TWI499377B - Aqueous dispersions containing antimicrobials in a hybrid network - Google Patents

Description

An aqueous dispersion comprising an antimicrobial agent present in a hybrid network

The present invention relates to a method of preparing a composition comprising:

(a) reacting a binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (PD), thereby obtaining a prepolymer, and then

(b) mixing or hydrolyzing and polycondensing the prepolymer in the presence of

- water, and

- at least one antimicrobial agent (Z) comprising at least one antimicrobial agent

The active agent (Z1) and, optionally, the 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 organodecane 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.

Increasingly high demands are placed on the efficacy, safety and environmental compliance of coating applications. Coatings based on acrylate copolymer dispersions are known to provide high chemical resistance, flexibility, abrasion resistance, weatherability and impact resistance. The protection provided by such coatings is of particular importance in the automotive, construction, marine and chemical fields.

There is a need in the art to develop coatings having the above advantages while having long-term antimicrobial properties. Therefore, several different coatings have been proposed in the prior art.

The use of aluminum citrate or zeolites containing certain metal ions in antimicrobial coatings 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 the reaction product of at least one polyisocyanate, an organofunctional decane and a polyol. However, US-P 6,596,401 does not disclose a hybrid network.

U.S. Patent No. 6,572,926 discloses a polymer matrix which is exposed to a polymerizable quaternary ammonium salt such as dimethyl octadecyl-[3-(trimethoxydecyl)propyl]ammonium chloride dissolved in a solvent. . The quaternary salt in the solvent is adsorbed and polymerized by the polymeric matrix, thereby producing a substrate having an antimicrobial agent impregnated on the surface. The polymeric antimicrobial agent also penetrates the surface to a certain depth to form an interpenetrating network.

The process is limited to the infiltration of the polymer matrix or the swelling of the polymer matrix by 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.

It is an object of the present invention to provide an antimicrobial composition wherein the antimicrobial active agent is not leached from the composition. 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 an antimicrobial composition, in particular a coating, which exhibits high efficacy against Staphylococcus aureus and Escherichia Coli. In addition, the antimicrobial coating should effectively kill these bacteria for 24 hours or less at room temperature.

Meanwhile, it is an object of the present invention to provide an antimicrobial coating which exhibits chemical and weather resistance and exhibits high optical quality, sufficient flame retardancy, excellent adhesion to polycarbonate and aluminum substrates, and high abrasion resistance.

The foregoing problems can be solved by the method of the present invention and the compositions and coatings obtainable by the method. The preferred embodiments are summarized below and in the scope of the patent application. Combinations of the preferred embodiments are also within the scope of the invention.

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 compositions of the invention are preferably present in the form of a coating.

Step (a)

According to the invention, step (a) comprises a reaction

- reacting a binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (PD)

Thus, a prepolymer was obtained.

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.

Adhesive 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 (B1) which is incapable of reacting in step (b) and at least one alkoxydecane (B2).

The binder (B1) which cannot be reacted in the step (b) is preferably a binder which does not have an alkoxyalkyl group.

Polymer dispersion PD

The glass transition temperature T _g of the polymer P comprising at least two monomers M is in the range of -20 ° C to +60 ° C. The polymer dispersion (PD) can be obtained by free radical emulsion polymerization of at least one ethylenically unsaturated monomer M.

In general, the polymer P is a copolymer obtained by copolymerizing two or more monomers M. A skilled worker can, in this case, prepare a polymer having a glass transition temperature in the range of -20 ° C to +60 ° C by skillfully selecting a monomer composition.

According to Fox (see Ullmanns Enzyklop Die der technischen Chemie, 4th edition, Vol. 19, Weinheim (1980), pp. 17, 18), can estimate the glass transition temperature _Tg . In a good approximation, the glass transition temperature of a copolymer with little or no cross-linking is obtained by high molar mass by the following formula:

Wherein X ¹ , X ² , ..., X ⁿ are mass fractions 1, 2, ..., n and T _g ¹ , T _g ² , ..., T _g ⁿ are in each case only from monomers 1, 2, ..., The glass transition temperature of the polymer synthesized in one of n is expressed in Kelvin temperature. The latter has been, for example, from Ullmann's Encyclopedia of Industrial Chemistry, VCH, 5th edition, Weinheim, Vol. A 21 (1992), page 169 or from J. Brandrup, EH Immergut, Polymer Handbook, 3rd edition, J. Wiley, New York 1989. know.

In general, monomer M is selected from the group consisting of α,β-ethylenically unsaturated monocarboxylic acids and esters of dicarboxylic acids with C ₁ -C ₂₀ alkanols and C ₅ -C ₁₀ cycloalkanols; arylene monomers; vinyl alcohol Ester with C ₁ -C ₃₀ monocarboxylic acid; ethylenically unsaturated nitrile; vinyl halide; vinylidene halide; monoethylenically unsaturated carboxylic acid and sulfonic acid; phosphorus monomer; α,β-ethylenically unsaturated monocarboxylic acid An acid and an ester of a dicarboxylic acid and a C ₂ -C ₃₀ alkanediol; an α,β-ethylenically unsaturated monocarboxylic acid and a dicarboxylic acid and a C ₂ -C ₃₀ 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 mercaptoamine compound; an ester of allyl alcohol with a C ₁ -C ₃₀ monocarboxylic acid; an ester of an α,β-ethylenically unsaturated monocarboxylic acid and a dicarboxylic acid with an amino alcohol; α,β-olefinic unsaturation a monocarboxylic acid and a dicarboxylic acid and a guanamine containing at least one primary or secondary amine; N,N-diallylamine; N,N-diallyl-N-alkylamine a nitrogen heterocyclic ring substituted with a vinyl group and an allyl group; a vinyl ether; a C ₂ -C ₈ monoolefin; a non-aromatic hydrocarbon having at least two conjugated double bonds; Acrylate; a monomer containing a urea group; or a mixture thereof.

When (meth) acrylate is mentioned in the context of the present application, it means not only the corresponding acrylate, in other words a derivative of acrylic acid, but also a methacrylate, ie a derivative of methacrylic acid.

Examples of suitable monomers include the following:

(a): an ester of an α,β-ethylenically unsaturated monocarboxylic acid and a dicarboxylic acid with a C ₁ -C ₂₀ alkanol, especially an ester of acrylic acid, methacrylic acid and ethacrylic acid, such as (meth)acrylic acid Ester, methyl ethacrylate, ethyl (meth) acrylate, ethyl ethacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Dibutyl methacrylate, tert-butyl (meth)acrylate, tert-butyl ethacrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) acrylate Octyl ester, 1,1,3,3-tetramethylbutyl (meth)acrylate, ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, n-decyl (meth)acrylate, N-undecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate, ( Heptadecyl methyl methacrylate, pentadecanyl (meth) acrylate, eicosanyl (meth) acrylate, behenyl (meth) acrylate, tetracosyl (meth) acrylate , hexadecyl (meth) acrylate , trialkyl (meth) acrylate, palm oleyl (meth) acrylate, oleyl (meth) acrylate, linoleyl (meth) acrylate, linoleyl (meth) acrylate, ( Stearic acid methyl methacrylate and dodecyl (meth) acrylate.

(b): an arylene monomer, preferably styrene, 2-methylstyrene, 4-methylstyrene, 2-(n-butyl)styrene, 4-(n-butyl)styrene, 4 -(n-decyl)styrene and ?-methylstyrene, and more preferably styrene and ?-methylstyrene.

(c): an ester of vinyl alcohol with a C ₁ -C ₃₀ monocarboxylic acid such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, propionic acid Vinyl esters and vinyl esters of Versatic acid.

(d): ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile.

(e): vinyl halide and vinylidene halide such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride.

(f): an ethylenically unsaturated carboxylic acid and a sulfonic acid or a derivative thereof are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, and clothing. a monoester of a natural acid, a citraconic acid, a methyl fumaric acid, a glutaconic acid, an aconitic acid, a fumaric acid, or a monoethylenically unsaturated dicarboxylic acid, which has 4 to 10, preferably 4 to 6 C atoms, such as monomethyl maleate, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfonyl methacrylate Ester, 2-hydroxy-3-propenyloxypropylsulfonic acid, 2-hydroxy-3-methylpropenyloxypropylsulfonic acid, styrenesulfonic acid and 2-propenylamino-2-methyl Propane sulfonic acid. Suitable styrene sulfonic acid and its derivatives are styrene-4-sulfonic acid and styrene-3-sulfonic acid and alkaline earth metal or alkali metal salts thereof, such as sodium styrene-3-sulfonate and styrene-4-sulfonate Sodium. Particularly preferred are acrylic acid and methacrylic acid.

(g): Phosphorus monomers such as vinylphosphonic acid and allylphosphonic acid. Furthermore, monoesters and diesters of phosphonic acid and phosphoric acid with hydroxyalkyl (meth)acrylates, especially monoesters, are suitable. Furthermore, phosphonic acids and diesters of phosphoric acid which are esterified individually by (meth) acrylate and individually esterified with different alcohols (for example alkanols) are suitable. Suitable hydroxyalkyl (meth) acrylates for such esters are esters of the following individual monomers, more specifically 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, and the like. The corresponding dihydrogen phosphate monomer comprises a phosphorus alkyl (meth) acrylate such as 2-phosphoric acid ethyl (meth) acrylate, 2-phosphopropyl (meth) acrylate, 3-phosphonium (meth) acrylate Ester, phosphobutyl (meth)acrylate and 3-phospho-2-hydroxypropyl (meth)acrylate. Esters of phosphonic acid and phosphoric acid with alkoxylated hydroxyalkyl (meth) acrylates are also suitable, examples being ethylene oxide condensates of (meth) acrylates such as H ₂ C=C ( CH ₃ )COO(CH ₂ CH ₂ O) _n P(OH) ₂ and H ₂ C=C(CH ₃ )COO(CH ₂ CH ₂ O) _n P(=O)(OH) ₂ , where n is 1 To 50. In addition, phosphorus crotonate, phosphoalkyl alkyl maleate, phosphorus alkyl fumarate, phosphorus dialkyl (meth) acrylate, dialkyl crotonate and phosphate Propyl ester is suitable. Other suitable monomers containing a phosphorus group are described in WO 99/25780 and U.S. Patent 4,733,005, the disclosures of each of each of

(h): an ester of an α,β-ethylenically unsaturated monocarboxylic acid and a dicarboxylic acid with a C ₂ -C ₃₀ alkanediol, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethyl 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, methacrylic acid 3 - Hydroxybutyl ester, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate and 3-hydroxy-2-ethylhexyl acrylate.

(i): a monodecylamine of an α,β-ethylenically unsaturated monocarboxylic acid such as acrylamide and methacrylamide.

(k): N-alkyl decylamine of α,β-ethylenically unsaturated monocarboxylic acid and N,N-dialkylguanamine such as N-methyl(meth)acrylamide, N-ethyl (Meth) acrylamide, N-propyl (meth) acrylamide, N-(n-butyl) (meth) acrylamide, N-(t-butyl) (meth) acrylamide , N-(n-octyl)(meth)acrylamide, N-(1,1,3,3-tetramethylbutyl)(meth)acrylamide, N-ethylhexyl (methyl) Acrylamide, N-(n-decyl)(meth)acrylamide, N-(n-decyl)(meth)acrylamide, N-(n-undecyl)(meth)acrylamide , N-tridecyl (meth) acrylamide, N-tetradecyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (methyl Acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-icosyl (meth) acrylamide, N-II Dodecyl (meth) acrylamide, N-tetracosyl (meth) acrylamide, N-hexadecyl (meth) acrylamide, N-triaconyl (A Acrylamide, N-palmitole (meth) acrylamide, N-oleyl (meth) acrylamide, N-linoleyl (methyl) Enamine, N-linoleyl alkenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-dodecyl (meth) acrylamide, N, N-II Methyl (meth) acrylamide, N,N-diethyl (meth) acrylamide and morpholinyl (meth) acrylamide.

(o): an α,β-ethylenically unsaturated monocarboxylic acid and an ester of a dicarboxylic acid and an amino alcohol, such as N,N-dimethylaminomethyl (meth)acrylate, (meth)acrylic acid N , N-dimethylaminoethyl ester, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-(meth)acrylate Diethylaminopropyl propyl ester and N,N-dimethylaminocyclohexyl (meth)acrylate.

(p): an α,β-ethylenically unsaturated monocarboxylic acid and a carboxylic acid of a dicarboxylic acid and a diamine containing at least one primary or secondary amine group, such as N-[2-(dimethylamino)ethyl ] Acrylamide, N-[2-(dimethylamino)ethyl]methacrylamide, N-[3-(dimethylamino)propyl]propenylamine, N-[3-(two Methylamino)propyl]methacrylamide, N-[4-(dimethylamino)butyl]propenylamine, N-[4-(dimethylamino)butyl]methacrylamide , N-[2-(diethylamino)ethyl]propenylamine, N-[4-(dimethylamino)cyclohexyl]propenylamine and N-[4-(dimethylamino)cyclohexyl ] Methacrylamide.

(s): C ₂ -C ₈ monoolefins having at least two conjugated double bonds and non-aromatic hydrocarbons such as ethylene, propylene, isobutylene, isoprene and butadiene.

(t): a polyether (meth) acrylate is a compound of the formula (A)

Wherein the sequence of the alkylene oxide unit is arbitrary, k and l are each independently from 0 to 100, the sum of k and l is at least 3, and R ^a is hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₈ -cycloalkyl or C ₆ -C ₁₄ aryl, R ^b is hydrogen or C ₁ -C ₈ alkyl, Y is O or NR ^c , R ^c is hydrogen, C ₁ -C ₃₀ alkyl or C ₅ -C ₈ -cycloalkyl.

The polyether (meth) acrylate is, for example, a polycondensation product of the above α,β-ethylenically unsaturated monocarboxylic acid and/or dicarboxylic acid and acid chloride thereof, decylamine and anhydride, and polyether alcohol. The polyether alcohol can be easily prepared by reacting ethylene oxide, 1,2-propylene oxide and/or epichlorohydrin with ^a starting molecule such as water or a short-chain alcohol Ra-OH. The alkylene oxide can be used individually, in an alternating sequence or as a mixture. The polyether acrylate can be used alone or in a mixture to prepare an emulsion polymer for use in accordance with the present invention. Suitable polyether (meth) acrylates can be, for example, the name Bisomer Various product forms are available from Laporte Performance Chemicals, UK. It includes, for example, Bisomer MPEG 350 MA, which is methoxypolyethylene glycol monomethacrylate.

Preferred compounds of formula (A) are those wherein Y is O (in other words, an ether bridge).

Preferred compounds of formula (A) are those wherein k is an integer from 3 to 50, more specifically 4 to 25. Also preferred are compounds of formula (A) wherein l is an integer from 3 to 50, more specifically 4 to 25. Particularly preferred compounds are those wherein Y is O, R ^b is hydrogen or methyl, l is 0 (zero) and k is an integer from 3 to 15, preferably from 4 to 12. Further preferred are the compounds wherein Y is O, R ^b is hydrogen or methyl, k is 0 (zero) and l is an integer from 3 to 15, preferably from 4 to 12.

R ^a in the formula (A) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, octyl or 2-ethyl. Hexyl, decyl, dodecyl, palmity or stearyl.

R ^b in the formula (A) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl or n-hexyl, more specific It is hydrogen, methyl or ethyl. R ^{b is} particularly preferably hydrogen or methyl.

(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-vinyl-imidazolidin-2-one and N-allyl imidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one, N-(2-(A) Acrylaminoethyl)imidazolidine-2-one, N-(2-(methyl)propenyloxyethyl)imidazolidine-2-one (=2-ureido(meth)acrylate , UMA) and N-[2-((meth)acryloxy)ethoxyamino)ethyl]imidazolidin-2-one. Preferred monomers containing a ureido group are N-(2-propenyloxyethyl)imidazolidin-2-one and N-(2-methylpropenyloxyethyl)imidazolidine-2-one. Especially preferred is N-(2-methacryloxyethyl)imidazolidin-2-one (2-ureido methacrylate, UMA).

(v): a monomer containing an alkoxyalkyl group such as vinyltrimethoxydecane, vinyltriethoxydecane, vinyltriisopropoxydecane, vinyl quinone (0-methoxyethoxyl) Base) decane, vinyl methyl dimethoxy decane, vinyl methyl diethoxy decane, vinyl dimethyl methoxy decane, vinyl dimethyl ethoxy decane, 3-methyl propylene oxime Propyltrimethoxydecane, 3-methylpropenylpropyltriethoxydecane, 3-methylpropenylpropylmethyldimethoxydecane, 3-methylpropenylpropylpropyl Diethoxy decane, bis(2-acetoxyethyl dimethyl decyloxy) decyl propyl acrylate and methacrylic acid ginate (2-acetoxyethyl dimethyl decyloxy)矽Methyl propyl ester, bis(2-carboxyethyl dimethyl decyloxy) decyl propyl acrylate and bis(2-carboxyethyl dimethyl decyloxy) decyl propyl methacrylate, acrylic acid ( 3-hydroxypropyl dimethyl alkoxy) decyl propyl acrylate and methacrylic acid ginseng (3-hydroxypropyl dimethyl alkoxy) decyl propyl acrylate, acrylate and methacrylate functional groups Substituted fluoro-substituted alkyl/aryl siloxanes such as: acryl(3,3,3-trifluoropropyldimethyl decyloxy)decyl propyl acrylate and methacrylic acid ginseng (3,3,3- Trifluoropropyl dimethyl alkoxy) decyl propyl acrylate, acrylic acid [3-heptafluoroisopropoxypropyl)] dimethyl decyloxy decyl propyl propyl ester and methacrylic acid ginseng [3- seven Fluoroisopropoxypropyl)] dimethyl decyloxy decyl propyl propyl ester, acrylic acid (pentafluorophenyl dimethyl decyloxy) decyl propyl propyl ester and methacrylic acid ginseng (pentafluorophenyl dimethyl hydride) Base alkoxy) decyl propyl ester.

The above monomers M may be used individually, in the form of a mixture of monomers or a mixture of different classes of monomers, with the proviso that the polymer P has a temperature of from -20 ° C to +60 ° C, preferably from -10 ° C to +50 ° C. More specifically, the glass transition temperature T _{g in the} range of 0 ° C to 30 ° C.

Monomer M generally comprises at least 80% by weight, preferably at least 85% by weight, more preferably at least 90% by weight of monoethylenically unsaturated monomer M1 (main monomer) having a water solubility of less than 30 g/l at 25 ° C and 1 bar ). These monomers include, inter alia, the monomers of categories (a), (b), (c) and (s). The main monomer M1 is preferably a monomer of the categories (a) and (b).

For the emulsion polymerization, it is preferred to use at least 80% by weight, more preferably at least 85% by weight and especially at least 90% by weight, based on the total weight of the monomers M, of at least one monomer M1, preferably selected from the group consisting of α,β-olefins. An ester of an unsaturated monocarboxylic acid and a dicarboxylic acid with a C ₁ -C ₂₀ alkanol and an aromatic vinyl monomer. For the emulsion polymerization, the monomer M1 is preferably used in an amount of up to 99.9% by weight, more preferably up to 99.5% by weight and especially up to 99% by weight, based on the total weight of the monomers M.

The main monomer M1 is preferably selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate , (butyl) (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, (methyl) ) n-octyl acrylate, 2-ethylhexyl (meth) acrylate, styrene, 2-methyl styrene, and mixtures thereof.

In addition to the at least one main monomer M1, at least one other monomer M2 may be used for the free radical emulsion polymerization for the preparation of (PD), the at least one other monomer M2 being water soluble at 25 ° C and 1 bar. 30 g/l, especially 50 g/l. These monomers M2 are usually present in smaller proportions (secondary monomers). Preferred monomers M2 are monomers of the classes (f), (g), (h) and (i).

For the emulsion polymerization, it is preferred to use up to 20% by weight, more preferably up to 15% by weight, especially up to 10% by weight, based on the total weight of the monomers M, of at least one monomer M2, preferably from an ethylenically unsaturated monocarboxylic acid. Acids and dicarboxylic acids and anhydrides and monoesters of ethylenically unsaturated dicarboxylic acids, (meth)acrylamide, C ₁ -C ₁₀ hydroxyalkyl (meth)acrylate, C ₁ -C ₁₀ hydroxyalkyl (Meth) acrylamide and mixtures thereof. For emulsion polymerization, when monomer M2 is present, it is preferably used in an amount of at least 0.1% by weight, more preferably at least 0.5% by weight, especially at least 1% by weight, based on the total weight of monomer M.

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, 2-hydroxy acid acrylate. Ethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, and mixtures thereof.

Particularly suitable monomers for use in the process according to the invention are, for example, n-butyl acrylate and methyl methacrylate; n-butyl acrylate, methyl methacrylate and styrene; n-butyl acrylate and styrene; N-butyl acrylate and ethyl hexyl acrylate; n-butyl acrylate, ethyl hexyl acrylate and styrene.

The above-mentioned particularly suitable combination of the main monomers M1 can be combined with a particularly suitable monomer M2, which is preferably selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide and mixtures thereof.

In a particular embodiment, in addition to M1 and M2 (if present), at least one polyether (meth) acrylate is also used to carry out the free radical emulsion polymerization for the preparation of (PD). The latter is preferably used in an amount of from 0.5% by weight to 15% by weight, based on the total weight of the monomers M, preferably from 1% by weight to 10% by weight, and more specifically from 1% by weight to 5% by weight. Suitable polyether methacrylates are compounds of the above polymer class (t). The polyether (meth) acrylate is preferably selected from the compounds of the formula (A) wherein Y is O, R ^b is hydrogen or methyl, l is 0 (zero) and k is an integer from 3 to 15, preferably 4 to 12, and a compound of the following formula (A) wherein Y is O, R ^b is hydrogen or methyl, k is 0 (zero) and l 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. Crosslinking can also be carried out, for example, via functional groups which are 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, methacrylates, allyl ethers of at least dihydric alcohols or vinyl ethers. The OH group of the parent alcohol may be fully or partially etherified or esterified; however, the crosslinking agent comprises at least two ethylenically unsaturated groups.

Examples of the parent alcohol are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3- Butylene glycol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1 ,6-hexanediol, 1,10-nonanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5 -diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1,4 - cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis(4-hydroxyphenyl)propane, 2,2-double [4-(2-Hydroxypropyl)phenyl]propane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiapentane-1,5- A diol and, in each case, polyethylene glycol, polypropylene glycol and polytetrahydrofuran having a molecular weight of from 200 to 10000 g/mol. In addition to a homopolymer of ethylene oxide or propylene oxide, a block copolymer of ethylene oxide or propylene oxide may be used, or an infused oxirane group and a propylene oxide group may be used. Copolymer. Examples of parent alcohols having more than two OH groups are trimethylolpropane, glycerol, isovalerol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, melamine Acid, sorbitan, sugar, such as sucrose, glucose and mannose. It is of course also possible to use polyols after reaction with ethylene oxide or propylene oxide, respectively as the corresponding ethoxylates or propoxylates. The polyol can also be first converted to the corresponding glycidyl ether by reaction with epichlorohydrin.

Other suitable crosslinking agents are vinyl esters or monohydroxy unsaturated alcohols with ethylenically unsaturated C ₃ -C ₆ carboxylic acids (examples are acrylic acid, methacrylic acid, itaconic acid, maleic acid or antibutene) Ester of acid). Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octene-3-ol, 9-nonen-1-ol, dicyclopentene Alcohol, 10-undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. A possible alternative is to esterify the monohydroxy unsaturated alcohol with a polycarboxylic acid (example being malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid).

Other suitable crosslinking agents are esters of unsaturated carboxylic acids with the abovementioned polyols, examples being esters of oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.

Other suitable crosslinking agents are linear or branched, linear or cyclic aliphatic or aromatic hydrocarbons having at least two double bonds, in the case of aliphatic hydrocarbons, which are not conjugated, for example divinylbenzene , divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or a molecular weight of 200 to 20000 g/mol Butadiene.

Further, acrylamide, methacrylamide and at least a difunctional amine N-allylamine are also suitable as crosslinking agents. Examples of such amines are 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-ten Dialkyldiamine, piperazine, diethylenetriamine or isophoronediamine. The above-mentioned allylamines and decylamines of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or at least divalent carboxylic acids are also suitable.

Other suitable crosslinking materials are, for example, triallylamine and triallylmonoalkylammonium salts, such as triallylmethylammonium chloride or triallylmethylammonium methylsulfate.

N-vinyl compounds of urea derivatives, at least bifunctional guanamines, cyanurates or urethanes are also suitable, such as urea, ketamine, propionaldehyde or tartaramide. a vinyl compound such as N,N'-divinylacetamide or N,N'-divinylpropionaldehyde.

Other suitable crosslinking agents are divinyl dioxane, tetraallyl decane or tetravinyl decane. It will be appreciated that mixtures of the above compounds may also be employed.

Further, the crosslinking monomer also includes a monomer containing an ethylenically unsaturated double bond and a reactive functional group, an aldehyde group, a ketone group or an oxirane group (for example, a group capable of reacting with a crosslinking agent to be added) . The functional group is preferably a keto group or an aldehyde 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 acrolein; methacrolein; vinyl alkyl ketone having from 1 to 20, preferably from 1 to 10 carbon atoms in the alkyl group; formazan styrene; one or two in the alkyl group a keto or aldehyde group or an aldehyde group and a keto group of alkyl (meth)acrylate, the alkyl group preferably comprising a total of 3 to 10 carbon atoms, an example being (meth) propylene decyloxyalkyl Propionaldehyde as described in DE-A-2722097. Further, N-side oxyalkyl (meth) acrylamides of the kind known from, for example, US-A-4,226,007, DE-A-20,612,213 or DE-A-2,207,209 are also suitable. Particularly preferred is acetamidine (meth)acrylate, acetamethylene ethyl methacrylate and especially propylene decylamine. 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 crosslinking reactions with functional groups of the polymer, especially ketone groups or aldehyde groups. . For this purpose, for example, an anthracene, a hydroxylamine or an anthracene 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, rhodium polycarboxylates having a molar weight of up to 500 g/mol. More preferably, the ruthenium compound is diruthoyl dicarboxylate preferably having 2 to 10 C atoms. It includes, for example, diterpene oxalate, diammonium malonate, diterpene succinate, diammonium glutarate, diammonium adipate, diterpene sebacate, diammonium maleate Antimony, diammonium fumarate, diterpene itaconate and/or diterpene isophthalate. Particular attention is paid to the following compounds: diterpene adipate, diterpene sebacate and dioxonium isophthalate. Suitable compounds having hydroxylamine or oxime ether groups are described in detail, for example, in WO 93/25588.

Surface cross-linking can also be produced by means of appropriate addition of an aqueous polymer dispersion (PD). This includes, for example, the addition of a photoinitiator or a desiccant. Suitable photoinitiators are, for example, photoinitiators initiated by sunlight, such as derivatives of benzophenone or benzophenone. Suitable desiccants are metal compounds recommended for use in aqueous alkyd resins, such as metal compounds based on Co or Mn (reviewed in U. Poth, Polyester und Alkydharze, Vincentz Network 2005, page 183 f).

The crosslinking component is preferably used in an amount of from 0.0005% by weight to 5% by weight, more preferably from 0.001% by weight to 2.5% by weight, based on the total weight of the monomers used for the polymerization (including the crosslinking agent), more specifically, From 0.01% by weight to 1.5% 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 M can be carried out in the presence of at least one regulator. The regulator is preferably used in an amount of from 0.0005% by weight to 5% by weight, more preferably from 0.001% by weight to 2.5% by weight and more specifically from 0.01% by weight to 1.5% by weight, based on the total weight of the monomers used for the polymerization.

The term "regulator" (polymerization regulator) is generally used for compounds having a high transfer constant. The modifier 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, monofunctionality modifiers, difunctionality modifiers, and polyfunctionality modifiers can be distinguished depending on the number of functional groups in the molecule that can cause one or more chain transfer reactions. Suitable regulators are described, for example, by K. C. Berger and G. Brandrup in J. Brandrup, E. H. Immergut, Polymer Handbook, 3rd edition, John Wiley & Sons, New York, 1989, page II/81-II/141.

Examples of suitable regulators include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, and isobutyraldehyde.

Further, the following may also be used as a regulator: formic acid, a salt or ester thereof such as ammonium formate; 2,5-diphenyl-1-hexene; hydroxylammonium sulfate and hydroxylammonium phosphate.

Other suitable regulators are halogen compounds, examples being tetrachloromethane, chloroform, bromotrichloromethane, tribromomethane, allyl bromide alkyl halides and benzyl compounds such as benzyl chloride or benzyl bromide. .

Other suitable regulators are allyl compounds such as allyl alcohol, functionalized allyl ethers such as allyl ethoxylates, alkyl allyl ethers or glycerol monoallyl ethers.

Other suitable regulators are inorganic acid sulfites, bisulfites and dithionites or organic sulfides, disulfides, polysulfides, arsenic and bismuth. It includes di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethyl thioethanol, diisopropyl disulfide, di-n-butyl disulfide, Di-n-hexyl disulfide, diethylidene disulfide, sulfurized diethanol, di-tert-butyl trisulfide, dimethyl hydrazine, dialkyl sulphide, dialkyl disulfide and/or Aryl sulfide.

In addition, thiol (a compound that retains sulfur in the form of an SH group, also known as 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, mercaptoacetic acid, 3-mercaptopropionic acid, mercapto succinic acid, thioglycerol, thioacetic acid, thiourea, and alkyl mercaptan, such as n-butyl mercaptan, n-hexyl mercaptan or n-xyl Alkyl mercaptan.

Examples of bifunctionality modifiers 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-propanol, Dimercaptoethane, dimercaptopropane, dimercaptobutane, didecylpentane, dimercaptohexane, ethylene glycol bis-mercaptoacetate and butylene glycol bis-decyl acetate. An example of a polyfunctionality modifier is a compound comprising 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 following general formula:

HS-RS-SiR6 _3-x Z _x

Wherein RS is a divalent alkylene group, R6 is an alkyl group, x is 1, 2 or 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, decylmethylmethyldimethoxydecane, and the like, preferably γ-mercaptopropyl Trimethoxy decane. The amount of chain transfer agent used is similar to that disclosed in the prior art. When doing the second design, we tried to get more decyl decane. Can I get more decyl decane?

All of the modulators can be used individually or in combination with each other. A particular embodiment relates to a polymer dispersion PD prepared by free radical emulsion polymerization without the addition of a conditioning agent.

For the preparation of polymers, the monomers can be polymerized by means of initiators which form free radicals.

For the initiator for radical polymerization, a peroxy compound and/or an azo compound which is generally used for such purposes can be used, and examples are alkali metal persulfate or ammonium persulfate, diethylperoxy peroxide, peroxidation. Benzophenone, butyl bromide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl peroxypivalate, third cyanide-2-ethylhexanoate Ester, tert-butyl maleate, cumene hydroperoxide, diisopropyl peroxydicarboxylate, bis(o-tolylmethyl) peroxide, di-decyl peroxide Dioctyl sulfonate, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-third amyl peroxide, tert-butyl hydroperoxide, azobisisobutyronitrile 2,2'-azobis(2-methylamidinopropane) dihydrochloride or 2,2'-azobis(2-methylbutyronitrile). Mixtures of such initiators are also suitable.

Other initiators that can be used are reducing/oxidizing (= redox) initiator systems. The redox initiator system consists of at least one reducing agent (usually an inorganic 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 sulfite such as sodium sulfite, sodium hydrogen sulfite; an alkali metal salt of pyrosulfite, such as sodium metabisulfite; a bisulfite addition compound of an aliphatic aldehyde and a ketone, such as acetone bisulfite. Or a reducing agent such as hydroxymethanesulfinic acid and its salt, or ascorbic acid. The redox initiator system can be used in combination with a soluble metal compound in which the metal component can exist in a plurality of valence states. Examples of typical redox initiator systems include ascorbic acid/iron(II) sulfate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodium metabisulfite, and tert-butyl hydroperoxide/sodium hydroxymethanesulfinate. 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 0.1% by weight to 10% by weight, preferably from 0.1% by weight to 5% by weight, based on all the monomers to be polymerized. Two or more different initiators may also be used in the emulsion polymerization.

The polymer dispersion (PD) is usually prepared in the presence of at least one surface-active compound. A review suitable for protective colloids is found in Houben-Weyl, Methoden der organischen Chemie, Vol. XIV/1, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, pages 411 to 420. Suitable emulsifiers are also found in Houben-Weyl, Methoden der organischen Chemie, Vol. 14/1, Makromolekulare Stoffe, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.

Suitable emulsifiers include anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers. Emulsifiers having a relative molecular weight generally lower than the molecular weight of the protective colloid are preferably used as the surface active material.

Suitable nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, examples being ethoxylated monoalkyl phenols, ethoxylated dialkyl phenols and ethoxylated trialkyl phenols (EO degree: 3 To 50, alkyl: C ₄ - C ₁₀ ), long-chain alcohol ethoxylate (EO degree: 3 to 100, alkyl: C ₈ - C ₃₆ ) and polyethylene oxide / polypropylene oxide Polymers and copolymers. It may comprise alkylene oxide units copolymerized in random or block form. For example, EO/PO block copolymers are highly suitable. Preference is given to using long-chain alkanol ethoxylates (alkyl C ₁ -C ₃₀ , having an average degree of ethoxylation of from 5 to 100), and preferably having a linear C ₁₂ -C ₂₀ alkyl group and having an average An ethoxylate having a degree of ethoxylation of from 10 to 50 and an ethoxylated monoalkylphenol.

Examples of suitable anionic emulsifiers are alkali metal salts and ammonium salts of alkyl sulfates (alkyl: C ₈ -C ₂₂ ), sulfuric acid and ethoxylated alkanols (EO degrees: 2 to 50, alkyl groups: C ₁₂ -C ₁₈ ) an alkali metal salt and an ammonium salt of a monoester, and an alkali metal salt of a monoester of sulfuric acid and an ethoxylated alkylphenol (EO degree: 3 to 50, alkyl group: C ₄ - C ₉ ) An alkali metal salt, an alkali metal salt and an ammonium salt of an alkylsulfonic acid (alkyl group: C ₁₂ -C ₁₈ ), and an alkali metal salt and an ammonium salt of an alkylarylsulfonic acid (alkyl group: C ₉ -C ₁₈ ). Other suitable emulsifiers are found in Houben-Weyl, Methoden der organischen Chemie, Vol. XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192-208. One or two aromatic rings having a C ₄ -C ₂₄ alkyl bis(benzenesulfonate) ether and an alkali metal or ammonium salt thereof are also suitable as an anionic emulsifier. Such compounds are of general knowledge (for example from US-A-4,269,749) and may for example be Dowfax 2A1 (Dow Chemical Company) form is commercially available.

Suitable cationic emulsifiers are preferably quaternary ammonium halides such as trimethylhexadecyl ammonium chloride, methyl trioctyl ammonium chloride, benzyl triethyl ammonium chloride, or NC ₆ - C ₂₀ Alkylpyridine, NC ₆ -C ₂₀ alkylmorpholine or a quaternary compound of NC ₆ -C ₂₀ alkylimidazole, such as N-dodecylpyridinium chloride.

The amount of the emulsifier is usually from about 0.01% by weight to 10% by weight, preferably from 0.1% by weight to 5% by weight, based on the amount of the monomer to be polymerized.

In addition, typical auxiliaries and additives can be added to the polymer dispersion (PD). Such auxiliaries and additives include, for example, pH adjusters, reducing agents, and bleaching agents, such as alkali metal salts of hydroxymethanesulfinic acid (eg, Rongalit from BASF Aktiengesellschaft) C), a binder, a deodorant, a fragrance, an odorant, and a viscosity modifier such as an alcohol such as glycerin, methanol, ethanol, tert-butanol, glycol, and the like. These auxiliaries and additives can be added to the polymer dispersion in the initial charge, in one feed or after the end of the polymerization.

The polymerization is usually carried out at a temperature ranging from 0 ° C to 150 ° C, preferably from 20 ° C to 100 ° C, more preferably from 30 ° C to 95 ° C. The polymerization is preferably carried out under atmospheric pressure, but the polymerization can also be carried out under high pressure, an example being the autogenous pressure of the components used for 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 copolymer of the present invention includes an organic decane monomer having a hydrolyzable group used as a crosslinking site after exposure to moisture, there is no significant amount of water (which will cause organic decane to pass) It is important to carry out the polymerization in the case of early hydrolysis and subsequent reaction with each other to form a siloxane coupling. The polymerization medium should not substantially 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 relatively low, such as less than about 50% by weight of the reaction solution. Suitable solvents for the polymerization of acrylic copolymers having a polymerizable monomer having a hydrolyzable group bonded to a ruthenium atom are well known in the art and literature and include benzene, toluene, xylene, chloroform, tetrachloro Carbon, methyl acetate, ethyl acetate, dichloroethylene, acetone, dioxane, third butanol and other solvents, as well as aromatic hydrocarbons and aliphatic hydrocarbons.

The emulsion polymerization can be carried out batchwise or in the form of a feed process including a staged or gradient process. Preferably, the feed process is such that a portion of the polymerization batch or polymer seed is introduced as the initial charge, heated to the polymerization temperature and the polymerization begins, and then the remaining polymerization batch (usually separated by two or more spaces) The manner of feeding, wherein one or more of the feeds comprises monomers in pure form or in emulsified form, is supplied to the polymerization zone continuously, in stages or in a concentration gradient, during which polymerization is maintained.

The manner in which the initiator is added to the polymerization vessel during the free-radical aqueous emulsion polymerization is known to those of ordinary skill in the art. It may be included entirely in the initial charge introduced into the polymerization vessel or introduced continuously or in stages at its rate of consumption during the free-radical aqueous emulsion polymerization. In each case, this will depend on both the chemical nature of the initiator system and the polymerization temperature in a manner known to those of ordinary skill. Preferably, a portion of the initiator is included in the initial charge and the remaining initiator is supplied to the polymerization zone at its rate of consumption.

In addition to preparing the polymer dispersion (PD) in the absence of seed, according to another embodiment, it is also possible to prepare a defined particle size by emulsion polymerization by a seed latex process or in the presence of a seed latex prepared in the field. Polymer dispersion (PD). Such a polymerization process is known and described, for example, in EP-B 40419, EP-A-614 922, EP-A-567 812, and references cited therein, and "Encyclopedia of Polymer Science and Technology", Volume 5, John Wiley & Sons Inc., New York 1966, p. 847. The polymerization is preferably carried out in the presence of from 0.01% by weight to 3% by weight, preferably from 0.02% by weight to 1.5% 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 may be prepared in situ from a small amount of a monomer to be used for polymerization and a surface active material in an aqueous emulsion by heating the emulsion to a 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 or a mixture of two or more polymerization initiators at a suitable temperature for post treatment, by means of steam or ammonia vapor. Post-treating the polymer solution, or stripping with an inert gas, or treating the reaction mixture with an oxidizing agent or reducing agent, such as an adsorption process that adsorbs impurities on a selected medium, such as activated carbon, for example, or filter.

May be P by a glass transition temperature of the polymer-based emulsion polymerization of at least one ethylenically unsaturated monomer M is preferred to obtain T _g of less than 50 ℃, more preferably less than 40 ℃, in particular below 35 ℃.

The aqueous polymer dispersion (PD) typically has a solids content of from 20% to 65% by weight, preferably from 35% to 60% by weight.

Alkoxydecane (B2)

According to the invention, the alkoxydecane (B2) is an alkoxyfluorenyl monomer or a mercaptodecane selected from the group of monomers listed under the group (v) with respect to the polymer dispersion (PD), as exemplified as mercaptodecane Chain transfer agent.

The alkoxydecanes (B2) can be used individually, in the form of a mixture of a class of alkoxydecanes or in the form of a mixture of different classes of alkoxydecanes.

The alkoxydecane compound (B2) is preferably present in the range of 0.01% by weight to 5% by weight based on the total weight of the component B. It is especially preferred that the alkoxydecane compound (B2) is present in an amount of from 0.01% by weight to 3% by weight, and preferably from 0.01% by weight to 0.5% by weight, based on the total weight of the component B.

Step (b)

According to step (b) of the present invention, the prepolymer obtained in the hydrolysis and polycondensation step (a) in the presence of:

- water, and

- 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 active agent (Z) does not react during step (b).

The term "antimicrobial active agent" refers to a compound having antimicrobial activity, wherein the compound can be an organic molecule, an inorganic or organic ionic species or a particulate material.

Step (b) can be performed in a number of different ways. The presence of water, such as acetone, can be achieved by using an aqueous solvent for dissolving component (A) and/or (B), which is a preferred solvent. In this way, the water required to carry out the hydrolysis and initiate the polycondensation is inherently present in the system. Water may also be added independently before step (b).

Step (b) can be carried out at room temperature or at a high temperature of 30 ° C to 100 ° C, especially 30 ° C to 60 ° C. At the same time, step (b) can be carried out under normal pressure or at a vacuum of from 0.1 to 300 mbar, in particular from 1 to 100 mbar. Step (b) may also be referred to as a drying process in which hydrolysis and polycondensation are inherently occurring. Preferably step (b) is carried out such that a coating is formed. In other words, the formation of the coating of the present invention and the substrate is simultaneously occurring.

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 antimicrobial 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 result in the formation of 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 invention retains the antimicrobial active (Z1), preferably in the presence of water.

Antimicrobial agent (Z)

The antimicrobial agent (Z) may consist of a single antimicrobial active compound (Z1), consisting of a mixture of two or more different antimicrobially active compounds (Z1) or from a carrier material (Z2) in particulate form or One of or a mixture of more than one antimicrobially active compound (Z1).

According to the invention, at least one antimicrobial active agent (Z1) does not react as a prerequisite during step (b). The term "non-reactive" means that the antimicrobial active agent (Z1) does not react during the step (b), that is, it cannot co-react with the prepolymer during the hydrolysis and polycondensation reaction in the presence of water. The terms "reactive" and "reactive" refer to a chemical reaction, that is, a physical bond, such as a physical interaction, that forms a chemical bond. In other words, "not reacting during step (b)" means that no chemical bond is formed with the antimicrobial active agent (Z1) during step (b).

Step (b) comprises further polymerizing the prepolymer by means of component (B2) which is preferably covalently bonded to the prepolymer by hydrolysis and polycondensation.

The antimicrobial active agent (Z1) preferably does not contain any functional groups capable of reacting with Si-OH groups, and such Si-OH groups are preferably present as an intermediate in 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 (Z1) but also the particulate carrier material (Z2). In a particular embodiment, the carrier material (Z2) may contain a reactive group on the surface that is capable of reacting during step (b).

According to a first preferred embodiment, hereinafter referred to as "PE-1", the antimicrobial agent (Z) comprises silver ions as an antimicrobial active agent (Z1) and a group selected from the group consisting of zeolites and polymer hydrogels as particles Carrier substance (Z2).

According to a second preferred embodiment, hereinafter referred to as "PE-2", the antimicrobial agent (Z) comprises a number average particle size selected from the group consisting of (i) zinc oxide and (ii) titanium dioxide containing AgBr and apatite. Granular antimicrobial active agent (Z1) up to 500 nm.

Titanium dioxide encapsulated with AgBr and apatite is known to those skilled in the art. 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, hereinafter referred to as "PE-3", the antimicrobial agent (Z1) is selected from the group consisting of a quaternary ammonium salt and 2-bromo-2-nitropropane-1,3-diol. At least one of the groups.

The preferred embodiments PE-1, PE-2 and PE-3 are discussed in detail below.

According to the preferred embodiment PE-1, 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 having antimicrobial properties are known from the prior art. For example, silver zeolites which can be used for the purposes of the present invention are described in US Pat. No. 4,011,198, US Pat. No. 4,011,899, US Pat. No. 4,938,955, US Pat. No. 4,906,464, US Pat. No. 4,775,585, and WO 03/055,314.

These zeolites may be modified with an organic rhodium comonomer such as: bis(2-acetoxyethyl dimethyl decyloxy) decyl propyl acrylate and methacrylic acid (2) - ethoxylated ethyl dimethyl decyloxy) decyl propyl acrylate, bis(2-carboxyethyl dimethyl decyloxy) decyl propyl acrylate and methacrylic acid ginseng (2-carboxyethyl bis Methyl nonyloxy) decyl propyl acrylate, cis (3-hydroxypropyl dimethyl decyloxy) decyl propyl acrylate and benzyl (3-hydroxypropyl dimethyl decyloxy) decyl methacrylate Propyl ester, acrylate and methacrylate functional fluoro substituted alkyl/aryl siloxanes such as: acryl(3,3,3-trifluoropropyldimethyl decyloxy) decyl propyl acrylate And methacrylic acid ginseng (3,3,3-trifluoropropyl dimethyl decyloxy) decyl propyl acrylate, acrylic acid [3-heptafluoroisopropoxypropyl)] dimethyl decyloxy decane Propyl acrylate and methacrylic acid [3-heptafluoroisopropoxypropyl)] dimethyl decyloxy decyl propyl propyl acrylate (pentafluorophenyl dimethyl decyloxy) decyl propyl acrylate And methacrylic acid Fluorophenyl dimethyl silicone alkoxy) alkyl ester of silicon and silicon-containing alkyl or other chain transfer agent. Preferred decyl decane chain transfer agents for use in the present invention have the following general formula:

HS-RS-SiR6 _3-x Z _x

Wherein RS is a divalent alkylene group, R6 is an alkyl group, x is 1, 2 or 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, decylmethylmethyldimethoxydecane, and the like, preferably γ-mercaptopropyl Trimethoxy decane. The amount of chain transfer agent used is similar to that disclosed in the prior art.

Polymer hydrogels which retain silver ions are also known from the prior art. In principle, any polymer hydrogel capable of retaining silver 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 polymeric (i.e., long chain) molecules joined together to form a three-dimensional network. The polymeric 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 backbone of the hydrogel is typically formed from hydrophilic monomer units and can be neutral or ionic. Examples of neutral and hydrophilic monomer units are ethylene oxide; vinyl alcohol; (meth) acrylamide; N-alkylated (meth) acrylamide; N-hydroxymethyl (meth) propylene Indoleamine; N-vinylamine; N-vinylformamide; N-vinylacetamide; N-vinyl-N-methylacetamide; N-vinyl-N-methylformamidine Amine; hydroxyalkyl (meth) acrylate, such as hydroxyethyl methacrylate; vinyl pyrrolidone; polyethylene glycol monoallyl ether, allyl ether, polyethylene glycol (meth) acrylic acid An ester; a sugar unit such as glucose or galactose. Examples of cationic hydrophilic monomer units are ethylenediamine (in protonated form), diallyldimethylammonium chloride, and trimethylammonium propylmethylpropenylamine chloride. Examples of anionic monomer units are (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-acrylamido-2-methylpropane sulfonic acid, vinyl Sulfonic acid, vinylphosphonic acid, 2-methylpropenyloxyethanesulfonic acid, 4-vinylbenzenesulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid and vinylphenylphosphonic acid (the compound Each of them is in a deprotonated form).

Further, it can be suitably used as a particle carrier by polymerizing an unsaturated acid (for example, acrylic acid, methacrylic acid, and acrylamidopropanesulfonic acid) in the presence of a small amount of a polyethylenically unsaturated compound containing a specific organic germanium comonomer. a hydrogel of the substance (Z2), such as an acrylic acid (2-acetoxyethyl dimethyl decyloxy) decyl propyl acrylate and a methacrylic acid ginate (2-B)醯 ethoxyethyl dimethyl decyloxy) decyl propyl acrylate, bis(2-carboxyethyl dimethyl decyloxy) decyl propyl acrylate and methacrylic acid ginseng (2-carboxyethyl dimethyl矽 alkoxy) decyl propyl acrylate, phenyl (3-hydroxypropyl dimethyl decyloxy) decyl propyl acrylate and benzyl (3-hydroxypropyl dimethyl decyloxy) decyl propyl methacrylate , acrylate and methacrylate functional fluoro substituted alkyl/aryl oxa oxane, such as: acrylic acid (3,3,3-trifluoropropyl dimethyl decyloxy) decyl propyl acrylate and Acrylic acid (3,3,3-trifluoropropyl dimethyl decyloxy) decyl propyl acrylate, acrylic acid [3-heptafluoroisopropoxypropyl)] dimethyl decyloxy Base propyl propyl ester and methacrylic acid [3-heptafluoroisopropoxypropyl)] dimethyl decyloxy decyl propyl propyl acrylate (pentafluorophenyl dimethyl decyloxy) decyl acrylate Propyl and methacrylic acid pentoxide (pentafluorophenyl dimethyl alkoxy) decyl propyl acrylate, and other materials known as supersorbent polymers. In a preferred embodiment, the antimicrobial agent (Z) contains not only the antimicrobial active agent (Z1) but also the particulate carrier material (Z2). In a particular embodiment, the carrier material (Z2) may contain a reactive group on the surface that is capable of reacting during step (b).

Such hydrogels are described, for example, in US-P 4,057,521, US-P 4,062,817, US-P 4, 525, 527, US-P 4, 286, 082, US-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 4,076,663, and US-P 4,931,497.

Hydrogels are typically dried after pulverization 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 beds, moving beds, paddle or spherical bed dryers (Kirk-Othmer 7, 326-398; (3rd edition) 1, 598-624; 8, 75-130, 311-339; 5, 104-112; Ullmann 1, 529-609; 11, 642 ff.; (4th edition) 2, 698-721; vt Industrielle Praxis "Fortschritte auf dem Gebiet der Einbandtrockner", Teil 1: Auslegungsverfahren, E. Tittmann; 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 bimodal crosslinking agent can be used as the crosslinking agent singly, in a mixture or in various combinations. Polyethylene crosslinkers which are advantageously used in superabsorbent polymers are generally known in the art. Preferred compounds having at least two polymerizable double bonds include: divinyl compounds or polyethylene compounds such as divinylbenzene, divinyltoluene, divinylxylene, divinyl ether, diketene, and trivinylbenzene; unsaturated a diester or polyester of a monocarboxylic acid or an unsaturated polycarboxylic acid and a polyhydric alcohol, such as a di-(meth) acrylate or a tri-(meth) acrylate of a polyhydric alcohol, such as an ethylene glycol , diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol and polyoxypropylene glycol; An unsaturated polyester obtained by reacting the above polyol with an unsaturated acid such as maleic acid; an unsaturated monocarboxylic acid or a diester or polyester of an unsaturated polycarboxylic acid and a polyhydric alcohol, which are composed of C ₂ -C ₁₀ polyols with 2-8 hydroxyl groups per C ₂ -C ₄ alkylene oxide units of reaction is generated, such as trimethylolpropane triacrylate six ethoxylates; available by polyepoxide with ( Di-(meth) acrylate or tri-(meth) acrylate obtained by methyl methacrylate reaction Bis(meth)acrylamide, such as N,N-methylene-bisacrylamide; by such as toluene diisocyanate, diisocyanate dimethacrylate, methane diisocyanate a polyisocyanate of 4,4'-diphenyl ester and an NCO-containing prepolymer obtained by reacting the diisocyanate with an active hydrogen atom-containing compound and a hydroxyl group-containing monomer (such as by reacting the above diisocyanate with ( Aminomethyl methacrylate obtained by the reaction of hydroxyethyl methacrylate to obtain dimethyl (meth) methacrylate); such as alkanediol, glycerin, polyalkylene glycol, polyoxyalkylene polyol and Di-(meth)allyl ether or poly(methyl)allyl ether of a carbohydrate, such as polyethylene glycol diallyl ether, allylated starch, and allylated cellulose a bis-allyl or polyallyl ester of a polycarboxylic acid such as diallyl phthalate and diallyl adipate; and an unsaturated monocarboxylic or unsaturated polycarboxylic acid and a polyhydric alcohol An ester of mono (meth)allyl ester, such as (meth) acrylate of allyl methacrylate or polyethylene glycol monoallyl ether.

Preferred classes of crosslinking agents include, for example, bis(meth)acrylamide; allyl (meth)acrylate; diesters or polyesters of (meth)acrylic acid with polyols, such as diethylene glycol diacrylate , trimethylolpropane triacrylate and polyethylene glycol diacrylate; and unsaturated monocarboxylic acid or unsaturated polycarboxylic acid and by making C ₁ -C ₁₀ polyol with 2 to 8 C ₂ per hydroxyl group a diester or polyester of a polyol produced by the reaction of a -C ₄ alkylene oxide unit, such as ethoxylated trimethylolpropane triacrylate.

The antimicrobial agent (Z) according to the preferred embodiment PE-1 contains silver ions as the antimicrobial active agent (Z1). The antimicrobial active agent (Z1) is preferably present in the form of a silver salt.

Examples of the silver salt include, for example, silver acetate, silver acetylacetonate, 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 chlorate, silver chromate, silver citrate, silver cyanate, silver cyanide, (cis, cis-1,5-cyclooctadiene)- Silver 1,1,1,5,5,5-hexafluoroacetoxypyruvate, silver pyridinium (pyridine) complex, silver diethyldithiocarbamate, silver fluoride (I) , silver (II) fluoride, 7,7-dimethyl-1,1,1,2,2,3,3-heptafluoro-4,6-octanedioic acid, silver hexafluoroantimonate, hexafluoro Silver arsenate, silver hexafluorophosphate, silver iodate, silver iodide, silver isothiocyanate, potassium silver cyanide, silver lactate, silver molybdate, silver nitrate, silver nitrite, silver oxide (I), silver oxide (II) , silver oxalate, silver perchlorate, silver perfluorobutyrate, silver perfluoropropionate, silver permanganate, silver perrhenate, silver phosphate, silver picrate monohydrate, silver propionate, silver selenate, selenium Silver, silver selenite, silver sulfadiazine, silver sulfate, silver sulfide, silver sulfite, silver telluride, silver tetrafluoroborate, silver tetraiodide, tetratungstic acid , Silver thiocyanate, silver p-toluenesulfonic acid, trifluoromethanesulfonic acid silver salt, trifluoroacetic acid silver 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 lactate, silver molybdate, silver nitrate, silver nitrite, silver oxide (I), silver perchlorate, silver permanganate, selenium. Silver acid, silver selenite, silver sulfadiazine 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 0.07% 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 (Z1) having a number average particle size of from 1 to 500 nm selected from the group consisting of 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 100 nm, especially 10 to 50 nm, particularly preferably 15 to 45 nm, and most preferably 20 to 40 nm.

Stabilizing particles of the antimicrobial active agent (Z1) are preferably used. If Z1 is zinc oxide, it is preferably stabilized by means of an acrylic polymer.

Furthermore, it is preferred to use zinc oxide doped with a dopant as described in US-A 2005/0048010.

The dopant can be added to the zinc oxide dispersion by methods known to those skilled in the art. Suitable dopants for zinc oxide are, in particular, one or more electrons of metal ions on the outer shell. The main group metal and the sub-group metal in the oxidation state + III are particularly suitable. Extremely preferred are boron (III), aluminum (III), gallium (III) and indium (III). These metals may be added to the dispersion in the form of a soluble salt, the choice of which depends on whether it is dissolved in the dispersant at the desired concentration. In the case of aqueous dispersions, many inorganic salts or complexes are suitable, such as carbonates, halides, salts with EDTA, nitrates, salts with EDTA, acetylated pyruvate, and the like. It may also be doped with a noble metal such as palladium, platinum, gold or the like.

It is especially preferred to use surface-modified zinc oxide nanoparticles as the antimicrobial active agent (Z1). The surface modification of ZnO nanoparticles is known to those skilled in the art and is described, for example, in US-A 2006/0210495, which is incorporated herein by reference. Surface modification is preferably achieved by applying a surface modifier to the ZnO nanoparticle, in particular to the dispersion containing the nanoparticles. In particular, suitable surface modifiers are disclosed in paragraphs 89 (page 5) to 183 (page 6) of US-A 2006/0210495.

The surface of the ZnO nanoparticle can also be modified using a polymer as described in US-A 2007/0243145, the disclosure of which is incorporated herein by reference.

The polymers used for modifying the surface of the ZnO nanoparticles for the purposes of the present invention are preferably selected from the copolymers described in paragraphs 18 (page 2) through 35 (page 3).

Suitable titanium dioxides containing AgBr and apatite are known from M. R. Elahifard, S. Rahimnejad, S. Haghighi, M. R. Gholami, J. Am. Chem. Soc 2007; 129(31); 9552-9553.

The TiO ₂ used in the present invention is preferably surface-modified, in particular by surface modification by means of decane as a surface modifier.

The different decanes which are suitable as surface modifiers are listed in the literature, the entire contents of which are incorporated herein by reference, in particular:

- US-P 6,013,372, column 13 (column 54) to column 14 (column 54),

- US-P 6,663,851, column 2 (column 9) to column 2 (column 54), and

- US-A 2006/0159637, paragraph 44 (page 2) to paragraph 83 (page 3).

For the surface modification, a mixture of two or more of the above decane may be used.

It is also preferred to use a photocatalyst having an antibacterial enhancer as described in U.S. Patent No. 6,013,372, the disclosure of which is incorporated herein by reference.

Further, it is preferred to use a doped photocatalyst as described in US-P 6013372, page 15, lines 25-30.

U.S. Patent Nos. 6,627,173, 7,759,911 and 5,575,515 describe titanium dioxide doped with nitrogen, fluorine and carbon, which are also suitable.

In a preferred embodiment, TiO ₂ is coated with apatite calcium as described in US-A 2007/0154378, the contents of which are hereby incorporated by reference, in particular 16 paragraphs (page 2).

According to a third preferred embodiment "PE-3", the antimicrobial agent (Z1) is selected from at least one of the group consisting of a quaternary ammonium salt and a 2-bromo-2-nitropropane-1,3-diol. .

Preferably, the quaternary ammonium salt is benzyl-alkyldimethylammonium chloride or [2-[[2-[(2-carboxyethyl)(2-hydroxyethyl)amino]ethyl]] Amino]-2-oxo-ethyl]cocoalkylalkylammonium chloride, benzyl- _C12-14 alkyldimethylammonium chloride, benzyl- _C12-16 alkyl chloride Dimethylammonium, benzyl-C _12-18 alkyl-dimethylammonium chloride, C _12-14 alkyl [(ethylphenyl)methyl]dimethylammonium chloride, nC _10-16 Reaction product of alkyl propylene diamine and chloroacetic acid, di-C _8-10 alkyl dimethyl ammonium chloride, dialkyl (C _8-18 ) dimethyl ammonium compound, _dimercapto dimethyl chloride Ammonium, cetylpyridinium chloride, biphenyl-2-ol, bronopol, cetylpyridinium chloride, chlorocresol, chloroxylenol, D-gluconic acid and N , N"-bis(4-chloro-phenyl)-3,12-diimido-2,4,11,13-tetraazatetraoxanedioxin (2:1) compound, ethanol, formaldehyde , formic acid, glutaraldehyde, hexane-2,4-dienoic acid, 1-phenoxypropan-2-ol and 2-phenoxypropanol, oligomeric-(2-(2-ethoxyl) chloride Ethoxyethyl sulfonium salt), bis(peroxymonosulfuric acid) bis(sulfate) pentapotassium salt, 2-phenoxyethanol, o-phthalaldehyde, 6-(o-phenylene)醯imino)peroxyhexanoic acid, poly(chlorinated hexamethylenediamine sulfonium salt), (E,E)-hexan-2,4-dienoic acid, propan-1-ol, propan-2-ol , hydrazine hydroxymethyl sulfonium salt, o-phenylphenol and o-phenylphenol salt, 1-(3-chloroallyl)-3,5,7-triaza-1-azaindene adamantane, 5-Chloro-2,4-dichlorophenoxy)-phenol, 3,4,4'-trichlorodiphenylurea (triclocarban), o-benzo-p-chlorophenol, p-hydroxyl Benzoate, 2-(thiocyanomethylthio)benzothiazole, 3,5-dimethyl-1,3,5-thiodiazepine-2-thione, 2,4- Dichlorobenzyl alcohol.

It is especially preferred to use 2-bromo-2-nitropropane-1,3-diol as the antimicrobial active agent (Z1).

The following preferred embodiments refer to the preferred embodiments PE-1, PE-2 and PE-3 outlined above.

The antimicrobial agent Z is preferably present in an amount of from 1% by weight to 10% by weight based on the total dry weight of the composition.

Total dry weight refers to the weight of the composition after removal of the solvent.

In a preferred embodiment, the composition of the present invention further comprises an antimicrobial component (Z') capable of reacting with components (A) and/or (B) in the presence of water. Thus, the antimicrobial component (Z') is covalently bonded to the resulting mixed network.

The preferred antimicrobial agent (Z') comprises an alkoxydecane moiety and is represented by the following formula (II):

among them

- R ₁ is C ₁ -C ₃₀ alkyl, preferably C ₈ -C ₃₀ alkyl,

- R ₂ and R ₃ , R ₄ and R _{5 are} each independently C ₁ -C ₃₀ alkyl or hydrogen, and

- X is a relative ion such as Cl-, Br-, I- or CH ₃ COO-.

Examples of organoquinone quaternary ammonium salt compounds for use in accordance with the invention are 3-(triethoxydecyl)-propyl-dimethyloctadecyl chloride, 3-(tri-methoxy) chloride.矽alkyl)propyl-methyl-dioctylammonium, 3-(trimethoxyphosphonioalkyl)propyl-dimethylammonium chloride, 3-(trimethoxydecyl)-propyl chloride -Methyldimethylammonium chloride, 3-(trimethoxy-decyl)propyldimethyldodecylammonium chloride, 3-(tris-methoxydecyl)-propyl-methyl chloride Bis-dodecyl ammonium, 3-(trimethoxydecyl)propyl-dimethyltetradecyl ammonium chloride, 3-(trimethoxy-decyl)propyl-methylbis Hexaalkylammonium and 3-(trimethoxydecane)propyl-dimethyloctadecyl ammonium chloride.

The antimicrobial agent (Z') is preferably present in the composition in an amount from about 0.1% to about 50% by dry weight of the composition. The preferred amount of antimicrobial agent is from 1% to 10% of the composition, based on the dry weight of the composition.

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 (cyclo)aliphatic hydrocarbons and mixtures thereof and halogenated hydrocarbons. The 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, 1-methoxyprop-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 phthalate, such as ethylene glycol butyl acetate. Other examples are also carbonates such as preferably 1,2-ethanedicarbonate, 1,2-propylene dicarbonate or 1,3-propane carbonate.

The ether is, for example, tetrahydrofuran (THF), dioxane, and dimethyl ether, diethyl ether or di-n-butyl ether of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol. .

The alcohol is, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, second butanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-dodecanol (lauryl alcohol) ), 2-ethylhexanol, cyclopentanol or cyclohexanol.

The alkanoate alcohol is, for example, a poly(C ₂ to C ₃ ) alkanediol (C ₁ to C ₄ ) monoalkyl ether acetate. The ether alcohol is, for example, a poly(C ₂ to C ₃ ) alkanediol di(C ₁ to C ₄ ) alkyl ether or dipropylene glycol dimethyl ether, preferably ethylene glycol butyl ether.

The aromatic hydrocarbon mixture is a mixture mainly comprising an aromatic C ₇ to C ₁₄ hydrocarbon and capable of containing a boiling range of from 110 ° C to 300 ° C, particularly preferably toluene, o-xylene, m-xylene or p-xylene or trimethylbenzene. Structure, tetramethyl isomer, ethylbenzene, cumene, tetrahydronaphthalene, and mixtures thereof.

An example of this is Solvesso from ExxonMobil Chemical. Level, especially Solvesso 100 (CAS No. 64742-95-6, mainly C ₉ and C ₁₀ aromatics, boiling range from about 154 ° C to 178 ° C), Solvesso 150 (boiling range is about 182 ° C - 207 ° C) and Solvesso 200 (CAS number 64742-94-5), and Shellsol from Shell Level, Caromax from Petrochem Carless Level, such as Caromax 18, or products from DHC, such as Hydrosol A/170. Hydrocarbon mixtures containing paraffins, naphthenes and aromatics are also commercially available under the following names: Kristalloel (eg, Kristalloel 30, boiling range from about 158 ° C to 198 ° C, or Kristalloel 60: CAS number 64742-82-1), White petroleum brain (similarly, for example, CAS No. 64742-82-1) or solvent oil (light: boiling range from about 155 ° C to 180 ° C, weight: boiling range from about 225 ° C to 300 ° C). The aromatic compound content of the hydrocarbon mixtures is generally greater than 90% by weight, preferably greater than 95% by weight, more preferably greater than 98% by weight and most preferably greater than 99% by weight. Mixtures of hydrocarbons having a particularly low naphthalene content are preferred.

The density of hydrocarbons at 20 ° C (DIN 51757) may be less than 1 g/cm ³ , preferably less than 0.95 g/cm ³ and more preferably less than 0.9 g/cm ³ .

The aliphatic hydrocarbon content is usually less than 5% by weight, preferably less than 2.5% by weight and more preferably less than 1% by weight.

The halogenated hydrocarbon is, for example, chlorobenzene and dichlorobenzene or a mixture of isomers thereof.

The (cyclo)aliphatic hydrocarbon is a mixture of isomers such as decalin, alkylated decalin, and linear or branched paraffins and/or cycloalkanes.

Preferred are n-butyl acetate, ethyl acetate, 1-methoxyprop-2-yl acetate, 2-methoxyethyl acetate, and mixtures thereof.

Such a mixture may be prepared in a volume ratio of from 10:1 to 1:10, preferably in a volume ratio of from 5:1 to 1:5, and more preferably in a volume ratio of 1:1.

Preferred examples are butyl acetate/xylene, 1:1 methoxypropyl acetate/xylene, 1:1 butyl acetate/solvent oil 100, 1:2 butyl acetate/Solvesso 100 and 3:1 Kristalloel 30/Shellsol A.

The alcohol is, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, isobutanol, pentanol isomer mixture, hexanol isomer mixture, 2-ethylhexanol or octane alcohol.

Examples of other typical coating additives (E) that may be used include antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, Surfactant, viscosity modifier, plasticizer or chelating agent.

In addition to the free (co)polymerized (co)polymer, suitable thickeners also include typical organic thickeners and inorganic thickeners such as hydroxymethylcellulose or bentonite.

Examples of the chelating agent which can be used include ethylenediamineacetic acid and salts thereof, and ?-diketones.

Suitable fillers include phthalates, examples being citrates obtainable by hydrolysis of ruthenium tetrachloride (such as Aerosil from Degussa) ), diatomaceous earth, talc, aluminum citrate, magnesium citrate, calcium carbonate, and the like.

Suitable stabilizers include typical UV absorbers such as oxalic acid, triazine and benzotriazole (the latter available from Ciba-Spezialit) Tenchemie to Tinuvin Grade obtained) 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 0.1% by weight to 5.0% by weight based on the solid component contained in the preparation.

Pigments can also be included. According to CD R Mpp Chemie Lexikon - Version 1.0, Stuttgart/New York: Georg Thieme Verlag 1995, see DIN 55943, a pigment which is a particulate organic or inorganic colored or colorless colorant which is practically insoluble in the application medium.

It is almost insoluble here that the solubility at 25 ° C is less than 1 g per 1000 g of application medium, preferably less than 0.5 g per 1000 g of application medium, more preferably less than 0.25 g per 1000 g of application medium, and is preferably less than 1000 per 1000 g. g The application medium is 0.1 g and in particular 0.05 g per 1000 g of application medium.

Examples of pigments include any desired system for absorbing pigments and/or effect pigments, preferably absorbing pigments. There are no restrictions on the number and selection of pigment components. For example, it can be adapted to the needs of a particular requirement, such as a desired color effect.

Effect pigments mean all pigments that exhibit a sheet-like configuration and impart a specific decorative color effect to the surface coating. The effect pigments comprise, for example, all of the pigments which are generally useful for vehicle coating and industrial coatings. Examples of such effect pigments are pure metallic pigments, such as aluminum, iron or copper pigments; interference pigments, such as titania coated mica, iron oxide coated mica, mixed oxide coated mica (eg, titanium dioxide) And Fe ₂ O ₃ or titanium dioxide and Cr ₂ O ₃ coating), metal oxide coated aluminum; or liquid-crystalline pigment.

The color-imparting absorbing pigment is, for example, a typical organic or inorganic absorbing pigment that can be used in the coating industry. Examples of organic absorbing pigments are azo pigments, phthalocyanine pigments, quinacridone pigments, and pyrrolopyrrole pigments. Examples of inorganic absorbing pigments are iron oxide pigments, titanium dioxide and carbon black.

application

The compositions of the present invention are useful as coatings and, in particular, as primers, topcoats or as clearcoats and/or basecoats in clearcoat/basecoat compositions. It is also suitable for spray applications.

Coating material

The invention further provides 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 10% by weight to 70% by weight, of inorganic fillers and/or inorganic pigments,

- from 0.1% to 20% by weight of typical auxiliaries, and

- Make up to 100% by weight of water.

The aqueous coating material for the purposes of the present invention means that the continuous phase of the coating material consists of water in an amount of more than 80% by weight, preferably 90% by weight, and in particular only water. In addition, water-miscible liquids such as water-soluble monohydric alcohols (e.g., isooctanol), diols (such as diethylene glycol dimethyl ether), and polyols may be included as part of the continuous phase.

The adhesive composition of the present invention is preferably used for an aqueous coating material. These coating materials are in the form of, for example, a final coloring system (clear varnish) or a coloring system (latex or latex varnish coating). Portions of the pigment can be described using the pigment volume concentration (PVC). The ratio of the volume of the PVC describing the pigment (V _P ) and the filler (V _F ) to the total volume, the total volume consisting of the binder (V _B ) of the dried coating film, the pigment and the volume of the filler, expressed as a percentage: PVC = (V _P + V _F ) × 100 / (V _P + V _F + V _B ). The coating materials can be classified based on PVC, for example as follows:

Highly filled interior paint, washable, white/matte Approx. 85

Indoor paint, scrub resistant, white/matte 65-80

Semi-gloss paint, mercerized - matt about 35

Semi-gloss paint, mercerized about 25

High gloss paint 12-30

Exterior masonry with paint, white 30-65

Clear varnish 0

The composition of a typical latex paint is described below. The latex paint typically comprises from 30% to 75% by weight and preferably from 40% to 65% by weight of non-volatile ingredients. These ingredients mean all non-aqueous ingredients in the formulation, but at least the total weight of the binder, filler, pigment, low volatility solvent (boiling point above 220 ° C), such as plasticizers and polymerization aids. This figure is roughly as follows:

a) from 3% by weight to 90% by weight, more specifically from 10% by weight to 60% by weight of polymer dispersion (PD),

b) from 5% by weight to 85% by weight, preferably from 5% by weight to 60% by weight, more specifically from 10% by weight to 50% by weight, of at least one inorganic pigment,

c) from 0% by weight to 85% by weight, more specifically from 5% by weight to 60% by weight of the inorganic filler, and

d) from 0.1% to 40% by weight, more specifically from 0.5% to 20% 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 includes inorganic white pigments such as titanium dioxide (preferably in the form of rutile), barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, zinc antimony white (zinc sulfide + barium sulfate), or color pigments, Examples are iron oxide, carbon black, graphite, zinc yellow, zinc green, ultramarine blue, manganese black, black, manganese violet, Paris blue or Schweinfurt green. In addition to inorganic pigments, the latex paints of the present invention may also comprise organic color pigments, examples of which are sepia black, garcinia, Cassel brown, toluidine red, blood red, Hansa yellow, indigo, and even Nitrogen dyes, anthraquinoids and anthraquinone dyes, as well as dioxazines, quinacridones, phthalocyanines, isoindolinones and metal complex pigments. Synthetic white pigments with air inclusions to increase light scattering are also suitable, such as Rhopaque Dispersions.

Suitable fillers are, for example, aluminosilicates such as feldspar; citrates such as kaolin, talc, mica, magnesite; alkaline earth metal carbonates such as calcium carbonate (in the form of, for example, calcite or chalk), magnesium carbonate, white clouds Stone; alkaline earth metal sulfate, such as calcium sulfate; cerium oxide and the like. Of course, fine powder filler is preferred among coating materials. The filler can be used in the form of individual components. However, in practice, filler mixtures have proven to be particularly suitable, examples being calcium carbonate/kaolin and calcium carbonate/talc. Bright coating materials typically include only a small amount of very fine powdered filler or no filler.

Fine powder fillers can also be used to enhance hiding power and/or to save the use of white pigments. In order to adjust the hiding power, color tone and color density, it is preferred to use a blend of a color pigment and a filler.

The coating material (aqueous coating material) of the present invention may contain other auxiliary agents in addition to the binder component (B) and the antimicrobial agent (Z), the pigment, and other film-forming polymers as appropriate.

In addition to the emulsifiers used in the polymerization, typical auxiliaries also include wetting or dispersing agents, such as sodium polyphosphate, potassium polyphosphate or ammonium polyphosphate, alkali metal salts and ammonium of acrylic acid copolymers or maleic anhydride copolymers. Salts, polyphosphonates (such as sodium 1-hydroxyethane-1,1-diphosphate) and naphthalene sulfonates, more specifically sodium salts thereof.

Other suitable auxiliaries are flow control agents, defoamers, biocides and thickeners. Suitable thickeners are, for example, combined thickeners such as polyurethane thickeners. The amount of the thickening agent is preferably less than 1% by weight, more preferably less than 0.6% by weight, based on the solid content of the coating material.

Other suitable auxiliaries are film forming auxiliaries or coalescing auxiliaries. It is preferred to use, for example, white petroleum brain, ethylene glycol, propylene glycol, glycerin, ethanol, methanol, water-miscible glycol ethers and acetates thereof, such as diethylene glycol, 1-methoxy-2-propanol, 2-Amino-2-methyl-1-propanol, isooctanol, ethylene glycol butyl ether, diethylene glycol butyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether or dipropylene glycol monobutyl Ether, dipropylene glycol methyl ether, dipropylene glycol propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, 2, 2,4-trimethyl-1,3-pentanediol monoisobutyrate, diisobutyl ketone of long chain dicarboxylic acid (such as Lusolvan) FBH) or tripropylene glycol monoisobutyrate.

The coating material of the present invention is prepared by a known method by blending components in a mixing device commonly used for this purpose. 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. of.

The coating material of the present invention typically comprises from 30% to 75% by weight and preferably from 40% to 65% by weight of non-volatile ingredients. 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 of the present invention can be applied to a substrate by a typical method, for example, by spreading, spraying, dipping, roller coating, knife coating, or the like.

The compositions of the present invention produce a fast reactive durable coating having an extended pot life and excellent curability. The curable composition of the present invention provides a clear coating with improved scratch resistance. The compositions of the invention can also be used in principle as adhesives, elastomers and plastics.

The coating material of the present invention is suitable for coating substrates, including wood, paper, textiles, leather, non-woven fabrics, plastic surfaces, glass, ceramics, mineral building materials (such as cement moldings and fiber-cement sheets), coated or Uncoated metal. It is preferred to use a curable composition to coat plastic or metal (especially in the form of a sheet), more preferably for coating a surface made of metal.

Antimicrobial compositions and coatings comprising such antimicrobial compositions are particularly useful in hospital environments, medical equipment, water treatment facilities, meals and packaging, pharmaceutical laboratories, child care equipment, and other additional protection against microbes The field. Antimicrobial compositions and coatings comprising such antimicrobial compositions can be advantageously used in food equipment such as mixing tanks, service trays, salad sticks, sinks, road mats, coolers, display cases and service desks; household appliances , such as refrigerators, washing machines, dryers, shredders and garbage compressors; food processing, such as grinders, trays, conveyors, storage bins, slicers; and food processing equipment, medical equipment, such as instrument trays, shelves Shelves, sterilization equipment, potty, countertops, inspection tables, trolleys, beds and lighting fixtures, hospitals and public and private internal equipment such as pushers, kick boards, hand towel dispensers, doors, escalators, elevators and lounge equipment, and As part of the transport components, such as vehicle interior parts and surfaces, aircraft interior parts and surfaces, and train interior 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 of the coating material (drying) is removed by heating as appropriate. Repeat this operation one or more times if necessary. The substrate can be applied in a known manner, for example by spraying, smearing, knife coating, brushing, roller coating, roller coating or pouring. The coating thickness is usually in the range of from about 3 to 1000 g/m ² and preferably from 10 to 200 g/m ² . Curing can then be carried out.

After applying the coating material to the substrate, the coating is usually dried for at most 72 hours by a temperature of less than 80 ° C, preferably room temperature to 60 ° C and more preferably room temperature to 40 ° C, as appropriate. Up to 48 hours, more preferably up to 24 hours, excellent up to 12 hours and in particular 6 hours, and the applied coating is at 80 ° C and 270 ° C in an oxygen-containing atmosphere, preferably air or inert gas The curing is preferably carried out by heat treatment (curing) at a temperature between 100 ° C and 240 ° C and more preferably between 120 ° C and 180 ° C. The curing of the coating material occurs over a period of seconds, depending on the amount of coating material applied and the heat transferred via high energy radiation, self-heating surface or convection via a gaseous medium, such as in coil coatings and In the case of a NIR dry combination, it takes up to 5 hours, for example, in the case of a thick coating system on a heat sensitive material, usually after not less than 10 minutes, preferably not less than 15 minutes, more preferably not less than 30 minutes, and is excellent. Not less than 45 minutes. Drying essentially involves the removal of the existing solvent and, in addition, it is possible (even at this stage) to react with the binder, which essentially involves reacting with the binder.

In addition to or instead of thermal curing, curing can also be carried out by means of IR and NIR radiation, where the NIR radiation represents electromagnetic radiation in the wavelength range from 760 nm to 2.5 μm, preferably from 900 to 1500 nm.

Curing takes place 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 polymethyl methacrylate, polybutyl methacrylate, polyethylene terephthalate, butylene terephthalate, Polyvinylidene fluoride, polyvinyl chloride, polyester, polyolefin, acrylonitrile-ethylene propylene-diene-styrene copolymer (A-EPDM), polyether phthalimide, polyether ketone, polyphenylene sulfide, Polyphenylene ether or a mixture thereof.

Further mention may be made of polyethylene, polypropylene, polystyrene, polybutadiene, polyester, polyamine, polyether, polycarbonate, polyvinyl acetal, polyacrylonitrile, polyacetal, polyethylene Alcohol, polyvinyl acetate, phenolic resin, urea resin, melamine resin, alkyd resin, epoxy resin or polyurethane, block or graft copolymer thereof, and blends thereof.

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 (polymethyl methacrylate), PBT (poly(butylene terephthalate)), PA ( Polyamide), ASA (acrylonitrile-styrene-acrylate copolymer) and ABS (acrylonitrile-butadiene-styrene copolymer) and physical mixtures (blends thereof). Particularly preferred are blends of PP, SAN, ABS, ASA, and ABS or ASA with PA or PBT or PC. Particularly preferred are polyolefins, PMMA and PVC.

In particular, according to DE 196 51 350, ASA and ASA/PC blends are especially preferred. Also preferred is polymethyl 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 metal is in particular a metal which has been coated with another coating film, such as an electrocoating film, a surface coating film, a primer or a base coating. These coatings may be solvent based, water based or powder coating based coatings which may be crosslinked, partially crosslinked or thermoplastic, fully cured throughout their volume, or wet to wet coated.

As far as the relevant metal type is concerned, the suitable metal can in principle be any desired metal. However, in particular, it is a metal or alloy that is commonly used as a building metal material and requires corrosion protection.

The surface is in particular the surface of iron, steel, Zn, Zn alloy, Al or an Al alloy. These surfaces may be the surface of a structure that is entirely composed 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 can be the surface of a casting made of galvanized iron or galvanized steel. In a preferred embodiment of the invention, the surfaces are steel surfaces.

Zn alloys or Al alloys are known to the skilled worker. The skilled worker selects the nature and amount of the alloy composition based on the desired end use application. Typical compositions of zinc alloys include, in particular, Al, Pb, Si, Mg, Sn, Cu or Cd. The typical composition of the aluminum alloy specifically includes Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. The alloy may also be an Al/Zn alloy in which Al 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 treat the tinplate iron/steel (tinplate) using the coating composition of the present invention.

The coatings obtainable from the curable compositions of the present invention exhibit excellent antimicrobial properties.

It is known to those skilled in the art that the polyurethane-based polymer obtained according to the present invention is a polyurethane-polyurea-ceria under suitable conditions, especially in the presence of a suitable catalyst and water. polymer.

Another subject of the invention is a kit comprising a curable composition comprising the following as separate parts:

a) at least one binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (PD) as defined above, 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 Si-containing groups, comprising an antimicrobial agent that is not covalently attached to the network.

Furthermore, the present invention provides a hybrid network of polyurethane and cerium oxide chemically linked via a Si-containing group comprising an antimicrobial agent covalently attached to the network.

Instance

Use the following abbreviations in the following examples:

AMSI: 3-[bis(2-hydroxyethyl)amino]propyltriethoxydecane]

HDI: diisocyanate dihexyl diester

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'-tetramethylene diamine

MBA: N'N-methylenebis acrylamide

AP: ammonium persulfate

Quat: dimethyl octadecyl chloride [3-(trimethoxydecyl)propyl] ammonium chloride purchased from Sigma Aldrich

Hygate 4000 antimicrobial sample supplied by Ciba Specialty chemicals

AJ 100 D sample was purchased from AgION Technologies USA

Synthesis of polymer dispersion Example 1

87 g Seed T 6772 and 560 g of deionized water were charged at 95 ° C in a 4 L glass vessel with an anchor stirrer (125 rpm) at 95 °C. The internal temperature was lowered to 70 ° C, feed 1 and part of feed 2 were continuously added over a period of 3 hours and the remaining feed stream 2 was continuously supplied over a 3.5 hour time period, keeping the two feed streams in space at a slow rate Separated on. Feed 5 was then added over a period of 15 minutes with constant agitation. After the completion of the feed 5, the reactor was charged with feed 3 over a period of 30 minutes, followed by loading of feed 4 over a period of 45 minutes. The reactor was then cooled to room temperature and the polymerization was completed by adding the contents of feed 6 at 40 °C. The dispersion had a solids 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:

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 charged at 95 ° C in a 4 1 glass vessel with an anchor stirrer (125 rpm) at 95 °C. The internal temperature was lowered to 70 ° C, feed 1 and part of feed 2 were continuously added over a period of 3 hours and the remaining feed stream 2 was continuously supplied over a 3.5 hour time period, keeping the two feed streams in space at a slow rate Separated on. Feed 5 was then added over a period of 15 minutes with constant agitation. After the completion of the feed 5, the reactor was charged with feed 3 over a period of 30 minutes, followed by loading of feed 4 over a period of 45 minutes. The reactor was then cooled to room temperature and the polymerization was completed by adding the contents of feed 6 at 40 °C. The dispersion had a solids 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:

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 3.00g

Deionized water for rinsing (subsequent)

Paint formulation using Acronal dispersion

The decane-containing polymer prepared by the above procedure is mixed with three decane-functionalized biocides to produce an antibacterial dispersion. 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 dispersions

Example 3: 30 g of antimicrobial agent Quat and 300 g of deionized water were added to 750 g of the dispersion obtained using the procedure indicated in Example 1. After homogenization by shaking, the resulting dispersion was formulated into a paint. The resulting paint was then transferred as a coating to a polycarbonate slide and dried at room temperature for 3 days. The samples were tested for antibacterial activity.

Example 4: 0.5 g of Hygate 4000 powder was added to 500 g of the dispersion in Example 1. After homogenization by shaking, the resulting dispersion was formulated into a paint. The resulting paint was then transferred as a coating to a polycarbonate slide and dried at room temperature for 3 days. The samples were tested for antibacterial activity.

Example 5: To a 500 g dispersion of Example 1, 5 g of AJ100D powder was added. After homogenization by shaking, the resulting dispersion was formulated into a paint. The resulting paint was then transferred as a coating to a polycarbonate slide and dried at room temperature for 3 days. The samples were tested for antibacterial activity.

Example 6: 30 g of antimicrobial agent Quat and 300 g of deionized water were added to 750 g of the dispersion obtained using the procedure indicated in Example 2. After homogenization by shaking, the resulting dispersion was formulated into a paint. The resulting paint was then transferred as a coating to a polycarbonate slide and dried at room temperature for 3 days. The samples were tested for antibacterial activity.

Example 7: 5 g of AJ100D powder was added to 500 g of the dispersion in Example 2. After homogenization by shaking, the resulting dispersion was formulated into a paint. The resulting paint was then transferred as a coating to a polycarbonate slide and dried at room temperature for 3 days. The samples were tested for antibacterial activity.

Antimicrobial activity measurement

The test for antimicrobial activity was carried out according to the Japanese standard JIS Z 2801:2000 - Test for antimicrobial activity and efficacy. The following bacteria were used: Escherichia coli ( E. coli ), Staphylococcus aureus ( S. aureus ) and Methicillin Resistant Staphylococcus aureus (MRSA). Table 1 lists the antimicrobial activity of Acronal paints with varying amounts of various antimicrobial components.

Suppression zone test

To test whether the antimicrobial agent incorporated into the paint is leached from the coating, a zone of inhibition test is performed. The procedures for these tests are detailed here.

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 filter paper was then cut into individual pieces of 3 cm x 3 cm. The test for one type of test organism was repeated three times.

2. Test method

The inhibition zone test was carried out according to the test method JIS L 1902:2002 (halogen-based method) "Testing for antibacterial activity and efficacy on textile products".

3. Results of the suppression zone

None of the test samples of Examples 3-7 showed any zone of inhibition, clearly indicating the presence of a covalent attachment of the antimicrobial agent to the polymer backbone.

Claims (17)

A method of preparing a composition comprising: (a) reacting a binder component (B) comprising at least one alkoxydecane (B2) and a polymer dispersion (PD) to thereby obtain a prepolymer, and then (b) hydrolyzing and polycondensing 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). The method of claim 1, wherein the antimicrobial agent (Z) comprises silver ions as an antimicrobial active agent (Z1) and a group selected from the group consisting of zeolites and polymer hydrogels as the particulate carrier material (Z2). The method of claim 1, wherein the antimicrobial agent (Z) comprises particles having an average particle size of from 1 to 500 nm selected from the group consisting of (i) zinc oxide and (ii) particles comprising titanium dioxide, AgBr and apatite. Agent (Z1). The method of claim 1, wherein the antimicrobial agent (Z) comprises an antimicrobial activity selected from at least one of the group consisting of a quaternary ammonium salt and a 2-bromo-2-nitropropane-1,3-diol Agent (Z1). The method of claim 1, wherein the polymer dispersion (PD) comprises a polymer P comprising at least two monomers M selected from the group consisting of α,β-ethylenically unsaturated monocarboxylic acids and An ester of a carboxylic acid with a C ₁ -C ₂₀ alkanol and a C ₅ -C ₁₀ cycloalkanol; an aromatic vinyl monomer; an ester of vinyl alcohol with a C ₁ -C ₃₀ monocarboxylic acid; an ethylenically unsaturated nitrile; a vinyl halide; a vinylidene halide; a monoethylenically unsaturated carboxylic acid and a sulfonic acid; a phosphorus monomer; an α,β-ethylenically unsaturated monocarboxylic acid; and an ester of a dicarboxylic acid and a C ₂ -C ₃₀ alkanediol; α,β- a decylamine of an ethylenically unsaturated monocarboxylic acid and a dicarboxylic acid and a C ₂ -C ₃₀ amino alcohol having a primary or secondary amine group; a primary amide of an α,β-ethylenically unsaturated monocarboxylic acid and N-alkyl and N,N-dialkyl derivatives; N-vinyl decylamine; open-chain N-vinyl decylamine compounds; esters of allyl alcohol with C ₁ -C ₃₀ monocarboxylic acids; , β-olefinic unsaturated monocarboxylic acid and ester of dicarboxylic acid and amino alcohol; α,β-ethylenically unsaturated monocarboxylic acid and dicarboxylic acid and containing at least one primary or secondary amine group Amine amide; N,N-diallylamine; N,N-diallyl-N-alkylamine; nitrogen substituted with vinyl and allyl A ring; vinyl ethers; C ₂ -C ₈ monoolefins; non-aromatic hydrocarbon having at least two conjugated double bonds; polyether (meth) acrylate; ureido group-containing monomer of; and mixtures thereof. The method of claim 1, wherein the polymer dispersion (PD) comprises a polymer P comprising at least two monomers M and having a glass transition temperature in the range of -20 ° C to +60 ° C. The method of claim 5 or 6, wherein the monomer M has a main monomer M1 selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate, Isopropyl methacrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, (methyl) N-hexyl acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, 2-methylstyrene, and mixtures thereof. The method of claim 5 or 6, wherein the monomer M has a main monomer M1, and the combination of the main monomers M1 is selected from N-butyl acrylate and methyl methacrylate; n-butyl acrylate, methyl methacrylate and styrene; n-butyl acrylate and styrene; n-butyl acrylate and ethyl hexyl acrylate; n-butyl acrylate, acrylic acid Ethylhexyl ester and styrene. 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 vinyltrimethoxydecane, vinyltriethoxydecane , vinyl triisopropoxy decane, vinyl cis (0-methoxyethoxy) decane, vinyl methyl dimethoxy decane, vinyl methyl diethoxy decane, vinyl dimethyl Methoxydecane, vinyl dimethyl ethoxy decane, 3-methylpropenyl propyl trimethoxy decane, 3-methyl propylene propyl triethoxy decane, 3-methyl propylene oxime Propyl propyl dimethoxy decane, 3-methylpropenyl propyl methyl diethoxy decane, acrylic acid (2-acetoxyethyl dimethyl decyloxy) decyl propyl acrylate , bis(2-ethoxymethoxyethyl dimethyl decyloxy) decyl propyl methacrylate, bis(2-carboxyethyl dimethyl decyloxy) decyl propyl acrylate and methacrylic acid (2-Carboxyethyl dimethyl decyloxy) decyl propyl acrylate, propylene (3-hydroxypropyl dimethyl decyloxy) decyl propyl acrylate, acrylic acid (3-hydroxypropyl dimethyl hydrazine) Oxy) decyl propyl propyl ester and methacrylic acid ginseng (3-hydroxypropyl dimethyl decyloxy) decyl propyl acrylate, acrylate and methacrylate functional fluoro substituted alkyl / aryl oxa oxane , such as acrylic acid (3,3,3-trifluoropropyl dimethyl decyloxy) decyl propyl acrylate and methacrylic acid ginseng (3,3,3-trifluoropropyl dimethyl decyloxy) decane Propyl propyl ester, acrylonitrile [3-heptafluoroisopropoxypropyl)] dimethyl decyloxy decyl propyl propyl ester and methacrylic acid [3-heptafluoroisopropoxypropyl) dimethyl a decyloxy decyl propyl propyl ester, an acrylic acid pentoxide (pentafluorophenyl dimethyl decyloxy) decyl propyl propyl ester, and a methacrylic acid ginseng (pentafluorophenyl dimethyl decyloxy) decyl propyl acrylate, or Formula: HS-RS-SiR6 _3-x Z _x wherein RS is a divalent alkylene group, R6 is an alkyl group, x is 1, 2 or 3, and Z is a hydrolyzable group, or a mixture thereof. The method of any one of claims 1 to 4, wherein the alkoxydecane (B2) is present in a range from 0.01% by weight to 5% by weight based on the total weight of the component B. The method of any one of claims 1 to 4, wherein the antimicrobial agent (Z) is present in an amount of from 1% by weight to 10% by weight based on the total dry weight of the resulting composition. A composition obtainable by the method of any one of claims 1 to 11. 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 as defined in any one of items 1 to 11, up to 70% by weight, preferably 10% by weight to 70% by weight, 0.1% to 20% by weight of typical auxiliaries, and 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 hybrid network, such as those described in relation to polymer dispersions (PD) and ceria, which are chemically linked to one another via Si-containing groups, comprising an antimicrobial agent that is not covalently attached to the network. A use of the composition of claim 12 for the preparation of an antimicrobial coating.