DD287550A5 - WAITING PREPARATION FOR FIREFASTING AND METHOD FOR FIREFASTING A SUBSTRATE WITH WAESSED PREPARATION - Google Patents

Abstract

The invention relates to a liquid preparation for refractory and a method for refractoryizing a substrate with a waeszrigen preparation. The formulation imparting semi-permanent refractory properties to cellulosic substrates contains a condensed phosphate of ammonium or an organic quaternary ammonium compound and a dispersion of a fluoropolymer, and preferably a derivative of carbamic acid such as urea. The substrates are impregnated and quenched at 120 to 170 ° C. Fireproofing; substrate; Method; Phosphate of ammonium; quaternary ammonium compound; dispersion; Fluoropolymer; Urea}

Description

-2- 287 550 Field of application of the invention

The invention relates to an aqueous preparation for fouerfestmachen and a method for refractoryizing a substrate with an aqueous preparation.

The substrates are essentially textile substrates.

Characteristic of the known state of the art

Cotton fabrics can be made fireproof by incorporating a wide variety of chemicals, some of which provide permanent flame resistance and some non-permanent flame resistance. The latter chemicals include ammonium phosphate and polyphosphate, optionally with an added urea. While such compounds are inexpensive, their effectiveness is short-lived since they can be removed by washing with water. Attempts to increase the durability with such compounds included high temperature curing at above 15O ⁰ C (see FIG. Z. B. GB-PS 1 504 507). However, such high temperature treatments tend to discolor the fabric. The curing of the polyphosphate may be associated with co-cure with various common fabric treatments with agents such as, for example, dimethylolethyle.iurea (see, for example, GB Patent 1069946).

Object of the invention

Flameless formulations have now been discovered, as well as methods of applying them to cellulosic materials to achieve fabrics with increased flame resistance.

Explanation of the essence of the invention

The invention provides a refractory preparation consisting of an aqueous medium containing a phosphate condensed with ammonium or a quaternary ammonium compound in an amount of 7 to 24% by weight and a dispersion of a fluoropolymer. The preparation preferably also contains a carbamic acid derivative, e.g. Urea. The aqueous solution of polyphosphate and optionally carbamic acid may be present in a package of a two-pack system with the fluoropolymer dispersion in the other pack, with the contents of the two packs being provided to the mixer to form the compositions of the present invention.

The invention provides au., A method for flameproofing a cellulosic substrate, eg. A cellulose material comprising impregnating the substance with an aqueous preparation comprising a phosphate condensed with ammonium or an organic quaternary ammonium compound and a dispersion of a fluoropolymer, preferably with a refractory preparation according to the invention, drying and Curing at 120 ° C to 170 ° C, wherein the aqueous preparation also comprises a carbamic acid derivative, eg urea, when the curing at 147 ⁰ C to 17O ⁰ C is performed, wherein the derivative in a wt .-% rate (expressed as urea) of 50 to 300% by weight of the condensed phosphate (expressed as ammonium polyphosphate).

The polyphosphate salt is prepared by reacting a condensed phosphoric acid with ammonia or an organic amine or a quaternary ammonium hydroxide to yield a water-soluble product. The condensed phosphoric acid usually has an average degree of condensation greater than 3, for example 3 to 30, and usually a linear, branched or cyclic structure. Preferably, the salts N and P in an atomic ratio of 0.5 to 2: 1, in particular about 1: 1. The polyphosphate salt is preferably a mixture of the ammonium salts of a plurality of polyphosphoric acids, this mixture having been prepared by a process wherein an aqueous solution of phosphoric acid containing 80 to 86% by weight of phosphorus pentoxide with ammonia or a basic derivative thereof at one temperature from 15 ⁰ C to 70 ⁰ C, z. B. 15 ⁰ C to 4O ⁰ C, and at a pH of 4 to 12, wio 5 to 9, z. B. 6.5 to 7.5 or 5 to 12, in particular 6 to 8, is produced. Ammonium polyphosphate mixtures that may be used are described in British Patent 1504,507 and may be prepared as described therein.

The flame-retardant medium also preferably contains a carbamic acid derivative having two amino groups per molecule at a weight percent (expressed as urea) to the ammonium polyphosphate (expressed by weight as ammonium polyphosphate itself) of from 0.5 to 300%, such as 0.5 to 50%, z. B. 5 to 30% or 7 to 20% or 10 to 20%, while 50 to 300%, z. B. 50 to 200% and in particular 75 to 200% or 75 to 125% are preferred, in particular for the curing at a higher temperature; in general, the higher the temperature of the cure, the higher the amount of carbamic acid derivative should be. The carbamic acid derivative may be guanidine or dicyandiamide, but is preferably urea; the weights are expressed as urea, but equivalent weights of the other carbamic acid derivatives can be used. The presence of the carbamic acid derivatives tends to discolor the substance after heat conduction, especially at high temperature, and may increase wet pickup.

The flame-retardant medium also contains a dispersion of fluorocarbon polymer, which is preferably capable of at more than 16O ⁰ C, z. B. 160 ⁰ C to 200 ° C, to be thermoset. The fluorocarbon polymer is one which forms a dispersion in the flame-retardant medium, usually for at least a few days, e.g. B. at least two days, is stable; Thus, fluoropolymers which are incompatible with the condensed phosphate solution (with carbamic acid derivative, if any) and which form precipitates upon mixing are avoided. The medium is usually virtually free of other thermosetting, water-soluble resins or resin precursors, such as formaldehyde condensates with NH compounds, such as melamine, urea or ethyleneurea. Such aqueous dispersible fluorocarbon polymers usually have Perfluoralkylsoitenketten, for example in perfluoroacyl groups, perfluorosulfonyl groups or Perfluorsulfonamidogruppen, especially those groups having 3 to 12 carbon atoms in

the perfluoroalkyl group; Carboxy groups may also be present. The fluorocarbon polymers are preferably derived from acrylic or methacrylic acid esters of hydroxy compounds containing perfluoroalkyl groups, but may be derived from vinyl esters, vinyl ethers, allyl esters or thiomethacrylates having perfluoroalkyl side chains. Particularly preferred polymers are those which contain (N-alkyl-N-perfluoroalkylsulfonamido) alkylene side chains, e.g. B. 2- (N-propyl-N-perfluorooctylsulfonamido) ethylene side chains having an acrylate or methacrylate ester backbone. The polymers may be prepared only from monomers containing perfluoroalkyl groups, however, these monomers may have been copolymerized with other copolymerizable monomers, especially those which are fluorine-free, e.g. B. those containing one or two olefinic double bonds in particular / such. In halobutadienes, such as 2-chloro, 3-butadiene, olefinic monomer units containing carboxylic acid groups, such as acrylic, methacrylic or maleic groups, may be present in the polymer. The fluoropolymers are usually sold in the form of aqueous dispersions, e.g. For example, fluoropolymer-repellent finishing for fabrics. The polymer dispersion may be ionic but is preferably cationic or especially anionic. The fluoropolymer dispersions may also contain small amounts of water-miscible organic solvents, e.g. As acetone, methyl isobutyl ketone (MIBK) or ethylene glycol. A preferred polymer dispersion is sold by 3M under the trademark SCOTCHGARD 270 or by Ciba-Geigy Ltd. sold under the trademark SCOTCHGARD FC451. This polymer is believed to be a copolymer of a 2- (N-alkyl-N-perfluorooctylsulfonylamido) ethyl acrylate and a comonomer such as 2-chloro-1,3-butadiene. Another preferred fluoropolymer dispersion is that sold by Hoechst AG under the trademark NUVA FH or NUVA F. Fluoropolymer dispersions sold by Atochem SA under the trade name FORAPERLE, in particular FORAPERLE 145 and 344, or by Texchem UK Ltd. Manchester, England, sold under the trademark TEXFIN CPC may also be used. The weight percent of the fluorocarbon polymer (solid) to ammonium polyphosphate is usually 0.1 to 6%, e.g. 1 to 3% and especially 2 to 6%.

The flame-retardant medium preferably contains 7 to 18%, e.g. 8 to 15%, such as 9 to 13%, ammonium polyphosphate and usually 7 to 18%, e.g. 8 to 15%, such as 9 to 13%, of the carbamic acid derivatives, e.g. Urea, and 0.02 to 1.5%, e.g. 0.1 to

I% and in particular 0.3 to 0.8% fluoropolymer. However, amounts of the ammonium polyphosphate may range from 7 to 24%, such as 10 to 24%, e.g. 15 to 24%, and more preferably 15 to 23%, and amounts of 0 to 20%, e.g. 1 to 20%, or 0 to 15%, e.g. 1 to 15% or 1 to 10%, such as 1.5 to 4%, of the carbamic acid derivative, e.g. As urea, can be used. Preferably, the total content of polyphosphate, Carbaminsäurederivat, z. As urea, and fluoropolymer in the medium not more than 26%, z. B.

I1 to 26% or 15 to 26%, especially 20 to 24%.

The medium may also include a non-withdrawing agent, e.g. A volatile wetting agent, such as an alcohol, or an agent as sold by Warwick Chemicals under the trademark MYKON NRW, the amounts of such non-withdrawing agents preferably being from 1 to 10 g / l. However, if the substrate to be rendered flame retardant has already been degreased or otherwise treated to enhance the penetration of liquids, such an agent is not necessary, but may be present if desired. The aqueous medium is usually in the absence of extenders or cationic polymers, such as cationic synthetic resin waxes, sold under the trademark CEROL by Sandoz, and is usually substantially free of di-, tri-, or tetravalent metal salts, such as such as aluminum or zirconium. Some fluoropolymer dispersions are sold which also contain the extender or a cationic polymer. These should preferably not be used. Fluoropolymer dispersions primarily sold to impart soil repellency but not soil and water repellency are preferred because the latter tend to contain cationic polymer and may be incompatible with the concentrated polyphosphate solution.

In uiner Ausführungsfori preferred, particularly for use with subsequent curing at 120 to 147 ⁰ C, the fiammhemmende preparation may be an aqueous medium containing 7 to 24%, eg. 10 to 24%, by weight, of an ammonium or organic quaternary ammonium-condensed phosphate, 1 to 10% by weight of the carbamic acid derivative, e.g. Urea, wherein the weight percent of urea to polyphosphate is from 5 to 30 percent, and a dispersed fluoropolymer in an amount of from 0.02 to 1.5 percent, with a total phosphate and urea content of no more than 25%.

In another preferred embodiment, in particular for use in subsequent curing at 147 to 170 ° C ic: the flame retardant formulation comprises an aqueous medium containing 8 to 15%, e.g. 9 to 13%, by weight, of an ammonium or organic quaternary ammonium-condensed phosphate, 8 to 15% by weight of carbamic acid derivative, e.g. Urea, wherein the% by weight of urea to polyphosphate is 50 to 200%, and a dispersed fluoropolymer in an amount of 0.02 to 1.5% with a total content of the phosphate and urea of not more than 25%. , In both of these embodiments, these preparations are preferably present in the absence of cationic, water-soluble fluorine-free polymers and preferably contain the fluoropolymer having side chains of perfluoroalkylsulfonamide groups.

The polyphosphate, preferably together with the carbamic acid derivative, may be provided as a concentrated aqueous solution if the subsequent mixing with the fluoropolymer dispersion before or preferably after one or both have been diluted to the level required for the impregnating bath.

The fluoropolymer dispersion is preferably added to the medium if it is otherwise ready for prewound impregnation. The medium is preferably used for impregnation within a few days although, particularly in the case of anionic fluoropolymer dispersions, the medium may be stable for at least one week, e.g. B. at least one month.

The aqueous medium may also contain other textile auxiliaries in a manner and amount such that they are compatible with the other components of the medium and have not been significantly affected by the heat curing treatment or result in discoloration or loss of efficacy. Examples of such agents are plasticizers or conditioning agents which may be cationic, anionic or ionic, amphoteric or reactive and usually contain at least 1 to 2 alkyl chains of at least 10 carbon atoms. Examples of cationic plasticizers are quaternary ammonium salts of fatty acids, arrinoester or aminoamido and quaternary N-acyl-N-polyoxyalkylenepolyamines. Examples of anionic softeners are fatty acid salts, soaps, sulfonated fats and oils, fatty acid alkyl sulfates and

Fatty acid condensation products, sultosuccinates and sulfosuccinamates. Examples of amphoteric agents are alkylimidazolines and betaines and their salts, e.g. Methosulfate, acylamidobetaine, acylpolyamines, amine oxides, substituted amino acids and sulfobetaines. Examples of nonionic plasticizers are polyalkylene glycol ethers and esters, and other polyoxyalkylene condensation products and paraffin wax or polyethylene wax. The latter are used in aqueous dispersion or emulsion with nonionic, cationic or anionic but in particular amphoteric dispersants. Examples of reactive plasticizers are N-methylol derivatives of fatty acid amides, e.g. As N-methylol stearamides or N-methylol derivatives or fatty acid condensates with urea. The plasticizer, as such or as a dispersion, may be used in an amount of 0.01 to 5%, e.g. 0.5 to 3% by weight of the total aqueous impregnating medium. The presence of the plasticizer may allow the heat-curing process to produce a treated fabric having improved flame resistance and other properties, e.g. As mechanical strength, in particular tensile strength and color fastness, which is substantially the same as that of the non-treated materials, wherein the strength can also be improved.

The substrates to which the medium is applied may be woven or nonwoven. They are cellulose-based substrates, e.g. Textile fabrics or threads, such as cotton, linen, jute, burlap or regenerated cellulose materials, such as rayon or viscose, but may also be paper, cardboard or wallpaper. The substrate may also be based on cellulosic material and other fibers which are miscible therewith, such as e.g. As polyester or nylon, acrylics, acetate, polypropylene, silk or wool. These mixtures or mixtures of fibers may contain at least 50% of the cellulose matrix, e.g. 70 to 100%, like 50 to 80% of it.

The fabric weights can be 50 to 1000 g / m ² , for example 80 to 500 g / m ² . The fabric can have a florish texture or simply be. The fabric may be plain or undyed, or it may be colored or printed, especially with white or pastel colors. The fabric is usually free of debris, finishes, natural waxes and applied finishes before impregnation, although it may contain an optical brightener.

The flame-retardant medium is usually used at a pH of 5 to 8, e.g. B. 5.5 to 7.5 applied to the substrate by conventional procedures, for. B. padding, dipping or spraying, usually to a wet pick-up of 50 to 150%, e.g. 60 to 100%. The total uptake of solids before drying after squeezing off excess liquid is usually 10 to 35%, e.g. B. 10 to 20% or 13 to 25%, based on the dry initial weight of the substance. After impregnation, the substrate is dried, z. B. in textile substrates at 80 to 120 ° C 2 to 40min, z. For 2 to 10 minutes. The drying may be carried out in any conventional drying apparatus, e.g. B. in a forced air dryer or stenter. The solids uptake after drying is usually 8 to 25%, such as 10 to 20%, based on the original weight of the fabric.

The dried substrate is then cured, e.g. B. by heating to a temperature of 120 to 17O ⁰ C, such as 130 to 17O ⁰ C, z. 8. 140 to 17O ⁰ C or 147 to 17O ⁰ C 6 to 0.5 or 5 to 0.5 min, avoiding the combination of longer times and higher temperature to alleviate any tendency to discoloration. Preferred temperatures, especially at high levels of carbamic acid derivative to polyphosphate, are 147 to 165 ° C, such as 147 to 16O ⁰ C or 147 ⁰ C to 155 ⁰ C, 6 to 0.5min, eg, 5 to 2min. To the risk of any color formation, especially with small amounts of carbamic acid derivative to polyphosphine? '. to minimize, preferably the dried substrate is C 6 to 0.5 cured by heating at 120 to 147 ⁰ minutes, woliei the combination of longer times and higher temperature is avoided to decrease any tendency to discoloration. These preferred temperatures are 120 to 138 ⁰ C, such as 124 to 142 ⁰ C or 128 to 138 ⁰ C, 6 to 0.5 min, z. B. 6 to 1.5 minutes, while at temperatures of 138 to 147 ⁰ C times of 3.5 to 0.5 minutes, such as 138 to 142 ⁰ C or 142 to 147 ⁰ C, 3.5 to 0.5 minutes long can be. Curing at 130 to 14O ⁰ C at 4 to 2 min, for example. B. 3.5 to 2.5 minutes is preferred.

The curing at 147-170 ⁰ C with a higher proportion of carbamic acid derivative to polyphosphates usually has ei, ie greater curing efficiency than the lower temperature during curing, the higher amount of polyphosphates and higher amount thereof in the impregnation bath limited, however, the latter substance a lower tendency to discoloration especially in white and pastel-colored fabrics. The presence of the fluoropolymer increases the durability to soaking of the fabric, which has been cured at 120 to 147 ⁰ C, or 147-170 ° C.

The curing, which usually takes place continuously, can be caused by radiant heat, for. Infrared heating or heating by injecting water vapor and / or hot air through the substrate or by contacting the substrate with heated metal drums in a vertical heap, but preferably by causing hot air to be applied to the surface of the substrate, preferably both Flats to ensure uniformity of heating. Thus, preferably, the substrate is continuously passed to a stenter through a thermostatically controlled hot air oven by passing hot air streams onto the top and bottom surfaces of the substrate. The stenter gives the most even hardening with minimal scorching. In the case of the stenter oven, the curing temperature of the substrate is substantially the same as that of the hot air stream. Usually, at the end of curing, the substrate is rapidly cooled by passing or passing through cool air.

The cured fabric with the impingement usually has a solids content of 6 to 25%, such as 8 to 20%, usually contains 0.5 to 5% phosphorus, e.g. Such as 0.5 to 4%, preferably 1 to 3% or 2 to 4% P. The impregnated fabric has premanse flammability compared to the unknown substrate and can pass the BS 5852 test with sources of ignition 0 to 1. The substance can after solidifying once in hard water at 4O ⁰ C according to BS 5651 without eventual ironing usually a solids content of 3 to 10% or z. B. to 9%, a percentage of phosphorus content of 0.4 to 3%, preferably 0.9 to 3%, z. B. 1 to 3% P, and can pass the flammability test to BS 5852 Part 1 with ignition sources 0 to 1. The flammability-reducing equipment is usually durable for 1 to 3 washes in soft water at 74 ^° C., while some flame-retardant effect is still retained thereafter. The fabric after treatment usually has a handle that is not significantly different from that of untreated fabric, and usually has a color that is not significantly different from that which the unbehandolto fabric has. The fabric after treatment usually has some degree of repellency for water and oil, but is substantially removed when soaked in water at 40 ° C containing wetting agent. The synergistic combination of (1) fluoropolymer and (2) condensed phosphate (optionally with carbamic acid derivative) can yield substrates of improved flame retardancy which is not obtained by substrates treated only with (1) or (2).

The invention is illustrated by the following examples. In Examples 1 to 11, 13 and 14, the fluoropolymer was used as a 23% aqueous emulsion of slightly cationic fluoropolymer sold by 3M under the trade designation SCOTCHGARD FC208 or by Ciba Gelgy under the trademark SCOTCHGARD FC451. This fluoropolymer is believed to be a copolymer of 2- (N-propyl-N-perfluorooctylsulfonylamido) ethyl acrylate and 2-chloro-1,3-butadiene. In Example 12, the fluoropolymer is an anionic aqueous fluorocopolymer, having a pH of 7.5 to 8.5, sold by Hoechst AG under the name NUVA FH, which is believed to contain carboxy groups and Contains perfluoroalkyl groups. In Examples 15, 16, 19, 20, 23 and 24 and Comparative Examples A to D, the fluoropolymer was an aqueous acrylic acid fluoropolymer dispersion from Atochem S.A. under the trademark FORAPERLE 145. It is somewhat cationic and has a pH of 4.5 ± 0.5 and is likely to contain perfluoroalkyl, carboxyl and sulfonamido groups. In Examples 17, 18, 21 and 22, the fluoropolymer was an aqueous fluoropolymer dispersion which is slightly cationic, having a pH of 6 to 8, and is sold by Texchem UK Ltd., Manchester, England under the trademark Texfin CPC , It is believed that it contains perfluoroalkyl and carboxyl groups.

The ammonium polyphosphate used in all Examples was prepared by reacting polyphosphoric acid with 83 to 85% P ₂ O ₆ with ammonia according to British Patent 1,304,507 to give a product which is adjusted to a solution of pH 6.2 with 45% solids, 30% P ₂ O ₆ and a specific gravity of 1.36. In each case, the same general procedure was used. The aqueous solution of the ammonium polyphosphate and urea was prepared and mixed with the fluoropolymer emulsion after dilution with water optionally with stirring, in an amount (in terms of weight of the emulsion, based on the total weight of the solution and the emulsion) of 2% in the examples 1 to 11.13 to 22 and 1.5% in Example 12 and also in Examples 1 to 13 0.5% of a non-withdrawing agent sold under the trademark MYKON NRW, to obtain aqueous media containing the ammonium polyphosphate, Fluoropolymer and urea included. The aqueous medium obtained was stable, but was preferably used without undue delay. The fabric was impregnated with the aqueous medium and pressurized, and then the impregnated fabric at 90 to 100 ⁰ C or 11O ⁰ C dried in a forced air drier or stenter. The parts of the dried fabric were then moved slowly but continuously on a stenter through a thermostatically controlled stenter oven provided with hot air streams which acted on the fabric from above and below. The fabric was weighed after drying and after curing. The cured fabric was then tested according to the BS 5852 Part 1 test with ignition sources 0 and 1 for flammability after impregnation and after the leach once in hot water at 40 ° C. according to BS 5651 Part 1 without final ironing. Some of the impregnated fabrics were also subjected to a dry cleaning test with three commercial dry cleaning cycles in a solvent system loaded with 10% water.

Some fabrics were also tested for oil and water repellency according to AATCC 118 and BS 3702 and tested for color.

embodiments

example 1

The aqueous ammonium phosphate solution (94 parts) was mixed with urea (6 parts) and the maintained mixture was diluted with water (122 parts) and then the fluoropolymer emulsion and the NRW agent were added to obtain the impregnation medium. The medium was applied in a shortage to a 230g / m ² flower η printed cotton fabric and also to a defatted dyed yarn woven orange dyed cotton fabric of 410g / m ² with wet picks 71% and 81.5%, respectively. cheat. The impregnated fabrics were then cured on a stenter at 100 ⁰ C for 3.5 min and then dried at 135 ⁰ C 2.5 min. The flower fabric and the orange colored fabric after impregnation had a content of 3.19 and 5.63% P. All fabrics were subjected to BS Test 5852 after impregnation and after a caustic in hard water, using ignition puffs O and 1 were. The flower fabric and the orange colored fabric were also tested for flammability with char length in mm according to the test of BS 5438 No. 2. The results are shown in the following table. After the hard water leaching, the floral and orange colored matter contained 0.99% and 1.43% P. respectively.

Deceleration length (mm)

material waterproof leached dry cleaned Flowers orange Other properties: Fabric 108 84 impregnated 124 74 Oil repellent AATCC118 92 75 Water repellency BS 3702 Flowers print orange NT = not tested untreated treated untreated NT 3 NT 6 NT 7 υ NT 70

There were essentially no color changes in the treated floral fabric. In the white and colored parts of the flower musar compared with the same parts in the untreated fabric.

Example 2

The method of Examples 1 was repeated with a variety of substances of different weights and styles and flammability itest according to BS 5852 with sources of ignition 0 to 1. In all cases, the substances passed the experiments. The following substances were used:

(1) 100% cotton, plain, velvet, printed or woven with dyed yarn, weights in the order of 120 to 410g / m ² .

(2) Cotton blends with linen (48:42), viscose (46:54) (55:45) or rayon / nylon (25: 72: 3), printed, velor or color-woven, weighing from 330 to 540g / m * ,

(3) cotton blends with polyester (53:47) color-woven from 300g / m ² .

(4) Mixed velvet fabrics with C3 cotton, 37 Acrylflorstoff and 47 cotton, 28 acrylic acid, 25 of polyester, all in a weight basis 540g / m ^2, and with 100 Viskoseflor and 83 viscose, 10 cotton, 7 polyester base of weight 750 g / m ² .

Examples 3 to 8

The procedure of Example 1 was repeated with the following changes.

In these experiments, the material was a defatted cotton fabric of 220g / ^m2, colored red in the fabric. The results given in the following table were obtained:

Example 3 4 5 6 7 8

Cure Temp. ° C 130 130 130 130 140 140 Dauermin 2 3 4 5 2 3 % Wet pick 81.7 31.5 81.8 81.6 80.8 P1,2 % Uptake of dry matter 15.8 16.2 16.2 15.8 15.7 14.9 % Solids after curing 15.1 15.9 15.6 15.5 15.7 14.9

% Solids after 1st leach 5.7 7.8 7.0 7.8 7.0 7.6

All treated fabrics after leaching passed the BS 5852 ignition test with sources 0 and 1, and there was no significant color change as compared to the untreated fabric.

Examples 9 and 10

Pas procedure of Example 1 was repeated with a white cotton fabric of 270g / m ^2, which contained no optical brightener. The curing conditions at 135 ⁰ C were 3 min (Example 9) und3,5min (Boispiel 10). The fabrics after treatment and after a lye passed the BS 5852 test with sources of ignition 0 and 1. The fabrics after treatment and after leaching did not show any significant color loss as compared to the fabrics before treatment.

Example 11

The procedure of Example 1 was repeated with changes in the aqueous medium, in the fabric and in the curing conditions. The aqueous medium was prepared by mixing the aqueous ammonium polyphosphate solution (59 parts), urea (27 parts) and water (154 parts), after which the fluoropolymer emulsion and NRW were added.

The substance was a white Baumwolldrellstoff of 268g / m ^2. The fabric was impregnated to 75% wet pick-up and the drying was 2 minutes at 100 "C and the cure conditions 2.5 min at 145 ⁰ C. The fabric after impregnation contained 2.19% P, and contained by a No. leaching 1.19% P The fabric after leaching had a charring length of 128mm when tested in accordance with BS 5438 Run 2. The impregnated cloth did not show any appreciable color change upon leaching compared to the fabric before treatment.

Example 12

The procedure of Example 1 was repeated with the NUVA fluoropolymer emulsion in an amount of 1.5%. The impregnation medium was stable for at least two months at room temperature. The impregnated fabric was a red dyed cotton fabric of 220 g / m ² and the wet pick-up was 72.5%. After drying and curing according to Example 1, the fabric had a total solids uptake of 15.8% and a total solids uptake after leaching of 5.6%. The dyed impregnated fabric, after leaching, passed BS 5852-Tost with sources of ignition 0 and 1. The fabric did not show any significant color change after impregnation and after leaching compared to the fabric before treatment.

Example 13

The ancestor of Example 1 was repeated with a 3111 cotton gauze of 300 g / m ² with and without the presence of 2% (based on the total weight of the impregnating medium) of a plasticizer which was an aqueous amphoteric dispersion of an aliphatic hydrocarbon, probably a paraffin wax or polyethylene wax sold by Sandoz under the trademark SANDOLUBE NV. The curing conditions were 135 ⁰ C for 3 min. The cured fabric was tested for flame retardancy and tested for tear strength in the warp and weft directions according to Elmendorf. The cured fabric was impregnated, and after leaching, it passed the 8S 5852 test with the 0 and 1 sources of ignition and showed no significant color dif- ference compared to the untreated fabric. The results of the Roissfostigkeitsprüfung were the following:

Tear resistance g fabric

Chain

Shot

untreated 3162

treated

without SANDOLUBENV 3174

with SANDOLUBE NV 5414

4452

3853 5619

Example 14

The aqueous ammonium polyphosphate solution (59 parts) and urea (27 parts) and water (154 parts) were mixed and then the fluoropolymer emulsion and NRW were added to obtain the impregnating medium. The medium was applied in an order deficit on flowery printed cotton fabric of 230 g / m ² and also on a previously decolorized, brown through-dyed cotton fabric of 410g 'm ² with wet pick-ups of 71 and 96.5%. The impregnated fabrics were then then cured on a stenter at 100 ⁰ C for 0.5 min and dried at 150 ⁰ C 3min. The fabrics after impregnation contained 1.98 and 2.35% P. All impregnated fabrics, after leaching in hard water and after dry cleaning, passed the BS 5852 test with sources of ignition 0 and 1. The floral and brown fabric after impregnation after leaching into hard water after dry cleaning, they were also subjected to Flammability Test 2 to BS 5438 and showed carbonization lengths in mm according to the following table. After leaching in hard water the dioxides contained 1.27 and 1.83% P.

Charring length values (mm)

material as impregnated lengthened dry cleaned floral brown other characteristics: fabric 98 71 Impregnation 102 73 Oil Repellent AATCC118 91 65 Water repellency floral print orange untreated treated treated untreated NT 5 NT 5 NT 70 NT 70

NT = not loaded

The colors of the treated fabrics were not significantly different from those of the untreated fabrics.

Examples 15, 16, 17, 18

The procedure of Example 1 was repeated with a flowery printed plain weave cotton fabric of 225g / m ² and two different fluorocarbon polymer emulsions, one sold under the trademark FORAPERLE 14b (Examples 15,16) and oino sold under the trademark TEXFIN CPC (Examples 16) , 17), in each case with (Examples 15, 17) and without (Examples 16, 18) plasticizers according to Example 13. The impregnation baths were prepared from 34.8 parts of ammonium polyphosphate solution, 2.2 parts of urea and 59.5 parts of water 2 parts of the fluoropolymer emulsion and 1.5 parts of the plasticizer or 1.5 parts of extra water. The wet pick-up of the substances was 76% and after drying at 11O ⁰ C for 1 min, the dried material was baked at 135 ⁰ C for 3 min. The finished fabrics were soaked in water according to BS 5651 test and subjected to the flammability test 2 according to BS 5438 after drying. The finished fabrics were also tested for tear strength and tensile strength according to Elmendorf and for water and oil repellency. The results were the following:

example untreated 15 16 17 18 Tensile strength, chain, N / 5 mm 660 650 657 657 671 Tensile strength, weft, N / 50 mm 647 639 644 638 628 Tensile strength, chain, g 3349 3360 2679 3349 2740 Tear strength, weft, g 2410 2517 1920 2482 1860 Water repellent BS 3702 NT 80 80 70 70 Oil repellency AATCC118 NT 7 6 6 6 Flammability test after soaking, Charring length, mm NT 105 100 105 110

NT = not tested

N / 50mm = Newton's 50mm wide fabric

Examples 19 to 22

The procedure of Example 14 was repeated with the same cotton fabric and fluorocarbon emulsion used in Examples 15-18 using FORAPERLE 145 as emulsion in Examples 19 and 20 and TEXFIN CPC as Emulsion in Examples 21 and 22 , with (Examples 19,21) and without (Examples 20,22) the plasticizers

according to Example 13. The impregnating bath was prepared from 20.6 parts of ammonium polyphosphate solution, 9.28 parts of urea, 2 parts of fluorocarbon polymer emulsion, 61.5 parts of water and 1.5 parts of plasticizer (or 1.5 parts of extra water in Examples 20, 22). The wet pick-up of the substance was 76% and after drying at 110 ⁰ C1, the dried material at 150 ° C for 3 minutes was baked min. The finished fabrics were soaked in water according to BS 5651 and, after drying, subjected to Flammability Test 2 according to BS 5438. The finished fabrics were also tested for tensile strength and tear strength and for water and oil repellency. The following results were obtained:

example untreated 19 20 21 22 Tensile strength, chain, N / 5 mm 660 621 614 606 626 Tensile strength, weft, N / 50 mm 647 587 582 597 574 Tensile strength, chain, g 3349 3306 2344 3215 2411 Tear strength, weft, g 2410 2304 1630 2217 1688 WasserabstoßungBS3702 NT 90 90 80 80 ÖlabstoßungAATCC118 NT 7 7 6 6 Flammability test after soaking, Charring length, mm NT 71 82 75 88

NT = not tested

Example 23 and comparison instructions A and B

Substances which were treated according to the invention (for Example 23) were compared with the dyeing of those which were prepared by various methods using curing conditions according to Examples 1 and 2 of British Patent 1,504,507 (also for Examples A and B). The fabric was that of Example 19. The impregnation bath and the method in Example 23 were the same as in Example 19, while the comparative baths and procedures for Comparative Examples A and B with ammonium polyphosphate and urea were in concentrations in Example 1 of British Patent 1504,507 but with wet pick-up and drying conditions as in Example 20 and curing for 7 minutes at 150 ° C (Comparative Example A) and 5 minutes at 160 ° C (Comparative Example B). The cured fabrics were stained with a 1-5 gray scale compared to the untreated fabric, where the number 5 indicates little or no shade change and 1 maximum change. The results were as follows: Example 23 Shading 4/5, Comparative Example A Shading 2 and Comparative Example B Shading 1.

Example 24 and Interlibrary Bills C and D

Substances treated by the method of the present invention (Example 24) were compared with an aqueous medium containing both (1) ammonium polyphosphate and urea and (2) fluorocarbon polymers in terms of flammability and water repellency before and after soaking with appropriate materials which had been treated with aqueous media containing either (1) or (2) (Comparative Examples C and D, respectively). The fabric was the same as in Example 19. The process of Example 24 was that of Example 20, while the process of Comparative Example C was the same as in Example 20, but without fluoropolymer, and Comparative Example D was 2% impregnation of the fabric. igen dispersion of a fluoropolymer emulsion and drying and subsequent baking for 3 min at ISO ⁰ C included. The fabrics were tested for flammability according to BS 5438 and water repellency according to BS 3702. The soaking involved immersing the fabrics for 30 minutes in a 40 ° C bath of water with 5 g / l wetting agent. After soaking, the fabrics were dried and retested. The results were the followers.

Example charring length mm Wassorabstoßung

100 50

100 50

NS: The water rejection scale ranges from 100 (best) to 0.

24 after soaking 73 24 77 C after soaking 73 C 103 D after soaking _ D _

Claims (17)

An aqueous refractory composition, characterized in that it consists of a phosphate condensed with ammonium or an organic quaternary ammonium air in an amount of 7 to 24% by weight and a dispersion of a fluoropolymer. 2. Preparation according to claim 1, characterized by an additional content of a carbamic acid derivative. 3. A preparation according to claim 2, characterized by a content of urea as a carbamic acid derivative and by water-soluble ammonium polyphosphate as condensed phosphate. 4. Preparation according to claims 1 to 3, characterized in that the fluoropolymer has a perfluoroalkyl side chain. 5. A preparation according to claim 4, characterized in that the fluoropolymer is a polymer derived from an acrylic or methacrylic acid ester of an alcohol containing a perfluoroalkyl side chain. 6. Preparation according to claim 4 or 5, characterized in that the fluoropolymer is one which contains (N-alkyl-N-perfluorsulfonamido) alkylene side chains. 7. Preparation according to claims 1 to 6, characterized gek denotes that it is substantially free of cationic, water-soluble, fluorine-free polymers. 8. Preparation according to claims 3 to 7, characterized in that the weight ratio of urea to ammonium polyphosphate is 5 to 30%. 9. Preparation according to claims 3 to 7, characterized in that the weight ratio of urea to ammonium polyphosphate is 50 to 300%. 10. A preparation according to claim 8, characterized in that it consists of 10 to 24% ammonium polyphosphate, 1.5 to 4% urea and 0.1 to 1% of the fluoropolymer having a total content of polyphosphate, urea and fluoropolymers of 15 to 26% , 11. A preparation according to claim 9, characterized in that it contains 8 to 15% ammonium polyphosphate and 8 to 15% urea and 0.1 to 1% fluoropolymer having a total content of polyphosphate, urea and fluoropolymer of 15 to 26%, 12. Preparation according to claim 1 to 11, characterized in that it additionally contains a plasticizer. 13. A method of refracting a substrate by impregnating the substrate with an aqueous preparation containing an ammonium or organic quaternary ammonium condensed phosphate and a dispersion of a fluoropolymer, drying and curing at 12O ⁰ C to 170 ⁰ C, characterized in that the aqueous preparation also contains a carbamic acid derivative when the curing is conducted at 147 ° C to 170 ⁰ C takes place, wherein this derivative expressed in a weight percentage (as urea from 50 to 300%, based on the weight of the condensed phosphate (expressed as ammonium polyphosphate) present. 14. The method according to claim 13, characterized in that the impregnation of a cellulose substrate with an aqueous preparation containing urea and a water-soluble ammonium polyphosphate, takes place. 15. The method according to claim 13 or 14, characterized in that the fluoropolymer is one as defined in any one of claims 4 to 6. 16. The method according to claims 13 to 15, characterized in that the substrate is impregnated with an aqueous preparation containing 8 to 15% ammonium polyphosphate, 8 to 15% urea and the fluoropolymer, wherein a total solids absorption after drying from 10 to 20% (based on the original weight of the substrate) followed by curing at '.47 ⁰ C to 160 ⁰ C for 6 to 0.5 minutes long. 17. The method according to claims 13 to 15, characterized in that the substrate is impregnated with an aqueous preparation containing 15 to 24% ammonium polyphosphate and 1 to 10% urea and the fluoropolymer, wherein a total solids absorption after drying from 10 to 20% (based on the original weight of the substrate) followed by curing at 128 ⁰ C to 142 ⁰ C for 6 to 1.5 minutes long.