sigma-

Aldrich. TEOS: Tetraethyl orthosilicate, available from Sigma-Aldrich, 3050 St. Louis Bruce Street, 631〇3, Missouri, USA. Test Samples Test samples of the specified type of floor mat were cut into squares of size 5 cm><5 cm unless otherwise stated. Water Wash Test The coated test sample was subjected to a repeated water wash test in a standard top-mounted household washing machine (Whirlpo〇i m). Place the sample and the crushing load (9 〇χ 9 〇 cm hem cloth 139995.doc -26- 201042117 cotton or 50/50 cotton/polyester) of the unfinished plain fabric of 2S0 g/m2 in the washing machine The total weight of 18 g〇 2 kg (4 ± 〇 5 lb) is generated, and the ballast weight load is not less than 14 kg (3 lbs). A liquid detergent (75 g 3M Restained Respiratory Concentrated Shampoo concentrate, purchased from 3M Company, St. Paul, Minnesota) was added and water was injected into the washing machine to a high water mark at a water temperature of 41 ± 3 C. The samples were washed in a "standard" wash and dehydration cycle for 45 minutes for a total of 5 wash cycles, and then the test samples were dried overnight in a forced air circulation oven at 4 (rc). The tester may change the number of wash cycles to increase the number of wash cycles. Layer Persistence Challenge The water droplet absorption test performs a water droplet absorption test by applying 〇 2 mL of deionized water droplets from the drip to the surface of the test sample and recording the time required for the water droplets to completely absorb (according to visual judgment). For example, the value is the average of three tests at different positions on the surface of the test article. If the water absorption time is greater than i minutes, the test is terminated and the absorption time is recorded as >丨 minutes. Control 1 Test N in the water absorption test未 mad 6 〇〇〇 ground untreated sample (5 cm x 5 cm). The results are shown in Table 1. Control 2 by N-(2-aminoethyl)_3_aminopropyltrimethoxydecane The stirred sample (2 g) was added with 97.5 g of deionized water, followed by the addition of q2_5211 surfactant (0.5 g) to prepare a coupler solution. The N〇mad 6000 floor mat sample was coated with the coupler solution (5 c Mx5 cm) and dry. The results of the water absorption test after repeating the water wash cycle are shown in Table 1. 139995.doc •27- 201042117 Preparation Example 1 (surface modified nanoparticle with an average particle size of 5 nm) by 5 nm 2-hydroxy-3-[3-(trihydroxydecylalkyl) added to 3〇g deionized water in a stirred dispersion of cerium oxide nanoparticles (Nalco 2326, 33.3 g, 15°/solids) Propyloxypropane-indole-sulfonic acid (36 7 g, 9.07 ° / solid content) to prepare a surface-modified dioxin-deuterated nanoparticle dispersion, and obtained transparent after 1 hour at room temperature Solution (pH = 丨.78 and decane coverage: 100%). Preparation Example 2 (surface modified nanoparticles, average particle size 2 〇 nm) by adding 2 〇 nm cerium oxide nanoparticles to 40.6 g of water (Nalco 2327 '6·25 g, 40 wt〇/〇 solids), followed by the addition of 2-hydroxy-3-[3-(dihydroxydecyl)propoxy]propane_丨-sulfonic acid with stirring ( 3 13 g), and then heated at 80 C for 4 hours to prepare a surface-modified cerium oxide nanoparticle dispersion. Preparation Example 3 (surface modified nanoparticle + teos) Add to 42.5 g H20 33.3 g Nalco 2326 cerium oxide nanoparticle dispersion, followed by 2-hydroxy_3_[3 hydroxy(trihydroxydecyl)propoxy]propane-1-sulfonic acid (24.2 g), and heated at 8 〇t The mixture was allowed to cool for 4 hours, followed by cooling and then stirring until the TEOS was completely 'average particle size 5 nm, with coupling but to room temperature and 0.56 g of TEOis was added, and the solution was added to the hydrophilic coating solution. Example 1 (surface modified nanoparticle, flat agent)

The agent (0.5 g) was used to prepare a coupler solution. A Nomad 6000 floor mat sample (5 cm x 5 cm) was coated on a dyeing machine under a pressure of 3 kg with a 139995.doc -28- 201042117 coupler solution, followed by air drying at room temperature for 24 hours. The mat sample was then coated on the pad dyeing machine with a surface modified cerium oxide nanoparticle dispersion of Preparation Example 1 under a pressure of 3 kg, followed by heating at 9 Torr for 1 hour, and then applying the coated mat. Cool back to ambient temperature. The results of the water droplet absorption test performed after the repeated water washing according to the water washing test are shown in the table. Example 2 (surface modified nanoparticle, average particle size 2 〇 nm, with coupling agent) ❹ This example was basically carried out using the procedure of Example , except that the surface modified cerium oxide nanoparticle of Preparation Example 2 was used. Dispersion (2 sputum lung dioxide nanoparticles). The results of the water drop absorption test performed after the repeated water washing cycle performed according to the water washing test are shown in Table 1. Example 3 (surface modified nanoparticle, average particle size 5 nm with coupling agent, no surfactant) by adding 95 g hydrazine to a sample of 3-aminopropyltriethoxydecane (5 g) A coupler solution was prepared from ethanol. Spray the Nomad 6000 floor mat sample (5 cm x 5 cm) with a coupling agent solution and heat at 90 °C! hour. Next, the floor mat sample was sprayed with the surface-modified cerium oxide nanoparticle dispersion of Preparation Example 1 and then heated at 9 ° C for 1 hour, and then the coated mat was cooled to return to the ambient temperature. The results of the water drop absorption test performed after the repeated water washing cycle performed according to the water washing test are shown in Table 1. Example 4 (similar to Example 1, but using PET fibers) by adding 97.5 to the sample (2 g) of N-(2-aminoethyl)-3-aminopropyltrimethoxylate g Deionized water, followed by addition of Q2-5211 interface 139995.doc • 29· 201042117 agent (0.5 g) to prepare a coupling agent solution. pET fiber (丨5d pET fiber, fiber length 51 mm, purchased from Neumuenster, Germany)

The non-woven mesh sample of Nexis Faserwerke GmbH & c〇) of Germany) is immersed in the coupling agent solution, followed by removing the excess solution by dripping the sample, and then heating the sample at 90 ° C for 30 minutes; then immersing the sample in the preparation In the surface modified nanoparticle dispersion of the example, 'the sample was then dripped to remove excess solution, followed by heating the sample at 9 Torr for 丨 hours. The results of the water drop absorption test performed after the repeated water washing cycle performed according to the water washing test are shown in Table 1. Comparative Example A ("Comparative A", unmodified nanoparticle with coupling agent) by mixing sample with N-(2-aminoethyl)-3-aminopropyltrimethoxydecane (2 g A coupler solution was prepared by adding 97.5 g of deionized water followed by a noisy 5211 surfactant (0.5 g). The N_d 6_mantle sample was coated with a coupling agent solution at a pressure of 3 kg on a pad dyeing machine (5 coffee 5, followed by heating at 9 ° C for 3 minutes, and rinsed with water. Then on the milk dyeing machine The mantle sample was coated with the oxygen chopped nanoparticle dispersion at a pressure of 3 kg, followed by heating at 9 Torr for 1 hour, and then rinsing with water and drying in a 40 C box overnight. The results of the water drop absorption test performed after the repeated water wash cycle are shown in the table. 'Example 5 (including TEOS binder) Follow the method of Example 1, with the exception of using the hydrophilic coating solution of Preparation Example 3 (including TEOS) As a surface-modified smectite cerium particle dispersion, the results of the water absorption test performed after repeated water septic:~ revamping according to the water washing test are shown in Table 1. 139995.doc . 30- 201042117

Table 1

Example 6 (The coupling agent is polyethyleneimine) 制备 Prepare a polyethyleneimine containing 2 wt ° / hydrazine in water (prepared by diluting 5 〇 wt / 〇 polyethyleneimine aqueous solution with water) and 〇·5 wt % Q2_5211 Surfactant coupling agent solution. A Nomad 6000 floor mat sample (5 cm x 5 cm) was coated with a coupling agent solution under a pressure of 3 kg on a pad dyeing machine, followed by heating at 90 ° C for 30 minutes, and then the sample was cooled to ambient temperature, followed by washing with water. The floor mat samples were then coated on the pad dyeing machine with a surface modified cerium oxide nanoparticle dispersion of Preparation Example 1 under a pressure of 3 kg, followed by heating at 9 (rc for 1 hour) and then applying the coated mat. Cooling back to ambient temperature, then rinsing the sample with water' and then air drying overnight at 4 (rc). The results of the water drop absorption test performed after the repeated water wash cycle performed according to the water wash test are shown in Table 2. Example 7 (Coupling Agent) 8 〇 ethoxylated polyethyleneimine) 139995.doc •31 · 201042117 Follow the procedure of Example 6, with the exception that the coupling agent solution is diluted with 2 to 80% polyethyleneimine in water (8 〇 〇/.ethoxylated) and 〇5 wt% q2_521丄 surfactant composition. The results of the water droplet absorption test performed after the repeated water washing cycle performed according to the water washing test are shown in Table 2. Example 8 (The coupling agent is Polyethylenimine (branches, Mn i (GPS), Mw 25000 (LS)) followed the procedure of Example 6, with the exception that the coupling agent solution was diluted with 2 wt% of polyethyleneimine in water ( Branch 'Mn l〇〇〇〇 (GPS), Mw 25000 (LS)) 0.5 wt. / Q2-5211 surfactant composition. The results of the water drop absorption test performed after the repeated water wash cycle performed according to the water wash test are shown in Table 2. Example 9 (The coupling agent is an ethyleneimine oligomer mixture (viscosity 2〇〇, 〇〇〇cps)) Follow the procedure of Example 6, with the exception that the coupling agent solution is diluted from ethylene to 2 wt ° / 〇 ethylene imine oligomer mixture (viscosity is 2 〇〇, 〇 〇〇cps) and 0.5 Wt% Q2-5211 surfactant composition. The results of the water drop absorption test performed after the repeated water wash cycle performed according to the water wash test are shown in Table 2. Table 2 Water absorption time / sec (8) Example number initial After 5 washes, 10 washes, 15 washes, _f washes, 20 washes, <ls <ls <ls <ls 3s 7 <ls <ls <ls <ls <ls 8 < Ls <ls <ls <ls <ls 9 <ls <ls 4s 12s 16s 139995.doc •32· 201042117 H and test results are intended only for illustrative purposes and can be expected to result in changes to the test program. Different social fruits. /, the examples are only for the sake of clarity. 4 The purpose of the solution (10). _ It is understood that it is not for those who are familiar with this technology, this will be fixed, and will be:: Real:: Modified and / or combined. The inventor · All Ο :=: This Within the limits of the invention, therefore, the specific illustrative structure of the invention is intended to be limited by the equivalents of the application specific structure. In the present specification and the references in this document, there is a contradiction or divergence between (10) and the reference in the reference. The specification should prevail. ❹ 139995.doc •33·

Claims (1)

201042117 VII. Patent application scope: A fibrous article comprising: a polymeric fiber comprising a coupling agent and a surface-modified cerium oxide cerium particle, wherein the surface is modified with a dioxonacena #取人, 匕3 hydrophilic surface change. The fiber becomes hydrophilic. 2) The fiber stun of the claim 1 and the mouth of the material, wherein the polymeric fiber 3 is as requested by the fiber material, water. ❹ 醯 、 聚 聚 聚 聚 、 、 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : The fibrous article of item 1 wherein the hydrophilic surface is modified by two gasification 矽: the permanent particles have an average particle size of up to about 3 nanometers. The fibrous article of the item 1 wherein the hydrophilic surface-modified cerium oxide nanoparticles have an average particle size of up to about 10 nm. The fiber article of the term 1 of the term, wherein the coupling agent has the following formula: ❹ [(Y)e-R3]d(QR4)b(RV(b+d), wherein it is the same as the surface of the substrate a functional group, R is a covalent bond or optionally a divalent or trivalent hydrocarbon bridging group having from about 1 to 2 carbon atoms of the NH group, and R4 is independently hydrogen or optionally oxygen. An alkyl 'aryl or aralkyl group having 1 to 8 carbon atoms substituted with a nitrogen and/or sulfur atom; c is 1 or 2' b is 1 to 3 and d is 1 or 2 and (b + d) S4. 7. The fibrous article of claim 6, wherein the gamma is selected from the group consisting of an amine group and an ethylene oxide 139995.doc 201042117 functional group. 8. 9. A fibrous article according to claim 1 v. A hai coupling agent is selected from the group consisting of polyethyleneimine, ethoxylated polyethyleneimine, publicly available knives, polyethyleneimine, ethyleneimine oligomers, and mixtures thereof. The cerium oxide nanoparticle is the fibrous article of claim 1, wherein the surface modified particle comprises a surface modifying agent having the formula: [(Z)c-R7]d-Si-(〇R8)b(R8)4 Wherein Z is a hydrophilic group; R7 is a covalent bond or a divalent or trivalent tobacco bridging group having about 〇2 carbon atoms substituted by at least one oxygen atom and optionally substituted by an -OH group; and 'R is independently hydrogen or optionally oxygen, nitrogen And/or a sulfur atom-substituted alkyl, aryl or aryl group having 1 to 8 carbon atoms; 鸠1 or 2'鸱1 to 3 and d is 1 or 2 and (b+叱4. 10. The fibrous article of claim 9, wherein the towel 2 is selected from the group consisting of a tickic acid group, a reductive acid group, a phosphonic acid group, and a salt thereof. η. The fibrous article of claim 1, which is subjected to a water washing test to After the V 10-human water wash cycle, the article has an average absorption time of less than about 10 seconds as measured by the water drop absorption test. 12_In the fiber article 1 of claim 1, in the water wash test according to the water wash test to V 10- After entering the water washing cycle, the article has an average absorption time of less than about 5 seconds as measured by the water droplet absorption test. 13. The fibrous article of claim 1 is in accordance with the water washing test to 139995.doc 201042117 less. After the water washing cycle, weighed and right... According to the water absorption test, the article has An average absorption time of less than about sec. 14. A fibrous article as claimed in the claim, 1 ^ 螬 〃 该 该 该 该 该 该 该 该 该 该 该 该 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. 15. The summer system of the i ° hai surface modified cerium oxide nanoram is in the range of from about / 4 / 2 H g / m to about 70 g / m 2 . Ϊ 6. The fiber according to any one of claims 1 to Item, which is a floor mat. 17. A method of making a fibrous article, comprising: a) coating a polymeric fiber with a coupling agent, and subsequently b) coating the aqueous dispersion with a hydrophilic surface-modified two-gasoline The polymeric fibers, c) drying the coated fibers, and the hydrophilic surface-modified cerium oxide nanoparticles to render the dried polymeric fibers hydrophilic. 18. The method of claim 17, wherein the hydrophilic surface-modified cerium oxide nanoparticle aqueous dispersion has a pH in the range of from about 1 to about 5. 19. The method of claim 17, wherein the hydrophilic surface-modified cerium oxide nanoparticle aqueous dispersion has a pH in the range of from about 1 to about 3. 20_ A fibrous article comprising: a polymeric fiber comprising a coupling agent and a surface-modified cerium oxide nanoparticle, wherein the surface-modified cerium oxide nanoparticle comprises a hydrophilic surface modifying agent and the polymeric fiber is changed Hydrophilic; wherein the polymeric fiber comprises a polyamide resin; 139995.doc 201042117 wherein the surface is modified by a oxidized average particle size; ^ the water-free puller has a maximum of about 10 nm, wherein the s-sea coupling agent has the following formula. H2N-R3_Si_(〇R4)3' wherein, as the case may be, a divalent hydrocarbon bridging group having about a atom in the main chain, and R is independently hydrogen, methyl or ethyl; The hydrophilic surface modifier has the formula: H03S-R7-Si-(〇R8)3, wherein R is a covalent bond or, optionally, substituted with at least one oxygen atom and optionally substituted with an -OH group, having about 1 to a divalent or trivalent hydrocarbon bridging group of 2 carbon atoms, and R8 is independently hydrogen, sulfhydryl or ethyl; wherein, after at least 1 wash cycle according to the water wash test, according to the water drop absorption test Measurement, the item has less than The average absorption time of 5 seconds. 21. The fibrous article of claim 20 which is a floor mat. 139995.doc 201042117 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) 139995.doc