JPH11509585A - Compositions and methods for imparting sustained liquid repellency to a support - Google Patents

Abstract

  (57) [Summary] A fluorochemical treating agent composition comprising: And fluorochemicals. The composition can be used to impart sustained water and oil repellency, stain removal, and resistance to dry soil to various substrates.

Description

DETAILED DESCRIPTION OF THE INVENTION Compositions and methods for imparting sustained liquid repellency to a support Field of the invention   The present invention provides a water-repellent or oil-repellent support for a support such as carpet, cloth, paper, and leather. Or compositions and methods for imparting resistance to spots and stains. Background of the Invention   Fluorochemicals are repellent to a support, especially a fibrous support such as a carpet. Widely used to impart water and oil repellency and resistance to dry stains You. Thus, the fluorochemical allows the support to retain its original aesthetic appearance. It becomes possible.   For example, fluorochemicals with high glass transition temperatures are polished during use. Then, it may come off from the support to be treated. As a result, the unprotected area of the support Areas are exposed and subsequently lose their resistance to stains and dirt. Weak brittleness Fluorochemical treatment agents that are difficult to remove may not be able to withstand the cleaning process. Many.   Therefore, in the technical field, it is necessary to prevent persistent water repellency, oil repellency and dry stain. There is a need for fluorochemical treatments that exhibit sustained resistance to. Such processing The agent also preferably has sustained stain removal properties, and in addition to recent environmental concerns. Considering the problem, it is necessary that the treating agent can be sent using water without using an organic solvent. is there. Summary of the Invention   Briefly, in one embodiment, the invention is directed to carpets, fabrics (wovens). For both fabric and non-woven fabrics), paper, wood, concrete, leather and other supports Water and oil repellency, sustained stain removal, and lasting resistance to dry stains Provided is a fluorochemical treating agent composition that can be used for imparting properties. this The composition includes (a) a substantially discrete, substantially monodisperse, polymer-grafted inorganic microparticle. Sol containing a colloidal dispersion in which the particles are dispersed in a liquid, and (b) at least And one fluorochemical. Also prepared from a monodisperse blend Microparticles with a modified multimodal size distribution can be used for sol formation. Wear. The sol preferably comprises an aqueous dispersion of polymer-grafted silica microparticles. More preferably, the polymer has at least one free-radically polymerizable ethylenic monounsaturation. It preferably contains a polymerized unit of a sum monomer. The fluorochemical has at least one Containing two fluoroaliphatic or fluorocycloaliphatic groups and attached to microparticles It is preferred that As used herein, "polymer grafted mi “Particles” are essentially one (through a coupling agent immobilized on the surface) Linear or branched, substantially cross-linked covalently attached to the microparticles only at the ends Refers to microparticles with no polymer chains.   Surprisingly, using the compositions of the present invention, It is possible to impart various types of supports with high removal properties and resistance to dry stains. Wear. Moreover, since this composition is based on water, it is environmentally friendly and durable. Satisfies the need in the art to be a fluorochemical treatment . In another aspect, the present invention also provides sustained water and oil repellency, stain removal One- and two-stage treatments to impart resistance and resistance to dry soiling And useful for imparting sustained stain removal and resistance to dry soiling A treating agent composition (provided that the composition comprises a substantially discrete, substantially monodisperse When the macrografted inorganic microparticles are liquid (water or water Containing a colloidal dispersion dispersed in water). Included in the support for sustained stain removal and resistance to dry stains A treating method for applying; and a treating agent composition of the present invention or a dry group corresponding thereto. A processed product comprising the composition. Detailed description of the invention   Suitable inorganic microparticles for use in the compositions of the present invention include colloidal size (E.g., the average particle size is from about 1 nanometer (1 millimicron) to about 200 nanometers Range). Colloidal silica is preferred, for example, colloidal titania, Lloyd alumina, colloidal zirconia, colloidal vanadia, colloidal chromia, Colloidal iron oxide, colloidal antimony oxide, colloidal tin oxide, and these Other colloidal metal oxides, such as mixtures, can also be used. Colloidal microparticles include It may contain essentially a single oxide, such as silica, or one type of acid May contain another type of oxide deposited on the core of the oxide No. Generally, the size (average particle size) of the microparticles is from about 1 nanometer to about 100 nanometers. Nanometers, more preferably, in the range of about 2 nanometers to about 75 nanometers.   Also, the size of the colloidal microparticles is relatively uniform (ie, substantially Have a scattered size distribution or two or more substantially monodisperse distributions. Has a multimodal distribution obtained by mixing) and does not substantially condense It is preferable to maintain a state (ie, a substantially discrete state). Monkey If the microparticles settle, precipitation, gelling, or a significant increase in the viscosity of the sol will occur. May occur, and furthermore, both the adhesion to the support and the optical clarity may be reduced. There is also. For this reason, particularly suitable compounds for use in preparing the composition of the present invention are described. Examples of the microparticles include inorganic microparticle sols (for example, inorganic microparticles in a liquid medium). Colloidal dispersion of black particles), in particular, a sol of amorphous silica. Unlike fumed silica, which contains irregular aggregates of colloidal particles, these zones Are substantially monodisperse in size and shape and therefore have good optical clarity Compositions that exhibit good and smoothness and, surprisingly, good adhesion to substrates Can be prepared. These sols can be prepared using various techniques, In this case, water is used as a liquid medium), and an organosol (in this case, an organic liquid is used) Used), mixed sols (in this case, the liquid medium includes both water and organic liquids) ) Can be prepared in various forms. For example, U.S. Pat. No. 5 (Iler) and No. 4,522,985 (Das et al.) And R.K.Iler, The Chemistry o f About techniques and shapes described in Silica, John Wiley & Sons, New York (1979) Please refer to the description.   In terms of surface chemistry, low cost, and environmental considerations, the preparation of the compositions of the present invention Silica hydrosols are preferred for use. Such hydrosols are, for example, Nyacol Products, Inc., Ashland, MD; Nalco, Oakbrook, IL  Chemical Company; and E.M. of Wilmington, Del. I. duPont de Nemours  and Company offer a variety of particle sizes in both acidic and alkaline forms. Available in sizes and concentrations. About 2% by weight to about 50% by weight of silica in water It is useful. If necessary, for example, an aqueous solution of an alkali metal silicate Prepare silica hydrosol by partially neutralizing with acid to pH about 8-9 (The sodium content of the solution thus obtained is Less than about 1% by weight). Other preparation methods for silica hydrosols, for example, Electrodialysis, ion exchange of sodium silicate, hydrolysis of silicon compounds, And the dissociation of the silicon element,aboveIt is described in Iler's literature.   In preparing the compositions of the present invention, generally, the zoning of the polymer-grafted microparticles is If water and oil repellency are desired, then at least It can be mixed with one fluorochemical. When preparing sols, In some cases, at least a part of the surface of the inorganic microparticles is chemically reacted with a coupling agent. It is necessary to modify by reaction (or strong physical interaction). Suitable mosquito The coupling agent reacts (or has strong interaction) with chemical groups on the surface of the microparticles. Can function as a chain transfer site for free radical polymerization At least one functional group (chain transfer group: for example, -CH_TwoSH, -CH_TwoNH_TwoEtc.) It can be contained.   For example, silanol groups on the surface of silica microparticles Under conditions that form a silicon-oxygen-silicon covalent bond by chemical bonding with a group, The particles can be treated with an organosilane containing a dissolvable chain transfer group. Shi The surface of the particles of Rica (or other metal oxides) can be treated with other compounds. Wear. Other compounds include, for example, chemical bonds (covalent or ionic bonds) Or it can be bonded to the particle surface by strong physical bonding At least one functional group capable of functioning as a chain transfer site (eg, -CH_TwoSH, -CH_Two NH_Two) Containing organotitanates containing a hydrolyzable chain transfer group. You.   Treating agents containing hydrolyzable chain transfer group-containing organosilanes are generally preferred . A preferred class of such compounds can be represented by the formula: And their partial hydrolysates and condensates).                     Y-R-Si (R¹)_a(X)_3-a         (I) In the formula, Y is a chain transfer group (preferably, a mercapto group, an amino-containing group, R is a moiety selected from the group consisting of an oxygen-containing group and a halogen-containing group); Alkylene groups having from 1 to about 12 carbon atoms and from about 6 to about 12 carbon atoms; X is a divalent group selected from the group consisting of an arylene group having Anionic groups (preferably halogen, having 1 to about 12 carbon atoms and optionally Alkoxy groups, acyloxy groups, amino groups having from 1 to about 11 ether oxygen atoms R, a group selected from the group consisting of:¹Is 1 ~ Selected from the group consisting of lower alkyl groups having about 4 carbon atoms and phenyl groups A is an integer of 0 to 2 (preferably 0).   Representative examples of preferred hydrolyzable chain transfer group-containing organosilanes include: 3-mercaptopropyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyldimethoxymethylsilane, 6-mercaptohexyltrimethoxysilane, 4-mercaptocyclohexyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutyldimethoxymethylsilane, 6-aminohexyltrimethoxysilane, 4-aminocyclohexyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 4-chlorobutyldimethoxymethylsilane, 6-chlorohexyltrimethoxysilane, 4-chlorocyclohexyltrimethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, Glycidoxypropyltrimethoxysilane, and mixtures thereof .   In preparing sols of polymer-grafted microparticles, hydrosols (eg, silica Cahydrosol), mixed sol (for example, when the liquid medium is methanol, ethanol, Seton, tetrahydrofuran, ethylene glycol, propoxyethanol, etc. Silica gel containing an aqueous solution of at least one organic solvent (preferably water-soluble) ), Or organosol (for example, when the organic liquid medium is benzene, toluene, Ropoxyethanol, dimethylformamide, isopropanol, ethylene glycol Silica organosols containing coal, etc.) are generally (One or more) and reacting the resulting mixture. Promote the reaction To this end, heat (and stirring) may be applied. Reaction with coupling agent and its To improve stability (and minimize viscosity during subsequent reaction with the monomer) Sol concentration and / or pH may need to be adjusted It will be apparent to those skilled in the art. Coupling agents are generally micro- At least a portion of the surface of the particles is sufficiently modified to allow efficient graft polymerization (mono- (In combination with the initiator and initiator).   Preferably, the amount of coupling agent is, for example, unit square of the surface area of the microparticle. The amount of coupling agent per meter is about 2 × 10^{ー 4}Mmol to about 3 × 10^-3Millimol , More preferably about 3 × 10^-FourMmol to about 2 × 10^-3Millimoles selected to be It is. The obtained mixture is, for example, about 20 ° C to about 100 ° C, preferably about 50 ° C to about 1 ° C. Stirring at a temperature of 00 ° C. (eg, about 1 hour to about 24 hours) and maintaining that temperature Depending on the reaction of the coupling agent with the chemical groups on the surface of the microparticles (or other Interaction). Thus, fixed to the surface Colloidal dispersion of inorganic microparticles with organic groups attached or bound to the surface Is obtained.   Next, one or more free-radically polymerizable ethylenically monounsaturated monomers are obtained from such a product. Can be added to the resulting colloidal dispersion of surface modified microparticles. (Place Optionally, add a small amount of one or more free-radically polymerizable ethylenically polyunsaturated monomers. , The desired degree of crosslinking. ) Monomers are commonly used It is necessary to add a larger amount than the number of moles of the coupling agent. For example, SiO2 From about 0.001 mole to about 0.10 mole of monomer (s) per gram of Can be used. The resulting mixture (grafted water-soluble monomer in aqueous medium) Surfactants may be included to allow for polymerization) Add an effective amount of a thermally or radioactive free radical initiator and then heat the mixture. (Heat to a temperature sufficient to decompose the free radical source, for example, from about 20 ° C to about 130 ° C. ) Or irradiated with radiation to polymerize the monomer.   Suitable for use in preparing polymer-grafted microparticles of the composition of the present invention The monomer is a free radical polymerizable ethylenically unsaturated monomer (or monomer mixture) . Useful monomers include, for example, ethylenically unsaturated acids and anhydrides; Unsaturated macromers; ethylenically unsaturated substituted or unsubstituted esters, amides, And nitriles; vinyl monomers; vinylidene monomers; other olefin monomers (eg For example, styrene, ethylene, tetrafluoroethylene, and hexafluoropropylene Lopen); fluorochemical-containing acrylates and methacrylates; Heterocyclic monomers are included.   Representative monomers include, for example, acrylic acid; methacrylic acid; itaconic acid; Citraconic acid; aconitic acid; maleic acid; maleic anhydride; fumaric acid; Acid; Cinnamic acid; Oleic acid; Vinyl sulfone Acids; vinylphosphonic acids; alkyl, cycloalkyl, and fluoroalkyl Esters of the above acids contained (provided that the alkyl group, cycloalkyl group, and Fluoroalkyl groups have from 1 to about 18 carbon atoms): Tyl, 2-ethylhexyl, octadecyl, 2-sulfoethyl, 3-sulfoethyl, a Sethoxyethyl, cyanoethyl, hydroxyethyl, and hydroxypropyl Acrylates and methacrylates of the above; amides of the above acids (eg, , Acrylamide, methacrylamide, methylolacrylamide, and 1,1- Dimethylsulfoethylacrylamide); acrylate or methacrylate powder Edge-protected polyethylene glycol; acrylonitrile; methacrylonitrile; styrene Len; α-methylstyrene; p-hydroxystyrene; chlorostyrene; sulfos Tylene; N-vinylpyrrolidone; vinyl acetate; vinyl chloride; vinylfur Oride; vinyl ether; vinyl sulfide; vinyl toluene; butadiene; Soprene; Chloroprene; Ethylene; Isobutylene; Vinylidene chloride; Ridenfluoride; Tetrafluoroethylene; Hexafluoropropene; Sulfated Castor oil; sulfated black whale oil; sulfated soybean oil; and sulfated dehydrated castor oil. I can do it. Particularly useful monomers, for example, have from 1 to about 18 carbon atoms Alkyl acrylate and alkyl methacrylate, styrene, acrylic acid , Methacrylic acid, itaconic acid, acrylamide and methacrylamide, fluoro Acrylic and methacrylate containing chemicals and sodium sulfo Styrene is mentioned. Monomers that do not dissolve in the liquid medium are Adding a sufficient amount of solubilizing organic liquid and / or dispersant to effect Therefore, it can be dissolved.   Useful free radical initiators include inorganic and organic peroxides, hydroperoxides Oxide, persulfate, azo compound, redox type (example For example, K_TwoS_TwoO₈And Na_TwoS_TwoO_FiveAnd free radical photoinitiators (eg, K.K. By Dietliker,Chemistry & Technology of UV & EBFormulation for Coatings,  Inks & Paints, Volume 3, paqes276-298, SITA Technology Ltd., London (199 Initiators described in 1). Typical examples are hydrogen peroxide and persulfuric acid. Lium, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxide Benzoate, cumene hydroperoxide, and azobis (isobutyronitrile (AIBN). The choice of initiator depends on the reaction conditions (eg, choice of solvent). ) Will be apparent to those skilled in the art.   The polymerization of ethylenically monounsaturated monomers leads to polymer-grafted microparticles. A colloidal dispersion is obtained. These microparticles include a coupling agent fixed on the surface. Linear or branched substantially cross-linked essentially covalently attached to the agent at one end Not included polymer chains. (As mentioned earlier, the degree of crosslinking (that is, The percentage of the site) can, if necessary, be derived from one or more ethylenically polyunsaturated monomers. Can be given by entering. ) Coating obtained from treatment composition of the present invention Treatments (including polymer-grafted microparticles) to maximize their durability. Depending on the surface energy of the support to which the composition is applied, a monomer (one or more Is plural kinds). Therefore, the support with high surface energy Supports that can use polar monomers and have low surface energy For, a non-polar monomer can be selected. In addition, specific chemistry with the support It is also possible to select monomers capable of physical or physical interaction.   Utilizing a colloidal dispersion of polymer-grafted microparticles, In some cases, such as containing carboxylic or sulfonic acid groups, (If using a monomer) Leaving properties can be imparted to the support. Dispersion, for example, about 0.01% solids The support is diluted to about 20% (preferably, solid content of about 0.05% to about 10%) with a dispersing solvent. Or concentrated (for storage or transport) to a low solvent content. Or essentially solvent-free (ie essentially free of a dispersing liquid medium) ). Surprisingly, in general, this solventless material It can be essentially completely redispersed in the solvent without setting.   Sustained water repellency (in addition to sustained resistance to dry stains and stain removal) If oil and oil repellency are desired, the colloidal dispersion of polymer-grafted microparticles should be reduced. It can be mixed with at least one fluorochemical. In some cases, The resulting mixture is stirred and / or heated to obtain the fluorochemical and microparticles. It can promote a reaction or interaction with a chemical group on the daughter surface. (For example, A temperature of about 20C to about 100C can be maintained for 1 hour to about 24 hours. ) Fluorochemical (s) are generally desired for a particular application. It can be added at a concentration sufficient to impart a certain level of liquid repellency. Liquid medium The fluorochemical (s) that are not soluble in And / or a sufficient amount of solubilized organic liquid to dissolve or emulsify Alternatively, it can be solubilized by adding a surfactant.   The fluorochemical-containing treating agent composition thus obtained has, for example, a solid content of about 0. It can be diluted with a dispersing solvent to a concentration of 01% to about 20% and applied to a support, It can also be concentrated (for storage or transport) to a low solvent content. Necessary Depending on the two-stage process, the colloid content of the polymer-grafted microparticles is The powder is applied to a support and then contains the fluorochemical (s) The composition can be applied.   Well-known fluorochemicals that can impart water repellency and oil repellency are Can also be utilized in the composition of the present invention. Fluorochemicals are microparticles Preferably, it can cause chemical reactions or strong physical interactions with chemical groups on the surface. However, fluorochemicals that do not have such performance can also be used.   Suitable fluorochemicals that can be blended include water repellent and oil repellent substrates. Fluorochemical group-containing polymer compounds known in the art for imparting properties And oligomeric compounds. The fluoro of these polymers and oligomers The chemical treating agent typically has about 3 to about 20 carbon atoms, more preferably about 3 to about 20 carbon atoms. One or more fluors comprising a perfluorinated carbon chain having from 6 to about 14 carbon atoms Contains olochemical groups. These fluorochemical groups can be straight chain, branched, Or a cyclic fluorinated alkylene group or any combination thereof. Wear. Fluorochemical groups preferably contain polymerizable olefinic unsaturation But not oxygen, divalent or hexavalent sulfur, or nitrogen. Including any catenary (ie, in a chain attached only to carbon) heteroatoms Can be. Fully fluorinated groups are preferred, but no more than one for every two carbon atoms If so, a hydrogen atom or a chlorine atom may be present. In addition, any full Orochemical groups are also preferably about 40% to about 80% by weight fluorine, more preferably Those containing from about 50% to about 78% by weight fluorine are preferred. The terminal end of the group is generally Is fully fluorinated, but preferably has at least 7 fluorine atoms Includes (for example, CF_ThreeCF_TwoCF_Two-, (CF_Three)_TwoCF-, SF_FiveCF_Two-) Is good. Perfluorinated Aliphatic groups (eg, C_nF_{2n + 1}-) Is the most preferred fluorochemical group.   Representative examples of suitable fluorochemicals that can be blended include fluorochemicals. Urethane, urea, ester, ether, alcohol Epoxides, allophanates, amides, amines (and their salts), acids ( And their salts), carbodiimide, guanidine, oxazolidinone, isocyanate Homopolymers of annulate, biuret, acrylate and methacrylate and And copolymers, and mixtures thereof.   Representative blendable fluorochemical group-containing polymers useful in the present invention Is a fluorochemical type acrylate monomer, for example, Fluorochemical acrylate and methacrylate homopolymer Lima or copolymers include: methyl methacrylate, butyl acrylate , Octadecyl methacrylate, oxyalkylene and polyoxyalkylene Acrylate and methacrylate esters of polyol oligomers (eg, Ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate G, polyethylene oxide diacrylate, and polyethylene glycol mono Acrylate), glycidyl methacrylate, ethylene, butadiene, styrene , Isoprene, chloroprene, vinyl acetate, vinyl chloride, vinylidene Chloride, vinylidene fluoride, acrylonitrile, vinyl chloroacetate , Vinyl pyridine, vinyl alkyl ether, vinyl alkyl ketone, acrylic Acid, methacrylic acid, 2-hydroxyethyl acrylate, N-methylol acrylate Amide, 2- (N, N, N-trimethylammonium) ethyl methacrylate, and 2- Lylamido-2-methylpropanesulfonic acid (AMPS). Of the various comonomers used The relative amounts generally depend on the substrate to be treated, the properties desired and the form of application to the substrate. Depending on the case, it is selected empirically. Useful fluorochemical treating agents also include Examples include blends of the various fluorochemicals described above.   Other useful materials for the present invention include fluorochemicals. For example, a blend with a fluorine-free extender compound such as RU: Siloxane, (meth) acrylate and substituted acrylate polymers and copolymers Lima, N-methylolacrylamide-containing acrylate polymer, urethane, block Polymers and oligomers containing octocyanate, urea or melamine and forma Condensates or precondensates with aldehyde, glyoxal resin, fatty acids and melamine Or condensates with urea derivatives, fatty acids and polyamides and their epichlorohydrides Condensate with adduct, wax, polyethylene, chlorinated polyethylene, alkyl Ketene dimers, esters, and amides. These extracts do not contain fluorine Blends of tender compounds can also be used. For fluorochemicals The relative amount of the extender compound is not a critical factor. However, full The overall composition of the orochemical treatment agent generally has a solid content relative to the solids present in the system. At least about 3% by weight, preferably at least about 5% by weight, of carbon-bonded fluorine It is included in the form of the aforementioned fluorochemical group.   Blends containing fluorine-free extender compounds as described above may also be used. Many fluorochemicals are commercially available, including off-the-shelf products. These products Is, for example, Scotchgard^TMBranded carpet protector (Saint Paul, Minnesota) 3M Co.) and Zonyl^TMBranded carpet treatment (W Delaware) E.I. of ilmington. dupont de Nemours and Company).   Useful fluorochemicals are described in U.S. Patent Nos. 3,728,151 (Sherman et al.); 816,229 (Bierbrauer), 3,896,035 (Schultz et al.), 3,901,727 ( No. 3,916,053 (Sherman et al.), No. 4,043,923 (Loudas), No. 4 No. 4,043,964 (Sherman et al.), No. 4,264,484 (Patel), No. 4,624,889 No. (Bries) and No. 5,274,159 (Pellerite et al.).   Preferred fluorochemicals for use in the compositions of the present invention are microparticle tables. A compound that can chemically react or strongly interact with chemical groups on a surface is there. Most preferred compounds have at least one hydrolyzable group or It is a fluorochemical silane containing the group shown. Such compounds include, for example, At least one which can react with silanol groups present on the surface of the silica microparticles. Compound containing at least one silicon atom bonded to two groups, mixture of compounds Object, polymer, or copolymer. Useful fluorochemical silanes Las can be represented by the following general formula (however, these partial hydrolysates And condensates):             R_f-[R^Two-Si (R¹)_a(X)_3-a]_d            (II) Where R¹, X, and a are as defined above for Formula I;_fIs less At least about 4 carbon atoms and at least about 25 (preferably about 50) weight percent fluorine. A monovalent or divalent fluoroaliphatic or fluoroalicyclic group containing; d. Is an integer of 1 or 2 (preferably 1);^TwoIs preferably arylene (good Preferably phenylene) and alkylene of 1 to about 12 carbon atoms A divalent linking group containing at least one group but substantially stable to hydrolysis One or more divalent groups (eg, -CO-, -CONR^Three-, -SO_Two-, -SO_TwoNR^Three-,-(C_TwoH_FourO)_b-,and -(C_ThreeH₆O)_b-: Where b is an integer of 1 to about 4, R^ThreeIs hydrogen or 1 to about 4 charcoals Which is an alkyl of a prime atom).   Preferably, R_fIs about 4 to about 24 (preferably Or from about 4 to about 12) carbon atoms. A fluoroalicyclic group which is an aliphatic group or has about 4 to about 24 carbon atoms is there. R_fMay be Can contain catenary ether oxygen atoms (attached to carbon atoms only) And the condition that no more than one hydrogen or chlorine is present per two carbon atoms. Can contain a small amount of hydrogen or chlorine. Most preferably, R_fIs about Linear or branched perfluoroaliphatic radicals having 4 to about 12 carbon atoms; Or a perfluoroalicyclic group.   Representative examples of useful fluorochemical silanes include the following compounds: Is: Fluorochemical silanes can be used with other non-fluorinated silanes Can be mixed. Partial condensates of such mixtures are also available. Wear.   Useful fluorochemical silanes include, for example, at least one reactive functional group. At least one fluorochemical compound having from 1 to about 3 hydrolysable Group and at least one functionality of the fluorochemical compound (s) At least one alkyl substituted with at least one functional group capable of reacting with a group To mix with silanes having groups, aryl groups, or alkoxyalkyl groups Therefore, it can be prepared. Suitable fluorochemical compounds are, for example, rice It can be adjusted by the method described in National Patent No. 5,274,159 (Pellerite et al.). Wear.   Utilizing the treatment composition of the present invention, a continuous resistance to dry stain In the case of using a fluorochemical-containing composition, Water and oil repellency on carpets, fabrics (both woven and non-woven), paper , Leather, plastic, wood, metal, glass, ceramics, stone, cement, etc. It can be applied to a support. The composition generally comprises (e.g., a solid content (From about 0.01% to about 20% by weight) and diluted by conventional methods known in the art. Either (e.g., padding, spraying, exhaustion, knife coating, dipping, roll coating, And foaming techniques). (By exhaustion technique When treating a nylon support, the pH of the composition is adjusted to about 1.5 to about 1.5 with a non-volatile acid. It can be adjusted to about 3 and a salting agent can be further added. ) Other conventional Additives, such as wetting agents, antistatic agents, stain removers, biocides, antioxidants, etc. Can be included in the composition of the present invention.   If necessary, turn the fiber or yarn support into a finished product such as carpet or rug. Before processing. The treated support is external It can be dried at temperature or elevated temperature.   The amount of treating agent utilized depends on the nature of the support, the nature of the components of the composition, and the purpose. It can vary widely, depending on the nature of the process. This amount is in the desired degree These when combined with stain removal properties, stain prevention properties, oil repellency and water repellency Must be sufficient to provide the properties of   The following examples further illustrate the objects and advantages of the present invention. The specific substances and their amounts listed in the examples and other conditions and details Accordingly, the invention should not be construed as improperly limited. In an embodiment, All temperatures are in degrees Celsius and parts and percentages are Unless otherwise stated, by weight.                                  Example Test method Stain removal (SR)   20ml cherry-flavored KOOL-A for stain removal of carpet samples IDTM Soft Drink Mix (available from Kraft General Foods, Northfleld, IL) (Or 0.1% by weight FD & C Red Dye # 40 solution adjusted to pH 3.2 with citric acid) The test solution is applied to an open screen placed on the tufted surface of the test sample on the carpet. Characterize by pouring into a Linda (5 cm high, 5 cm diameter) Was. If the carpet first repels the test solution, the cylinder or carpet This liquid was allowed to penetrate into the pile of the carpet by tapping. Remove cylinder The stained carpet sample was left at room temperature (about 22 ° C.) for 24 hours. So After the effluent has no color The carpet sample was rinsed with water until it was. Next, a carpet sample Was centrifuged to remove most of the water and dried at 65 ° C. Minolta CR-310 L Use iqht Meter to remove residual blots (ie redness) on dry carpet Measured and stained against an uncolored control sample of the same carpet that had been stain-removed. Chromaticity was compared. The degree of coloring is Δa (difference between colored sample and uncolored sample) It is reported that the lower the Δa value, the better the stain removal property, that is, This indicates that few stains remain on the carpet. (3D CIE L^★a^★b^★ Based on color scale: where a^★Represents a red-green vector, L^★Is light / Dark ratio, b^★Represents the blue / yellow ratio. )Dynamic water resistance (DWR)   For the dynamic water resistance of carpet samples, test samples (15.2 cm x 30.5 cm) Through a 5 mm inside diameter tube placed 45 ° from the sample, tilted 45 degrees from the horizontal direction The measurements were made by bombarding the center of the carpet sample with deionized water. Trial The water repellency was indicated by the weight increase of the test sample. Therefore, the smaller the weight increase, the more repellent Indicates good aqueous properties.Oil / water repellency (OR / AR)   The ability of a carpet to repel test oils (OR) is determined by the American Association of Text Measured using ile Chemists and Colorists (AATCC) Standard Test Method No. 118-1983 . This test method is based on the resistance of the treated fabric to penetration of oils of various surface tensions. Things. The oils and their associated grade numbers are as follows:   Place 5 drops of each test oil on a carpet sample and 1 minute later Of each test oil remaining on top (ie, not penetrating into the carpet pile) The number of oil drops was recorded. The value of "oil repellency" indicates that all five test oil droplets are carpet. Soak into the sampleDid not showThe highest grade of test oil (ie Oil with low surface tension). The higher the oil grade, the higher the carpet Shows good oil repellency.   The ability of the carpet to repel aqueous test liquids (AR) is water / isopropyl alcohol It was measured using a test solution. The test solutions and their associated grade numbers are: Is as follows:   Place 5 drops of each test aqueous liquid on a carpet sample and 1 minute later Liquids that remain on the surface (ie, do not seep into the carpet pile) The drop number was recorded. The “water repellency” values indicate that all five test droplets Soak into the sampleNot shown Was The determination was based on the highest grade liquid (ie, the liquid with the lowest surface tension). The higher the water rating, the better the water repellency of the carpet.Si Elemental analysis   The Si element content of the treated carpet sample is calculated based on the treated carpet containing Si. A solution of cut fiber is prepared, and Si in this solution is separated by inductively coupled plasma (ICP) analysis. It was measured by analysis.   Add sulfuric acid (15ml) to about 1g of treated carpet fiber and warm hot plate The mixture was placed on top to form a char from the fibers. The charred mixture becomes transparent Nitric acid was added to the mixture until it turned bright yellow. Perchlorine when it turns yellow Acid (3 ml) was added to give a colorless sample. Next, evaporate this sample To 5 ml, cooled, and rinsed the vessel with deionized water. Acid solution and washing solution Transfer to a plastic volumetric flask (100 ml) and add hydrofluoric acid ( 3 ml) was added, followed by the addition of deionized water to dilute the sample to 100 ml. next With the same acid matrix, using a Thermo Jarrel Ash ICAP 61E spectrophotometer The sample was analyzed for the Si standard solution. 1 mole of Si is 1 mole of SiO_TwoCorresponding to And that all MAA is grafted to silica during the graft polymerization reaction. The Si content on the carpet based on the_Two/ Methacrylic acid (MAA) graft Converted to% solids (SOC). Si content is reported as ppm Si. Any place In some cases, untreated carpet samples are analyzed for other sources of Si elements. Source (eg, silicone oil) affects Si content on treated carpet samples Was not given.Durability simulation   Characterization of the resistance of carpet treatments to "steam cleaning" Simulates the effects of multiple "steam cleaning" processes Under conditions, DUPONOL WAQE (a surfactant system based on sodium lauryl sulfate) (Available from Witco Corp., Greenwich, Conn.) This was done by immersing the treated carpet in it. 1 liter of surfactant Solution at a concentration of 7 ml per solution and maintain the solution pH at 10 using trisodium phosphate. Was. After soaking, rinse the carpet sample well with tap water and centrifuge Any water was removed and dried at room temperature. Carpets that have undergone such testing The stain removal, dynamic water repellency, and silica content described above for the sample And the test results as WAQE SR, WAQE DWR, and WAQE ppm Si respectively. reported. After the "WAQE" test treatment, the carpet treatment agent may have reduced its original performance. Also have good resistance to steam cleaning Will be.Walking dirt   Attached and untreated (control) rectangular carpets to particleboard Place the attached sample in the commercial area and walk the carpet Dirt on the pull. Carpet sample for monitoring walking distance and applying dirt Use patterns designed to minimize the effect of location and orientation The position of each test sample in the test location was changed daily. Apply dirt A predetermined test period (measured by the number of cycles: one cycle is about 10,0 steps) (Equivalent to 00 steps) has elapsed, a sample is taken out, and the pressure is reduced to remove unbonded debris. I left. The amount of dirt remaining on each sample is determined by colorimetry. Decided. At this time, the amount of dirt on the sample And the corresponding sample after soiling was assumed to be proportional to the color difference. Teru Use a Minolta CR-310 Chroma Meter with a light source D65 to keep 3 L of the sample that was washed and subsequently the sample that was stained^★a^★b^★Color seat The target was measured. The color difference value ΔE was calculated using the following equation.       ΔE = [(ΔL^★)^Two+ (Δa^★)^Two+ (Δa^★)^Two]^1/2       Where ΔL^★ = L^★ _pollution -L^★ _{Uncontaminated}               Δa^★ = a^★ _pollution -a^★ _{Uncontaminated}               Δb^★ = b^★ _pollution -b^★ _{Uncontaminated}   The ΔE values calculated from such colorimetric measurements are calculated using conventional visual evaluation values (eg, AATCC (Stain evaluation value proposed)), but the accuracy was good and the evaluation was good. It has the further advantage that the value environment and the influence by the operator do not appear. Each sump The final ΔE value for each sample was determined as the average of five to seven replicate measurements.   Express the sample performance improvement over the untreated control sample as ΔΔE and use the following equation: Calculated.       ΔΔE = ΔE_{Untreated control} -ΔE_{Pollution treatment}                  Preparation of silica precursor treated with coupling agent   The chain transfer coupling agent treatment was prepared according to the following general procedure. Siri Addition of the coupling agent to the kasol suspension typically involves the solids concentration of the silica sol. Performed at 5% to 20% degrees. If the solids concentration of the obtained sol exceeds 20%, Typically, it is diluted with deionized water to obtain a more workable concentration (ie, cup During the ring treatment or subsequent graft polymerization, gelation or Concentration that does not become too high). Suspended by adding acetic acid, sulfamic acid or sulfuric acid After adjusting the pH of the suspension to about 2.5-3.5, the coupling agent was added. Shown in Table 1 Silane coupling agent is added to the acidic suspension and the resulting mixture is Stirred at 〜80 ° C. for 16-24 hours. (The silane coupling agent was initially used An oily film formed on the surface of the aqueous suspension, but was mixed after reacting for 16 to 24 hours. The mixture was homogenized. Table 1 shows the amount of the silane coupling agent used in this reaction. Was adjusted so that the ratio of the coupling agent mmol / g of silica sol was as shown in the above. Anti After completion of the reaction, the reaction mixture is diluted with deionized water to approximately 2.5% to 7.5% solids (preferably In other words, a suspension of silica sol treated with a coupling agent having a solid content of about 3%) was prepared. 1.Illinois C as a 34% solids suspension in water at pH 3.2 and viscosity <10 cp Colloidal SiO with average particle size of 20 nm available from Nalco Chemical Co. of hicago_Two Suspension. 2.Nalco Chemic as a 30% solids suspension in water at pH 4.2 and viscosity 15 cp Al with an average particle size of 20 nm available from al Co._TwoO_ThreeShell-containing colloidal SiO_Twocore Suspension (~ 4% Al_TwoO_Three). 3.NalcoChemical as a 15% solids suspension in water at pH 9.2 and viscosity 5 cp  Colloidal SiO with an average particle size of 5 nm available from Co._TwoSuspension. 4.Nalco Chemic as a 30% solids suspension in water at pH 9.2 and viscosity 10 cp Colloidal SiO with an average particle size of 75 nm available from al Co._TwoSuspension. 5.Cabot C from Tuscola, Ill. As an aqueous slurry at pH 9.5-10 and 15% solids Amorphous fumed silica available from orp., Cab-O-Sil Division. 6. Mercap available from Aldrich Chemical Co., Milwaukee, Wis. Topropyltrimethoxysilane (MPTMS). 7. Glycidoxypropyltrimethoxysila available from Aldrich Chemical Co. (GPTMS).                               Examples 1 to 10   The polymer grafted silica sol was prepared according to the following general procedure.   At the silica / monomer ratio shown in Table 2, the monomers were added to a suspension of the described precursor ( Solids 3%) and the reaction mixture_TwoDeoxygenation for about 5 minutes by purging And an initiator (e.g., potassium persulfate or t-butyl hydroperoxy). Was added to the reaction mixture, typically to a monomer concentration of approximately 1%. this The reaction mixture is_TwoIn an atmosphere, stir at 65 ° C to 70 ° C for 24 hours while stirring. The raft polymerization was terminated. The resulting clear blue suspension has no monomeric odor, Used without purification. 1. Methacrylic acid (MAA) available from Aldrich Chemical Co. Inhibitor from this MAA Immediately after removal of the MAA, the MAA was saturated with From Polysciences, Inc. of Warrinqton, Virginia in the form of cracked chloride beads (Available) column for graft polymerization. 2. Butyl acrylate (BA) available from Aldrich Chemical Co. Suppress from MAA The inhibitor was removed from BuA in the same manner as the agent was removed. 3. The reaction mixture also includes St. Minnesota. Sulfo available from Paul's 3M Co. Novolak resin 3M^TM Stain Release Concentrate FC-369 also included Was. 4. This example was used as a comparative example, and silica particles were substantially separated according to the present invention. It contains not aggregated particles but aggregates.                                 Comparative Example C-2   NALCOAG^TM Add 1042 (36.75 g) to deionized water (450 g) and add approximately 2.5% solids An id suspension was prepared. This silica suspension is added to freshly distilled methacrylic acid (12. 5 g) and the resulting mixture is_TwoDeoxygenate for about 5 minutes by purging, This mixture is N_TwoHeat to 80 ° C in an atmosphere and further add t-butyl hydroperoxide (1.5 g of a 70% aqueous solution of the active ingredient available from Aldrich Chemical Co.) to the mixture Was added. The mixture thus obtained is mixed with N_TwoWith stirring at 80 ° C under atmosphere The polymerization was terminated for 24 hours. The resulting clear blue suspension has no monomeric odor. And used without further purification.                            Carpet treatment procedure   The polymagnes of the present invention can be prepared by the following exhaustion or flex nip method. Apply rafted silica sol to various nylon 6 or nylon 66 carpets did.Exhaust treatment (EX)   Aqueous dispersion 1% solids by weight of the composition of the present invention in a 1000 ml stainless steel beaker 500 g was exhausted onto a carpet sample. Optionally, MgSO_Four(0.5 weight %) And / or Karawet^TMDOSS (0.1 wt%; Rhone, Baltimore, MD) Dioctyl sulfosuccinate available from Poulenc) was added to the dispersion. Was. The pH of the dispersion was adjusted to 2 with a 10% by weight solution of sulfamic acid, then A part of the car was immersed in a 100 ° C. oil bath. When the temperature of the dispersion reaches 76 ° C, Approximately 10g of nylon carpet sample (area weight about 1.2kg / m^TwoPale blue with Nylon 66 carpet) is completely immersed in the dispersion and the carpet is Stir for 15 minutes. Then remove the carpet from the bath and add enough deionized water Rinse. Apply a cloth towel to the sample and apply shiatsu. Water was absorbed. At this point, the sample is dried at room temperature for Si analysis, or Or a water-soluble fluorocarbylalkoxysilane (FCSi) as described below (essentially Prepared as described in Example 6 of US Pat. No. 5,274,159 (Pellerite et al.). Was sprayed.Flex nip treatment (FN)   Weigh a weighed carpet sample (approximately 15 cm x 30 cm) in deionized water for at least 5 After immersion for 5 minutes, pressurized steam treatment in Mathis Laboratory Steamer Type DH () I did. This steam treatment is performed at a steam temperature of about 100 ° C for 2 minutes, and the sample passes through the steam. In this case, the tufted surface of the sample was set to face upward. Steamed car Centrifuge the pet and impregnate 10% to 15% by weight based on the dry weight of the carpet And then store the sample in a sealed plastic bag (up to 3 hours) And then processed.   The carpet is full bath (typically 4-5 times the dry weight of the carpet sample) The amount of the treatment bath was determined so that the amount of the treatment bath was absorbed. Car based on carpet weight Calculate the desired% solids (% SOC) on the pet and treat the appropriate concentration of treatment ingredients (eg, (Grafted silica sol, wetting agent, etc.) to deionized water and bath to desired weight And the pH of the bath was adjusted to 2 with a 10% aqueous solution of sulfamic acid. Scripture Formally, 1% SOC grafted silica is replaced with 0.5% SOC MgSO_FourMixed in the bath with . (For example, to deposit 1% SOC treatment agent on 100 g of carpet sample, 1 g of grafted silica solid and MgSO_Four Add 0.5g to water to bring total bath weight to 500g ). Pour this bath into a 6 "x 12" pan and tuft the steamed carpet It was immersed in the bath for 1 minute with the surface facing upward. At this time, promotes liquid impregnation A weight was placed on the carpet sample to remove. Next, the tufted surface faces downward Place the carpet in the steamer and flush the remaining bath on the carpet Left, and a second steam treatment on the carpet using the same conditions as described above Was given. Immediately after steaming, place the carpet in approximately 2 liters of deionized water. Dip twice, then centrifuged 10% to 15% impregnation based on dry weight of carpet I made it.   Carpet treated with fluorochemical treatment immediately after flex nip treatment Or alternatively between the flex nip and spray treatment Store wet processed samples in sealed plastic bags for up to 3 hours did.Fluorochemical component treatment   Following the exhaustion or flex nip treatment of the grafted silica component, Applying fluorochemical components of pet treatment composition to wet carpet samples did. Dry weight of sample with 15% wet weight gain The solid content is adjusted so that the impregnation rate of element F is about 500 ppm based on the amount. A topical spray of an aqueous solution of the lurochemical component onto a wet carpet test sample Was. Carpet samples were dried at 121 ° C. and left at room temperature for at least 8 hours Later, it was subjected to the test.                      Examples 10-40 and Examples 46-54   As shown in Table 3, the grafted silica of the present invention and the grafted silica Carpet using lica / fluorochemical composition as well as application method described above A sample was prepared. 1. Carpet finished sample. 2.Area weight about 1.3kg / m^TwoA gray-white nylon 66 carpet having For evaluation of walking dirt used. The reason is that there is good contrast between the contaminated and uncontaminated parts and This is because consistent reproducibility is obtained for each test. 3. Essentially as described in Example 6 of US Pat. No. 5,274,159 (Pellerite et al.) Fluorocarbylalkoxysilane prepared as follows. 4. Scotchgard, a commercially available carpet protective agent^TM FC-1373M. Fluorochemical urethane And is available from 3M Co. as a 31% by weight solids treatment. 5. Scotchqard, a commercial carpet protectant^TM FC-1355. Aqueous containing 46.5% solids A fluoroaliphatic polymer treatment available from 3M Co. 6.Area weight about 1.2kg / m^TwoA light blue nylon 6 carpet having Resistance to spots Used for evaluation. 7.Surface weight about 1.4kg / m^TwoLight blue nylon 66 carpet with. Oil and water repellency It was used for gender evaluation. 8. The silica particles used in this treatment are not substantially discrete particles of the present invention, It was an aggregate of smaller silica particles. 9.Surface weight about 1.2kg / m^TwoLight blue nylon 66 carpet with. 10. NALCOAG exhausted to carpet 4^TM 1042 (SiO in bath_Two1% solids). 11. The treating agent suspension of Example 3 was evaporated to dryness in a rotary evaporator, and Redisperse in water using the same procedure used to redisperse the silica sol prepared in 9. Scattered.   The performance characteristics of the protective composition of the present invention on the carpet sample prepared earlier Characterization using the test method described above. Was conducted. Table 4 shows the test results.   For the carpet subjected to the protection treatment described in Examples 10 to 40 and Examples 46 to 54, Performance data will depend on the type of carpet used in the test and the specified performance characteristics. (That is, carpet 1 is used for the evaluation of walking dirt, 2 was used for evaluation of stain resistance, and carpet 3 was evaluated for oil repellency and water repellency. The carpet 4 was used to measure the Si level before and after the exhaust treatment. used). ^★  By definition, ΔΔE for the control is zero. ≠ F = No liquid repellency was observed for any of the test liquids.                                 Example 39   5) Initiator-free methacrylic acid (22.4 g), 3-mercaptopropyltrimethoxysilane (MPTMS; 0.56 g), and initiator (0. 23 g; azobis (isobutyronitrile) available from Aldrich Chemical Co. (AIBN )), Newly dried Methanol (198 g; CaH_TwoAnd distilled with N)_TwoAbout 10 due to purging It was deoxygenated for minutes. Next, the reaction mixture is_TwoDo not stir while sealing with gas. The mixture was heated to reflux for 24 hours. NALCOAG was added to 50 g of this methanol polymer solution.^TM 104 2 (29.4 g) was added and the reaction mixture was heated under reflux for 24 hours. The resulting mixture is Evaporated to dryness in a tally evaporator, MPTMS 0.06 mmol / SiO_Two 1g ratio and SiO_Two A pale yellow solid having a: MAA ratio of 2: 1 was obtained.   Add 5 g of this solid to 495 g of deionized water and add enough HO_ThreeSNH_TwoTo adjust the pH to 2. And using this solution by the exhaust treatment method described above. Processed.                                 Example 41   NH_Four500 g of a 2% by weight solids suspension of the grafted silica of Example 1 was 6 and mix this suspension with a solution of 10 g of FCSi dissolved in 490 g of deionized water. Thus, a treating agent solution was prepared by preparing a clear suspension. One of this suspension Apply the part to the wooden tongue depressor, apply finger pressure and rub the wood, then apply the tongue depressor to 140 Dry for 3 minutes at ° C. After cooling down to ambient temperature, from the height of about 30 cm on the tongue depressor When subjected to a water flow, it exhibited excellent dynamic water repellency. For processed tongue depressor Oil repellency test, oil droplets up to oil # 3 were formed, and after 30 seconds, oil # 6 Oil drops were retained until.   Similarly, the treatment agent suspension was applied to the second pressure vessel, but at this time, the pressure vessel was removed. Dry overnight at ambient temperature. The second pressure vessel also showed good dynamic water repellency.                                 Example 42   NALCOAG^TM TX-8800 (29% solids suspended in isopropanol) Colloid with an average particle size of 20 nm available from Nalco Chemical Co. as a suspension of Silica dispersion) with 3-mercaptopropyltrimethoxysilane (0.25 mmol / g silica). Rica 1.423 g) and the resulting mixture was heated with stirring at 65 ° C. overnight. this 17.01 g of dispersion and Fluorad^TMFluorochemical acrylate FX-13 (Minnesota S 13.5 g and 1.5 g of methacrylic acid in acetone (65 ml). The dissolved solution was mixed, and the mixture was heated to 65 ° C. The reaction mixture is N_Twopurge Deoxygenation treatment for about 5 minutes with t-butyl hydroperoxide (active ingredient 70% Compound (0.215 g) was added and heating continued with stirring for 22 hours. The resulting reaction mixture The compound had no monomeric odor. This mixture has a grafted polymer / silica ratio of 3: 1. There was a suspension (20% solids).   Immerse a wooden tongue depressor in this suspension and wipe off the tongue depressor with tissue paper And remove the tongue depressor at room temperature for at least 15 minutes. After drying, they were subjected to a liquid repellency test. Oil repellency of treated tongue depressor was examined However, granular oil droplets were generated up to oil # 3, and the oil droplets were held up to oil # 6. Treated tongue pressure When the water repellency of the aqueous kit was examined, the granular droplets were formed up to oil # 1, Droplets were held until # 3. Water flow impinging on the tongue depressor from a height of about 30 cm This tongue depressor exhibited excellent dynamic water repellency.                                 Example 43   A treatment solution was prepared substantially according to the procedure of Example 41. At this time, FCSi aqueous solution (1.0 g of FCSi dissolved in 49 g of deionized water) was added to the polymer graph of Example 1. To silica (pre-diluted with deionized water to 2% solids) (50 g) Produce 100 g of FCSi / polymer grafted silica suspension as a dispersion with about 2% solids Was. This FCSi / The polymer-grafted silica is concentrated (rotary evaporator treatment) to a solid content of about 10 % Dispersion was prepared and 2.02 g of an aliquot was removed from this dispersion and tested for liquid repellency. Provided. The remaining dispersion was further concentrated (rotary evaporator treatment) to a solid content of about 50 % Dispersion was prepared. This dispersion had a waxy solid consistency . Both 10% and 50% solids dispersions can be reconstituted by adding an appropriate amount of deionized water. By dispersing, it was possible to return to a dispersion having a solid content of 2%.   Redispersed FCSi / polymer grafted silicone essentially as described in Example 41. Treat the tongue depressor with a sample to test the oil repellency and dynamic water repellency of the oil kit Was. The tongue depressor treated with the redispersion gives up to 4 oil droplets with respect to the repellency of the oil kit. And showed good dynamic water repellency while retaining oil droplets up to 6.                                 Example 44   Acetone (65.6 g) was added to a dispersion (29.4 g) of the precursor P-1 having a solid content of 17%. The Lloyd dispersion was mixed. Methyl methacrylate (5.0 g) was added dropwise to this dispersion, The resulting mixture is N_TwoHeat to 65 ° C under atmosphere, then N_Two5 minutes by purging A deoxidation treatment was performed during the period. t-butyl hydroperoxide (Aldrich Chemical Co. (071 g) of a 70% solids aqueous solution available from Co., Ltd._Two Heating in an atmosphere for 24 hours gave a clear suspension of polymer-grafted silica. FCSi (0 .250 g) in acetone (4.75 g) was added to poly (methyl methacrylate) Aliquots (5 g) of bleached silica were added dropwise and the resulting mixture was stirred at 65 ° C. While heating for 24 hours.   The tongue is obtained with the FCSi / polymer graft suspension obtained essentially as described in Example 41. The indenter was treated and tested for oil kit and dynamic water repellency. Processed tongue The indenter produces granular oil droplets up to 4 and oil up to 6 It retained the drops and exhibited excellent dynamic water repellency.                                 Example 45   Deionized water (50g) with SiO_TwoSuspension (50g; 88SN-123; 20% solids; particle size <10nm; pH10 (Available from Nalco Chemical Co.) to obtain a colloidal suspension with about 10% solids. Prepared. Mercaptopropyltrimethoxysilane (0.25q; 0.13mM / g) Added to the suspension and the mixture was heated at 80 ° C. with stirring for 16 hours.   Hydroxyethyl acrylate (2.0 g; HEA; available from Aldrich Chemical Co.) Was added to a 20 g aliquot of the resulting sol and the mixture was heated to 60 ° C._TwoTo And then degassed with t-butyl hydroperoxide (30 mq; 70% solids aqueous solution). Added to the reaction mixture. Heat this mixture at 65 ° C for 16 hours, slightly opaque And stable SnO_TwoA suspension of -g-HEA (1: 1) graft was obtained. Various modifications and alterations of this invention can be made without departing from the scope and spirit of this invention. That will be obvious to those skilled in the art.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), AU, CA, JP (72) Inventors Hamrock, Stephen Jay.             United States, Minnesota 55133-3427,             St. Paul, P. Oh. Box             33427 (72) Inventors Pererite, Mark Jay.             United States, Minnesota 55133-3427,             St. Paul, P. Oh. Box             33427

Claims (1)

[Claims]   1. (a) substantially discrete substantially monodisperse polymer-grafted inorganic microparticles A sol containing a colloidal dispersion dispersed in a liquid, and (b) at least one A fluorochemical treating agent composition comprising: a fluorochemical;   2. The liquid is water, at least one organic liquid, and at least one organic liquid. 2. The composition of claim 1, wherein the composition is selected from the group consisting of an aqueous solution of a mechanical liquid.   3. The inorganic microparticles are silica, titania, alumina, zirconia, Zia, chromia, iron oxide, antimony oxide, tin oxide, and mixtures thereof The composition of claim 1, comprising a metal oxide selected from the group consisting of:   4. The inorganic microparticles have an average of about 1 nanometer to about 200 nanometers. The composition of claim 1 having a particle size.   5. The inorganic microparticles may comprise at least one free radically polymerizable ethylene-based monopoly. 2. The composition of claim 1 which is grafted with a polymer containing polymerized units of a saturated monomer.   6. The inorganic microparticles can function as a chain transfer site for free radical polymerization. Via at least one coupling agent containing at least one functional group The composition of claim 1 which is grafted with a polymer.   7. The fluorochemical is at least one fluoroaliphatic group or 2. The composition of claim 1 which comprises an oloalicyclic group.   8. The fluorochemical reacts chemically with chemical groups on the surface of the inorganic microparticle. 2. The composition of claim 1, wherein said composition is capable of effecting a strong or strong physical interaction.   9. The composition of claim 1 in a substantially liquid-free form.   10. Substantially discrete, substantially monodisperse, polymer-grafted inorganic matrix Treatment comprising a sol containing a colloidal dispersion in which chroma particles are dispersed in a liquid Composition.   11. Substantially discrete, substantially monodisperse, polymer-grafted silica microparticles Is a treating agent composition comprising a sol containing a colloidal dispersion dispersed in water. And the inorganic microparticles contain methacrylic acid and a fluorochemical. Including polymerized units of at least one monomer selected from the group consisting of acrylates The treatment agent composition grafted with a polymer.   12. Sustained water and oil repellency, stain removal, and against dry stains A method for imparting resistance to a support, and further comprising contacting the support with the composition of claim 1. The method comprising the step of touching.   13. Sustained water and oil repellency, stain removal, and against dry stains A method of imparting resistance to a support, wherein (a) the support and substantially discrete Colloid with substantially monodisperse polymer-grafted inorganic microparticles dispersed in a liquid Contacting with a sol containing a metal dispersion, and (b) at least one of the support and Contacting the compound with a fluorochemical.   14． Sustained stain removal and / or resistance to dry soiling A step of contacting the support with the composition of claim 10. The method comprising:   15. A composition according to claim 1 or a substantially liquid-free composition corresponding thereto. Processed product comprising.   16. 11. The composition of claim 10, or a corresponding substantially liquid-free composition. A processed product comprising an object.