MXPA99005565A - Compositions in dispersion ignifuga - Google Patents

Abstract

The present invention relates to: Aqueous dispersion which can be prepared on the basis of at least one water-insoluble organic polymer, at least one silicon compound dispersed in water and at least one soluble or dispersible phosphorus compound in water

Description

COMPOSITION IN IGNIFUGANT DISPERSION The invention concerns an aqueous dispersion, its preparation, its use and the products containing it. The use of halogen-containing additives or comonomers, optionally in combination with antimony compounds, is known for the flame retardant finishing of polymers. Flame retardant agents based on metal hydroxides such as AI (OH) 3 or Mg (OH) 2 generally have too little effect or impair the mechanical properties of the polymer because of the high amount used. Phosphorus-containing flame retardants, such as p. ex. Ammonium polyphosphate alone show, compared to halogenated compounds, also minor effects. In the case of aqueous dispersions of polymers, special requirements for flame retardants are raised: they must be water soluble or water dispersible; the dispersion containing the flame retardant agent must be stable, ie flocculation or coagulation must not be reached; in the dispersion film the flame retardant agent must be distributed in a stable and homogeneous manner. DE 3803030 C2 describes the use of phosphonates as flame retardants in synthetic materials such as a polyurethane, a polyvinyl chloride, a polyester and an epoxy resin.

European Patent EP 0733638 A1 discloses phosphorus-containing aromatic dicarboxylic acid esters as halogen-free flame retardants for polyester fiber materials. The German patent application publication document DE OS 1950 8530 describes the simultaneous use of functionalized monomers and phosphorus compounds reactive with these functional groups in aqueous dispersion compositions in order to improve fireproofing. In the U.S. patent document US 5412014 A describes a process for the flame retardant finish of thermoplastic materials or thermosetting resins by a mixture of a silicone polymer powder (consisting of a polydiorganosiloxane and silicon dioxide) and a phosphorus-containing flame retardant. The invention was based on the mission to improve the state of the art and especially to make available aqueous dispersion compositions, which also without halogen and antimony compounds produce in the subsequent use p. ex. as a coating or impregnation agent, sufficient protection against flames. The invention was also based on the mission of making aqueous dispersion compositions available, which are suitable at the same time for the consolidation of fibrous materials and batts as well as for finishing and sizing of textile materials.

An object of the invention are aqueous dispersions which can be prepared on the basis of at least one water-insoluble organic polymer, at least one silicon compound dispersible in water and at least one phosphorus compound soluble or dispersible in water. Suitable water-insoluble organic polymers are preferably homopolymers and copolymers which are present in the form of an aqueous dispersion and which, if necessary at elevated temperature and / or in an alkaline medium, form a solid film after desiccation and, optionally, cross-linking . Preferred as water-insoluble polymers are vinyl ester homopolymers or copolymers containing one or more monomer units taken from the group consisting of vinyl esters of unbranched or branched alkyl carboxylic acids, preferably having 1 to 15 carbon atoms. , especially preferably from 1 to 10, and very particularly preferably from 1 to 3 C atoms; homopolymers or copolymers of (meth) acrylic acid esters containing one or more monomer units taken from the group consisting of esters with methacrylic acid and esters with acrylic acid of unbranched or branched alcohols with 1 to 12 carbon atoms C, especially preferably from 1 to 8, and very particularly preferably from 1 to 4 C atoms; homopolymers or copolymers of monoesters or diesters with fumaric and / or maleic acids of unbranched or branched alcohols with 1 to 12 C atoms, particularly preferably 1 to 8, and very particularly preferably 1 to 4; the homopolymers or copolymers of dienes such as butadiene or isoprene, as well as of olefins such as ethene or propene, the dienes being able to be copolymerized for example with styrene, esters with (meth) acrylic acid or the esters with fumaric or maleic acids; homopolymers or copolymers of vinylaromatic compounds such as styrene, methyl styrene or vinyl toluene. If appropriate, polyaddition and polycondensation film-forming polymers, which are insoluble in water, such as polyurethanes, polyesters, polyethers (except polyethylene oxide), polyamides, melamine and formaldehyde resins, phenol and formaldehyde resins, optionally are also suitable. also in the form of its oligomer precursor products. Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethyl-hexanoate, vinyl laurate, 1-methyl-vinyl acetate, vinyl pivalate and vinyl esters of branched monocarboxylic acids in a with up to 15 C atoms, particularly preferably from 1 to 10, for example VeoVa9®-vinyl ester of neononanoic acid or VeoVa10®-vinyl ester of neodecanoic acid. Especially preferred are vinyl esters having a high ratio of O to CH, such as vinyl acetate.

Preferred esters with methacrylic acid or esters with acrylic acid are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, t-butyl acrylate, methacrylate n-butyl, t-butyl methacrylate, 2-ethylhexyl acrylate. Especially preferred are the compounds methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate. Esters with methacrylic acid or esters with especially preferred acrylic acid are those having a high ratio of O to CH, such as methyl acrylate and methyl methacrylate. Preferred groups of esters with fumaric and maleic acids are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, t-butyl, hexyl, etii-hexyl and dodecyl groups. Esters with especially preferred fumaric and maleic acids are those having a high ratio of O to CH, such as dimethyl fumarate and dimethyl maleate. The copolymers of vinyl esters can optionally contain from 1.0 to 65% by weight, based on the total weight of the comonomer phase, preferably of α-olefins such as ethylene or propylene and / or vinyl aromatics such as styrene and / or or esters with acrylic acid or esters with methacrylic acid of alcohols with 1 to 15 C atoms such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate , t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and / or esters with ethylenically unsaturated dicarboxylic acids or their derivatives, such as diisopropyl fumarate, containing the esters of dimethyl, methyl and t-butyl, di-n-butyl, di-t-butyl and diethyl of maleic acid or fumaric acid, or maleic anhydride. Especially preferred are esters with acrylic acid or esters with methacrylic acid of alcohols having 1 to 8 carbon atoms, particularly preferably with 1 to 4 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate and t-butyl methacrylate. Preferably, the copolymers of vinyl esters contain less than 20% by weight, based on the total weight of the comonomer phase, of α-olefins and / or vinylaromatic compounds and / or esters with acrylic acid or esters with methacrylic acid of alcohols with more than 4 C atoms and / or esters with ethylenically unsaturated dicarboxylic acids of alcohols with more than 4 C atoms, so that a low O to CH ratio results in the copolymer. The copolymers of (meth) acrylic acid esters can optionally contain from 1.0 to 65% by weight, based on the total weight of the comonomer phase, preferably of α-olefins such as ethylene or propylene and / or vinyl aromatic compounds. such as styrene and / or esters of ethylenically unsaturated dicarboxylic acids or their derivatives such as diisopropyl fumarate, containing dimethyl, methyl and t-butyl, dibutyl and diethyl esters of maleic acid or fumaric acid, or acid anhydride maleic In a preferred embodiment, the copolymers of vinyl esters and the copolymers of (meth) acrylic acid esters additionally contain 0.05 to 10.0% by weight, based on the total weight of the comonomer mixture, preferably of monomers auxiliaries taken from the group of ethylenically unsaturated carboxylic acids, preferably acrylic acid or methacrylic acid; among the group of ethylenically unsaturated carboxylic acid amides, preferably acrylamide; among the group of ethylenically unsaturated sulphonic acids or their salts, preferably vinyl sulfonic acid; and / or among the group of comonomers several times ethnically unsaturated, for example divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate. Suitable auxiliary monomers are also comonomers which have a crosslinking action, for example acrylamido glycolic acid (AGA), methylacrylamido glycolic acid methyl ester (MAGME), N-methylol acrylamide (NMAA), N-methylol methacrylamide, N- allyl methylol carbamate, alkyl ethers such as isobutoxy ether, or esters of N-methylol-acrylamide, of N-methylol-methacrylamide or of allyl N-methylol-carbamate. The corresponding to the copolymers of vinyl esters and to the copolymers of esters with (meth) acrylic acid serves for the copolymers of the esters with the maleic or fumaric acids. The preparation of the said water-insoluble, radically polymerizable polymers is preferably carried out in accordance with the emulsion polymerization process. The polymerization can be carried out discontinuously or continuously, with or without the use of seed latices, by previously arranging all the constituents or individual constituents of the reaction mixture, or by previously partially and subsequently dosing all the constituents or individual constituents of the reaction mixture, or according to the dosing process without previously having any constituent. All the dosages are preferably carried out as the respective component is consumed. The polymerization is preferably carried out in a temperature range from 0 to 100 ° C, particularly preferably from 20 to 100 ° C, most preferably from 30 to 90 ° C, and is initiated with the methods usually employed for emulsion polymerization. The initiation is carried out by means of the usual water-soluble radical-forming compounds, which are preferably used in amounts of 0.01 to 3.0% by weight, based on the total weight of the monomers. All the emulsifiers and / or protective colloids which are usually used in the case of emulsion polymerization can be used as dispersing agents. If necessary, up to 6% by weight of an emulsifier is used, based on the total weight of the monomers when carrying out the emulsion polymerization. Suitable emulsifiers are anionic or cationic as well as nonionic emulsifiers, provided that they are not soluble in the protective colloid. Preference is given to using protective colloids, especially preferably in amounts of up to 15% by weight, based on the total weight of the monomers. Examples thereof are preferably poly (vinyl alcohols) and their derivatives such as vinyl alcohol and vinyl acetate copolymers, poly (vinylpyrrolidones); polysaccharides in water-soluble form such as starches (amylose and amylopectin), cellulose, guar gum, tragacanthic acid, dextran, alginates and their carboxymethyl, methyl, hydroxyethyl and hydroxypropyl derivatives; proteins such as casein, soy proteins, gelatins; synthetic polymers such as poly [(meth) acrylic acid], poly [(meth) acrylamide], poly (vinyl sulfonic acids) and their water soluble copolymers; melamine and formaldehyde sulfonates, naphthalene and formaldehyde sulfonates, copolymers of styrene and maleic acid and of vinyl ethers and maleic acid. The organic polymers are present in an amount of preferably 30 to 70% by weight, particularly preferably 40 to 60% by weight, very particularly preferably 40 to 55% by weight, based on the total weight of the aqueous dispersion. Suitable water-dispersible silicon compounds are preferably silicic acid esters Si (OR ') 4, organo-organoxy-silane SiRn (OR') 4-n with n = 1 to 3, oligo-siloxanes of the general formula R3SiO (SiR2?) NSR3 with n = from 0 to 4, or its hydrolysis and condensation products, the R 'radicals representing alkyl radicals or alkoxyalkylene radicals with 1 to 4 carbon atoms, the same or different, preferably meaning methyl or ethyl , and R "being the same or different and meaning branched or unbranched alkyl radicals preferably having from 1 to 22 C atoms, particularly preferably from 1 to 10, most preferably from 1 to 4 C atoms, cycloalkyl radicals preferably having from 3 to 10 carbon atoms, particularly preferably from 5 to 6, very especially preferably 6 carbon atoms, alkylene radicals preferably having from 2 to 4 carbon atoms, aryl radicals, arylalkyl radicals and alkylaryl that have preferred preferably from 6 to 18 C atoms, particularly preferably from 6 to 12, very particularly preferably from 6 to 8 C atoms, said radicals R may also be substituted with ether, thioether, ester, amide groups, nitrile, hydroxyl, amine, carboxyl, sulfonic acid, carboxylic acid anhydride and carbonyl. Especially preferred silicon compounds are for example tetraethoxy-silane, methyl-tri (m) ethoxy-silane, methyl-tripropoxy-silane, methyl-tri (ethoxyethoxy) -silane, vinyn-tr (methoxyethoxy) s. lano, (meth) acryloxypropyl-triethoxy- or -trimethoxy-silane, ß-nitriloethyl-triethoxy-silane, mercapto-propyl-triethoxy- or -trimethoxy-silane, phenyl-triethoxy-silane, iso-octyl-triethoxy-silane, dipropyl -dietoxy-silane, methyl-phenyl-diethoxy-silane, diphenyl-dimethoxy-silane, methylvinyl-tri (ethoxyethoxy) silan as well as their disiloxanes and / or trisiloxanes. In addition, hexamethyl-diethoxy-trisiloxane, octamethyl-cyclotetrasiloxane, tetramethyl-diethoxy-disilane, trimethyl-trimethoxy-disilane, dimethyl-tetramethoxy-disilane and pentamethyl-disilane-disiloxane are to be mentioned. Said silicon compounds can be used preferably as such or in the form of their hydrolysis and condensation products. The said silicon compounds can be used alone or as a mixture. The preparation of organic silicon compounds can be carried out according to procedures such as those described in the works of Noli, Chemie und Technologie der Silicone, 2nd edition 1968, Weinheim, and Houben-Weyl, Methoden der organischen Chemie, tome E20, pages 1782 et seq., 2219 et seq., Georg Thieme Verlag, Stuttgart, 1987. The organosilicon compounds dispersible in water are preferably present in an amount of 0.5 to 60% by weight, particularly preferably 0, 5 to 20% by weight, very preferably from 0.5 to 10% by weight, based on the organic polymer portion. The silicon compounds are preferably added in the form of an emulsion of the organic polymer dispersion. Suitable emulsifiers are ammonium or cationic as well as nonionic emulsifiers. Suitable emulsifiers are common to one skilled in the art and are found, for example, in the work of Houben-Weyl, Methoden der organischen Chemie, volume XIV, 1, Makromolekulare Stoffe (macromolecular substances), Georg Thieme Verlag, Stuttgart, 1961, 192-208. Examples of emulsifiers are preferably anionic emulsifiers: 1. Alkyl sulfates, especially those having a chain length of 8 to 18 carbon atoms, alkyl- and alkylaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic radical and 1 to 40 units of ethylene oxide (EO) or propylene oxide (OP). 2. Sulfonates, especially alkyl sulfonates with 8 to 18 carbon atoms, alkylaryl sulfonates with 8 to 18 carbon atoms, taurides, esters and semi esters of sulfosuccinic acid with monovalent alcohols or alkylphenols having from 4 to 15 carbon atoms.; optionally, these alcohols or alkylphenols can also be ethoxylated with 1 to 40 units of EO. 3. Alkali metal and ammonium salts of carboxylic acids with 8 to 20 C atoms in the alkyl, a alkylaor alkyl radical. 4. Partial phosphoric acid esters and their alkali metal and ammonium salts, especially alkyl- and alkylaphosphates with 8 to 20 carbon atoms in the organic radical, alkyl ether or alkylaether phosphates with 8 to 20 carbon atoms. C atoms in the alkyl or alkylaradical and 1 to 40 units of EO. The nonionic emulsifiers are preferably: Poly (vinyl alcohol), which still has from 5 to 50%, preferably from 8 to 20% units of vinyl acetate, with a degree of polymerization of 500 to 3000. 6. Alkyl polyglycol ethers, preferably those having from 8 to 40 OE units and alkyl radicals from 8 to 20 C atoms. 7. Alkylapolyglycol ethers, preferably those having from 8 to 40 units of OE and 8 to 20. C atoms in the alkyl and aradicals. 8. Copolymers of ethylene oxide / propylene oxide (OE / OP) blocks, preferably those having from 8 to 40 units of EO or OP. 9. Products of addition of alkyl amines with alkyl radicals of 8 to 22 C atoms with ethylene oxide or propylene oxide. 10. Fatty acids with 6 to 24 carbon atoms. 11. Alkyl polyglycosides of the general formula R * -0-Zo, in which R * means a linear or branched, saturated or unsaturated alkyl radical, having on average 8 - 24 C atoms and Zo means an oligo-glycoside radical which has on average or = 1-10 hexose or pentose units or mixtures thereof. 12. Natural substances and their derivatives, such as lecithin, lanolin, saponins, celluloses; alkylic ethers of cellulose and carboxyalkylcelluloses, the alkyl groups of which each have up to 4 carbon atoms. 13. Linear organ (poll) siloxanes containing polar groups, especially those having alkoxy groups with up to 24 C atoms and / or up to 40 OE and / or OP groups. The cationic emulsifiers are preferably: 14. Salts of primary, secondary and tertiary fatty amines of 8 to 24 C atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acids. 15. Alkyl- and alkylbenzene-ammonium quaternary salts, especially those whose alkyl groups have from 6 to 24 C atoms, especially the halides, sulphates, phosphates and acetates. 16. Alkyl-pyridinium, alkyl-imidazolinium and alkyl oxazolium salts, especially those whose alkyl chain has up to 18 carbon atoms, especially the halides, sulphates, phosphates and acetates. The ampholytic emulsifiers are preferably: 17. Amino acids substituted with long chains such as N-alkyl-di (aminoethyl) glycine or salts of N-alkyl-2-amino-propionic acids. 18. Betaines, such as N- (3-acylamido-propii) -N: N-dimethylammonium salts with a C 8 -C 8 acyl radical and alkyl imidazolium betaines. The emulsifiers are generally used in amounts of preferably up to 10% by weight, based on the silicon compounds. Preferably, the amount amounts to < 1% by weight, based on organic polymers. Suitable water soluble or dispersible phosphorus compounds are preferably esters, amides or ester-amides of alkyl- or aryl-phosphonic acids, phosphoric acid or pyrophosphoric acid, tetrakis- (hydroxyalkyl) -phosphonium salts, salts of polyphosphoric acid , especially ammonium polyphosphate or triaryl- or trialkyl-phosphine oxides. Preferred phosphorus compounds are for example methane phosphonic acid diethyl ester, methane phosphonic acid dimethyl ester, d, (p) ethyl pentaerythritol diphosphonate, (m) ethyl-neopentyl phosphonate, triphenyl phosphate, tricresyl phosphate , resorcinol phosphate and bis-diphenyl, diphenyl phosphate and pentaerythritol, phenyl phosphate and neopentyl, nitrile-tris-methylenephosphonates of mono-, di- and tri-ammonium, dimethyl ester of [3 - [(hydroxy-methyl)] amino] -3-oxo-propyl] -phosphonic chloride, tetrakis (hydroxymethyl) -phosphonium chloride, ammonium polyphosphate, tritolyl-phosphine oxide and triphenyl-phosphine oxide. Especially preferred phosphorus compounds are the compounds diethyl ester of methane-phosphonic acid, dimethyl ester of methane-phosphonic acid, nitrile-tris-methylenephosphonates of mono-, di- and tri-ammonium, dimethyl ester of [3 - [(hydroxy -methyl) amino] -3-oxo-propyl] -phosphonic acid. The phosphorus compounds are used in amounts of preferably 0.1 to 90% by weight, particularly preferably 0.1 to 50% by weight, most preferably 5 to 30% by weight, based on the total weight of the organic polymers. Further preferred phosphorus compounds are those which additionally carry silicon in the molecule, such as, for example, diethyl ester of 2-triethoxysilyl-ethane-phosphonic acid, diethyl ester of 2-trimethoxysilyl-ethane-phosphonic acid, diethyl ester of 3-trimethoxysilyl -propane-phosphonic acid, diethyl ester of 2-tri [methoxyethoxy] silyl-ethano-phosphonic acid and 1,3-bis [diethylphosphonoethyl] -tetramethyl-di-loxane. The phosphorus compounds with silicon in the molecule are used in amounts of preferably 0.1 to 90% by weight, particularly preferably 0.1 to 50% by weight, very especially preferably 5 to 30% by weight , referred to the total weight of organic polymers.

The phosphorus compounds are preferably added as an aqueous solution or in the form of an emulsion - for whose composition the same as mentioned in the case of silicon compounds - is used for the dispersion of polymers. The mentioned phosphorus compounds can be used alone or as a mixture. Another object of the invention is a process for the preparation of an aqueous dispersion, the constituents being mixed together. In particular, an aqueous dispersion of a polymer, a silicon compound and a phosphorus compound are mixed together. In this case, the constituent of the polymer dispersion type is always used as an aqueous dispersion. The component component with silicon can be used as a 100% substance or as an aqueous emulsion. The constituent component with phosphorus can be used as a 100% substance, or in the case of a solid material as an aqueous solution or dispersion or in the case of a liquid as an aqueous solution or emulsion. All combinations of the above formulations are possible. A possibility of the process is preferred, according to which an aqueous dispersion of a polymer is mixed with an aqueous solution of the component with phosphorus and with an emulsion of the component with silicon.

A possibility of the process is also preferred, according to which an aqueous dispersion of the polymer is mixed with the component with 100% phosphorus and with an emulsion of the component with silicon. The constituents of the polymer dispersion types, silicon component and phosphorus component are mixed together by stirring or shaking, the dispersion of the polymer being preferably pre-arranged and the component with silicon and the phosphorus component then added. Preferably, the component is first mixed with silicon and the component with phosphor then the mixture is added to the polymer dispersion. The dispersions according to the invention are preferably used in coating compositions, impregnation agents or adhesives. In addition, these are used for the consolidation of fibrous materials or batts. The dispersion compositions can be used in typical applications sectors. For example, in coating agents or protective paints against fires, in adhesives or as binders for textile goods. The dispersion compositions according to the invention are especially suitable for the consolidation of fibrous materials, such as webs or wadding or also for the finishing and finishing of textile materials. Another object of the invention are fibrous materials, which contain the dispersions according to the invention. The substrates treated with the dispersion composition according to the invention are finished or prepared in a flame-retardant manner against untreated substrates. In the case of the finishing or sizing of textile materials, the dispersion according to the invention is used in a dilution of preferably 5 to 40% by weight in water. The dilution is adapted to the respective finishing or sizing process. Thus, when spraying it is from 10 to 25% by weight, when impregnated by a single face it is from 5 to 35% by weight and when applied in the form of foam it is from 20 to 30% by weight.

EXAMPLES Preparation of the emulsion solution: 0.50 g of Aerosol A 102 (half ester-salt of sulfosuccinic acid) and 4.60 g of Genapol PF 40 (polymerization product based on propylene oxide and ethylene oxide) were dissolved in 232 g of H2O.

Preparation of the polymer films: A film on a flat base was spread out from the dispersion by means of a doctor blade, so that after drying a film thickness of approximately 250 μm was obtained. After drying in air for about 20 h, the polymer film was tempered in a drying oven for 5 min at 150 ° C. From the film, pieces with a size of 140 mm x 52 mm were cut and stored for at least 24 h in a desiccator over blue gel (Blaugel).

Determination of the oxygen index (LOI): The determination of the LOI was carried out in accordance with ISO 4589, with the difference that the samples, before the measurement, were stored for at least 24 h in a desiccator over blue gel (Blaugel).

EXAMPLE 1 4.22 g of methyl triethoxy silane and 2.94 g of dimethyl phosphonate (DMMP) were added with stirring in 15.8 g of the emulsion solution. The resulting emulsion was incorporated with stirring in 200 g of a crosslinkable dispersion of vinyl acetate and butyl acrylate (LT 420 from Wacker-Chemie GmbH) with a solids content of 48% and thoroughly mixed for 2 hours. h. The LOI of the polymer film obtained was 23.5.

EXAMPLE 2 8.44 g of methyl triethoxy silane and 5.88 g of DMMP were added with stirring in 31.6 g of the emulsion solution. The resulting emulsion was incorporated with stirring in 200 g of a crosslinkable dispersion of vinyl acetate and butyl acrylate (LT 420 from Wacker-Chemie GmbH) with a solids content of 48% and thoroughly mixed for 2 hours. h. The LOI of the obtained polymer film was 24.2.

EXAMPLE 3 7.8 g of Wacker's SiP ester (triethoxysilyl ethanophosphoric acid diethyl ester) were added with stirring in 15.8 g of the emulsion solution. The resulting emulsion was incorporated with stirring in 200 g of a crosslinkable dispersion of vinyl acetate and butyl acrylate (LT 420 from Wacker-Chemie GmbH) with a solids content of 48% and thoroughly mixed for 2 hours. h. The LOI of the polymer film obtained was 23.2.

EXAMPLE 4 4.22 g of methyl triethoxy silane and 6.59 g of n-decane phosphonic acid diethyl ester were added with stirring in 15.8 g of the emulsion solution. The resulting emulsion was incorporated with stirring in 200 g of a crosslinkable dispersion of vinyl acetate and butyl acrylate (LT 420 from Wacker-Chemie GmbH) with a solids content of 48% and thoroughly mixed for 2 hours. h. The LOI of the obtained polymer film was 22.6.

EXAMPLE 5 8.44 g of Wacker TES-40 (product of hydrolysis and condensation of tetraethoxysilane with a Si content of 40%) and 5.88 g of DMMP were incorporated with stirring into 31.6 g of the emulsion solution. The resulting emulsion was incorporated with stirring in 200 g of a crosslinkable dispersion of vinyl acetate and butyl acrylate (LT 420 from Wacker-Chemie GmbH) with a solids content of 48% and thoroughly mixed for 2 hours. h. The LOI of the obtained polymer film was 22.7.

EXAMPLE 6 (COMPARATIVE EXAMPLE) The LOI of a crosslinkable dispersion of vinyl acetate and butyl acrylate (LT 420 from Wacker-Chemie GmbH) without the addition of additives containing silicon and phosphorus was 19.5.

EXAMPLE 7 (COMPARATIVE EXAMPLE) .88 g of DMMP were incorporated with stirring into 31.6 g of the emulsion solution. The resulting emulsion was incorporated with stirring in 200 g of a crosslinkable dispersion of vinyl acetate and butyl acrylate (LT 420 from Wacker-Chemie GmbH) with a solids content of 48% and thoroughly mixed for 2 hours. h. The LOI of the polymer film obtained was 21.5.

Claims (14)

NOVELTY OF THE INVENTION CLAIMS

1. - Aqueous dispersion which can be prepared on the basis of at least one water-insoluble organic polymer, at least one silicon compound dispersible in water and at least one phosphorus compound soluble or dispersible in water.

2. Aqueous dispersion according to claim 1, characterized in that the water-dispersible silicon compound and the water soluble or dispersible phosphorus compound can also be replaced by a single compound, which is soluble or dispersible in water and contains both phosphorus and water. also silicon.

3. Aqueous dispersion according to claim 1 or 2, characterized in that the water-insoluble organic polymer consists of one or more polymers taken from the group consisting of homopolymers or copolymers of vinyl esters containing one or more monomer units taken from the group consisting of group of vinyl esters of unbranched or branched alkyl carboxylic acids; homopolymers or copolymers of (meth) acrylic acid esters containing one or more monomer units taken from the group consisting of esters with methacrylic acid and esters with acrylic acid of alcohols, homopolymers or copolymers of monoesters or diesters with fumaric acids and / or maleic of branched or unbranched alcohols; the homopolymers or copolymers of dienes as well as olefins, the dienes being able to be copolymerized with styrene, esters with (meth) acrylic acid or the esters with fumaric or maleic acids; homopolymers or copolymers of vinyl aromatic compounds such as styrene, methyl styrene and vinyl toluene.

4. Aqueous dispersion according to claim 1, characterized in that one or several silicon compounds are taken from the group formed by the silicic acid esters Si (OR ') 4, organo-organoxy-silanes SiRn (OR') 4-n with n = from 1 to 3, oligo-siloxanes of the general formula R3SiO (SiR2?) NSiR3 with n = 0 to 4 or their products of hydrolysis and condensation, the radicals representing alkyl or alkoxyalkyl radicals being the same or different and being the R equal or different and meaning branched or unbranched alkyl radicals, cycloalkyl radicals, alkylene radicals, aryl, arylalkyl or alkylaryl radicals, said radicals R may also be substituted with ether, thioether, ester, amide groups, nitrile, hydroxyl, amine, carboxyl, sulfonic acid, carboxylic acid anhydride and carbonyl, tetraethoxy-silane, methyl-tri (m) ethoxy-silane, methyl-tripropoxy-silane, methyl-tri (ethoxyethoxy) silane, vinyl-tri ( methoxyethoxy) sil anus, (meth) acryloxypropyl-triethoxy- or -trimethoxy-silane, ß-nitriloethyl-triethoxy-silane, mercaptopropyl-triethoxy- or -trimethoxy-silane, phenyl-triethoxy-silane, iso-octyl-triethoxy-silane, dipropyl-diethoxy -silane, methyl-phenyl-diethoxy-silane, diphenyl-dimethoxy-silane, methyl vinyl-tri (ethoxy-ethoxy) silane and their disiloxanes and / or trisiloxanes; hexamethyl-diethoxy-trisiloxane, octamethyl-cyclotetrasiloxane, tetramethyl-diethoxy-disilane, trimethyl-trimethoxy-disilane, dimethyl-tetramethoxy-disilane, pentamethyl-disilane-disiloxane and their hydrolysis and condensation products.

5. Aqueous dispersion according to claim 1, characterized in that one or more compounds are contained as phosphorus compounds from the group consisting of esters, amides or ester-amides of alkyl- or aryl-phosphonic acids, phosphoric acid or acid pyrophosphoric, salts of tetrakis (hydroxyalkyl) -phosphonium, salts of polyphosphoric acid, especially ammonium polyphosphate, or triaryl- or trialkyl-oxides of phosphines, diethyl ester of methane-phosphonic acid, dimethyl ester of methane-phosphonic acid, di (m) ) ethyl-pentaerythritol diphosphonate, (m) ethyl-neopentyl phosphonate, triphenyl phosphate, tricresyl phosphate, resorcinol phosphate and bis-diphenyl, diphenyl diphosphate and pentaerythritol, phenyl phosphate and neopentyl, nitrile-tris-methylene mono-di- and tri-ammonium phosphonates, [3- (hydroxymethyl) amino] -3-oxo-propyl-phosphonic acid dimethyl ester, tetrakis (hydroxymethyl) -phosphonium chloride, ammonium polyphosphate, tritolylphosphine I-oxide and triphenyl-phosphine oxide.

6. Aqueous dispersion according to claim 2, characterized in that the compound soluble or dispersible in water, containing both phosphorus and silicon, consists of one or more taken from the group consisting of diethyl ester of 2-triethoxysilyl-ethane-phosphonic acid , 2-trimethoxysilyl-ethane-phosphonic acid diesyl ester, 3-trimethoxysilyl-propane-phosphonic acid diethyl ester, 2-tri [methoxyethoxy] silyl-ethane-phosphonic acid diethyl ester and 1,3-bis [diethylphosphonoethyl] ] -tetramethyl-disiloxane.

7. Process for the preparation of an aqueous dispersion according to one or more of claims 1 to 6, characterized in that the constituents are mixed together.

8. Process for the preparation of an aqueous dispersion according to claim 7, characterized in that an aqueous polymer dispersion is mixed with the silicon and phosphorus compounds.

9. Process for the preparation of an aqueous dispersion according to claim 7, characterized in that an aqueous polymer dispersion is mixed with a solution, emulsion or dispersion of the silicon compounds and with a solution, emulsion or dispersion of the phosphorus compounds. .

10. Process for the preparation of an aqueous dispersion according to claim 9, characterized in that an aqueous dispersion of polymer is mixed with an aqueous solution of the component with phosphorus and with an emulsion of the component with silicon.

11. Process for the preparation of an aqueous dispersion according to claim 9, characterized in that an aqueous dispersion of polymer is mixed with the component with 100% phosphorus and with an emulsion of the component with silicon.

12. Use of dispersions according to one or more of claims 1 to 6 or prepared according to one of claims 7 to 11 in coating agents, impregnation agents or adhesives.

13. Use of dispersions according to one or more of claims 1 to 6 or prepared according to one of claims 7 to 11 for the consolidation of fibrous materials or batts.

14. Fibrous material, characterized in that it had been treated with dispersions according to one or several of claims 1 to 6 or prepared according to one of claims 7 to 11.