PL160446B1 - Method of reducing inflammability of fabrics - Google Patents

Abstract

Aqueous compositions imparting semi durable flame retardant properties to fabrics from cellulosic and synthetic polymer fibres contain an ammonium or organic quaternary ammonium condensed phosphate and a cyclic organic phosphonate and preferably a carbamic acid derivative such as urea.

Description

The subject of i ^^ lszku jett tpotób zweiJszseil flammability of cardboard substrates.

The flammability of carbon fabrics can change by incorporating various chemicals into them, some of which salt permanently reduce flammability, and some cause an initial cooling of flammability. To these ottst nts are photoforsn smono ^ and mononic polyphosphate, eoenically with the addition of moozniks. Even though these connections were made, the texture of their effect was short, for they were trapped in the water. Attempts were made to increase the durability of today's compounds by tie-tying them at an elevated temperature, above 150 ° C (speck, e.g. British Platinum No. 1504507). Pledding polyphosoorane can be combined with the simultaneous thiecooling of various agents, usually tosoose for treating fabrics, e.g. The textile fibers, especially those made of pulp fibers, are more difficult than buffalo cloth to be treated with a permanent resistance to burning.

WyyeSazdk reduces the flammability potential of cellulose and other fibers, thereby permanently reducing their flammability,

Well, you know. tpotó ^ b zmee,) the flammability azseil, this is due to the fact that the tissue from cellulosic and non-cellulose fibers is impregnated with an aqueous medium in which the agent enters the solvent of the simmonium photo-phosphate or the organic tetraternary zetoolon, and one photophome lm. cyclic etter fftffeisnowy of formula 1 in which s ozusczs a number 0, 1 or 2, b Ozum a number 0, 1 or 2, c fzelczs l-icztię 1, 2 l-uti 3, ^p y ^y or gums s + b + c is ^t ^ wnl 3 ^, R ^{l r1} this tlme or different, denote the silkyl, slktyl, solid, silktyl, silkyl and TH, slkylfarylktyl, lrylosSkilowa, lrySoktysktylowa or srySktysktylowy or other one hydroctyl group, but it cannot erode the halogen, some of the Bryls can have at least one 2 stom of chlorine, bromine or a hydroxyl group, the second is a slkyl group, a hydroxyl group

160 446 or aryl, R ^J is lower alkyl, e.g. with 1-4 carbon atoms / or hydroxyalkyl group / e.g. with 1 - 4 carbon atoms /, or cyclic phosphonoate ester of formula 2, in which d is 0, 1 or 2, e is 1, 2 or 3, the sum of d + 3 is equal to 3,

3 4

And R Raja ^ descent defined above, R is an alkyl, aryl, alkylaryl, aryloalkioową or aryloxyalkyl group, in which groups the aryl portion may optionally contain at least ^them down en a bromine atom, c ^hl ol or ^g ru ^{PE h} ydrokθ ^yl OOA ^, and R ' ^{represents one of a} divalent, divalent or trivalent alkyl, alkene, aryl or arylene group, the aryl or arylene group of which optionally contains at least one bromine, chlorine, alkyl or hydroxyl group and is dried and crosslinked at a temperature 130-18O ° C.

The agent may also contain a water-dispersible fluoropolymer, but preferably contains a carbamate karst derivative, e.g.

The polyphosphate salt can be recycled by reacting the complexed phosphorus karst with ammonia or an organic amine, or with a fourth ^ (^^^ d <3o ^ ^ ammonium hydroxide to give a water-soluble product. The complexed phosphorus karst usually has an average degree of over 3, e.g. - 30, and has a nicely linear, branched or cyclic structure. Preferably, the salts contain R and P in an atomic ratio of 0.5-2: 1, especially about 1: 1. The polyphosphate salt is preferably a mixture of ammonium salts of numerous polyhydric karsts produced by by reacting an aqueous solution of phosphoric karst containing 80 - 86% Rago ^ ch pięcioteenku phosphorus, with ammonia or a basic ^^ renewable, at Ί5 - 7 ⁰ ° ^C, n ^p. 15 - ⁴⁰ ° C, and p ^y pH ⁴ - 12, e.g. 5-9, ^6, 5-7 ^, 5 or 5-12, especially 6-8. Mixtures of ammonium polyphoxylates which are suitable for use in the compositions according to the invention are described in British Patent No. 1504507.

The cyclic flsfoniano ester is described in U.S. Patent Nos. 3,849,368 and 3,789,091. It may be prepared as set forth in these patents by reacting halogen-free phosphorus, carboxylic, or sulfonic acid alkali esters with bicyclic phosphites, e.g. z 1-alkyl-4-frsfα-3.5 · 8-thioksabic ^ lo / ^, 2.2 ⁷ of the ^angle . Α device The number ^{lk group,} alkoxycarbonyl ^ lowe or pods Ławione-alkyl and ^{R 1} - R may contain 1-6 carbon atoms, while the style group may be aromatic hydrocarbyl groups and may contain 6 - 19 carbon atoms and the groups may be αrsloalkl0owe with hydrocarbon groups and eat 7 - 19 gold of coal. Examples substituents R and ^{R 1} are ^{A C} i_g allcil, phenyl chlotowcofenyl ^ ^h ^ ro ketenes tolyl, xylyl, b ^ with y ^ ² ^ -phenyl ^^ hydroxy you enoksyetyl ^ ^f ^ i ^ ulbomo nokaymety Ex ^ ^ and ^p ^ Charge odstawnikami n are C.j_ ₄ alkyl, phenyl, halophenyl, hydrokeyfensyl, hydrollrayetyl, phenoxyethyl, ^{dwubromofenlk8yetyl, t} olyl, was ^{wrong, benzyl,} or phenyl ^ ^ ^ you and ^p y ^{y y k} Charge I p ^ with moieties ^R are jednorartościowy C ^ alkyl omicron , chlorophenyl, mono-, di- or tribromophenyl, hydroxyphenyl, naphthyl, tolyl, kaylyl, benzyl or 2-phenylethyl, dihydric alkylene, vinylene, o-, m- or p-phenylene, tetrachloro- or tetrabromophenylene, m or p / and trivalent phenyl. Preferred compounds II are those in which each of R and R ^ kt ^about Re may ^{be C} C ^± HAT same l.ub means than ^that with the ^group A ^{lk l} and ^b head and at ^{± f} s ^± ni ru ^{g PE} alkoxy, e.g. of 1 - 6 carbon atoms, especially 1 - 3 carbon atoms, especially p

methyl, ethyl, methoxy and ethoxy, while each of R and R ^5, k ^is re ^± may ^{be C} C ^ki and e the same or different ^Ne, is leorzystnie ru ^{g PE} Alkylation ^A, n, ^p. having 1-6 carbon atoms, such as methyl or ethyl. Mixtures of cyclic frβphonate may be used, in a ratio of e.g. two phosphonates 95s 5-5: 95, e.g. 25: 75-75: 25, especially a first phosphonate where a, b and c are 1 and a second phosphonate where a is the number 1, b is the number 0 and c is the number 2, and each 2-3 of R, R and R independently in one phos- phonin are the same as the corresponding substituents on the other phosphonate.

Raj more preferred are 40: 60-60: 40 mixtures of these two phosphonates in which 2 3 1 each of R, R and R is methyl or ethyl and R is methoxy

160,446 or ethoxy as set out in Example Ib in US Patent

1 No. 3,849,368, in particular where R and R- are each meeyl, R is ethyl and R is methocayl, an exemplary mixture of such a mixture is a mixture by weight ratio 3 1 2:50 / in which R and R are meeyl, R is methoxy and R is ethyl (marketed by Albright and Wilson Americas Inc. under the trade name Antiblaze 19 or by Albright and Wilson Ltd. under the trade name Amgard CJ. The weight ratio of cyclic phosphonate to ammonium polyphosphate is usually 0.1-2: 1, especially 0.31 and 1 or 0.4-1.3: 1.

The medium for rendering the fabrics flame-retardant usually contains a carbamate derivative with 2 amino groups per molecule in an amount in% by weight (based on urine) (based on ammonium polyphosoorate) (based on the weight of ammonium polyphosphate alone). - 300%, e.g. 0.5 - 50%, especially 5 - 30%, e.g. 7 - 20% or 10 - 20%, preferably 50 - 300%, especially 75 - 125%, especially for high temperature. Usually, the higher the cross-linking temperature, the higher the amount of the carbamate derivative of carbamate may be guanidine or diccyancdouam.d, but the preferred derivative is urea. use equal weight equivalents of another carbamate karst derivative The presence of the carbam.nooegc karst derivative reduces any tendency to discoloration of the fabric upon heat exposure, especially at elevated temperature, and may increase wet absorption.

environment to impart to fabrics zmnejszonej flammability may also comprise a polymer dispersion fluorowęgowwodorowego / capable of being heat cured at a temperature of ^{at p} ^^ than ^16O ° C, n ^{p. 1} 6 ⁰ - ² 00 ° G /. PoHmerem fluorocarbon ⁰ owodirow ^m thi ^td owoln ^white polymer forming a medium for transmitting the fabrics zmltejszcnej flammability dispersion zwrkle stable for at least several days, for example. As most pleasant 2 days, and so should be avoided Η ^ ηροί! Mers immiscible with a solution of complex phosphate and cyclic phosphonate / and a derivative of carbamate karst, if present / and forming sediments after mixing The environment usually does not eat other crosslinkable water-soluble resins or precursors of these resins, such as e.g. formaldehyde condensates with compounds containing an NH group in the molecule, such as melamine, urea, and ethylene urea. Such water-dispersible polymers usually have perfluorinated alkyl side chains, e.g. in perfluirinyl, polyhydryl or -bulithmidine groups, especially those with 3 to 12 carbon atoms in the perfluoroalkyl group, and carboxyl groups may also be present. The hydrofluorocarbon polymers are preferably derivatives of acrylic or methacrylic esters of hydroxyl compounds containing perfluoroFanr alkyl groups, but can also be derivatives of vinyl esters, vinyl ethers, alpha esters or thiomethacrylates with perfluirial side chains. / Perfluoranes are groups in which all hydrogen atoms are replaced by Πιμί /. Particularly preferred are / N-alkyl-N-perfluoalkylosphonamido / alkylene side chain polymers, e.g. 2- (N-pripyli-N-peΓfluiiiiktylisulfonamido / ethylene), while the backbone is acrylic or methacrylic ester. Such polymers can only be obtained from monomers containing perfonated alkyl groups, but these monomers can be copolymerized with other monomers and become susceptible. copolymerization, especially with monomers containing no fluorine atoms, e.g. monomers containing one, especially two, olefinic double bonds, e.g. with chlirivjibutadienes such as 2-chliri-1,3-butadiene. The polymer may contain naphthalene monomer units containing carboxylic acid groups, e.g., acrylic, methacrylic or maleic. Pluiripilimers are usually sold in the form of aqueous dispersions, e.g. The polymer dispersion may be non-ionic, but is preferably cationic and especially anionic. FluoΓopilmlrl dispersions may also contain a small amount of water-consumable organic solvents, e.g. acetone, MIBK or ethylene glycol. A preferred fluoΓopilemeil dispersion is that sold by 3M Company under

160,446 under the tradename Scotchgard 270 or by Ciba-Geigy under the tradename Scotchgard FC451. This polymer is believed to be a copolymer of 2- (N-alkyl-N-perfluorooctylsulfonylamido) ethyl acrylate and a comonomer preferably being 1,3-chlorobutadiene.

Another preferred fluoropolymer dispersion is sold by Hoechst AG under the trade name Nuva FH or Nuva F. Dispersions sold by Atochem SA under the trade name Foraperle, especially Foraperle 145 and 344, or by Finmna Texchem UK Ltd. Mncheeser, UK can also be used. , under the tradename Texfin CPC. The proportion of the fluoropolymer (solid) in percent by weight with respect to the ammonium polyphofforne 13 is generally from 0.1 to 6%, for example from 1 to 3%, in particular from 2 to 6%.

The cold flame retardant medium usually contains 7 - 18%, e.g. 7 - 13% or 8 - 15%, especially 9 - 13% ammonium polyphosphate, and 1 - 20%, e.g. 3 - 10% or 5 -1 % of cyclic SOS and typically 7 - 18%, e.g. 7 - 13% or 8 - 15%, especially 9 - 13%, of a carbamate patch derivative, e.g. urea, and optionally 0.02 - 1, 5%, e.g. 0.1-1%, especially 0.3-0.8%, of a fluoropolymer. However, 7 - 24%, preferably 10 - 24%, e.g. 15 - 24% and especially 15 - 23% ammonium polyphosphate and 0 - 2C%, preferably 1 - 2C% or 0 - 15%, e.g. 1 - 15%, can be used. % or 1-10%, especially 1.5-4% of the carbamate crossover derivative. Preferably, this total content of polyphosphate, carbamate loom derivative, e.g. urea, and fluoropolymer (if present) in the environment does not exceed 26%, preferably 11-26% or 15-26%, especially 20-24%.

The environment may also contain a non-re-decay agent, e.g. a volatile wetting agent such as alcohol or an agent sold by Waidch.Cheπmcals under the trade name Mykon NRWj, the content of such agent is preferably 1-10 g / l.

However, if the flame retardant substrate has already been washed or has undergone any other treatment to facilitate liquid penetration, then no such agent is needed, although it may possibly be present. For example, when the aquatic medium contains a fluoropolymer, it is typically devoid of cationic fillers or polymers, such as cationic synthetic resin waxes, e.g. , tri-and quadripartite, e.g. aluminum or zirconium salts. Some of the commercially available Sluoropolymer dispersions also contain a neuter or a cationic polymer of such dispersions, it is preferred not to use such dispersions. Commercial dispersions of fluoropolymers which primarily provide soil resistance and de dispersions which provide resistance to dirt and water are preferred, since the latter tend to contain the cationic polymer and may not be miscible with the concentrated concentrated polyphosphate solution.

In a preferred embodiment, the aqueous ethane flame retardant comprises 7-15% horned, e.g. 8-13% horned ammonium phosphate complex or organic quaternary complex ammonium phosphate, 3-10% by weight cyclic SosSOnate, preferably of formula II. (especially the rainfall of such Sosfonirnes), 7 - 15% of horned carbamate derivative, e.g. urea, where the percentage by weight of urea in relation to polyphosphate is 50 - 200%, and the total total phosphate and urea content is not exceeds 25%. These comeditions preferably contain cationic, water-soluble polAsrowes containing fluorine atoms, and preferably they may contain a fluoropolymer that tears the ufluorphylamine side chains.

The polyphosphate, preferably with a derivative of the carbamate patch, may be provided as a concentrated aqueous solution for subsequent mixing with cyclic phosphodium before or preferably after diluting one or both of them to the concentration of the impregnating bath.

If the medium is to be eroded by the fluoropolymer, the fluoropolymer dispersion is advantageously transferred to the environment when it is ready for impregnation, and the medium is preferably used for impregnation within a few days, so especially in the case of anionic fluoropolymer dispersions, the medium must be stable for months, tolerating at least one wash, e.g. at least one wash per month.

the aquatic environment may also contain other textile aids of such a kind and quantity that they are compatible with the other components of the environment and

160 446 for non-substantially thermal cross-linking treatment, e.g., causing a discoloration or loss of effect. Examples of such agents are softeners and conditioning agents, which may be cationic, anionic, nonionic, amoteric or reactive, and typically contain at least 1, and often 2, alkyl chains of at least 10 carbon atoms.

Examples of cationic softeners are fatty ammonium quaternary ammonium, ammonium ammonium and ammonium salts and quaternary H-acyl-N-polyoxyalkene polyamines. Exemplary anionic softeners are fatty acid salts, milks, sulfonated fats and oils, fatty acid and fatty acid condensates, sulfoburitinates and sulfo-sulfurates.

Exemplary amoteric agents are alkylmidisoles and betaines and their salts, e.g., methanesirchiιes, acylamidobeeaines, acylpolyemines, aninoHenes, substituted amino acids and anidobeeaines. Examples of polyalkylene glycol ethers and esters and other poloxyalkylene condensation products and paraffin or polyethylene wax, the latter two being used in the form of an aqueous dispersion or emulsion with nonionic, cationic or anionic, especially amoteric dispersants, are exemplary. Examples of reactive softeners are N-moleylol amide derivatives of tetanic acids, e.g. N-moeylol dimidyl of stearic acid or N-mtylol derivatives of koi ^ <^^ n ^^ <^; Urea fatty acid ji, an emollient as such or in the form of a dispersion % of aqueous impregnation may be used in an amount of 0.01-5% by weight, e.g. 0.5-3% by weight of the total amount of the aqueous impregnating medium. The presence of the emollient may enable the thermal cross-linking process to produce a finished fabric with a reduced flammability and other properties, e.g. strength, especially tensile strength, and a color substantially the same as that of untreated fabric, and the strength may even be increased.

The substrates to which the flame retardant environment is applied can be woven or non-woven. These are cellulose-based substrates, e.g. fiber fabrics such as cotton, linen, jute, hesim or regenerated cellulose materials such as rayon or cotton wool, mixed with other fibers, e.g. polyester or nylon, acrylic, acetate These fiber mixtures or meshes may contain at least 30%, e.g. 30-100% or 30-90%, but preferably at least 40%, e.g. 40-75% and especially at least 40%, e.g. 50% cellulose grind, e.g. 50 - 90%, 50 - 80% or 70 - 90%.

Fabrics of non-melange blends of cellulosic fibers, e.g. cotton, and a synthetic polymer, e.g. polyester or nylon, are preferred. The fibers used making up at least part of the fabric may if desired be composed of a core and a sheath, but preferably are not. Fabrics can be made of mixed fibers, e.g. have at least one of the wefts, in particular a predominantly warp / e.g. 50 - 100%), especially entirely, of synthetic polymer fibers and a warp predominantly of polyester, a nylon warp and a cotton weft, especially cotton embossed, are preferred. In the absence of cyclic flsfoil, the application of a flame to such woven fabrics can cause the polyester to shrink and separate from the cotton and then burn, completely canceling the flammable flammability effect of a fabric used for example as an upholstery.

The method of reducing flammability enables: and this more homogeneous coldness of flammability:!, At least semi-permanently, of such fabrics made of mixed fibers, preferably boiled, and in particular fabrics with heterogeneous distribution of synthetic polymer and cellulose material on the surface, here called fabrics with a different surface area . Fabrics with a diversified surface are particularly important fabrics with the front side with a different (usually lower) content of cellulosic material than on the reverse / left side;} /, as well as large areas usually bursting on the front surface made of predominantly / e.g. . 50 - 100% / with synthetic polymer fibers on the surface, as well as large areas mainly made of / e.g. 50 100% / made of fibers made of cellulose material. Examples of such fabrics of various

160 446 of the surfaces are fabrics with a polyester warp and a dyed polyester weft, especially with more than one differently colored cotton weft, whereby the fabric is woven with a pattern of dyed cotton in this way against a polyester warp background and a non-patterned left side with an essentially cotton surface. Fabrics with such a diversified surface can be used as upholstery fabrics.

Gramtura fabrics is usually ⁰ 050 - 1.0 kg / m ^, for example. ^0, 0 ⁸ 0 - 0.500 kg / m ^. ^K EF ^y the components of the fabric color may be natural or non-pigmented, or may be colored, especially in white or pastel shades. Prior to impregnation, the fabric is usually freed of dirt, glue, natural waxes and applied finishing materials, although it may contain optical brightener.

A flame retardant medium, typically with a pH of 5-8, e.g. 5.5-7.5, is applied to the substrate in a known manner, e.g. by padding, soaking or spraying, usually until 50-150% has been absorbed, e.g. 60-100% % moisture. The total amount of solids introduced before drying and after the excess liquid has been squeezed out is usually 10 - 35%, e.g. 10 - 20% or 13 - 25% (based on the initial weight of the dry fabric). After the substrate CVT ^{s y,} eg. Ground tex ^ lne at ⁸⁰ - 120 ° C for 2-40 minutes, n ^p. 2-10 minutes. Drying may be carried out in any known dryer, e.g. The solids absorption after drying is typically 8-25%, e.g. 10-20% (based on the initial weight of the fabric).

The dried substrate is then cured eg. By heating at a temperature of at least 130 ° ^{C, t} and ^k nd I ^k of at least 14 ⁰ ° ^C, eg. 14 ⁰ - 180 ^ esp ^A happy 140 17 ⁰ ° ^C, 14 ⁰ - 1 ⁶ 5 ° ^{C or b} 14 ⁷ - 1 ⁷⁰ % n ^p . in a ^sequence of ⁶ - ^0, 5 mLnut, wherein the spinning ^y ^ ^ay is dodge the combination of longer times and higher temperatures, to the cold sewing tends to change zabanwenia. Thus, the preferred temperature is 147 - 165 ° C, especially 147 - 16O ° C or 147 - 155 ° C for the crosslinking of 6 - 0.5, for example. MLnut 5-2, though, the temperature may be 13 ⁸ --147 ^{C, p} y ^y during curing 3,5 - ^0, 5 minutes. ^The presence of any fluoropolymer in the impregnating agent, and thus in the fabric, may increase the non-flammability resistance of the fabric and increase the fabric's resistance to staining.

Cross-linking, which is usually a continuous process, is usually carried out by radiant heating, e.g. by infrared irradiation or heating by injection of steam and / or hot air through the substrate, or by contacting the substrate with a heated metal drum in a vertical chimney, but preferably by heating is carried out by impinging hot air on the surface of the substrate, preferably the surfaces on both sides, to ensure the uniformity of the heating. Thus, preferably, the coolant is passed continuously through the dryer - tensioned by a thermostatic dryer, in which the heated air flows along the upper and lower surfaces of the substrate. The dryer-stretcher provides the most uniform cross-linking with minimal premature formation. In the case of a stretching dryer, the cross-linking temperature is substantially the same as the temperature of the heated air flowing through it. Usually, after the end of the netting, the substrate is cooled down by the rapes, either by blowing them with reduced air or by sucking cold air through them.

The fabric after post-cross-linking typically contains 6 - 25%, e.g. 8 - 20% solids, and typically 0.5 - 4%, preferably 1 - 3% P or 2 - 4% P. After finishing, the fabric has dm ^^ , with lower flammability compared to untreated substrate, and meets the requirements of the tests conducted by BS 5852 with the use of ignition sources 0 and 1.

After a single leach in hard water at 40 ° C according to BURIAN BS 5651 without final ironing, the fabric typically contains 3 - 10%, e.g. 4 -% solids, and the percentage of P in the fabric is typically 0.4 - 3%, preferably 0.9-3%, e.g. 1-3%, and meets the test of British Standard BS 5852 Port 1 when using ignition sources 0 and 1. The flame retardant performance is usually stable within 1-3 wash in soft water at 74 ° C, then retain some curl in flammability. A fabric finished in this way usually has a slightly different grip

160,446 and color compared to untreated fabric.

The synergistic combination of / i / polyphosphate salt and / ii) of cyclic phosphonium, especially with a carbamic acid derivative, gives treated fabrics with densified and more permanent non-flammability, which are not found in fabrics treated with / and / or / ii / alone.

The following examples illustrate the invention. The fluoropolymer, if present, was used as a 23% aqueous, slightly cathartic emulsion sold by 3M under the trade name Scotchgard FC 208 or by Ciba-Geigy under the trade name Scotchgard FC 451. This fluoropolymer is considered to be a copoimeter 2- (N-propyl-N-perfluorooctylsulfonylamdo) ethyl acrylate and 2-chloro-butadiene - 1,3.

The ammonium polyphosphate used was prepared by reacting a polyphosphoric acid containing 83 - 85% ± 2 ° 5 2 with ammonia as described in British Patent No. GGB-P 1504507 to give a product whose pH was adjusted to 6.2, containing 45% solids. , 30% µg ° 5,10 specific weight, m 1.36.

The cyclic phosphonate was a mixture of 50 tons of 50 cyclic phosphonites sold under the trade name Antiblaze 19 or Angard CU (as previously described). The softening agent was an aqueous amphoteric dispersion of an aliphatic hydrocarbon, presumably a paraffin wax or polyethylene wax, sold by Sandoz under the trade name Sandolube NV.

The same procedure was followed in each case. An aqueous solution of polyphostolmonium, urea and cyclic phosphonate, if present, was prepared, and then diluted to the desired degree with water, mixed with mechanical mixing, with a 2% softening agent (based on the total weight of the impregnating medium), emutej ^ uo ^ pornieru, if used, in an amount of 2% emutej! based on the total weight of the solution and emulsion, as well as 0.5% of the non-rewetting agent sold under the trade name - Mr ^ on NB'W, making up a ^ -water medium containing ammonium phosphate urea, wetting and softening agent, and optionally a cyclic phosphonate and / or a fluoropolymer. The prepared aqueous medium was stable, but was preferably used without further delay, especially in the presence of fluoropolymer. Each fabric, which is upholstery fabric, was impregnated with an aqueous medium and wrung, ^p ^ part of the impregnated fabric dried at a temperature of ⁹⁰ - 1 ⁰⁰ ° ^C for 1 minute in an oven with forced circulation oven or pożetrza - stenter. Portions of the dried fabric were then moved slowly but continuously on the dryer-tensioner through the thermostated drying chamber of the-tension dryer, with the flow of heated air hitting the fabric from above and below. The fabric siectowaaiu were tested flammability according to British Standard BS 5852 Part 1 with ignition sources 0 and 1, and after finishing and after one fold ^L u ^g crossing in teardej water at ⁴⁰ ° C zgotinie of ^b r ^ tyj £ ^ k ^± BS ⁵⁶⁵¹ Part 1 standard without final pressing.

Examples VII-XII and ΧΧΙΙ-ΧΧΧΙ are comparative examples.

Examples Ι-ΧΙΙ. In Examples 1-6, an aqueous solution of ammonium polyphosphate (59 parts) and urea (27 parts) and water (139 parts) was mixed and then the cyclic phosphonate (15 parts) was added. fluoropolymer, a zmękczający and lessening agent, preparing environment environment is applied to the calender padding for each of the six mixed fabrics of cotton fibers and having a basis weight poliestowwych ^0, 270 kg / rn ^ with wychwytaniem »oiypowiednio about 8 ^{0%. By} l ^s fabric made from ^{65% b} Aroi ^AEG bawwlnianego ^of weft and 35% polyester warp and were obtained from three suppliers. The fabrics represented a different rate of wear, with a different ratio of polyester to cotton on their faces and a different ratio of polyester to cotton on their faces compared to the left side of the fabrics. The fabrics used in Comparative Examples 7 and 8 had a substantially homogeneous polyester to cotton distribution on their faces, while the fabrics used in

160,446 used in Comparative Examples IX, X, XI and XII on the front surface of the fabric had dyed cotton in the gel of the places in the form of deforestation on the polyether, while the left surface of the fabrics was dominated by dyed cotton. The impregnated fabrics were then dried on a freeze drier for 1 minute at 100 ° C, and then cross-linked on this dryer-stretcher for 3 minutes at 150 ° C. All fabrics when finished and leached once in hard water comply with British Standard BS 5852 with ignition source 0 and 1.

In comparative examples VII-XII the described procedure was repeated without using cyclic phosphonate. All fabrics after one hard water leach did not meet British Standard BS 5852 with ignition sources 0 and 1, with the fabrics in Examples ΙΧ-generally igniting immediately.

Examples ΧΙΙΙΧΧΧ. The procedure of Examples 1-6 was followed, except that a fluoropolymer emulsion was not used, but different mixed fiber fabrics and different amounts of cyclic phosphoniene were used. Wet extraction was about 80%, but the amount of water added in the impregnating medium was adjusted so that in each case there was substantially constant deposition on the fabric of ammonium polyphosphate and urea / mlanoz, 6% ammonium polyphosphate and 7% urea, respectively, based on on solid /. The type of fabric and the amount by weight of the cyclic phosphonate applied to the fabric are given in the table below. Each fabric had a cotton weft and polyester warp with a raised sack of dyed cotton warp and weft on the front face of the polyester with a background groove, with a significant exposed polyester warp surface but with a cut polyester to cotton ratio on the front face similar to that of the fabric as a whole. The drying pots and ^ θο ^^ ο ^ were as in Examples 1-6. All fabrics, after completion and single leaching in hard water, met the test for flammability both before and after leaching. In comparative examples ΧΧΙΙ-sposób the same procedure was repeated, but without the use of cyclic phosphonate, and all fabrics did not meet the requirements of British Standard BS 5852 after leaching in sight.

Table I

Example or Polyester / Cotton% % by weight of phosphonate on the fabric Grammture ^k g / m ² XIII 30:70 5.4 0.320 XIV 30 and 70 5.4 0.400 XV thirty ; 70 5.2 0.440 XVI 35: 65 5.6 0.380 XVII 35: 65 5.4 0.420 XVIII 39 «6i 5.8 0.340 XIX 46: 54 5.2 0.520 XX 49 «51 6.5 0.300 XXI 50 s 50 6.0 0.550

In order to demonstrate the tyoethical effect of kimCiioaji of the pilifosOtaonoate salt and the cyclic phosphonate, in the next example, the fabric was only treated with cyclic phosphonate.

160 446

Example XXXI - comparative. The following two types of fabrics were processed: Sample A: Bawwennappoieater 60: 40 (weft-cotton, oenoraappoleatrora /, fabric weight ⁰ , 27 ⁰ k ^g / m ² j

Sample 3: Cotton / polyester 70: 30 / thread, cotton, polyester warp /, weight woven ^{and y} n ^0, k ⁰ 32 ^g / m ^2.

A procedure similar to the previous examples of pores ^^ and ^ ws ^^^ c ^ h was used. The fabrics were impregnated with a 7.5% bright solution of cyclic phosphonium, and then dried at 100 ° C for 1 minute, and then cross-linked at 150 ° C for 3

Summary of machining data.

Table II

Sample A Sample B Wychiwttyraaae through the fabric 80,% 800% % by weight of phosphonate on the fabric 6% 6%

After cross-linking and single leaching, both fabrics were flame tested in accordance with British Standard BS 5651.

Fabrics impregnated with cyclic phosphonate only did not meet the requirements of BS 5651 with ignition source 1.

Claims (15)

A process for the cold retardation of flammability of fabrics, characterized in that the fabric made of cellulose and non-cellulose blended fibers is impregnated with an aqueous medium consisting of a compound containing ammonium phosphate or an organic quaternary complex ammonium phosphate and at least one cyclic phosphonate ester of the formula 1, where a is 0, 1 or 2, b is 0, 1 or 2, c is 1, 2 or 3, the sum of a + b + c is equal to 3, R and R are the same or different, represent an alkyl, alkoxy, aryl, aryloxy, alkylaryl, alkylcyclooxy, arylalkyl, aryloxyalkoxy or arylalkoxy group, the groups of which the alkU can optionally contain at least one hydroxyl group but may not contain a halogen atom, and the aryl portion may contain at least one chlorine, bromine or hydroxy group, R is an alkyl, hydroxyalkyl or aryl group; ykliczn ^y · ^f osfoninnowy ester of formula 2, wherein d is lLiic BE ^^ 0, 1 or 2, e is 1,2, or 3, the sum d + e is 3, R and R ^ I defined above, R is an alkyl, aryl, alkyl £ ^ · yl <group, iryllilkiOową or aryloxyalkyl group, in which groups the aryl portion may optionally contain at renting one bromine, chlorine or hydroxyl, and ^R * is suggested ^d nlrortośc ^{and yl, d} miwartościow ^± lu ^b trójwaΓtl ^{COG-linked group} of a ^{l kiloaą,} alkylene, blocky or arylene group, wherein the aryl or arylene optionally containing at least one bromine, chlorine, a alkUową or hydroxy, then it is dried and subjected to curing at a temperature I ³⁰ - Ί8 ^{0 <} υ. 2. The method according to p. The process of claim 1, wherein the composition comprises ammonium polyphosphate 3. The method according to p. 1 or 2, characterized in that the agent is used in which p ^Ke enters c ^{d y} kli.czny phosphonate of the formula 1, órym ^{angle R and R} is ^± 2 ^and lower 3 alkUową group or alkoxy group having 1 - 6 carbon atoms atoms, and each of R and R alkUową ^J is a group having 1 - 6 carbon atoms. 4. The method according to p. 3, characterized in that the agent is used in which the voice ^{of k} order comes from the ^binding of the ^angle of formula 1 kt ^ zym each ^Y R, and ^R * is a group ^e meth ^y low ^± lu ^b eliylow ^ and ^{R 1 g} ru ^EP rescue ^k βyloa lu ^{± b} ^ etotoylow The method according to p. 3 or 4, characterized in that the agent is used, which consists of two phosphonates of formula 1, in a weight proportion of 25-75> 75-25, where in one of them a, b and c are 1, and in the other a is the number 1, b is zero and c is the number 2. 6. The method according to p. 3. The process as claimed in any one of the preceding claims, characterized in that the composition comprises cyclic phosphate and complex phosphate, calculated as ammonium polyphosphate, in a weight ratio of 0.1-2 µl. 7. The method according to p. 6. The process of claim 6, wherein the composition comprises cyclic phosphonate and polyphosphate in a weight ratio of 0.3-1: 1. R. The method according to p. A composition according to any of the preceding claims, wherein the agent is a carbamic acid derivative. 9. The method according to p. R, characterized in that the agent is used, which contains 50 - 200% of urea, calculated on the weight of the complex phosphate, expressed as ammonium polyphosphate 160 446 10. The method according to p. 3 or 4 or 5 or 6 or 7 or 8 or 9, characterized in that it contains 8 - 15% ammonium polyphosphate, 3 - 10% cyclic photonate and 8 - 15% urea, water. 11. ppotbb according to summarization 1 or 2 or 3 words 4 words 6 or 7 or 8 words 9 or 10 variable in that the medium containing the fluoroacrylate polymer in the form of a water emulsion is included. 12. ppotbb according to zlstrz. The method of claim 1, wherein the baby is allowed to heat at 140-170 ° C within 6-0.5 minutes. 13. Pp ^ do according to the list of figures. 1 or 12, alternating in that it tints the fabric which loses 30 - 90% of the cellulose fibers. 14. Ppotób according to zsstrz. 1 or 12, characterized in that this fabric is treated with 50-80% cellulose fibers and other non-cellulose, tangled polyester or nylon fibers. 15. Ppotób according to zlstrz. 1 or 12 or 14, alternating in that the material is treated with an abrasive tissue, predominantly made of polyether. 16. Ppotób according to zsstrz. 1 or 12 or 14, alternating in that the fabric is treated with a bsTwo weft fabric with detangled cotton and a polyetherette. 17. Ppotób according to zsstrz. 1 or 12 or 13 or 14 or 15 or 16, characterized by the fact that this tissue with different sub-activity is treated.