TW201127296A - Aqueous dispersions containing antimicrobials in a hybrid network - Google Patents

Abstract

The invention relates to a method of preparing a composition comprising (a) reacting a binder component (B) comprising at least one alkoxysilane (B2), and a polymer dispersion (PD), thus obtaining a prepolymer and subsequently (b) mixing or hydrolyzing and polycondensing said prepolymer in the presence of water and at least one antimicrobial agent (Z) comprising at least one antimicrobial active (Z1) and optionally a particulate carrier substance (Z2), wherein the at least one antimicrobial agent (Z) is unreactive during step (b).

Description

201127296 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of preparing a composition comprising: (a) bonding comprising at least one alkoxydecane (B2) and a polymer dispersion (PD) Component (B) is reacted, thereby obtaining a prepolymer, and then (b) mixing or hydrolyzing and polycondensing the prepolymer-water in the presence of: and - at least one antimicrobial agent (Z)' At least one antimicrobial active (Z1) and optionally a particulate carrier material (Z2), wherein the at least one antimicrobial agent (Z) does not react during step (b). Further, the present invention relates to a composition obtainable by the method, a coating comprising the composition, and a kit comprising a dispensing portion of the curable composition for use in combination, the curable composition containing the same Components (B) and (z). The present invention is also directed to a mixed network of an acrylate copolymer (Polymer P) and cerium oxide which are chemically linked to each other via an Si-containing group, comprising an antimicrobial agent, wherein the antimicrobial active agent (Z1) is not covalently attached thereto. The network, but the carrier material (Z2) has a functional group that can react with the organic stone in the polymer dispersion to form a ceria network (hybrid network). Furthermore, the invention relates to the use of such compositions for the preparation of antimicrobial coatings. [Prior Art] Increasingly high demands are placed on the suitability, safety and environmental compliance of coatings. Coatings based on dispersions of acrylic acid vinegar copolymers are known to provide high chemical resistance, flexibility, abrasion resistance, weatherability and impact resistance. The protection provided by such coatings is particularly important in the automotive, construction, marine and chemical fields. 150132.doc 201127296 There is a need in the art to develop a coating having the above advantages while having long-term antimicrobial properties. Therefore, several different coatings have been proposed in the prior art. The use of a second acid or a zeolite containing certain metal ions in an antimicrobial coating is known, for example, from U.S. Patent Nos. 452,410 and 5,556,699. However, coatings comprising zeolite or aluminum niobate are opaque and their use is generally limited to coatings having a thickness of less than 15 microns. It is known from US-A-6,596,401 to use a composition comprising a decane copolymer and an antimicrobial agent, wherein the copolymer is a reaction product of at least one polyisocyanate, an organofunctional sulphuric acid and a polyhydric alcohol. However, US-P 6,596,4〇1 does not disclose a hybrid network. U.S. Patent No. 6,572,926 discloses a polymer which is exposed to a polymerizable quaternary ammonium salt such as vaporized didecyl octadecyl-[3-(tridecyloxydecyl)propyl]ammonium dissolved in a solvent. Matrix. The quaternary salt in the solvent is adsorbed and polymerized by the polymeric matrix, thereby producing a substrate having a surface impregnated with the antimicrobial agent. The polymerized antimicrobial agent also penetrates the surface to a certain depth to form an interpenetrating network. The process is limited to permeating the polymer matrix or swelling the polymer matrix with certain mixtures of polymerizable quaternary ammonium salts and solvents. In another embodiment, it is disclosed that a polymerizable quaternary ammonium salt is added to a commercially available coating to form an interpenetrating network in situ. However, the leaching of the coating can only be avoided by polymerizing the antimicrobial agent. Again, the disclosed coatings still do not show sufficient antimicrobial activity against E. coli. SUMMARY OF THE INVENTION 150132.doc 201127296 The present invention is directed to providing an antimicrobial composition in which an antimicrobial active agent is not self-assembled. A related object of the present invention is to provide a coating having an enduring antimicrobial activity (specifically, a period of five years under weathering conditions). The antimicrobial coating should be useful for a wide range of antimicrobial agents. Another object of the present invention is to provide a coating of the antimicrobial composition, which exhibits high efficacy against Staphylococcus C〇ccus aureus and Escherichia C〇H. In addition, antimicrobial coatings should effectively kill these bacteria for up to 24 hours or less. At the same time, it is an object of the present invention to provide an antimicrobial coating which has the properties of wintering and weathering and exhibits high optical quality, sufficient flame retardancy, excellent adhesion to polycarbonate and aluminum substrates, and high resistance. Grinding. The foregoing problems can be solved by the method of the present invention and the compositions and coatings obtainable by the method. The preferred embodiment is outlined below and in the scope of the patent application. Combinations of the preferred embodiments are also within the scope of the invention. [Embodiment] The process of the invention for preparing a composition comprises steps (a) and (b) as defined above. Steps (a) and (b) are outlined in more detail below. The composition of the present invention is preferably present in the form of a coating. Step (a) According to the invention, the step (a) comprises a reaction - reacting a binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (PD) to thereby obtain a prepolymer. 150132.doc 201127296 Prepolymers are referred to as polymerization systems which still contain reactive groups or sites that can be further polymerized and/or crosslinked. In the case of the present invention, the alkoxydecane (B2) contains a hydrolyzable group which forms an inorganic network according to step (b) as part of the resulting mixed network. Crosslinking occurs as the dispersion dries, forming an inorganic/cerium oxide network. Reference to each of the average values of the functionalities refers to a number-weighted average. Binder component (B) According to the invention, the binder component (B) comprises at least one alkoxydecane (B2) and a polymer dispersion (PD). In a preferred embodiment, the binder component (B) comprises at least one binder (B丨) which is incapable of reacting in step (b) and at least one alkoxydecane (B2) in the step ( b) The binder (b 1) for the reaction in the reaction is preferably a binder having no oxiranyl group.

The polymer dispersion PD contains a glass transition temperature of at least two monomer Μ of the polymer P § 〇 〇. (: to +60 ° C. The polymer dispersion (PD) can be obtained by free radical emulsion polymerization of at least one ethylenically unsaturated monomer. Generally, §, the polymer is obtained by making two or A copolymer obtained by copolymerization of two or more monomer oximes. A skilled worker can prepare a composition having a glass transition temperature of _2 〇 t: to +6 经由 by skillfully selecting a monomer composition in this case. Polymer. According to Fox (see Ullmanns Enzyklop Sdie der technischen Chemie, 4th edition, Vol. 19, Weinheim (1980), p. 17, p.), 150132.doc 201127296, the glass transition temperature Tg can be estimated. In the good approximation The following formula gives the glass transition temperature of a copolymer with little or no cross-linking in high molar mass: fox = 2 £l xn

Tg Tg1+Tg2+ ...... where χ1, χ2.....Χη is the mass fraction 1, 2.....η and Tg1

Tg2.....Tgn is the glass transition temperature of the polymer synthesized in only one of the monomers 1, 2, ..., η in each case, expressed in Kelvin temperature. The latter is for example from Ullmann's Encyclopedia of Industrial Chemistry, VCH, 5th edition, Weinheim, Vol. A 21 (1992) p. 169 or from J. Bran (jrUp, e. H_Immergut, Polymer Handbook 3rd edition, J. Wiley, New York 1989 is known. In general, the monomer M is selected from the group consisting of α,β·ethylenically unsaturated monocarboxylic acids and dicarboxylic acids and oxime--: ester of 2 stanol and C5_C10 cycloalkanol; Ether; ester of ethyl alcohol with Ci-Cw monocarboxylic acid; ethylenically unsaturated nitrile; ethylene; partial ethylene; monoethylenically unsaturated carboxylic acid and sulfonic acid; monomer; α,β_ene An ester of a saturated monocarboxylic acid and a dicarboxylic acid with a C2-C3 decanediol; an α,β-ethylenically unsaturated monocarboxylic acid and a dicarboxylic acid and a C2-C3G amine group having a primary or secondary amine group Alcohol decylamine; α,β-ethylenically unsaturated monocarboxylic acid monoamine amide and its N-alkyl and N,N-dialkyl derivatives; N-vinyl decylamine; open chain N-ethylene a base amide compound; an ester of allyl alcohol and q-Cw monocarboxylic acid; an ester of an α,β-ethylenically unsaturated monocarboxylic acid and a dibasic acid with an amino alcohol; an α,β-ethylenically unsaturated monocarboxylic acid Acid and dicarboxylic acid with at least one level Amidyl or amine amine diamine amide; hydrazine, hydrazine-diallylamine; hydrazine, hydrazine-diallyl decylamine; nitrogen substituted by vinyl and ally 150132.doc 201127296 a heterocyclic ring; a vinyl group; a C2_c8 monoolefin; a non-aromatic hydrocarbon having at least two conjugated double bonds; a polyether (fluorenyl) acrylate; a ureido group-containing monomer; or a mixture thereof. When referring to (mercapto) acrylate in the context of the case, it not only means that the corresponding acrylic acid is cool, in other words, a derivative of acrylic acid, but also means a derivative of methacrylic acid vinegar, which is a methacrylic acid. Examples of the body include the following: (a): an ester of an α,β-ethylenically unsaturated monocarboxylic acid and a dicarboxylic acid with a Ci_CM alkanol, especially an ester of acrylic acid, mercaptoacrylic acid and ethacrylic acid, such as (methyl) Methyl acrylate, decyl ethacrylate, ethyl (meth) acrylate, ethyl ethacrylate 'n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate Butyl ester, second butyl (meth) acrylate, tert-butyl (meth) acrylate, ethyl propylene Tert-butyl acid ester, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, M,3,3 tetramethylbutyl (meth)acrylate, (曱Ethylhexyl acrylate, n-decyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, (methyl) ) myristyl acrylate, pentadecyl (decyl) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, pentadecanyl (meth) acrylate, (meth) acrylate Twenty burned ester, (mercapto)acrylic acid twenty-two yards cool, (decyl)acrylic acid tetracosyl ester, (decyl)hexadecyl acrylate (tridecyl) acrylate tridecyl ester (曱Base) palmitol acrylate, (meth) oleyl acrylate, linoleyl (meth) acrylate, 150132.doc 201127296 (meth) linolenic linoleic acid, (meth) acrylate stearyl vinegar and 12 (meth)acrylic acid vinegar. (b). Vinyl monomer, preferably styrene, 2-methylstyrene, methylstyrene, 2-(n-butyl)styrene, 4_(n-butyl)styrene, 4_(正癸Styrene methyl styrene, and more preferably styrene and α-mercapto styrene. (c) an ester of vinyl alcohol with a Cl_C3 hydrazine monocarboxylic acid, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate and Vinyl ester of Versatic acid. (d): an ethylenically unsaturated nitrile such as acrylonitrile and methacrylonitrile. 0). Halogenated vinyl and vinylidene halides such as ethylene, vinylidene chloride, vinyl fluoride and vinylidene fluoride. (0: whey-unsaturated carboxylic acid and sulfonic acid or its derivatives are acrylic acid, mercapto-propyl ketone acid ethyl acetoacetate, α-apo-propionic acid, butyric acid, maleic acid's a monoester of enedic anhydride, itaconic acid, citraconic acid, decyl fumaric acid, glutaconic acid, aconitic acid, fumaric acid, monoethylenically unsaturated dicarboxylic acid having 4 to 1 ,, preferably 4 to 6 C atoms, such as monomethyl maleate, vinyl sulfonic acid, allyl sulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate , sulfopropyl decyl acrylate, 2-hydroxy-3-propenyl propyl sulfonic acid, 2-hydroxy-3-mercapto acryloxypropyl sulfonic acid, styrene sulfonic acid and 2-propenyl decylamine Benzyl-2-methylpropanesulfonic acid. Suitable styrene sulfonic acid and its derivatives are styrene-4-sulfonic acid and styrene - 150132.doc •10· 201127296 3_hemeic acid and its soil test or test Metal salts such as sodium styrene-3-threne I and sodium stearate 4-sulfonate. Particularly preferred are acrylic acid and methacrylic acid. (g): phosphorus monomers such as vinylphosphonic acid and allylphosphine. Acid. In addition, phosphonic acid and phosphoric acid Monoesters and diesters of hydroxyalkyl methacrylates, especially monoesters, are suitable. In addition, phosphonates and phosphoric acids which are esterified individually by (meth) acrylates and individually esterified with different alcohols (for example alkanols) Diesters are suitable. Suitable hydroxyalkyl hydrazide acrylates for such esters are esters of the following monomers, more specifically 2-hydroxyethyl acrylate , (mercapto) 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, etc. The corresponding dihydrogen phosphate monomer comprises a phosphorus alkyl (meth) acrylate such as (mercapto) acrylate 2 _ Phosphate ethyl ester, 2-phosphoryl (meth) acrylate, 3-phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate and 3-phosphono-2-hydroxypropyl (meth) acrylate. Esters of phosphonic acid and mothic acid with an alkoxylated (hydroxy) hydroxyalkyl ester are also suitable as examples of (nonyl) acrylate ethylene oxide condensates, such as Η20=0: ( (:Η3)(:00(;(:Η2(:Η20;)ηΡ(〇Ιί;)Α H2C = C(CH3)COO(CH2CH20)np(=〇)(OH)2, where „ is 1 to 5 0. In addition , crotonic acid-filled ester, cis-butyl succinate, phosphorus fumarate, phosphorus dialkyl (meth) acrylate, crotonic acid dialkyl ester and scaly acid The propyl esters are suitable. Other suitable monomers containing a constituting group are described in WO 99/25780 and US Pat. No. 4,733,005, the disclosure of each of which is hereby incorporated by reference. Esters of β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids with C2_C3q alkanediols, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, acrylic acid 2_ Hydroxypropyl ester, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyrate Ester, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate and 3-hydroxy-2-ethyl methacrylate Hexyl ester. (i): a mono- guanamine of an α,β-ethylenically unsaturated monocarboxylic acid such as acrylamide and mercapto acrylamide. (k): Ν-alkyl decylamines of α,β-ethylenically unsaturated monocarboxylic acids and hydrazine, hydrazine-dialkyl decylamines such as fluorenyl-mercapto (meth) acrylamide, hydrazine-ethyl (Meth) acrylamide, Ν-propyl (decyl) acrylamide, Ν-(n-butyl)(methyl) acrylamide, hydrazine-(t-butyl)(fluorenyl) acrylamide , Ν-(n-octyl)(methyl) acrylamide, 1,1,3,3-tetradecylbutyl (meth) acrylamide, hydrazine-ethylhexyl (meth) propylene Guanamine, Ν-(n-decyl) (meth) acrylamide, Ν-(n-decyl) (meth) acrylamide, Ν-(n-undecyl)(fluorenyl) acrylamide, Ν-tridecyl(fluorenyl) acrylamide, hydrazine-tetradecyl sulfonyl decylamine, hydrazine-pentadecanyl (fluorenyl) acrylamide, hydrazine-standard network (曱Acetylamine, hydrazine-heptadecyl (meth) acrylamide, decyl-nonadecyl (meth) acrylamide, decyl-decyl (decyl) acrylamide, hydrazine _ Twenty-two alkyl (mercapto) acrylamide, hydrazine-tetracosyl (decyl) acrylamide, hydrazine-hexadecyl (fluorenyl) acrylamide Ν·30-alkyl (meth) acrylamide, 150132.doc -12· 201127296 N-palmitole olefinic (meth) acrylamide, N-oleyl (mercapto) acrylamide, N-linolenic acid (mercapto) acrylamide, N-linolenic acid (mercapto) acrylamide, N-stearyl (meth) acrylamide, N-dodecanyl (methyl Acrylamine, N,N-dimethyl(indenyl)propanolamine, N,N-diethyl(meth)acrylamide and morpholinyl(mercapto)acrylamide. (〇广α,β-ethylenically unsaturated monocarboxylic acid and ester of dicarboxylic acid and amino alcohol, such as fluorenyl (mercapto) acrylate, fluorenyl-didecylamino oxime ester, bismuth (mercapto) acrylate, Ν-didecylaminoethyl ester, ruthenium acrylate, ruthenium-diethylaminoethyl ketone, ruthenium (mercapto) acrylate, ruthenium-dimethylaminopropyl propyl ester, fluorenyl hydrazide -Diethylaminopropyl propyl ester and (decyl)acrylic acid ν,Ν-dimethylaminocyclohexyl self-propelled. (Ρ) · α,β-rare unsaturated mono- and mono-rebel and containing at least a primary or secondary amine diamine amide such as Ν-[2-(diguanyl)ethyl]propenylamine, Ν-[2-(dimethylamino)ethyl]decyl propylene Indoleamine, Ν-[3-(diamidopropyl)propyl]propenylamine, hydrazine-[3-(dimethylamino)propyl]decyl acrylamide, hydrazine-[4-(dimethylamine) Butyl] acrylamide, Ν-[4-(diguanidino)butyl] decyl acrylamide, hydrazine-[2_(diethylamino)ethyl] acrylamide, Ν·[4 -(Diammonium)cyclohexyl]propenylamine and Ν-[4-(diguanidino)cyclohexyl]methacrylamide. (s): c2_c8 monoolefin having at least two conjugated double bonds Non-aromatic hydrocarbons, such as ethylene, propylene, isobutylene 'isoprene and butadiene. ⑴. Polyether (Yue-yl) acrylate of the general formula (A) of the compound 150132.doc 201127296

Rb 〇

_l I H2C—c—c— Y (CH2CH20)k(CH2CH(CH3)0), Ra (A) wherein the sequence of the epoxy unit is arbitrary, and k and 1 are independent of each other from 〇 to ι00, let And the sum of 丨 is at least 3, R is hydrogen, Ci-Cw alkyl, c5-C8 cycloalkyl or (6-〇14 aryl, Rb is hydrogen or CVCs alkyl, Y is 0 or NRC, Re is Hydrogen, C|_C3G alkyl or C5_C8 cycloalkyl. Polyether (fluorenyl) acrylate is, for example, the above α,β-ethylenically unsaturated monocarboxylic acid and/or dicarboxylic acid and its acid vapor, guanamine and a polycondensation product of an anhydride and a polyether alcohol, which can be easily reacted by reacting ethylene oxide, hydrazine, 2-propylene oxide and/or epigas alcohol with a starting molecule such as water or a short-chain alcohol Ra_〇H The polyether alcohols can be prepared. The alkylene oxides can be used individually, in an alternating sequence or in the form of a mixture. The emulsion polymers used in accordance with the invention can be prepared singly or in the form of a mixture. Suitable polyether (fluorenyl) acrylic acid Esters may be purchased from Laporte Performance Chemicals, UK, for example, in various product forms known as Bis〇mer 8. It includes, for example, Bisomer® MPEG 350®, which is a methoxy polymerization. Ethylene glycol monomethacrylate. The compound of ruthenium (Α) is a compound of γ is 〇 (in other words, a bridge) 150132.doc •14- 201127296 The preferred compound of formula (A) is 3 to 5 An integer, more specifically a compound of 4 to 25. Also preferred is a compound of formula (A) which is a compound of 33 to 5〇, more specifically 4 to 25. Particularly preferred compounds are the following compounds, wherein γ is 〇, Rb is hydrogen or methyl, 1 is 〇(zero) and k is an integer of 3 to 15, preferably 4 to 12. Further, the following compounds are particularly preferred, wherein γ is ruthenium and Rb is hydrogen or ruthenium The base, k is 〇 (zero) and 1 is an integer of 3 to 15, preferably 4 to 12. The Ra in the formula (A) is preferably hydrogen, decyl, ethyl, n-propyl, isopropyl, N-butyl, t-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, palmitoyl or stearyl. Rb in formula (A) is preferred. Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl or n-hexyl' more specifically hydrogen, methyl or ethyl Rb is particularly preferably hydrogen Methyl group (u): a suitable monomer containing a ureido group, such as a derivative of N-vinylurea or N-allylurea or imidazolidin-2-one. These monomers include N-ethylene.唾 ° 定 定 酮 ketone and N-allyl ° m. sitbit-2-one, N-acetoxyethyl imidazolidin-2-one, N-(2-(methyl) propylene oxime Aminoethyl)imidazolidine-2-one, N-(2-(indenyl)propenyloxyethyl)imidazolidinium-2-guj (=2-ureido(methyl) acrylate, UMA) and N-[2-((indenyl) acryloxy)ethylamino)ethyl]imidazolidin-2-one. Preferred monomers containing a ureido group are N-(2-propenyloxyethyl)imidazolidine-2-one and N-(2-mercaptopropenyloxyethyl)imidazolidine-2-one. It is especially preferred that N_150132.doc -15- 201127296 (2-mercaptopropene oxyethyl) sigma η sit (7-deno-2-indole (2-ureido methacrylate, UMA). v). A monomer containing a oxyalkyl group, such as a ethoxylated trimethoxy sulphate, a vinyl diethoxy sulphur, an ethyronyl triisopropoxy sulphate, an acetaminophen (0) -decyloxyethoxy)decane, vinylmethyldimethoxycarbazide, vinylmethyldiethoxylate, ethylene dimethyloxycarbazide, ethylene dimethyl Ethoxylated stone court, 3-methylpropenyl propyl trimethoxy decane, 3-methylpropenyl propyl diethoxy sulphur, 3-mercaptopropyl propyl propyl methyl dimethyl Oxygen sulphur, 3-methyl propyl propyl propyl methyl diethoxy sylvestre, acrylic acid (2-acetoxyethyl dimethyl decyloxy) decyl propyl vinegar and methacrylic acid ((2-ethoxylated ethyl bisfluorenyloxy) decyl propyl ester, acrylic acid (2-carboxyethyl dimethyl decyloxy) decyl propyl acrylate and f-based acrylic acid ginseng (2- Carboxyethyl dimethyl decane oxygen矽Alkylpropyl propyl ester, acrylic acid ginseng (3-hydroxypropyl dimethyl oxanthoxy) sulfanyl propyl ester and methyl acrylate acid (3- propyl propyl fluorenyl oxyalkylate) a sulfanyl, acrylate, and decyl acrylate functional fluoro substituted alkyl/aryl siloxane such as: acrylic acid (3,3,3-trifluoropropyl decyl decane) Oxy) decyl propyl propyl ester and methacrylic acid ginseng (3,3,3-trifluoropropyl decyl decyloxy) decyl propyl acrylate, acrylic acid [3-heptafluoroisopropoxypropyl)] Dimethyl decyloxy decyl propyl propyl ester and mercapto acrylic acid [3-heptafluoroisopropoxypropyl)] decyl decyl decyl oxyalkyl propyl acrylate, acrylic acid (pentafluorophenyl decyl decane) Mercapto) decyl propyl acrylate and thioglycol ginseng (pentafluoro 150132.doc • 16 · 201127296 phenyl dimethyl sulphur oxide base) The above-mentioned monomer (7) early body k early body Μ can be used individually, in the form of a mixture of a type of ++, Japanese, and an early limb, the restriction condition being that the poly a has -20C to +60 ° C, preferably · Mail to + machine, more specific. " Glass transition temperature in the range of 30 ° C & 疋. 〇 C to monomer Μ usually contains at least 8 〇 。. / . > Chuanzhongli / 〇, preferably at least 85 weighs at least 90% by weight At 2 5 °c and 1 ρ, k 卜 仕 仕 and 1 bar under water solubility less than 3 〇 unsaturated monomers ΜΗ Φ ΐ § § §, ^ s heart early (main early body). These monomers include, in particular, categories (5) Early bodies of carcass (4) and (s). The main monomer Μι is preferably classified into categories (4) and (8). For emulsion polymerization, it is preferred to use at least rib% by weight, more preferably at least 85% by weight of the monomer river. % by weight and especially at least 9% by weight of at least monomer M1, which is selected from the group consisting of α,β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids and CVQ(tetra)μ and arylethylene monomers. For emulsion polymerization, The monomer M1 is preferably used in an amount of up to 9% by weight, more preferably up to 99.5% by weight and especially up to 99% by weight. The monomer M1 is preferably selected from the group consisting of (sub)acrylic acid cerium. S, (methyl) acetoacetate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (methyl) propylene δ ΐ Quoting Ss, (meth)acrylic acid, second butyl s, (mercapto) acrylic acid, dibutyl phthalate, n-pentyl methacrylate, n-hexyl (meth) acrylate, (meth) propylene ^ n-heptyl ester, n-octyl acrylate, 2-ethylhexyl acrylate, styrene, 2-methyl styrene and mixtures thereof. The free radical emulsion polymerization for the preparation (pD) can be carried out using at least one other monomer M2, the at least one I50132.doc 201127296 other monomer M2 is water soluble at 25 ° C and 1 bar ^ 30 g / l, especially > 50 g / Ι. The 4 monomer M2 is usually present in a small proportion (minor monomer). Preferably, the monomer M2 is a monomer of the categories (f), (g), (h) and (1). The emulsion polymerization preferably uses up to 2% by weight, more preferably up to 15% by weight, especially up to 10% by weight, based on the total weight of the monomers, of at least one monomer M2, preferably selected from ethylenically unsaturated monocarboxylic acids. Acids and dicarboxylic acids and anhydrides and monoesters of ethylenically unsaturated dicarboxylic acids, (meth) acrylamide, hydroxyalkyl (meth) acrylate, Ci_Ci () hydroxyalkane (mercapto) acrylamide and mixtures thereof. For emulsion polymerization, when monomer 2 is present, it is preferably used in an amount of at least 0% by weight, more preferably at least 〇 based on the total weight of the monomers. 5 wt%, especially at least 1 wt. The monomer M2 is particularly preferably selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, acrylamide, methacrylamide, and acrylic acid. Ethyl ester, 2-hydroxyethyl methacrylate, 2-ethylidene propyl amide, 2- benzylethyl propyl aryl amine, and mixtures thereof. Particularly suitable combinations of the main monomers M1 used in the process according to the invention are, for example: n-butyl acrylate and methyl methacrylate; n-butyl acrylate, decyl methacrylate and styrene; n-butyl acrylate and styrene ; n-butyl acrylate and ethylhexyl acrylate; n-butyl acrylate, ethyl hexyl acrylate and styrene. The above-mentioned main monomer M1 is particularly suitable for combination with a particularly suitable monomer. The combination of the monomers M2 is preferably selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, and methacrylic acid. Amines and mixtures thereof. In a particular embodiment, in addition to Ml and M2 (if present), at least one polyether (fluorenyl) acrylate is used to carry out the free radical emulsion polymerization for the preparation of (PD). The latter is preferably used in an amount of from 5% by weight to 5% by weight, preferably 1% by weight based on the total mass of the monomers M. /. Up to 1% by weight, and more specifically 1% to 5% by weight. Suitable polyether methacrylates are the compounds of the above polymer class (1). The polyether (meth) acrylate is preferably selected from the group consisting of a compound of the formula (Α) wherein Υ is hydrazine, Rb is hydrogen or fluorenyl, 1 is 0 (zero) and is an integer from 3 to 15, preferably 4 To 12, and the following compound of the formula (A) wherein 丫 is O' Rb is hydrogen or fluorenyl ' k is 〇 (zero) and 1 is an integer from 3 to 15, preferably from 4 to 12. In the preparation of the polymer dispersion of the present invention, in addition to the above monomer M, at least one crosslinking agent may also be used. The monomer having a crosslinking function is a compound having at least two polymerizable, ethylenically unsaturated, non-conjugated double bonds in the molecule. Crosslinking can also be carried out, for example, via actinic activation. For this purpose, in order to prepare PD, at least one monomer having a photoactivatable group may be additionally used. A photoinitiator can also be added independently. It is also possible to carry out crosslinking, for example, via a functional group capable of participating in a chemical crosslinking reaction with a functional group complementary thereto. These complementary groups can all be attached to the emulsion polymer and crosslinked using a crosslinking agent capable of participating in a chemical crosslinking reaction with a functional group of the emulsion polymer. Examples of suitable crosslinking agents include acrylates, methacrylic esters, allyl ethers of at least one hydroxy alcohol or vinyl ethers. The parent alcohol group may be fully or partially etherified; however, the crosslinking agent comprises at least two dilute groups of 150132 'doc -19- 201127296 unsaturated groups. Examples of the parent alcohol are dihydric alcohols such as hydrazine, 2-ethylene glycol, hydrazine, 2-propylene glycol, l3-propanediol, .1,2-butanediol, 1,3-butanediol, 2,3-butyl Glycol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1> 6_hexanediol, ^0-decanediol, dialkyl glycol, l12-dodecanediol, neopentyl glycol, 3-decylpentane-1,5-diol, 2,5_2 Mercapto_1,3_hexanediol, 2,2,4·trimethylpentanediol, anthracene hexanediol, cyclohexanediol, M-bis(hydroxydecyl)cyclohexane, hydroxyl Penicillin owes neopentyl glycol monoester, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxypropyl)benzyl]propane, diethylene glycol, Triethylene glycol, tetraethylene glycol, dipropanol, dipropylene glycol, tetrapropylene glycol, 3- thiapentane-indole, 5-diol and, in each case, a molecular weight of 2 to 1 〇〇〇〇 G/m〇1 of polyethylene glycol, polypropanol and polytetrahydroethylene. In addition to the homopolymer of ethylene oxide or propylene oxide, a block copolymer of ethylene oxide or propylene oxide or a copolymer comprising an incorporated oxirane group and a propylene oxide group may also be used. Things. Examples of the parent alcohol having more than two OH groups are trimethylolpropane, glycerin, isoprene, '5-pentane-alcohol, 1,2,6-hexanetriol, cyanuric acid, dehydrated sorbus Sugars such as sucrose, glucose and mannose. It is of course also possible to use polyols after reaction with alkylene oxide or % oxypropylene as the corresponding ethoxylates or propoxylates, respectively. The polyol can also be first converted to the corresponding glycidyl ether by reaction with epigas alcohol. Suitable & parent agents are vinyl esters or monohydroxy unsaturated alcohols with cations and carboxylic acids (examples are acrylic acid, methacrylic acid, itaconic acid, cis-butane diacid or fumaric acid) Vinegar. Examples of such alcohols are allyl alcohol, bl 150132.doc 201127296 butyl 3 alcohol 5-hexanol, octene -3- alcohol, 9 decene alcohol, dicyclopentenol, 10 undecene Alcohol, cinnamyl alcohol, citronellol, crotyl alcohol or octadecene pentoxide. A possible alternative is to esterify the monohydroxy unsaturated alcohol with a polycarboxylic acid (example being malonic acid, tartaric acid, stupid tricarboxylic acid, phthalic acid, terephthalic acid, citric acid or succinic acid). Other suitable parenting agents are esters of unsaturated carboxylic acids with the above polyols, exemplified by oleic acid, crotonic acid, cinnamic acid or an ester of decanoic acid. 8. The substance that he uses as a parent to be a parent is a linear or branched chain, a linear or cyclic erythrene or aromatic hydrocarbon having at least two double bonds, in the case of aliphatic hydrocarbons, not conjugated, such as diethylene Benzobenzene, divinyltoluene, oxime octadiene, 1,9-decadiene, 4_vinyl_丨_cyclohexene, trivinylcyclohexane or 200 to 20000 g/m in the molecule i polybutadiene. Further, acrylamide, mercapto acrylamide and at least a difunctional amine N-propylpropylamine are also suitable as crosslinking agents. Examples of such amines are hydrazine, 2-diaminoethane, 1,3-diaminopropane, 14-diaminobutane, i,6-diaminohexane, 1,12-dodecane Diamine, piperazine, diethylenetriamine or isophorone diamine. The decylamines of the above-mentioned types of allylamine and unsaturated carboxylic acids such as acrylic acid, mercaptoacrylic acid, itaconic acid, maleic acid or at least divalent carboxylic acid are also suitable. Other materials which are suitable as crosslinking agents are, for example, triallylamine and triallyl-monosylamine salts such as gasified triallylmethylammonium or trimethylallylammonium methylsulfate. N-vinyl compounds derived from gland derivatives, at least bifunctional guanamine, cyanurate or amino phthalic acid are also suitable, such as urea, acetaminophen, and propylene 150132.doc -21 - 201127296 urea Or an N-ethylene compound of tartaramine, such as n, N'-diethylene extended ethylurea or hydrazine, Ν-divinylpropanoid. Other suitable cross-linking agents are diethylene-based dioxin, tetraallyl or sulphur-based stone garden. It will be appreciated that a mixture of the above compounds can also be used. In addition, the 'parental monomer' also includes monomers containing an ethylenically unsaturated double bond and a reactive functional group, a benzyl group, a ketone group or an oxirane group (for example, a group capable of reacting with the added parent agent). . The functional group is preferably a keto group or an acid group. The keto or aldehyde group is preferably attached to the polymer via copolymerization of a copolymerizable ethylenically unsaturated compound containing a keto group or an aldehyde group. The suitable compounds are propylene; mercaptopropenal; vinyl alkyl ketone having 1 to 2, preferably 1 to 1 carbon atoms in the alkyl group; mercaptostyrene; Or two keto groups or a ketone group or an aldehyde group and a keto group (alkyl) alkyl acrylate, the alkyl group preferably comprising a total of 3 to 1 carbon atoms, an example being (fluorenyl) propylene oxime Alkylpropanal as described in DE-A-2722097. Further, anthracene-side oxyalkyl (meth) acrylamides of the type known from US-A-4,226, 007, DE-A-20, 612, 213 or DE-A-2,207, 209 are also suitable. Particularly preferred are (mercapto)ethyl acetoacetate, (mercapto)acrylic acid acetoxyacetate and especially diacetone acrylamide. The crosslinking agent preferably comprises a compound having at least two functional groups, more specifically two to five functional groups, which are capable of participating in a parent reaction with a functional group of the polymer, in particular a keto group or an aldehyde group. . For this purpose, for example, an anthracene, a hydroxylamine or an oxime ether or an amine group may be included as a functional group for crosslinking a ketone group or an aldehyde group. Suitable compounds having an anthracene group are, for example, polycarboxylates having a molar weight of up to 5 μg/mc^. Particularly preferred. The ruthenium compound is preferably a dicarboxyl group having from 2 to 10 C atoms. Doc -22· 201127296 The acid is brewed. It includes, for example, diterpene oxalate, diammonium malonate, monodecyl succinate, diammonium glutarate, diammonium adipate, diterpene azelaic acid, diammonium maleate肼, bismuth fumarate, dipone of itaconic acid or spleen. Particular attention is paid to the following compounds: adipic acid, bismuth, bismuth sebacate and diammonium isophthalate. Suitable compounds having hydroxylamine or a singular group are described in detail, for example, in WO 93/25588. Alternatively, surface parent associations can be produced by means of an appropriate addition of an aqueous polymer dispersion (D). This includes, for example, the addition of a photoinitiator or a desiccant. Suitable photoinitiators are, for example, photoinitiators which are initiated by sunlight, such as derivatives of a clomazone or benzophenone. Suitable desiccant is a metal compound recommended for use in alcoholic saplings, such as c〇 or Mn based metal compounds (reviewed in U. Poth, P〇lyester und Alkydharze, Vincentz Network 2005, 183 f) In the page). The crosslinking component is preferably used in an amount of from 0.0005% by weight to 5% by weight, more preferably from 3% by weight to 2.5% by weight, based on the total weight of the monomers used for the polymerization (including the crosslinking agent), more preferably Specifically, it ranges from 1% by weight to 5% by weight. A polymer dispersion (pD) which does not contain a crosslinking agent in a copolymerized form constitutes a specific embodiment. The free radical polymerization of the monomer mixture can be carried out in the presence of at least one regulator. The amount of the regulator used is preferably from 0. _5% by weight to 5% by weight based on the total weight of the monomers used for the polymerization, and more preferably from 5% by weight to 25% by weight and more specifically from 0.01% by weight to 1.5% by weight. weight%. The term "regulator" (polymerization regulator) is generally used for compounds having a high transfer constant of 150132.doc -23· 201127296. The regulator accelerates the chain transfer reaction and thus reduces the degree of polymerization of the resulting polymer without affecting the overall reaction rate. Among the regulators, a monofunctional regulator, a bifunctional regulator, and a polyfunctional 6-week agent can be distinguished depending on the number of functional groups in the molecule capable of scooping up one or more chain transfer reactions. Suitable regulators are reviewed, for example, by KC Berger and G. Brandrup at J. Brandrup, EH Immergut, Polymer Handbook, 3rd edition 'John Wiley & s〇ns, New Y〇rk, 1989, II/81-II/141 In the page. Examples of suitable s Weekly agents include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyric acid and isobutylidene. Further, the following may be used as a regulator: formic acid, a salt or ester thereof, samarium ammonium, 2,5-diphenyl-1.hexene, hydroxylammonium sulfate and hydroxylammonium phosphate. A further suitable regulator is a halogen compound, examples of which are, for example, tetrachloromethane, gas imitation, > odorous tricarboacetate, smectite & propylidene, and such as benzyl gas or Benzoyl bromide benzyl compound. The octaplic 5 modulator is a dilute propyl compound such as allyl alcohol, a functionally diluted propylene (tetra)' such as allyl ethoxylate, leukolyl hydrazine or glycerol monoallyl ether. Suitable S regulators are inorganic acid sulfites, bisulfites and sulphite disulfites or organic sulfides, disulfides, polysulfides, and ^ which include di-n-butyl sulfide, two - n-octyl sulfide "diphenyl sulfide, thiodiglycol, ethyl thioethanol, diisopropyl disulfide, di-n-butyl disulfide, - r - oj. ▲ - · hexyl disulfide Ether, diethylidene disulfide, sulfurized diethanol, di-tert-butyl trisulfide, dimethyl sulfoxide, dialkyl sulfide, dioxane 150l32.doc •24- 201127296 bis-disulfide and/or Diaryl sulfide. Further, a thiol (a compound which retains sulfur in the form of a SH: group, also called a mercaptan) is also suitable as a polymerization regulator. Preferred regulators are monofunctional, difunctional and polyfunctional thiols, mercaptoethanols and/or mercaptocarboxylic acids. Examples of such compounds are allyl mercaptoacetate, ethyl mercaptoacetate, cysteine, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1 , 4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercapto succinic acid, thioglycerol, thioacetic acid, thiourea, and alkyl mercaptan, such as n-butyl mercaptan, n-hexyl Mercaptan or n-dodecyl mercaptan. Examples of bifunctionality regulators comprising two sulfur atoms in the form of a bond are, for example, difunctional thiols such as dimercaptopropane sulfonic acid (sodium salt), dimercaptosuccinic acid, dimercapto-1-propene Alcohol, dimercaptoethane, dimercaptopropane, dimercaptobutane, dibenzyl pentane, dimercaptohexane, ethylene glycol bis-decyl acetate and butylene glycol bis-decyl acetate. An example of a polyfunctionality modifier is a compound containing more than two sulfur atoms in the form of bonds. Examples thereof are trifunctional and/or tetrafunctional thiols. Preferably, a mercapto chain transfer agent is used to position the crosslinking sites at one end of the copolymer molecule to improve the cohesive strength of the cured composition. Preferred decyl decane chain transfer agents for use in the present invention have the general formula: HS-RS-SiR63_xZx wherein RS is a divalent alkylene group, R6 is an alkyl group, X is 1, 2 or 3, and Z is hydrolyzable. Group. The alkyl, alkyl and hydrolyzable groups are generally the same or similar to those described for the decane functional addition monomer. Suitable decyl decane chain transfer agents include γ-mercaptopropyltriethoxy decane, 150132.doc -25- 201127296 γ-mercaptopropyltrimethoxydecane, decylmethylmethyldimethoxydecane and the like Preferably, it is γ-silyltrimethoxy zephyr. The amount of key transfer agent used is similar to that disclosed in the prior art. When the second design was carried out, I tried to get more Shuji dreams. Is it possible to obtain more "basestones?" All of the modifiers can be used individually or in combination with each other. One specific embodiment relates to a polymer dispersion PD prepared by free radical emulsion polymerization without the addition of a regulator. For the preparation of polymers, the monomers can be polymerized by means of initiators which form free radicals. For initiators used in free radical polymerization, peroxy compounds and/or azo compounds which are commonly used for such purposes, examples It is alkali metal persulfate or persulfate, diethylperoxy peroxide, diphenyl peroxide, butyl bromide, di-tert-butyl peroxide, tert-butyl formate, peroxy Terpene acid third vinegar, peroxy-2-ethylhexanoic acid third vinegar, cis-butane dicarboxylic acid third butyl vinegar, cumene hydroperoxide, diamino carbamic acid diisopropyl vinegar , peroxy bis(o-benzonitrile), tridecyl peroxide, perindole-octyl, peroxidic dilaurin, perisobutyric acid, third vinegar, peracetic acid, third vinegar, Oxidized di-tertiary pentyl, hydrogen peroxide tert-butyl azobisisobutyl , 2,2,-azobis(2-methyl-l-propylpropan) dihydrochloride or 2,2,-azobis (2-methylbutyl). Mixtures of such initiators are also suitable. The initiator which can be used is a reduction/oxidation (= redox) initiator system. The redox initiator system consists of at least one reducing agent (usually inorganic 150132.doc -26 - 201127296 reducing agent) and an organic or inorganic oxidizing agent. The oxidizing component is, for example, an emulsion polymerization initiator as described above. The reducing component comprises, for example, an alkali metal salt such as sodium sulfite, sodium hydrogen sulfite, bismuth sulfite, such as sodium metabisulfite; a bisulfite addition compound of a aldehyde and a ketone, such as acetone bisulfite; or a reducing agent such as hydroxydecane sulfinic acid and a salt thereof, or ascorbic acid. The redox initiator system can be combined with a metal component A plurality of soluble metal compounds present in a valence state are used in combination. Examples of typical redox initiator systems include ascorbic acid/iron (II) sulfate/sodium peroxodisulfate, dibutyl hydroperoxide/sodium metabisulfite, hydrogen Oxidizing the second butyl/hydroxydecane sulfinate. Individual components, such as reducing components, may also be a mixture: an example is a mixture of sodium hydroxymethanesulfinate and sodium metabisulfite. The amount of the initiator is usually from 〇i to 10% by weight, preferably from 1% by weight to 5% by weight. Two or more different initiators may also be used in the emulsion polymerization. Preparation of a polymer dispersion (PD) in the presence of a surface active compound. A review of suitable protective colloids is found in Houben_Weyl,

Methoden der organischen Chemie, Volume XIV71, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961 pp. 411-420. Suitable emulsifiers are also found in H〇uben_Weyl, Methoden der organischen Chemie, Volume 14/1.

Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, pp. 192-208. Suitable emulsifiers include anionic emulsifiers, cationic emulsifiers and nonionic 150132.doc •27· 201127296 emulsifiers. It is preferred to use an emulsifier in a relative molecular weight as a surfactant. The molecule is generally lower than the protective colloid. The nonionic emulsifier is an araliphatic or aliphatic nonionic emulsifier. The ethoxylated single-yard age, ethoxylate A ethoxylated tricalcium phenol (EO degree '3 to 50, alkyl: C4_Ci.), long-chain alcohol ethoxylate (EO degree. 3 to 1 〇〇' alkyl) : c8_C36) and polyethylene oxide, polypropylene oxide homopolymer and copolymer. It may comprise an epoxy burn unit which is copolymerized in a random distribution or in the form of a block. For example, 〇 block copolymers are highly suitable. It is preferred to use an ethoxylate of a long-chain alkanol (alkyl Ci_C3〇, having an average degree of ethoxylation of 5 to 1 Å), and preferably having a linear Cl2-C2Q alkyl group and an average ethoxy group. An ethoxylate having a degree of 10 to 50 and an ethoxylated monoalkyl group. Examples of suitable anionic emulsifiers are alkali metal salts and ammonium salts of alkyl sulfates (alkyl groups: C8_C22), sulfuric acid and ethoxylation. Alkali metal salt and ammonium salt of monoester of alkanol (2:5 to 5 〇, alkyl: C^-C! 8), and sulfuric acid and ethoxylated alkylphenol (EO degree: 3 Alkali metal salts and ammonium salts of monoesters of 50, alkyl: c4-C9), alkali metal salts and ammonium salts of alkylsulfonic acids (alkyl: C12_c18), and alkylarylsulfonic acids (alkyl: Alkali metal salt and ammonium salt of C9-C18). Other suitable emulsifiers are found in Houben-Weyl, Methoden der organischen

Chemie ’第χΐν/l 卷,]\^1〇>〇111〇161<;111316 81;〇££6,〇6〇犷§-Thieme-Verlag, Stuttgart, 1961, pp. 192-208. One or two aromatic rings carrying a C4-C24 alkyl bis(benzenesulfonate) ether and an alkali metal or a salt thereof are also suitable as an anionic emulsifier. Such compounds are of general knowledge (e.g., from US-A-4,269,749) and may be, for example, Dowfax® 2Al (Dow 150132.doc -28 · 201127296)

The Chemical Company) form is commercially available. Suitable cationic emulsifiers are preferably quaternary ammonium compounds such as gasified tridecyl hexadecyl ammonium, decyl trioctyl ammonium chloride, phenyl decyl triethyl ammonium chloride, or N-Cs-Cm A quaternary compound of an alkylpyridine, N_C6_C2G alkylmorpholine or n_c6_Cm alkylimidazole, such as a gasified N-dodecylpyridinium. The amount of the emulsifier is usually from about 〇 〇丨 to 10% by weight based on the amount of the monomer to be polymerized. Λ, preferably 〇% by weight to 5% by weight. In addition, typical auxiliaries and additives can be added to the polymer dispersion (PD). Such auxiliaries and additives include, for example, cation regulators, reducing agents, and bleaching agents.

An alkali metal salt such as hydroxydecane sulfinic acid (eg from BASF)

Aktiengese Uschafe R〇ngalit (g) c), a binder, a deodorant fragrance, an odorant and a viscosity modifier such as an alcohol such as glycerin, decyl alcohol, ethanol first butanol, glycol or the like. These auxiliaries and additives can be added to the polymer dispersion in the initial charge, in one feed or after the poly σ L bundle. The pass* is from 〇C to 150 ° C, preferably from 20»c to 1〇〇〇c, more preferably 3〇. It is carried out at a temperature within the range of 咖. The polymerization is preferably carried out under atmospheric pressure without = poly σ can also be carried out under a south pressure, an example being a wide autogenous pressure for the components of the polymerization. For example, in a suitable embodiment, the polymerization is carried out in the presence of at least one inert gas such as nitrogen = or argon. ~ However, since the acrylic acid copolymer of the present invention includes an organic sputum having a hydrolyzable base® exposed to the ruthenium and hydrazine, it is in the (four) amount of water (which will cause organic (4) Performing polymerization in the case of premature hydrolysis and post-reaction, and hydrazine formation to form a siloxane coupling is important. 150132.doc •29·201127296 The polymerization of f should not react with the monomer and does not significantly affect the polymerization ( Such as by providing significant chain transfer effects). Therefore, the solvent content is preferably kept low, such as less than about 5% by weight of the reaction solution. Suitable solvents for the polymerization of an acrylic acid copolymer having a polymerizable monomer bonded to a Zeolite atom having a hydrolyzable group have been exemplified in the art and literature by benzene, toluene σ, MV, and IV. Gasified carbon, methyl acetate, ethyl acetate, dichloroethylene, acetone, and aromatic smoke and aliphatic cigarettes. 4 帛 dibutanol and other solvents, in the order of or u feed process (including staged or gradient VIII polymerization. Preferably the following feed process: where a bismuth polymerization batch or polymer is introduced ° and the basin is initially entangled, heated to the polymerization temperature to two::' then the remaining polymerization batch (usually one or more of the monomers in two or two or emulsified form) Including a purely shaped polymerization zone, which maintains a polypulping stage or is supplied with a concentration gradient to the polymerization process during the free-radical aqueous emulsion polymerization process. The way of adding the initiator is the way of adding the initiator. In the initial feed = known ° which can be fully included in the introduction of the polymerization capacity consumption rate continuous or stepwise = from the way known to the skilled person in the aqueous emulsion polymerization process, in various cases, this will be Preferably, the chemical nature of the polymerization system and the polymerization temperature are both to the polymerization zone. The initiator is included in the initial charge and the remaining initiator is supplied by the τ. In addition to the embodiment without the seed stick. , can also be prepared separately from the polymer dispersion (pd) Said to be the fine emulsion by the seed latex process 150132.doc • 30 · 201127296

A polymer dispersion (PD) having a prescribed particle size is prepared in the presence of a seed latex prepared in situ. Such polymerization processes are known and are described, for example, in Ep_B 40419, EP-A-6 14 922, EP A as 7 q 1η 4+ tP-A-567 812 and references cited therein and "Encydopedia of Polymer Science _ Techno" ^", Vol. 5, John Wiley & Sons Tnr, J ouns lnc., New Y〇rk 1966, p. 847. The polymerization is preferably carried out in the presence of 0.01% by weight to 3% by weight, preferably 〇2% by weight to 5% by weight of the seed latex (solid content of the seed latex, based on the total amount of the monomers). Preferably, the seed latex is added at the beginning. Further, the seed latex can also be prepared in the aqueous emulsion from a small amount of the monomer to be used for the polymerization and the surface active material by heating the emulsion to the polymerization temperature and adding a part of the initiator. After the polymerization procedure, the dispersion formed in the polymerization can be subjected to physical or chemical post-treatment. Examples of such processes are known processes for the reduction of residual monomers 'such as by adding a polymerization initiator at a suitable temperature or a mixture of two or two polymeric hair styling agents, by means of steam Or ammonia steam to post-treat the polymer solution 'either by stripping with an inert gas or by treating the reaction mixture with an oxidizing agent or reducing agent, such as an adsorption process that adsorbs impurities onto a selected medium, such as activated carbon, for example' Or perform ultrafiltration. The glass transition temperature of the polymer p obtainable by emulsion polymerization of at least one ethylenically unsaturated monomer M is preferably less than 5 (rc, more preferably less than 4 Å, especially less than 35 ° C. The dispersion (PD) generally has a solids content of from 2% by weight to 65% by weight, preferably from 35% by weight to 60% by weight. Alkoxydecane (B2) 150132.doc 31 201127296 According to the invention, alkoxydecane (B2) is an alkoxyfluorenyl monomer or a sulfhydryl group selected from the group of monomers listed in the group (v) with respect to the polymer dispersion (PD), as exemplified as the sulfhydryl chain transfer agent. The compound Oxygen Stone Court (B2) can be used individually, in the form of a mixture of a kind of alkaloids or in the form of a mixture of different types of alkoxydecane. The alkoxyline compound (B2) is preferably used in comparison with The total weight of the component b is in the range of 重. 〇1% by weight to 5% by weight. Particularly preferably, the alkoxylated compound (B2) is 0.01% by weight to 3% by weight based on the total weight of the component B. 'Extremely preferred. 〇1% by weight to 〇.5% by weight. b) a prepolymer obtained in step (b) of the present invention in the hydrolysis and polycondensation step (a) in the presence of: - water, and - at least one antimicrobial agent (Z) comprising at least one antimicrobial The active agent (Z1) and optionally the particulate carrier material (Z2), wherein the at least one antimicrobial active agent (Z) does not react during the step (b). The term "antimicrobial active agent" means having an antimicrobial agent The active compound 'wherein the compound may be an organic molecule, an inorganic or organic ionic substance or a particulate substance. Step (b) may be carried out by a number of different means. It may be used to dissolve component (A) and/or (B) An aqueous solvent to achieve the presence of water, such as acetone, which is the preferred solvent. In this way, the hydrolysis and initial polycondensation are required 150132.doc •32· 201127296. It can also be added independently before step (b). The water is inherently present in the system. Step (b) can also be carried out at temperatures up to or from 30 ° C to 1 Torr. Also at &, especially 30 ° C to 60 ° C high temperature

Step (b) is such that a coating is formed. Hydrolysis and polycondensation occur in the back. Preferably, in other words, the formation of the composition of the present invention and the coating on the substrate occurs simultaneously. The catalyst may be utilized to catalyze the hydrolysis and polycondensation of step (b) as appropriate. Suitable catalysts such as acids and bases are known to those skilled in the art. Step (b) produces a polymeric network containing the antimicrobial active (Z1). The anti-microbial active agent (Z1) is not covalently bonded to the ceria network obtained during step (b) and can be automatically released or released upon triggering in certain embodiments. Step (b) comprises condensing the hydrolyzed decyloxy group to form a cerium oxide network which is covalently bonded to the polymer and which contains the antimicrobial active agent (Z1) in an embedded form rather than a covalently linked form. Preferably, the composition of the present invention retains the antimicrobial active agent (Z1)' which releases the antimicrobial active agent (Z1) in the presence of water. Antimicrobial Agent (Z) The antimicrobial agent (Z) may consist of a single antimicrobially active compound (Z1), consisting of a mixture of two or more different antimicrobially active compounds (Z1) or a carrier in the form of particles. A mixture of one or more of the substances (Z2) or a mixture of more than one antimicrobially active compound (Z1). According to the invention, at least one antimicrobial active agent (Z1) is not required to react between step (b) 150132.doc • 33· 201127296. The term "non-reactive" means that the antimicrobial active agent (zi) does not react during the step (8), i.e., does not co-react with the prepolymer during the hydrolysis and polycondensation reaction in the presence of water. The terms "reactive" and "reactive" refer to chemical reactions, i.e., different from physical interactions such as retention, to form chemical bonds. In other words, "no reaction during the step (b)" means that the chemical bond is not substantially formed with the antimicrobial active agent (ζι) during the step (b). Step (b) comprises further polymerizing the prepolymer by preferably reacting the component (B2) covalently bonded to the prepolymer by means of hydrolysis and polycondensation. The antimicrobial active agent (Z1) preferably does not contain any functional groups capable of reacting with the si 〇 H group, and the Si-OH groups are preferably present in the form of an intermediate in the step (b). In other words, the antimicrobial active agent is not covalently bonded to the inorganic portion of the mixed network formed during step (b). In principle, any antimicrobial agent (Z) can be used under the conditions defined above. In a preferred embodiment, the antimicrobial agent (z) contains not only the antimicrobial active agent (zi)' but also the particulate carrier material (Z2). In a specific embodiment, the carrier material (Z2) may have a reactive group capable of reacting during the step (b) on the surface. According to a first preferred embodiment 'hereinafter referred to as "PE-丨", the antimicrobial agent (Z) comprises silver ions as an antimicrobial active agent (z 1) and a group selected from the group consisting of zeolites and polymer hydrogels. Particulate carrier material (22). According to a second preferred embodiment, hereinafter referred to as r PE_2", the antimicrobial agent (Z) comprises a titanium oxide selected from the group consisting of (1) zinc oxide and (Π) containing AgBr and apatite. 150I32.doc • 34- 201127296 Granular antimicrobial active agents having a particle size of 1 to - are known as AgBr and whey encapsulated titanium dioxide. It is known to those skilled in the art that AgBr is known to enhance the photocatalytic and/or antimicrobial efficacy of titanium dioxide. Apatite encapsulation is known to help prevent degradation of the surrounding organic polymer. According to a third preferred embodiment, τ is referred to as "pE_3", and the antimicrobial agent (Z1) is selected from the group consisting of a quaternary ammonium salt and a bromo-2-nitropropane·1>3-diol. At least one of them. The preferred embodiments pE_1, PE_2, and pE_3 are discussed in detail below. According to a preferred embodiment PE_i, the antimicrobial agent (z) comprises silver ions as the antimicrobial active agent (Z1) and a group selected from the group consisting of zeolites and polymer hydrogels as the particulate carrier material (Z2). In principle, any zeolite capable of retaining silver ions is suitable as the particulate carrier material (Z2) of the present invention. Zeolite particles which retain silver ions of antimicrobial properties are known from the prior art. For example, silver <RTI ID=0.0>>>> These zeolites may be modified by organic comonomers such as: acrylic acid ginsyl (2-acetoxyethyl dimethyl decyloxy) decyl propyl acrylate and thioglycol ginseng (2-Ethyloxyethyl dimethyl fluorene oxime) 矽 基 丙 丙, 150132.doc -35- 201127296 acrylic acid (tetrakisylethyl dimethyl hydroxyoxy) (tetra) propyl glycerol Phthalate (2, ylethyl dimethyloxy) (tetra) propyl vinegar, acrylic acid ginseng (3-propyl propyl dimethyl oxalate alkoxy) oxalate propyl vinegar and f Acrylic acid ginseng (3-hydroxypropyl decyl decyloxy) decyl propyl acrylate, acrylic acid vinegar and methyl acrylate acid functionalized by IL substituted aryl / aryl oxime, such as: acrylic ginseng ( 3,3,3·trisyl:methyl(tetra)oxy)glycol propyl and methacrylic acid ginseng (3,3,3-difluoropropyl decyl decyloxy) decyl propyl acrylate, acrylic acid ginseng 3-heptafluoroisopropoxypropyl)] dimethyl decyloxy decyl propyl propyl ester and methacrylic acid ginseng [3-heptafluoroisopropoxy propyl decyl decyl alkoxy sulphide , acrylic acid (pentafluorophenyl dihydrazide) Alkoxyalkyl) decyl propyl acrylate and methacrylic acid quinone (pentafluorophenyl dimethyl decyloxy) decyl propyl propyl ester, and other or containing a stagnation chain transfer agent. The preferred brewing base chain transfer agent for use in the present invention has the following formula: HS-RS-SiR63.xZx wherein RS is a divalent alkylene group and R6 is an alkyl group. 2, 3, and Z is a hydrolyzable group. The alkyl, alkyl and hydrolyzable groups are generally the same or similar to those described for the decane functional addition monomer. Suitable decyl decane chain transfer agents include γ-mercaptopropyltriethoxy decane, γ-mercaptopropyltrimethoxydecane, fluorenylfluorenyl decyloxydecane, and the like, preferably γ- Mercaptopropyltrimethoxydecane. The amount of chain transfer agent used is similar to that disclosed in the prior art. 150132.doc -36 · 201127296 Polymer hydrogels which retain silver ions are also known from the prior art. Principles A polymer hydrogel having a sufficient amount of nuclear ions can be used as the particulate carrier material (Z2) of the present invention. The term "gel" refers to a material containing a liquid phase and a solid phase composed of a (also long P) knife that is connected to form a three-dimensional network. The polymerization network is embedded in a liquid medium. The gel preferably has a bicontinuous phase. Hydrogel refers to a gel in which the liquid phase is water. The polymer of the water shouting glue is the main clock culvert. The key hang is formed by a hydrophilic monomer unit and can be neutral or ionic. Examples of neutral and hydrophilic monomer units are ethylene oxide 'vinyl alcohol' (meth) acrylamide; N-alkylated (mercapto) acrylamide; N-methyl (meth) propyl Dilute amine; N_ethenylamine; n_ethylene decylamine; N_vinylacetamide; N-vinyl-N-mercaptoacetamide; N_vinyl m-carbamide; Hydroxyalkyl (meth) acrylate such as methacrylic acid m-ethyl s s; ethylene _ a ketone; polyethylene glycol mono propyl propyl, allyl ether, polyethylene glycol (meth) acrylate An ester; a sugar unit such as glucose or galactose. Examples of cationic hydrophilic monomer units are ethylenediamine (in protonated form), vaporized diallyldimethylammonium chloride and trimethylammonium chloride propylmethacrylamide. Examples of anionic monomer units are (mercapto)acrylic acid, crotonic acid, maleic acid 'fumaric acid, itaconic acid, 2-propylene acrylamido-2-methylpropane sulfonic acid, vinyl Sulfonic acid, vinylphosphonic acid, 2-methacryloxy ethanesulfonic acid, 4-vinylbenzenesulfonic acid, allyl acid, vinyl toluenesulfonic acid, and vinyl phenylphosphonic acid (the compound Each is in a deprotonated form). In addition, unsaturated acids (eg, acrylic acid, methacrylic acid, and acrylamidopropane sulfonic acid) can be obtained by the presence of a small amount of a rare compound 150132.doc-37-201127296 unsaturated compound containing a specific organic cation comonomer. Polymerization to obtain a hydrogel suitable for use as a particulate carrier material (Z2) - such organic oxime comonomers such as: acrylic acid (2-acetoxyethyl dimethyl decyloxy) decyl propylene (2-Ethyloxyethyl dimethyl decyloxy) decyl propyl methacrylate, bis(2-carboxyethyl dimethyl decyloxy) decyl propyl acrylate and thioglycol ginseng (2-Carboxyethyl dimethyl decyloxy) decyl propyl acrylate, propylene (3-hydroxypropyl dimethyl decyloxy) decyl propyl acrylate and methacrylic acid ginseng (3 - hydroxy propyl dimethyl Alkoxyalkyl) decyl propyl acrylate, acrylate and methyl acrylate functional fluoro substituted alkyl/aryl oxacyclooxane, such as: acrylic acid ginseng (3,3,3-trifluoropropyl Dimethyl sylvestre oxy) sulphate and decyl acrylate (3,3,3 -trifluoropropyl Alkyl oxyalkyl) propyl propyl acrylate, acrylic acid [3-heptafluoroisopropoxypropyl)] dimethyl decyloxy decyl propyl propyl thiophene Fluoroisopropoxypropyl)] dimethyl oxa oxime oxime ketone propyl S, acrylic acid (pentafluorophenyl dimethyl fluorenyloxy) decyl propyl acrylate and thiol acrylate ( Pentafluorophenyl decyl decyloxy) decyl propyl propyl ester, and other materials known as supersorbent polymers. In a preferred embodiment, the antimicrobial agent (Z) contains not only the antimicrobial active (Z1) but also the particulate carrier material (Z2). In a particular embodiment, the carrier material (Z2) may comprise on the surface a reactive group capable of reacting during step (b). Such hydrogels are described, for example, in US-P 4,057,521, US-P 4,062,817, 150132.doc -38-201127296

US P 4,525, 527, US-P 4, 286, 082, XJS-P 4, 340, 706 and US-P 4,295, 987. Hydrogels obtainable by graft copolymerization of ethylenically unsaturated acids on different substrates (e.g., polysaccharides, polyalkylene oxides, and derivatives thereof) are also suitable as particulate carrier materials (Z2). Such graft copolymers are known, for example, from US-P 5,011,892, US-P 4, 〇76,663, and US-P 4,93 1,497. Hydrogels are typically dried after they have been comminuted using known contact or convection drying processes. Examples of contact dryers are heating plates, membranes, cans, contact strips, screen cylinders, screw, rotary or contact tray dryers. Examples of convection dryers are trays, chambers, channels, flat screens, plates, drums, free fall axes, screen belts, flow, atomization, fluidized bed, moving bed, paddle or spherical bed drying. (Kirk-Othmer 7, 326-398; (3rd edition) 1, 598-624; 8, 75-130, 3 1 1-339; 5, 104-112; Ullmann 1, 529-609; Ff.; (4th edition) 2, 698-721; vt Industrielle Praxis: Fortschritte auf dem Gebiet der Einbandtrockner", Teil 1. Auslegungsverfahren, E. Tittmann ϊ Research Disclosure 96-38363: "Drying of Pasty Materials using a Continuous Through -Circulation Belt Dryer"). • The hydrogel used in the present invention is preferably lightly crosslinked. The vinyl, non-vinyl or two-mode cross-linking agent may be used as a crosslinking agent singly, in the form of a mixture or in various combinations. Polyethylene crosslinkers which are advantageously used in the superabsorbent polymer are generally known in the art. Preferred compounds having at least two polymerizable double bonds include: a divinyl compound or a polyethylene compound such as acetophenone, monothylene toluene, diethylene xylene, diethyl squama, diethyl propylene 150132.doc-39 - 201127296 ketene and divinylbenzene; unsaturated monocarboxylic or unsaturated polycarboxylic acid and diester of polyester or polyester, such as di-(meth) acrylate or tris (meth) acrylate of polyol Esters, such polyols are, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylolpropane, glycerin, polyoxyethylene An alcohol and a polyoxypropylene glycol; an unsaturated polyester obtainable by reacting any of the above polyols with an unsaturated acid such as maleic acid; an unsaturated monocarboxylic acid or an unsaturated polycarboxylic acid and a poly 7G alcohol a diester or a polyester produced by the reaction of a C2_Ci 〇 polyol with 2 to 8 CrC4 alkylene oxide units per hydroxy group, such as trihydromethane propane hexaethoxylate triacrylate; The polyepoxide is reacted with (meth)acrylic acid to obtain the second Acrylate or tris-(meth) acrylate; bis(meth) acrylamide, such as N,N-methylene bis decylamine; by making a vinegar such as isoamyl lactate, A polyisocyanate of 4,4'-diphenyl isocyanate and an NC-containing prepolymer obtained by reacting the diisocyanate with an active hydrogen atom-containing compound. An amine oxime ester obtained by reacting a hydroxyl group-containing monomer such as a mono-(mercapto) propyl methacrylate obtained by reacting the above diisocyanate with hydroxyethyl (meth) acrylate; Di-(indenyl) allyl ether or poly(indenyl) allyl ether of diols, glycerol, polyalkylene glycols, polyoxyalkylene polyols and polyols of carbohydrates, such as polyethylene glycol Diallyl ether, allylated starch and allylated cellulose, poly-acidified bis-dipropyl or propylene glycol, such as diallyl phthalate and diene adipate Propyl ester; and an ester of an unsaturated monocarboxylic acid or an unsaturated polyphenolic acid with a mono (meth)allyl ester of a polyhydric alcohol, such as allyl mercapto acrylate or Of ethylene glycol monoallyl ether (Yue-yl) acrylate. 150132.doc -40· 201127296 Preferred classes of crosslinking agents include, for example, bis(indenyl) acrylamide; allyl (meth) acrylate; diesters or polyesters of (meth)acrylic acid and polyols, such as Diethylene glycol diacrylate, trihydroxymercaptopropane triacrylate and poly(ethylene glycol diacrylate); and unsaturated monocarboxylic acid or unsaturated polycarboxylic acid and by using a core. A diacetate or polyester of a polyol produced by reacting a polyol with 2 to MigC2_C4 alkylene oxide units per hydroxyl group, such as ethoxylated trimethylolpropane triacrylate. The antimicrobial agent PE according to the preferred embodiment PE-1 contains silver ions as the antimicrobial active agent (Z1). The antimicrobial active agent (z丨) is preferably present in the form of a silver salt. Examples of the silver salt include, for example, silver acetate 'silver acetyl acetonate, silver azide, silver acetylide, silver arsenate, silver benzoate, silver difluoride, silver monofluoride, silver fluoride, silver fluoroborate , silver bromate, silver bromide, silver carbonate, silver chloride, silver silicate, silver chromate, silver citrate silver cyanate, silver cyanide (cis, cis-1,5-cyclooctadiene) -l,l,i,5,5,5-hexafluoroacetoxypyruvate silver, silver dichromate ruthenium (pyridine) complex, silver diethyldithiocarbamate, silver fluoride (I ), silver (II) fluoride, 7,7-dimethyl-l,l,i,2,2,3,3-heptafluoro-4,6-octanedioic acid, silver hexafluoroantimonate, six Silver fluoroarsenate, silver hexafluorophosphate, silver iodate, silver iodide, silver isothiocyanate, potassium silver cyanide, silver lactate, silver molybdate, silver nitrate, silver nitrite, silver oxide (I), silver oxide (Π ), silver oxalate, silver peroxylate, silver perfluorobutyrate, silver perfluoropropionate, silver permanganate, silver perrhenate, silver phosphate, silver picrate monohydrate, silver propionate, silver selenate, Silver selenide, silver selenite, silver sulfadiazine, silver sulfate, silver sulfide, silver sulfite, silver telluride, four Silver borate, silver tetraiodide, silver tetratitanate, silver thiocyanate, p-I50132.doc •41 · 201127296 Silver benzenesulfonate, silver trifluorosulfonate, silver trifluoroacetate and silver vanadate . Mixtures of various silver salts can also be used. Preferred silver salts are silver acetate, silver benzoate, silver bromate, silver chlorate, silver lactic acid, silver molybdate, silver nitrate, silver nitrite, silver oxide (I), silver peroxyacid, silver sulphate, Silver citrate, silver sulfite, and amine feeding. Silver and silver sulfate. The best silver salts are silver acetate and silver nitrate. Mixtures of silver salts can also be used. The preferred silver content in the hydrogel is from 0.01% by weight to 0.7% by weight based on the total dry weight of the hydrogel. According to the preferred embodiment PE-2, the antimicrobial agent (z) comprises a particulate antimicrobial active agent (z丨) having a number average particle size of from 1 to 5 nm selected from zinc oxide and titanium dioxide containing AgBr and apatite. . The number average particle size refers to the value determined by the combination of TEM measurement and image analysis. The number average particle size of the particulate antimicrobial active as component (Z1) is preferably in the range of 5 to 1 〇〇 nm, especially 1 〇 to 5 〇 nm, particularly preferably 15 to 45, and most preferably 20 to 40 nm. Inside. Stabilizing particles using an antimicrobial active agent (z丨) Zinc is preferably stabilized by means of an acrylic polymer. Further, zinc oxide doped with a dopant as described in US_A 2〇〇5/〇〇48〇1〇 is preferably used. The dopant can be added to the zinc oxide dispersion by a method known to those skilled in the art. Suitable dopants for zinc oxide are, inter alia, metal ions of the outer shell or less than one electron. Group J metals in the oxidation state + III are particularly suitable. Extremely preferred are boron (1) I), aluminum (work) 150132.doc • 42- 201127296 gallium (III) and indium (III). These metals can be added to the dispersion in the form of soluble salts. The choice of metal salt depends on whether The desired concentration is dissolved in the dispersant. In the case of aqueous dispersions, many inorganic salts or complexes are suitable 'such as carbonates, halides, salts with EDTA, nitrates, salts with EDTA Ethyl pyruvate or the like may also be doped with a noble metal such as palladium, ruthenium, gold, etc. It is especially preferred to use surface-modified zinc oxide nanoparticles as an antimicrobial active agent (Z1). The surface modification is known to those skilled in the art and is described, for example, in US-A 2006/0210495, which is incorporated herein by reference. The surface modification agent is applied to the dispersion containing the nanoparticles to achieve surface modification. The details of the 'suitable surface modifiers are disclosed in paragraph 89 (page 5) to paragraph 183 of US-A 2006/0210495 (the first 6 pages). It can also be used as described in US-A 2007/0243 145 The polymer is described to modify the surface of the ZnO nanoparticle, the contents of which are incorporated herein by reference. The polymers for modifying the surface of the Zn nanoparticles are preferably used for the purpose of the present invention. Selected from copolymers as described in paragraphs 18 (page 2) to 35 (page 3). From MR Elahifard, S. Rahimnejad, S. Haghighi, MR Gholami, J. Am. Chem. Soc 2007; 129(31); 9552-9553 Suitable titanium dioxide containing AgBr and apatite is known. The TiCh used in the present invention is preferably surface-modified, in particular by surface modification by means of calcination as a surface modifier. .doc -43 - 201127296 The different decanes that are suitable as surface modifiers are listed in the literature, the entire contents of which are hereby incorporated by reference, in particular: - US-P 6,013,372, column 13 54 columns) to 14th stop (column 54), -US-P 6,663,851, column 2 (column 9) to block 2 (column 54), and -US-A 2006/0159637, paragraph 44 ( Page 2) to 83 (page 3). Two or more of the above-mentioned Shi Xi can be used for surface modification. A mixture of calcined. It is also preferred to use a photocatalyst having an antibacterial enhancer as described in US-P 6, 〇 13, 372, the contents of which are hereby incorporated by reference, in particular It is further preferred to use a doped photocatalyst as described in US-P 6013372, page 15, lines 25-30. U.S. Patent Nos. 6,627,173, 7, 17,591, and 5,575,5, each of which are incorporated herein by reference to the entire disclosure of the disclosure of the the the the the the the In a preferred embodiment, Ti02 is coated with apatite calcium as described in US-A 2007/01543 78, the contents of which are hereby incorporated by reference, in particular 16 segments (page 2 According to the third preferred embodiment "PE-3", the antimicrobial agent (Z1) is selected from the group consisting of a quaternary salt and a 2-bromo-2-propane-propane-1,3-diol At least one of the group consisting of. Preferred quaternary ammonium salt is gasified benzyl-alkyldicylidene ammonium, hydrogen peroxide [2-[[2-[(2-methyl))) Amino]ethyl]amino group μ2·sideoxy-ethyl] cocoa dimethyl ammonium, benzyl chloride, Ci2i4 alkyl dimethyl ammonium, benzyl chloride-Ci^6 Alkyl dimethyl ammonium, gasified benzyl-(: 12.18 alkyl-di 150I32.doc -44 - 201127296 decyl ammonium, gasified C^m alkyl [(ethylphenyl) methyl] dimethyl Base record, reaction product of n_Cio·!6 alkyl propylenediamine and gas acetic acid, vaporized di-C8 i〇; J^-based monomethyl, two-compartment (C8·^) dimethyl money compound, Gasification of dimercapto-indenyl, hexachloropyrustyylpyrazine, hydrazin-2-ol, bronopol, cetylpyridinium chloride, gas Phenol, gas bis-phenanthrene, 'D-gluconic acid and N,N,,-bis(4-a-phenyl)-3,12-diimido-2,4,11,13-tetrazo a compound of heterotetraoxane dioxane (2:1), ethanol, formaldehyde, citric acid, glutaraldehyde, hexa-2,4-dienoic acid, fluorenyl-phenoxypropan-2-ol and 2-phenylene oxide Propyl alcohol oligo-(vaporized 2-(2-ethoxy)ethoxyethyl sulfonium salt), bis(peroxymonosulfuric acid) bis(sulfate) pentapotassium salt, 2-phenoxyethanol, O-phthalaldehyde, 6-(o-o-xamethyleneimine) peroxyhexanoic acid, poly(chlorinated hexamethylenediamine sulfonium salt), (£,£)_hexyl-2-propenoate , propylene-alcohol, propan-2-ol, hydrazine hydroxy sulfonium salt, o-phenylphenol and o-phenylphenol salt, helium gas chloroallyl)_3,5,7_triaza 1-azaindene adamantane salt, (5_gas-2,4-dichlorophenoxy)-phenol, 3,4,4,-tris-phenylurea (tricl〇carban), O-benzo-p-phenol hydroxy-p-hydroxyformate, 2-(thiocyanomethylthio)benzothiazole, 3,5-diindenyl-1 I3,5-thiodiazepine-2- Thiol, 2,4-di-benzene benzyl alcohol, especially in the car, using 2-bromo-2-nitropropane 丨, 3 diol It is an antimicrobial active agent (Z1). The following preferred examples refer to the preferred examples pE_丨, pE 2 and PE-3 outlined above. The presence of the antimicrobial agent Z based on the total dry weight of the composition The amount is preferably from 1% by weight to 10% by weight. The total dry weight refers to the weight of the composition after removal of the solvent. 150I32.doc • 45- 201127296 In a preferred embodiment, the composition of the present invention is further contained in An antimicrobial component (z,) which is capable of reacting with components (A) and/or (B). + Therefore the 'antimicrobial component (Z1) is covalently bonded to the resulting mixed network. The preferred antimicrobial agent (Z') comprises an alkoxy oxime moiety and is represented by the following formula (II): Χ·r2-N-R4-Si(〇R5)3

(Π) wherein -RigCi-Cw alkyl ' is preferably c8-C3 alkyl, -R2 and R3, RAR5 are each independently Cl_c3() alkyl or hydrogen, and _X is a relative ion 'such as Cl-, Br-, I- or CH3COO-. An example of an organophosphonium quaternary ammonium salt compound used in accordance with the present invention is gasified 3-(triethoxydecyl)-propyl-didecyloctadecyl ammonium, vaporized 3_(tri-decyloxydecanealkyl) Propyl-methyl-dioctylammonium, gasified 3_(tridecyloxyphosphonylalkyl)propyl·didecylmercaptoammonium, 3-(tridecyloxydecyl)propyl chloride Methyldimercaptoammonium, gasification of 3_(trimethoxy-decyl)propyldimethyldodecylammonium, gasification of 3-(tris-decyloxydecyl)-propyl-fluorenyl double Dodecyl ammonium, gasified 3-(trimethoxydecylalkyl)propyl·dimethyltetradecyl ammonium, gasified 3-(trimethoxy-decyl)propyl-fluorenyl double Hexaalkylammonium and gasification. 3-(Dimethoxymethoxyoxane)propyl-dimethyloctadecyl ammonium. The antimicrobial agent (Z,) is preferably present in the composition in an amount of from about 1% to about 5% by weight relative to the dry weight of the composition. The preferred amount of antimicrobial agent is from 1% to i 〇 0 / Torr of the composition, based on the dry weight of the composition. 150132.doc • 46- 201127296 Other components The composition of the present invention preferably further comprises a solvent (D). Examples of the solvent (D) are alcohols, esters, ester alcohols, ethers, ether alcohols, aromatic and/or (%) aliphatic hydrocarbons and mixtures thereof and hydrocarbons. Alcohol can also be introduced into the mixture via an amine based resin. Preferred are alkyl alkanoates, alkyl alkanoates, alkyl alkanoates and mixtures thereof. Examples of the ester include, for example, n-butyl acetate, ethyl acetate, cesium-methoxypropan-2-yl acetate, and 2-methoxyethyl acetate, and ethylene glycol, diethylene glycol, and triethylene glycol. , propylene glycol, dipropylene glycol or tripropylene glycol monoethyl decyl ester and diethyl hydrazine S are intended to be brewed such as ethylene glycol acetate. Other examples are also carbonated, such as preferably carbolic acid & ethylenediacetate, carbonic acid & propylene glycol or 1,3 - propylene dicarbonate. The ethylenediyl ether is, for example, tetrahydrofuran (THF), dioxane, and ethylene glycol, alcohol, triethylene glycol, propylene glycol, propylene glycol or tripropylene glycol, diethyl ether or di-n-butyl ether. ▲ Alcohols are, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, second butanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-dodecanol (laurel Alcohol), 2-ethylhexanol, cyclopentanol or cyclohexanol. (4) (4) For example, poly(C"C3m diol (Ci^4) single-base acetazide. (iv) (iv) such as poly(6) to (iv): alcohol: heart ke, propylene glycol dimethyl ether, preferably ethylene glycol butyl Ether. J di-smoke mixture is a mixture mainly containing aromatic fluorene, and can contain a full range of 3 〇〇C, especially preferably f benzene, o-dimethyl hydride 150I32.doc • 47· 201127296 benzene, m-dioxene Or p-terpene benzene, triterpene benzene isomer, tetraterpene benzene isomer, ethylbenzene, cumene, tetrahydronaphthalene, and mixtures thereof. Examples thereof are Solvesso® grades from ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, mainly C9 and C 丨〇 aromatic compounds, boiling range is about 154. (: -178 ° C), Solvesso® 150 (boiling range is about 182 ° C - 207 ° C) ) and Solvesso® 200 (CAS No. 64442-94-5), and Shellsol® grades from Shell 'Caromax® grades from Petrochem Carless, such as Caromax® 18, or products from DHC, such as Hydrosol® A/170. Hydrocarbon mixtures containing paraffins, naphthenes and aromatics are also available under the following names: Kristalloel (eg, Krist) Alloel 30 'boiling range is about 158 ° C - 198 ° C ' or Kristalloel 60 : CAS No. 64742-82-1), white petroleum brain (similarly 'such as cas number 64742-82-1) or solvent oil (light: The boiling range is about i55^_18〇〇c, and the weight: the boiling range is about 225 C _3006 C. The aromatic compound content of the hydrocarbon mixture is usually greater than 90% by weight. Preferably, it is greater than 95% by weight, more preferably greater than % by weight and preferably more than 99% by weight. It is preferred to use a hydrocarbon mixture having a particularly low naphthalene content. The density of smoke at 2 ° C (DIN 51757) may be less than 1 g/cm3, preferably less than 0.95 g/cm3. More preferably, it is less than 〇9 g/cm3. The content of ruthenium is usually less than 5% by weight 'preferably less than 2.5% by weight and more preferably less than 1% by weight. Toothed hydrocarbons are, for example, benzene and diphenylbenzene or their isomers. (%) Known hydrocarbons are, for example, decalin, alkylated decalin, and isomer mixtures of linear or branched bond soot and/or cycloalkanes. 150132.doc • 48 - 201127296 Acetic acid 1- The methoxypropan-2-yl group is preferably n-butyl acetate, ethyl acetate, 2-methoxyethyl acetate and mixtures thereof, which may be from 10:1 to 1:10. The volume ratio is more preferably prepared in a volume ratio of 1 · 1 by volume, preferably in a volume ratio of 5:1 to 1:5. , 1:1 methoxypropyl acetate / dioxane 1:2 butyl acetate / Solvesso® 100 Preferred examples are butyl acetate / dimethyl benzene, 1:1 butyl acetate / solvent oil 10 〇, and 3 :1 Kristalloel 30/Shellsol® A. The alcohol is, for example, methanol, butanol, isobutanol, pentylhexanol or octanol ethanol, normal diol, isopropanol, n-butanol, a second alcohol isomeric exemplified, a mixture of hexanol isomers, Examples of other typical coating additives (E) that may be used include antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, mutating agents, Surfactant, viscosity modifier, plasticizer or chelating agent. In addition to the (co)polymerized (co)polymer, the suitable leveling agent also includes /, 51 thickening agent and inorganic thinning agent, such as the mixture of methyl cellulose or bentonite 0 can be used. Examples include ethylenediamineacetic acid and its #, and diketone. The δ-filler contains bismuth citrate, an example of which can be obtained by hydrolysis of tetragas hydrazine (blocking such as Aerosil® from Degussa), Shixiazao, talc, Shixi acid, and Shishi acid lock. Carbonated mom and so on. Suitable stabilizers include typical UV absorbers such as oxalic acid, triazine and benzobisazole (the latter available from Ciba-Spezialit Stenchemie as Tinuvin® 150132.doc -49-201127296) and benzophenone. It may be used alone or in combination with a suitable radical scavenger, examples of which are hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di- Tributyl piperidine or a derivative thereof, such as bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate. The stabilizer is usually used in an amount of from 1% by weight to 5% by weight based on the solid component contained in the preparation. Pigments can also be included. According to CD R6mpp Chemie Lexikon - page 1. ' Stuttgart / New York: Georg Thieme Verlag 1995, see DIN 55943 'Pigments are particulate organic or inorganic colored or colorless colorants which are almost insoluble in the media towel. Almost insoluble here means 25. The underarm solubility is less than 1 g per § application medium, preferably less than G.5 g per glang medium, and better than 0.25 g for g application medium, which is better than gJ| And especially below 5 g per 1000 g of application medium. Examples of the eight pigments include any desired system for absorbing pigments and/or effect pigments, preferably absorbing pigments. There are no restrictions on the number and choice of pigment components. For example, it can be adapted depending on the color effect. Insufficient need (please refer to all the pigments that have a sheet-like shape and give a specific decorative color effect to the surface coating.) Vehicles include "For example, pigments that can be used generally for Μ Μ Μ Such effects are pigments, such as sulphur, iron or copper pigments; interfering with titanium oxide coated mica, iron oxide coated mica, coated mica (eg via titanium dioxide and Fe2〇3 or dioxane). 150132.doc 201127296 Titanium and CoO3 coating), metal oxide coated aluminum; or liquid crystal pigment. The color of the day and the pigment are, for example, typical organic or inorganic absorbing pigments that can be used in the coating industry. Examples of organic absorbing pigments are azo pigments, ugly cyanine pigments, quinone ketone pigments and materials, and % pigments. Inorganic absorbing pigments are exemplified by iron oxide pigments, titanium dioxide and carbon black. The coatings and in particular can be used as primers, topcoats or as clearcoats and/or basecoats in clearcoat/basecoat compositions. They are also suitable for spray application. Providing, in one step, a coating material in the form of an aqueous composition comprising: _ at least one binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (pd), as defined above - at least one antimicrobial agent (Z), as defined above, - up to 70% by weight, preferably from 1.1% by weight to 7% by weight of inorganic filler and / or inorganic pigment, -0.1% by weight to 20% Typical auxiliaries of % by weight, and 'up to 100% by weight of water. The aqueous coating material for the purpose of the present invention means that the continuous phase of the coating material is from more than 80% by weight, preferably 90% by weight, of water. In particular, it consists solely of water. Further, it may comprise a water-miscible liquid such as a water-soluble monohydric alcohol (for example, isooctanol), a diol (such as diethylene glycol dimethyl ether), and a polyol as 150l32.doc-51. 201127296 Part of the continuous phase. The adhesive composition of the present invention is preferably used in aqueous coating materials, such as in the form of an uncolored system (clear varnish) or a coloring system (latex or latex varnish coating). Part of which is available The volumetric concentration (PVC) is used to describe the ratio of the volume of the pigment (vp) and the filler (Vf) relative to the total volume. The total volume is composed of the volume of the binder, pigment and filler of the dried coating film. Percentage: PVC = (Vp + Vf) x 100 / (Vp + Vf + Vb). Coating materials can be classified based on PVC, for example as follows: Highly filled interior paint, washable, white / matt about 85 65- 80 Approx. 35 Approx. 25 12-30 30-65 0 Indoor paint, scrub resistant, white/matte semi-gloss paint, mercerized-matt semi-gloss paint, mercerized light paint exterior masonry paint, white clear varnish A composition of a latex paint. The latex paint typically comprises from 5% by weight to 75% by weight and preferably from 4% by weight to 65% by weight of non-volatiles. These ingredients mean all non-aqueous ingredients in the formulation, but at least; ° ^ filler, pigment, low volatility solvent (boiling point above 22 )) such as the total weight of plasticizers and polymerization aids. This figure generally indicates the following, a "% by weight to 90% by weight, more specifically 1 〇 weight of the dispersion dispersion (PD), 〇 / 〇 / b) 5 wt% to 85% by weight, preferably 5 wt% . /〇 to 60% by weight of the 10 weight. /. Up to 50% by weight of at least one inorganic pigment. More specific I50I32.doc •52· 201127296 c) 〇% by weight to 85% by weight, more specifically 5% to 6 〇 weight 机 machine filler, and ... d" /. Up to 40% by weight, more specifically 5% by weight to 2% by weight of typical auxiliaries. The context of the present invention generally uses the term "pigment" to identify all pigments and fillers' examples being color pigments, white pigments, and inorganic fillers. It comprises an inorganic white pigment such as titanium dioxide (preferably in the form of rutile) of barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, rhodium = (zinc sulfide + barium sulfate), or color pigments, Examples are iron oxide, carbon black, stone, ink, yellow, zinc green, ultramarine, black, black, purple, Paris blue or swanwe green (Sehweinfun is called. In addition to inorganic pigment = The latex paint of the present invention may also contain organic color pigments, examples being squid black vine pages, Cassel brown, indoline red, blood red, Hansa yellow (Η _ ydl〇 W), indigo, azo dyes, Anthraquinoid and anthraquinone (4), as well as two materials, seven 丫, _, ugly, different, m hibiscus and metal complex pigments. Synthetic white pigments with air inclusions and light scattering are also suitable For example, a suitable filler is, for example, an aluminosilicate such as feldspar; a citrate such as meta-soil, talc, mica, magnesite; a soil metal carbonate such as carbon strontium. Office (for example, calcite or white scorpion Formula), magnesium carbonate, dolomite; soil test metal sulfate 'such as calcium sulfate; dioxide dioxide, etc. Of course: fine powder filling: preferably in the coating material. Filling can be used in individual components. However, in practice, it is proved that the filler mixture is particularly suitable, such as calcium carbonate/kaolin and calcium carbonate/talc. The bright coating material usually 150132.doc -53· 201127296 includes only a small amount of very fine powder filler or does not contain Filler. Fine powder filler can also be used to enhance hiding power and / or save the use of white materials. In order to adjust the hiding power, color tone and color density, it is better to use a blend of color pigment and filler. In addition to the agent component (B) and the antimicrobial agent (Z), the pigment and, if appropriate, other film-forming polymers, the coating material (aqueous coating material) of the present invention may also contain other auxiliary agents, in addition to the emulsification used in the polymerization. In addition to the agent, typical additives also include wetting or dispersing agents, such as sodium polyphosphate, potassium polyphosphate or ammonium polyphosphate, alkali metal salts and ammonium salts of acrylic acid copolymers or cis-succinic anhydride copolymers, polyphosphonic acids. (Zhi Shi 1-Ji Yi Yuan two filled sodium) and naphthyl acid salt, more specifically its sodium salt. Eight of his suitable additives for flow control agents, defoamers, biocides and thickening ^ The weight of the thickening agent is preferably less than 1% by weight, more preferably less than 〇. 6 weight, based on the solid content of the coating material, such as a combined thickening agent, such as a polyurethane thickening. %.

Single shout, two doses or coalescing aids. It is preferred to use, for example, white ethyl alcohol, propylene glycol, glycerin, ethanol, methanol, water, and its acetate, such as diethylene glycol, 1-methoxy-2-propylmethyl-1-propanol, Isooctanol, ethylene glycol butyl ether, diacetic acid, ethylene glycol monobutyl ether, dipropylene glycol monomethyl or dipropylene glycol monomethyl ether, dipropylene glycol propylene, dipropylene glycol n-butanol n-butyl ether, Propylene glycol phenyl ether, ethylene glycol butyl ether acetate butyl ether acetate, 2,2,4-trimethyl-1,3-pentanediol monoiso 150132.doc -54- 201127296 Ding Syi S, Long chain - tartrate - isobutyl ester (such as 8 or tripropylene glycol monoisobutyrate. The coating material of the present invention is prepared by blending the components in a mixing device commonly used for this purpose in a known manner. It has been found that aqueous pastes or dispersions are prepared from pigments, water and, if appropriate, auxiliaries, and then only polymeric binders (i.e., usually aqueous dispersions of polymers) and pigment pastes or pigment dispersions are suitable. The coating material of the present invention usually comprises 30% to 75% by weight and preferably 40% to 65% by weight. These ingredients mean all non-water components in the formulation, but at least the total amount of binder, pigment and auxiliaries, based on the solids content of the coating material. The volatile component is mainly water. The coating material can be applied to the substrate in a typical manner, for example, by spreading, spraying, dipping, rolling, knife coating, etc. The composition of the present invention produces an extended pot life and excellent curability. Rapidly Reactive Durable Coating. The curable composition of the present invention provides a clear: scratch-resistant clear coating. The compositions of the present invention can also be used in principle as adhesives, elastomers and plastics. Cloth materials are suitable for coating substrates, including wood, paper, textiles, leather, non-woven fabrics, plastic surfaces, glass, mineral construction materials (such as cement moldings and fiber and cement boards), coated or uncoated Metal of cloth. It is preferred to use a curable composition 纟 to coat plastic or metal (especially in the form of a sheet), more preferably for coating a surface made of metal. Antimicrobial composition and microbial composition comprising the same Coatings especially 150132.doc •55· 201127296 Suitable for hospital environments, medical equipment, water treatment facilities, meals and packaging, pharmaceutical laboratories, child care equipment and other areas where additional protection against microbes is required. The compositions and coatings comprising the same, can be advantageously used in food equipment such as mixing tanks, garments: trays, sinks, road mats, coolers, display cases and services. Equipment such as refrigerators, washing (four), dryers, sanders and garbage compressors; ^ _ A benefits, R 〇 processing, such as grinders, trays, conveyors, storage slicers, and food processing equipment , medical equipment, such as instrument trays, racks, sterilization equipment, potty, countertops, inspection tables, trolleys, beds and lighting appliances. 'Hospital and public and private internal equipment, such as pushers, kick boards, hand towel dispensers, doors , escalators, elevators and lounge equipment, and as part of transport components, such as interior parts and surfaces of vehicles, interior parts and surfaces of aircraft, and interiors of trains Parts and surfaces. The substrate is coated with the coating material of the present invention according to conventional techniques known to the skilled worker, and the techniques comprise applying at least one coating material or coating formulation of the present invention to the target substrate in a desired thickness, The volatile component (drying) of the coating material is removed by application when appropriate. Repeat this operation if necessary - or multiple times. The substrate can be applied in a known manner, for example by spray coating, clock coating, knife coating, brush coating, roller coating or wash coating. The thickness of the coating is usually in the range of about g/m2 and preferably from 1G to 1. Curing can then be carried out. After applying the coating material to the substrate, the coating is typically dried for at most 72 hours, preferably at most, at a temperature below _, preferably from room temperature to 6 〇t and more preferably from room temperature to (d). When calling, better at most ^ hours, 150132.doc •56· 201127296 Excellent for up to 12 hours and specific a > time special & 6 hours, and the coated layer in the oxygen atmosphere Good * * Over the main milk or inert gas at 8 (rc ,, preferably loot and 240. "Is called the skin - m walk better at a temperature between 12 ° ° C and 18 ° ° ° ° Heat treatment (curing, also) at the end of the curing. According to the coating material in the coating and through the high energy light, &

The heat transferred from the surface of the self-heating or the introduction of the convection through the gas-stricken medium, the curing of the coating material occurs within a few seconds, for example, in the case of a coil coating, the main 犋NIR drying combination, up to 5 Hours, for example, in the case of a thick coating system on the thermal π Tt, usually after not less than 10 minutes, preferably, the λ knife is in the middle, and more preferably not less than 30 minutes. Drying essentially involves the removal of the existing solvent, and furthermore (even at this stage) reacts with the binder, which in essence comprises reacting with the binder. In addition to,,,, curing, or in place of thermal curing, it can also be cured by means of claws and nir Lee shots, where NIR radiation is expressed in the range of 76 〇 甘 / ο υ nm to 2.5 μηη, preferably 900 to 1500 nm. The electromagnetic Han shot. The curing occurs in a period of from 1 second to 60 minutes, preferably from 1 minute to 45 minutes. Examples of substrates suitable for use in the coating materials of the present invention include thermoplastic polymers 'especially poly(methacrylic acid), polymethyl methacrylate, poly(p-phenylene)-ethyl ester Butyl ester, polyvinylidene fluoride, polyvinyl chloride, polystyrene, polyolefin, acrylonitrile-ethylene propylene-diene styrene copolymer (A-EPDM), polyether sulfimide, polyether ketone, poly Phenyl sulfide, polyphenylene ether or a mixture thereof. Further mention may be made of polyethylene, polypropylene, polystyrene, polybutadiene, -57·150132.doc 201127296 polyester, polyamide, polyether, polycarbonate, polyvinyl acetal, polyacrylonitrile Polyacetal, polyvinyl alcohol, polyvinyl acetate, phenolic resin, urea resin, melamine resin, alkyd resin, epoxy resin or polyurethane, block or graft copolymer thereof, and Blend. Preferred mention may be made of ABS, AES, AMMA, ASA, EP, EPS, EVA, EVAL, HDPE, LDPE, MABS, MBS, MF, PA, PA6, PA66, PAN, PB, PBT 'PBTP, PC, PE, PEC , PEEK, PEI, PEK, PEP, PES, PET 'PETP, PF, PI, PIB, PMMA, POM, PP, PPS, PS, PSU, PUR, PVAC, PVAL, PVC, PVDC, PVP, SAN, SB, SMS , UF, UP plastic (abbreviated name according to DIN 7728) and aliphatic polyketone. Particularly preferred substrates are polyolefins (such as PP (polypropylene), which may optionally be isotactic, syndiotactic or atactic polypropylene and optionally unoriented or oriented via uniaxial or biaxial stretching), SAN ( Styrene-acrylonitrile-copolymer), PC (polycarbonate), PVC (polyvinyl chloride), PMMA (polydecyl methacrylate), PBT (poly(tert-butylene terephthalate)), PA (polyamide), ASA (acrylonitrile-styrene-acrylate copolymer) and ABS (acrylonitrile-butadiene-styrene copolymer) and physical mixtures (blends thereof). Particularly preferred are PP, S AN, ABS, ASA, and blends of ABS or ASA with PA or PBT or PC. Particularly preferred are polyolefins, PMMA and PVC. In particular, according to DE 196 5 1 350, ASA and ASA/PC blends are especially preferred. Also preferred is polydecyl methacrylate (PMMA) or impact modified PMMA. Another preferred substrate that can be coated with the coating materials of the present invention is a metal. The 150132.doc • 58 - 201127296 metal is especially a metal that has been coated with another coating, such as an electrocoated film. Coating film, primer or base coat. These coating films may be solvent-based water-based or powder coating-based coatings which may be crosslinked, partially crosslinked or thermoplastic, and either integrally cured or wet-coated throughout their volume. As far as the relevant metal type is concerned, the metal may in principle be any desired gold, and in particular, it is a metal or alloy which is commonly used as a building metal material and requires corrosion protection. The surface is especially the surface of iron, steel, Zn, Zn alloy, or alloy. These surfaces may be in the form of structures consisting entirely of the metal or alloy. Alternatively, for example, the structures may be coated only with such metals and may themselves be constructed of other types of materials, such as other metals, alloys, polymers or composite materials. It may be a cast = surface made of galvanized iron or galvanized steel. In a preferred embodiment of the invention, the surfaces are steel surfaces 0

Zn alloys or A1 alloys are known to the skilled authors. The skilled author selects the nature and quantity of the alloy composition based on the desired end use application. The typical composition of the alloy includes, in particular, the Pb, Si, Mg, sn, & or the typical composition of the aluminum alloy, specifically containing Mg, Μη, Si, Zn, &, Cu or Ti. The alloy may also be an Al/Zn alloy in which a 丨 and zn are present in approximately equal amounts. Steel coated with these types of alloys is commercially available. The steel may comprise typical alloy components known to the skilled worker. It is also contemplated to use the coating composition of the present invention to treat tinplate/copper iron). The coatings obtainable from the curable compositions of the present invention exhibit excellent resistance to microbial 150132.doc-59-201127296. It is known to those skilled in the art that, under suitable conditions, especially in the presence of a suitable catalyst and water, the polyurethane-based polymer obtained in accordance with the present invention is a polyurethane, poly-adenine-cerium oxide. polymer. Another subject of the invention is a kit comprising a curable composition. The kit contains the following as separate parts: a) at least one binder component (B) comprising at least one of the oxoxanes as defined above ( B2) and a polymer dispersion (pd), and b) at least one antimicrobial agent (z) as defined above. Another subject of the invention is a hybrid network of polymer dispersions PD and ceria that are chemically linked via a Si-containing group, comprising a plurality of microbial agents that are not covalently attached to the network. Further, the present invention provides a mixed network of polyamino formate and cerium oxide chemically linked via a Si-containing group, which comprises an antimicrobial agent covalently attached to the network. EXAMPLES The following abbreviations are used in the following examples: AMSI: 3-[bis(2-hydroxyethyl)amino]propyltriethoxydecane] HDI: diisocyanate diphenyl dicarboxylate BNP: 2-bromo-2 -nitro-1,3-propanediol (bromonitrol alcohol) PPG : polypropylene glycol PD : 1,5-pentanediol NIPAM: N-isopropyl acrylamide TEMED : n, n, n', n'-four Methylene diamine 150J32.doc 201127296 MBA . N'N-methylene bis acrylamide AP · ammonium persulfate

Quat : Gasified dimercapto octadecyl [3-(tridecyloxydecyl)propyl]ammonium from Sigma Aldrich

Hygate 4000 antimicrobial sample supplied by Ciba Specialty chemicals AJ 100 D sample was purchased from AglON Technologies USA Polymer dispersion synthesis Example 1 87 g Seed T 6772 and 560 g deionized water were charged to 95 at 95 °C. Under the 4 glass container with a wrong type of mixer (125 rpm). The internal temperature was lowered to 70 ° C, the feed crucible and part of the feed 2 were continuously added over a period of 3 hours, and the remaining feed stream 2 was continuously supplied over a period of 3.5 hours, and the two feeds were maintained at a slow rate. The flow is separated in space. Feed 5 was then added over a period of 15 minutes with constant agitation. After the completion of feed 5, feed 3 was charged to the reactor over a period of minutes, and then feed 4 was charged over a period of 45 minutes. The reactor was then cooled to room temperature and at 4 Torr. The polymerization is completed by adding the contents of the feed 6 under the crucible. The dispersion had a solid content of 51.5% and the resulting composition had a viscosity of 7 mpas. Starting charge Deionized water pH 609.00 g

Seed T 6772 20.60 g From the feed part 6.75 g Feed 1: 150132.doc -61 - 201127296 Deionized water 419.00 g Emulphor NPS 25 110.70 g Ammonia 5.40 g AA 38.50 g Styrene 644.00 g BA 644.00 g MTMO 6.60 g Deionized water for rinsing (subsequent) 20.00 g Feed 2: Sodium persulfate 116.10 g Feed 3: t-BHP 14.00 g Deionized water for rinsing (subsequent) 8.00 g Feed 4: Deionized water 20.00 g Sodium metabisulfite 5.30 g Deionized water for rinsing (subsequent) 5.00 g Feed 5: Ammonia 16.20 g Feed 6:

Acticide MV 3.00 g Deionized water for rinsing (subsequent) Example 2

87 g Seed T 6772 and 560 g of deionized water were placed in a 4 1 glass vessel with a 4 seed mill (125 rpm) at 95 ° C 150132.doc • 62· 201127296 at 95 °C. Reduce the internal temperature to 7 ° ° C 'Continuously add feed 1 and part of feed 2 over a 3 hour time period and continuously supply the remaining feed stream 2 over a 3 '5 hour time interval, maintaining the two feeds at a slow rate The streams are separated spatially. Feed 5 was then added over a period of 15 minutes with constant agitation. After the completion of feed 5, feed 3 was charged to the reactor over a period of 3 minutes, and then feed 4 was charged over a period of 45 minutes. The cold reactor was then allowed to reach room temperature and the polymerization was completed by adding the contents of feed 6 at 4 °C. The dispersion had a solids content of 515% and the resulting composition had a viscosity of 7 m P a s. Starting charge Deionized water pH 609.00 g

Seed T 6772 20.60 g From the feed part 6.75 g Feed 1: Deionized water 419.00 Emulphor NPS 25 110.70 Ammonia 5.4 〇g AA 38.50 g Styrene 644.00 BA 644.00 MTMO 6.60 g Deionized water for rinsing (subsequent) 20.00 g Feed 2: sodium persulfate Π 6.10 g 150132.doc •63- 201127296 Feed 3 :

t-BHP 14.00 g Deionized water for rinsing (subsequent) 8 〇〇g Feed 4 : 20.00 g 5.30 g 5.00 g Deionized water sodium metabisulfite for rinsing (subsequent) deionized water feed 5 : Ammonia 16.20 g Feed 6 :

Acticide MV 3.〇〇g Deionized water for rinsing (subsequent) The paint formulation of Acronal Dispersion is used to mix the (iv) polymer prepared by the above procedure with three shixi functionalized biocides. An antibacterial dispersion is produced. The modified dispersion is then formulated into a paint. The blending of the paint can be carried out as described in the patent. Synthesis of Antimicrobial Dispersion Example 3: 30 g of the antimicrobial agent Quat and 300 g of deionized water were added to the 75 〇 g dispersion obtained by the procedure indicated in the Example 丨. The resulting dispersion was formulated into a paint after homogenization by shock. The resulting paint was then transferred as a coating to a polycarbonate slide and dried at room temperature for 3 days. Anti-bacterial testing of the samples. Example 4: To 500 g of the dispersion in Example 1, 〇.5 g of Hygate 4000 powder was added. After the homogenization by shaking, the resulting dispersion was formulated into oil 150132.doc ·64· 201127296 paint. The resulting paint was then transferred as a coating to a polycarbonate slide and dried for 3 days. The sample was tested for antibacterial activity. Example 5 • Add to the solution in the example i ^ ^ g knife dispersion After 5 g is homogenized with 1 〇 0: 〇 Γ 震 , , , 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均 均The sample was subjected to an antibacterial test. To the next example 6 xiao added (iv) g of the antimicrobial agent QuatW (10) g of deionized water to the 750 g of the dispersion obtained by the procedure indicated in Example 2. The resulting dispersion was formulated after the tremorization The paint was then transferred as a coating to a polycarbon_ slide and dried at room temperature for 3 days. The sample was tested for antibacterial activity. 5 g of AJ100D powder was added to the dispersion to make the resulting dispersion a paint. Example 7: To the end of 500 in Example 2. After homogenization by shaking, the resulting paint was transferred as a coating to a polycarbonate slide and dried at room temperature for 3 days. Antibacterial test was performed on the sample. Antimicrobial activity measurement according to Japanese standards j IS z 2801: 2 〇〇〇 Test for antimicrobial activity and efficacy for antimicrobial activity test. The following bacteria were used: large intestine rod U (Escherichia coli ·, E. coli) 'S. aureus QStaphyl

OCOCCUS (10); α (10)) and methicillin-resistant Staphylococcus aureus (Methlcillin Resistant awrewi; MRSA). Table 1 lists the antimicrobial activity of Acronal paints having various amounts of various antimicrobial components. Suppression zone test 150132.doc -65- 201127296 To test whether the antimicrobial agent incorporated into the paint is leached from the coating, a zone of inhibition test is performed. Here, the procedure for these tests is elaborated. 1. Sample preparation The antimicrobial paint obtained from the above example was applied to both sides of a 5 cm diameter filter paper. Dry the paint for 1 week under ambient conditions. The coated crepe paper is then cut into individual pieces of 3 emx3 em. The test for the type of test organism was repeated three times. 2 · Test method according to the test method JIS L 19〇2: 2〇〇2 (halogen method) "Testing f〇r antibacterial actmty and efficacy 〇n textUe pr〇 The ducted zone test was carried out. 0 3 Results of the zone of inhibition All of the test samples of Examples 3-7 did not show any zone of inhibition, clearly indicating the presence of covalent attachment of the antimicrobial agent to the polymer backbone. Table 1: Antimicrobial Activity of Antimicrobial Paint Examples Dispersion Antimicrobial Agent Antimicrobial Load (Weight Antimicrobial Activity, Type R (Type) Staphylococcus aureus Escherichia coli MRSA Control*0 ~~ 0.3 0 0 3-5 Examples 1 Quat 2.8 0.2 0 0 Hygate 4000 ΤΪ 1 0 0 0 AJ-100D Ί ~ 5.5 5.9 5.1 6-7 Example 2 Control 0 2.2 2.9 1.5 Quat 2.8 3.3 3.9 3.6 AglON 1 5.5 5.4 5.1 150132.doc • 66 ·

Claims (1)

201127296 VII. Patent Application Range: 1. A method for preparing a composition comprising: 0) reacting a binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (PD) This obtains a prepolymer, and then (b) hydrolyzes and polycondenses the prepolymer water in the presence of at least one antimicrobial agent (Z) comprising at least one antimicrobial active agent (Z1) and optionally A particulate carrier material (Z2), wherein the at least one antimicrobial agent (Z) does not react during step (b). 2. The method of claim 1, wherein the antimicrobial agent comprises silver ions as the antimicrobial active agent (Z1) and a group selected from the group consisting of zeolites and polymer hydrogels as the particulate carrier material (Z2). 3. The method of claim 1, wherein the antimicrobial agent (z) comprises a particle antimicrobial having a number average particle size of from 1 to 500 nm selected from the group consisting of (1) oxidized words and (ii) particles comprising titanium dioxide, AgBr, and apatite. Active agent (Z1). 4. The method of claim i, wherein the antimicrobial agent (z) comprises an antibiotic selected from the group consisting of a quaternary salt and a 2-bromo-2-nitropropane-1,3-diol Microbial active agent (Z1). The method of any one of claims 1 to 4, wherein the monomer of the polymer dispersion (PD) is selected from the group consisting of α,β-ethylenically unsaturated monocarboxylic acids and dicarboxylic acids and Ci-Cm Alcohol and C5_Cl〇 cycloalkanol ester; aryl vinyl monomer; vinyl alcohol and Ci-Cm monocarboxylic acid ester; ethylenically unsaturated nitrile; vinyl halide; vinylidene halide; monoethylenically unsaturated carboxylic acid and sulfonate Acid; phosphorus monomer; α, β_ene system 150132.doc 201127296 and mono-acid and dicarboxylic acid and C2-C3Q alkanediol ester; α, β-olefinic unsaturated monocarboxylic acid and dicarboxylic acid An amide of an acid with a C2_C3 guanylamino alcohol containing a primary or secondary amine group; a guanamine of an α,β-ethylenically unsaturated monocarboxylic acid and its oxime-alkyl and oxime, fluorenyl-dialkyl Derivatives; N-vinyl decylamine; open chain Ν _ vinyl decylamine compound; ester of allyl alcohol with Ci_c3 〇 monocarboxylic acid; α, olefinic unsaturated monocarboxylic acid and dicarboxylic acid and amino alcohol Esters; α,β-ethylenically unsaturated monocarboxylic acids and carboxylic acids with diamines containing at least one primary or secondary amine; hydrazine, hydrazine-diallylamine; hydrazine, hydrazine _Diallyl_Ν·alkylamine; via vinyl and olefin The substituent group azetidin; vinyl ethers; CRC8 monoolefin; having at least two conjugated double bonds of non-aromatic hydrocarbons; polyether acrylates (meth); the monomer containing a ureido group; and mixtures thereof. 6. The method of any one of clauses 1 to 4, wherein the polymer ρ comprising at least two monomer enthalpies has a glass transition temperature in the range of _2 〇〇 c to +601. 7. The method of any one of claims 1 to 4, wherein the main monomers are tannins selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate. , (isopropyl) (meth)acrylate, n-butyl methacrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, (A) Base) n-hexyl acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl hydrazide (meth) acrylate, styrene, 2-methyl styrene, and mixtures thereof. The method of any one of the preceding claims, wherein the combination of the main monomers is selected from the group consisting of n-butyl propionate and methyl methacrylate; 150132.doc 201127296 n-butyl acrylate , decyl acrylate and styrene; n-butyl acrylate and styrene; n-butyl acrylate and ethyl hexyl acrylate; n-butyl acrylate, ethyl hexyl acrylate and styrene. 9. The method of any one of claims 1 to 4, wherein the alkoxydecane (B2) is selected from the group consisting of alkoxyalkylene-containing monomers, such as vinyltrimethoxynonane, vinyltriethoxy Base decane, vinyl triisopropoxy decane, vinyl cis (0-decyloxy ethoxy) decane, vinyl decyl dimethoxy decane, vinyl methyl diethoxy decane, vinyl two Methyl methoxy decane, vinyl dimercapto ethoxy decane, 3 - decyl propylene propyl dimethyl oxalate, 3 - methacryl propyl propyl triethoxy sulphur, 3 _ Mercaptopropenylpropylmethyldimethoxydecane, 3_mercaptopropenylpropylmercaptodiethoxydecane, acrylic acid (2_acetoxyethyl dimethyl fluorenyloxy) ) decyl propyl acrylate, methacrylic acid ginseng (2 - ethoxylated ethyl dimethyl decyloxy) decyl propyl acrylate, acrylic acid (2-carboxyethyl monomethyl hydrazine oxy) decyl propyl Esters and methacrylic acid ginseng (2-carboxyethyl dimethyl decyloxy) decyl propyl acrylate, acrylic acid (3 hydroxypropyl decyl decyloxy) decane Propyl ester, acrylic acid ginseng (3-hydroxypropyl decyl sulfodeoxy) decyl propyl propyl ester and methacrylic acid ginseng (3 hydroxypropyl decyl decyloxy) decyl propyl acrylate, acrylate and A acrylate-functional fluoro-substituted alkyl/aryl siloxane such as bis(3,3,3-trifluoropropyl decyl decyloxy) decyl propyl acrylate and hydrazino acrylate (3, 3) , 3-trifluoropropyl decyl decyloxy) decyl propyl acrylate, acrylic acid [3 - heptafluoroisopropoxypropyl)] dimethyl decyloxy decyl propyl propyl ester and hydrazine 150132.doc 201127296 Acrylic acid [3-heptafluoroisopropoxypropyl dimethyl decyloxy decyl propyl propyl ester, acrylic acid (pentafluorophenyl decyl decyloxy) decyl propyl propyl ester and methacrylic acid ginseng (five Fluorophenyl dimethyl decyloxy) decyl propyl _ ' or has the formula: Hs-RS-SiR63.xZx wherein RS is a divalent alkylene group, R6 is an alkyl group, and hydrazine is 1, 2 or 3, and B is a hydrolyzable group, or a mixture thereof. 11. The method of any one of claims 1 to 4, wherein the alkoxydecane (B2) is 〇. 〇丨% by weight to 5 parts by weight relative to the total weight of the component B. The range of % exists. The method of any one of clauses 1 to 4 wherein the antimicrobial agent (8) is present in an amount of from 丨% by weight to 丨〇% by weight based on the total dry weight of the composition. Kind, and. The object can be obtained by the method of any one of the claims 丨 to 丨丨. An aqueous coating comprising the composition of claim 12. An aqueous composition comprising: at least one binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (PD), at least one antimicrobial agent (z), each as requested An inorganic filler and/or an inorganic pigment, wherein 0.1% by weight to 20% by weight of a typical auxiliary agent, as defined in any one of items 1 to 11, is 7% by weight, preferably 1% by weight to 7% by weight, of a typical filler, And 150132.doc 201127296 15. 16. 17. Make up to 100% by weight of water. A kit comprising a curable composition comprising as a separate part for combined use: a) a binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (pD), b) at least one antimicrobial agent (Z), each as defined in any one of claims 1 to 11. A acrylic acid vinegar copolymer as defined in relation to polymer dispersions (pD) and cerium oxide, via a mixed network comprising groups chemically linked to each other, comprising an antimicrobial agent not covalently attached to the network. Use of the composition of claim 1 2 for the preparation of an antimicrobial coating. 150132.doc 201127296 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the 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) 150132.doc