PT92783B - PREPARATION PROCESS FOR A FLAME RETARDER COMPOSITION AND FLAME RETARDATION PROCESS OF A FABRIC - 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

DESCRIPTION

GIVES

INVENTION PATENT

N ° 92,783

APPLICANT:

TITLE:

ALBRIGHT & WILSON UK LIMITED, British, based at 210-222 Hagley Road West, Oldbury, Warley, West Midlands, England, United Kingdom

PROCESS OF PREPARING A FLAME RETARDANT COMPOSITION AND FLAME RETARDING PROCESS OF A FABRIC

INVENTORS:

Robert William Black

Claim of the right of priority under article 4 of the Paris Convention of 20 March 1883. United Kingdom on 04 / .laneiro / 1989 under n ° 8900060.8.

INPI. MOD. 113 RF 16732

PR 687 / III / PT / AER

PATENT N2 92 783

Process of preparing a flame retardant composition and flame retardant process of a fabric so that

ALBRIGHT & WILSON UK LIMITED, intends to obtain privilege of invention in Portugal.

RESUME

The present invention relates to the process of preparing a flame retardant composition, characterized by mixing a condensed organic, quaternary ammonium or ammonium phosphate and at least one cyclic phosphonate ester of formula (A)

.. O

where a is 0.1 or 2; be 0.1 or 2; c is 1,2 or 3 and a + b + c is 3; R and R ¹ , which are the same or different, are alkyl, alkoxy, aryl, aryloxy, alkylaryl, alkylaryloxy, aralkyl, aryloxyalkoxy or aralkoxy, in which the alkyl portion of these groups may optionally contain at least one hydroxyl, but not halogen , and the aryl moiety may contain at least one chlorine, bromine or hydroxyl group; R ² is alkyl, hydroxyalkyl or aryl; R and lower alkyl or hydroxyalkyl,

WR.

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-2or a cyclic phosphonate ester of formula B

where d is 0.1 or 2; e is 1,2 or 3; d + e is 3; R is as previously defined 3 4; R is as previously defined; R is alkyl, aryl, alkylaryl, aralkyl or aryloxyalkyl, in which the aryl powder can contain at least one bromine, chlorine or hydroxyl; and R4 is an alkyl, alkylene, aryl or arylene, monovalently, divalent or trivalent radical in which the aryl or arylene radical may optionally contain at least one bromine, chlorine, alkali or hydroxyl group.

These compositions impart semi-durable flame retardant properties to fabrics made of cellulosic fibers and synthetic polymers.

I

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-3 DESCRIPTIVE MEMORY

This invention relates to a process for the preparation of flame retardant compositions and to flame retardant processes of textile substrates using said compositions.

Cotton fabrics can become flame retardant by incorporating a wide variety of chemicals, some of which provide durable flame retardancy and others provide non-durable flame retardancy. Among these latter chemicals is ammonium phosphate and ammonium polyphosphate, optionally, with added urea. Although some of these compounds are inexpensive, their effectiveness is short-lived as they are removed by washing with water. Some attempts to increase the durability of these compounds, included a high temperature cure at about 150 ° C (see eg GB-P 1504507). Curing polyphosphate can be associated with co-curing with various agents of the usual tissue treatment, e.g. ex. with dimethioleolide I will have to (see eg GB-P 1069946). Cotton / polyester fabrics, especially bonding fabrics, are more difficult to make / make flame retardants, even only semi-durable, than cotton fabrics.

It has been found that flame retardant compositions and their application processes to fabrics made of cellulosic or other materials, provide flame retardant fabrics, with increased durability.

In the present invention a straight flame composition is prepared, comprising a condensed organic phosphate of quaternary ammonium or ammonium and at least one cyclic phosphonate ester I of formula (A):

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-4 where a is 0, 1 or 2; b is 0, 1 or 2; c is 1, 2 or 3 and a + b + c is 3;

R and R ¹ , the same or different, are alkyl, alkoxy, aryl, arj. loxy, alkylaryl, alkyloxyoxy, aralkyl, aryloxyalkoxy or aralkoxy, in which the alkyl portion of these groups can contain at least one hydroxyl but not halogen and the aryl portion can contain at least one chlorine, bromine or hydroxyl group;

R is alkyl, hydroxyalkyl or aryl; R is lower alkyl (eg C ^-C ^) or hydroxyalkyl (eg C ^-CC), or a cyclic phosphonate ester of formula (b) (B)

R 0C in which d is

Z

R ', 4 eél, 2 or 3; d + eé 3 is defined before or is defined as before; R ^- 'is alkyl, aryl alkylaryl, aralkyl or aryloxyalkyl, in which the moiety

0, earlier; R11 may optionally contain at least one bromine, chlorine or hydrophilic; and R 4 is a monovalent, divalent or trivalent alkyl, alkyl, aryl or arylene radical, in which the aryl or rylene radical may optionally contain at least one bromine, chloro, alkyl or hydroxyl group. The composition may also contain a water-disoersable fluoropolymer but preferably contains a carbamic acid derivative, e.g. ex. urea.

The present invention also relates to a flame retardant process in a fabric, which comprises impregnating a bonding fabric with cellulosic and non-cellulosic fibers, with an aqueous medium comprising the flame retardant composition of the invention and then, drying and curing at a temperature of 130 180 ° C.

polyphosphate salt can be prepared by reacting a condensed phosphoric acid with ammonia or with an organic amine or with quaternary ammonium hydroxide, yielding a product

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-5to soluble in water. The condensed phosphoric acid usually has an average degree of condensation greater than 3, e.g. ex. 3 to 30, and usually has a linear, branched or cyclic structure. Preferably the salts contain N and P in an atomic ratio of 0.52: 1, especially about 1: 1. The polyphosphate salt is preferably a mixture of ammonium salts of various polyphoric acids, produced by a reaction process between an aqueous solution of phosphoric acids, containing 80-86% by weight, of phosphorus, and ammonia or a basic derivative thereof, at a temperature of 15-70 ° C, e.g. ex. 15-40 ° C and at a pH of 4-12, e.g.

5-9, p

6.5-7.5, or from 5 to 12, especially from 6 to 8.

a - l,,. - _c . ammonium,, _£ _

Mixtures of polyphosphates / that can be used are described in GB-P-1504507 and can be prepared as described therein.

cyclic phosphonate ester I is described in U5P 3849368 and 3789091, the descriptions of which are incorporated herein by reference. It can be prepared as described in those patents by reacting esters, free of alkyl halides, phosphorus acids or carboxylic acids or sulfonic acids, with a bicyclic phosphite, e.g. , a 1-alkyl -4-phosphate-3,5,8-trioxa-bicyclo - 2,2,2— octane. The alkyl, al ^L - ¹ 15 coxyl or substituted alkyl groups, for R and for R-R, can contain 1 to 6 carbons, while the aryl groups can be aromatic hydrocarbyl groups and can contain 6 to 19 carbons, and the groups aralkyl may be hydrocarbyl groups and may contain 7 to 19 carbon atoms. Examples of R and R3 are alkyl O2, phenyl, halophenyl, hydroxyphenyl, to1O1, x1O1, benzyl, phenyl, hydroxyethyl, phenoxyethyl and dibrornophenoxymethyl. Examples are R 5, C ^ _ ^alkyl, phenyl, halophenyl, hydroxyphenyl, hydroxyethyl, phenoxyethyl, dibromophenoxy-ethyl, -tolyl, lo, -benzyl or -phenethyl, while examples for R ' monovalent alkyl, chlorophenyl, mono-, di- or tri-bromo phenyl, hydroxy if enyl, naphthyl, tolyl, xylyl, benzyl or phenyl, alkylene C., divalent, vinyl, o-, m- or p-phenylene, 1 - □ tetrachloro- or tetrabrornophenylene (o, m or p) and trivalent phenethyl. Preferred compounds II are those in which each group

R and r !, the same or different, represent an lower alkyl group

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PR 687 / 1II / PT / AER lower or lower alkoxy group, e.g. ex. with 1 to 6 carbons, especially 1 to 3 carbons, especially methyl, ethyl, m 2 and 2 3 toxo and ethoxy, while each group R and R, which may be the same or different, preferably represents an alkyl group, p . ex. with 1 to 6 carbons, such as methyl or ethyl. Mixtures of cyclic phosphonates can be used, for example with proportions of 2 phosphonates from 95: 5 to 5:95, p. ex. from 25:75 to 75:25, especially a first phosphonate where each a, b and c is 1, and a second phosphonate where aél, bé0ecé2, otherwise 2 3 each of the groups R, R and R, independently of each other , in one phosphonate, equal to the corresponding group in the other phosphonate.

The most preferred mixtures are the 40:60 to 2 to 60:40 mixtures of these two phosphonates, where each of the groups R, R er \ represents a methyl or ethyl group and R ^ represents methoxy or ethoxy, as in Ex. Lb from USP-3849368, especially 3 2 1 when R and R are methyl, R is ethyl and R is methoxy; an example of this mixture is the 50:50 w / w mixture (where R, R are methyl, R 2 methoxy and R ethyl) sold by Albright & Wilson Américas Inc under the trademark ANTIBLAZE 19 or by Albright & Wilson Ltd under the brand registered AMGARD CU. The weight ratio between cyclic phosphate and ammonium polyphosphate is usually 0.1-2: 1, such as p. ex. 0.3-1.0: 1 or 0.4-1.3: 1.

flame retardant medium usually contains a carbamic acid derivative with 2 amino groups per molecule in a percentage by weight (expressed as urea), compared to ammonium polyphosphate (expressed by weight as 0.5% ammonium polyphosphate itself up to 300%, such as 0.5-50%, eg, 5-30% such as 7-20% or 10-20%, although 50-300% is preferred, eg 50-200? and, in particular, 75-125%, particularly for curing at higher temperatures; in general, the higher the curing temperature, the higher the proportion of the carbamic acid derivative. The carbamic acid derivative can be guanidine or dicyandiamide but is preferably urea, weights are expressed as urea but equivalent weights of other carbamic acid derivatives can be used.The presence of the carbamic acid derivative reduces any tendency to discolor the tissue after

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-7 heat cure, especially at elevated temperature, and can increase liquid absorption.

flame retardant medium may also contain a dispersion of fluorocarbon polymer (capable of being heat cured at more than 160 ° C, eg between 160 ° C-200 ° C). The fluorocarbon polymer is one that forms, in the flame retardant medium, a dispersion that is usually stable for at least a few days, e.g. ex. at least 2 days; This prevents fluoropolymers incompatible with the condensed phosphate and cyclic phosphonate solution (with the carbamic acid derivative, if present) and the formation of precipitates when mixing. The medium is generally substantially free of other water-soluble, heat-curable resins or of resin precursors such as formaldehyde condensers with NH compounds, such as melamine, urea or ethylene urea. These water-dispersible polymers usually have perfluoroalkyl side chains, e.g. ex. in perfluoro-acyl, -sulfonyl or -sulfonamido groups, especially those having 3 to 12 carbons in the perfluoroalkyl group; carboxyl groups may be present. Fluorocarbon p-polymers are preferably derived from acrylic or methacrylic esters of hydroxylated compounds containing perfluoroalkyl groups, but can be derived from vinyl esters, vinyl ethers, allyl esters or thiomethyls with perfluoroalkyl side chains. Especially preferred are polymers that contain (N-alkyl-N-perf-fluoroalkyl-sulfamido) alkylene side chains, e.g. eg 2 (N - pro pi 1-N-perf1uoroocti1su1fonamido) ethylene with an acrylate or methacrylate ester backbone. Polymers can be prepared only from monomers containing perfluoroalkyl groups, but these monomers may have been immersed with other limerizable glass monomers, fluorine free and fluorine free, e.g. ex. those containing one or especially two olefinic double bonds, e.g. ex. as in halo-butadienes such as 2-c 1 o r o-1, 3-bu t ad i en o. Units of olefinic monomers containing groups of carboxylic acids, e.g. groups of acrylic, methacrylic or maleic acid, may be present

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-8 in the polymer. Fluoropolymers are usually sold in the form of aqueous dispersions, e.g. for fluoropolymer finishes, stain repellents, for fabrics. The polymer dispersion can be non-ionic but is preferably cationic or especially, anionic. Dispersions of fluoropolymers may also contain small amounts of water-miscible organic solvents, e.g. , acetone, MIBK or ethylene glycol. A preferred fluoropolymer dispersion is that sold by 3M Company under the trademark SCOTCHGARD 270 or by Ciba Geigy under the trademark SCOTCHGARD FC151. This polymer is believed to be a copolymer of an acrylate of 2- (N-a1qui1-N-perf1uoroocti1su1foni1amido) ethyl and a co-monomer, probably the 2 - c 1 o r o -1, 3 - bu t a d i en. Another preferred dispersion of f1uoropolymers is that sold by Hoechst AG under the trademark NUVA FH or NUVA F; the fluoropolymer dispersions sold by Atochem SA under the trademark FORAPFRLE, especially FORAPERLE 115 and 311, or by Texchem UK Ltd, Manchester, England under the trademark TEXEIN CPC, may also be used. The weight percentage of fluoropolymer (solids) to ammonium polyphosphate is usually 0.1 to 6%, e.g. ex. , from 1 - 3% but, and sp ec i to 1 m and n, and from 2 - 6%.

flame retardant medium usually contains 7-18!

P. 7-13% or 8-15%, such as 9-13%, of ammonium polyphosphate and 1-20%, e.g. ex. 3-10% or 5-10%, of the cyclic phosphonate and usually 7-18%, p. 7-13% or 8-15%, such as 9-13%, of the carbamic acid derivative, e.g. urea, and optionally 0.02-1.5%, e.g. 0.1-1 and, especially, 0.3-0.8% fluoropolymer. However, amounts of 7 to 21% ammonium polyphosphate, such as 10-21%, e.g. e.g., 15-21% and especially 15-23% and quantities of 0-20%, e.g. 1-20% 'or 0-15%, e.g. 1-15% or 1-10%, such as 1.5-1% of the carbamic acid derivative. It is advantageous that the total content of polyphosphate, derived from carbamic acid, e.g. urea and fluoropolymer (if present) in the medium does not exceed 26!

ex. , 11-26% or 15-26%, especially 20-21!

medium may also contain a non-removing agent, e.g. , a volatile wetting agent such as an alcohol or an agent, such as that sold by Warwick Chemicals under the trademark MIKON NRW; quantities of these non-soaking agents of 1 are preferred

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-9 to 10 g / 1. However, if the substrate, which will receive the flame retardant, has been cleaned or otherwise treated in order to facilitate the penetration of liquids, then this agent will not be needed even though it may be present if it is desired In the particular case of the fluoropolymer being present, the aqueous medium is usually free of extenders or cationic polymers, such as cationic synthetic resin waxes, as well as those sold under the trademark CEROL from Sandoz, and usually is also substantially free of me salts. such di-, tri- or tretrahed lentes, p. eg those of aluminum or zirconium. Some dispersions of fluoropolymers are sold containing also the extender or the cationic polymer; preferably they will not be used. Fluoropolymer dispersions sold to give mainly stain repellency but not to stain and water repellency are preferred since the latter contain the cationic polymer and may be incompatible with the concentrated polyphosphate solution.

In the preferred arrangements, the flame retardant composition is an aqueous medium comprising 7-15%, e.g. 8-13% by weight of a condensed organic quaternary ammonium or ammonium phosphate, 3-10% by weight of cyclic phosphonate, preferably those of formula II (and especially mixtures thereof), 7 -15% by weight of the carbamic acid derivative, e.g. urea, the percentage by weight of urea, relative to polyphosphate, being 50-200%, with a total content of phosphate and urea not exceeding 25%. These compositions preferably do not have fluorine-free, water-soluble, cationic polymers and can advantageously contain the fluoropolymer having perfluoroalkylsulfonamide side chains.

polyphosphate, preferably with the carbamic acid derivative, can be supplied in the form of a concentrated aqueous solution for further mixing with the cyclic phosphonate, arytes or, preferably, after one or both have been diluted to concentration necessary for the impregnation bath.

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-10ani for nre at least once a

If the fluoropolymer is to be present in the medium, the fluoropolymer dispersion is preferably added to the medium when it is ready to be used for impregnation and the medium is preferably used for impregnation within a few days still, especially in the case of single fluoropolymer dispersions, the medium can be stable without at least 1 wash, e.g. ex month.

paraffin or wax dispersed in aqueous media may also contain other textile auxiliary agents, of a nature and in such quantity that they are compatible with the other components of the medium and that are not significantly affected by heat curing treatment, e.g. in order to cause discoloration or loss of effect. Examples of such agents are softening and conditioning agents, which can be cationic, anionic, non-ionic, amphoteric or reactive, and which usually contain 1 and, often, 2 alkyl chains of at least 10 carbon atoms.

Examples of cationic softening agents are the fatty salts of quaternary ammonium, amino and aminoamide esters, and quaternary polyamines of N-acyl-N-ρo-1-oxia-1-oxene. Examples of cationic softening agents are fatty salts / soaps, soaps, fatty oils and fats, fatty acids and fatty acid condensation products, sulfosuccinates and sulfosuccinates. Examples of amphoteric agents include the alkali metal and betaine and their salts, e.g. e.g., methosulfate, acylamide betaines, acyl polyamines, amine oxides, substituted amino acids and suphobetaines. Examples of non-ionic softening agents are the ρo 1ialkyleneglycol ethers and esters and other ρo1ioxia 1kenene condensation products, and the polyethylene wax, the latter two being used or aqueous emulsion, with nonionic, cationic or anionic agents, but , especially with amphoteric dispersing agents. Examples of reactive softening agents are N-methylol derivatives of fatty acid amides,

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PR 687 / III / PT / AER

-11p e.g., N-methyl1-stearamide or N-methylol derivatives of urea fatty acid condensate. The softening agent, as such or in dispersion, can be used in amounts of 0.01 to 5%, e.g. ex. 0.5-3%, by weight, in relation to the total aqueous impregnation medium. The presence of the softening agent can allow the heat curing process to produce a treated fabric, with improved flame retardancy and other properties, e.g. ex. , resistance, especially tear resistance, and of a color substantially the same as that of untreated fabric; resistance can even be improved.

The substrates to which the medium is applied can be woven or non-woven. They are cellulosic-based substrates, p. , textile fabrics such as cotton, linen, jute, raffia or regenerated cellulosic materials such as rayon or viscose, with other co-miscible fibers, e.g. eg, polyester or nylon, acrylics, acetates, polypropylene, seat or wool; these fiber mixtures can contain at least 30%, p

90%, but preferably contain at least 40 especially, at least 50% cellulosic material, p 50-90%, 50-80% or 70-90%.

e.g., 30-100% or 30ex. 40-75% e, e x. ,

Fabrics from non-combined mixtures of cellulosic material are preferred, e.g. eg cotton and synthetic polymer, e.g. polyester or nylon. The fibers used to make up at least part of the fabrics may, if desired, be of centrally reinforced construction but are preferably not. The fabrics are of construction by joining, for example, with at least a part of the weft and especially of the warp constituted predominantly (50-100%), especially essentially essentially in a complete way, of polyester fibers. synthetic mere, e.g. , a predominantly polyester warp; a polyester or nylon warp and a cotton weave especially with patterns printed on cotton are preferred. In the absence of cyclic phosphonate, the application of a flame to this type of bonding fabric can cause the polyester to collect and melt, separately from the cotton, and then be burned

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-12 thus reducing the overall effectiveness of flame retarded fabric when it is used, for example, in tapestry. The flame retardant compositions of the invention and the process of the invention allow for more uniform flame retardation, at least semi-durably1, in joining fabrics, preferably in the printed ones but especially in the non-uniform distribution of synthetic polymer and material cellulosic, on one surface, hereinafter referred to as differential surface fabrics. Particularly important are tissues with a differential surface, those whose front side has a different (generally smaller) proportion of cellulosic material compared to synthetic material, than on the opposite side, as well as those that usually have a face or front side with areas significant amounts of fibers predominantly (eg 50-100 ?;) of synthetic polymer on the surface, as well as those having significant areas of predominantly (eg 50-100 ?;) fibers of cellulosic material. Examples of fabrics with a differential surface are those with a polyester warp and a dyed cotton weave, especially with more than one differently colored cotton weave, with fabrics woven with front designs of this cotton woven over a bottom warp. made of polyester and an unpainted interior with a surface substantially 1 cotton. These fabrics with differential surface can be used in tapestry fabrics.

Weights per tissue area can be 0.050 to 1.0 2 2

Kg / m, p. 0.080-0.500 Kg / m. Each component of the fabric can be smooth or not colored or it can be colored especially with white or pastel tones. The impregnated fabric is usually free of dirt, glues, natural waxes and applied finishes even though they may contain an optical abrading agent.

flame retardant medium, usually at a pH of 5-8, e.g. 5.5-7.5, is applied to the substrate by conventional processes eg, filling, soaking or spraying usually up to a 50-150? liquid incorporation ;, p. ex.

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-1360 to 100%. The total solids added before drying and after elimination, by compression, of the excess liquid, are usually 10 to 35%, e.g. ex. 10-20% or 13-25% (based on the initial dry weight of the fabric). After impregnation, the substrate is dried, e.g. ex. for textile substrates at 80-120 ° C for 2 to 40 minutes, e.g. 2-10 minutes. Drying can be carried out in any conventional dryer, e.g. ex. in a forced air dryer or in a continuous drying oven. The incorporation of solids after drying is usually 8 to 25%, e.g. 10-20% (based on the original weight of the fabric).

dry substrate is then cured, e.g. eg by heating to a temperature of at least 130 ° C, e.g. ex. , at least 140 ° C, o. ex. 140-180 ° C, such as 140-170 ° C, 140-165 ° C or 147-170 ° C, for p. 6 to 0.5 minutes, avoiding the combination of longer times and higher temperatures to reduce any tendency towards discoloration. Thus, preferred temperatures are 147-165 ° C, e.g. 147-160 ° C or 147155 ° C for 6-0.5, eg 5-2 minutes, although 138-147 ° C can be used for 3.5-0.5 minutes. The presence of any fluoropolymers in the impregnation medium and therefore in the fabric, can increase the flame retardancy durability with the fabric's lava, and can increase the resistance to dirt of the fabric.

Curing, usually continuous, can be done by radiant infrared heating or heating by injection of steam and / or hot air through the substrate, or by contacting the substrate with heated metal drums, in a vertical pile but preferably, curing is carried out by heating by the impact of hot air on the surface of the substrate, preferably on both sides to ensure uniform heating. Thus, preferably, the substrate is passed continuously over a carpet, through a thermostatic oven in which hot air flows over the top and back surfaces of the substrate. With a continuous oven you have the most uniform cure with a minimum of burns. In the case of a continuous greenhouse at txlb

PR 687 / III / PT / AER

The temperature of the substrate is essentially the same as that of the heated air stream. Usually, at the end of curing, the substrate is cooled quickly by passing or drawing cold air through the substrate.

read from 6-25%, p finished cured fabric usually has a content of only 8-20% and usually contains 0.5-4% of P or 2-4% of P. The finished fabric has a

P. 4-9%, a P content ex. 1-3% and can pass the preference, 1-3 reduced flammability when compared to that of the untreated substrate and can pass the BS 5852 test with ignition sources 0 and 1. The fabric after percolating with 40 ° hard water C, according to BS 5651, without final ironing, usually has a solids content of 3-10%, 0.4-3%, preferably 0.9-3%, for the flammability test of the BS 5852, Part 1, with ignition sources 0 and 1. The reduced flammability finish usually lasts 1-3 washes in soft water at 74 ° C even though some flame retardant effect is retained thereafter. The finished fabric usually has a handling not significantly changed from that of the untreated fabric, and usually has a color not significantly different from that of the untreated fabric.

The synergistic combination of (i) polyphosphate salt and (ii) cyclic phosphonate, especially with the derivative of carbamic acid, can give fabrics treated with improved flammability and durability, not possessed by fabrics treated with only (i) or (ii) .

invention is illustrated by the following Examples. The fluoropolymer, when present, was used in the form of a 23% aqueous fluoropolymer emulation with a slight cationic character, sold by 3M under the trademark SCOTCHGARD EC 208 or by Ciba Geigy under the trademark SCOTCHGARD EC 451. this fluoropolymer is a copolymer of acrylate of

2- (N-profi1-N-perf1uoro-octi1 sulfoni1amido) ethyl and of 2-chlorousado

1,3-butadiene. The ammonium polyphosphate / was prepared by reacting polyphosphoric acid with 83-85% P0 0, ^{with am (} 5n a, according to GP-P 1504507, to give a product which was adjusted to

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-15 to obtain a solution of pH 6.2, containing 45% solids, 30% ^{and a} density of 1.36.

cyclic phosphonate was a 50:50 mixture of cyclic phosphonates sold under the trademark ANTIBLAZE 19 or AMGARD CU (as described above). The softening agent was an aqueous amphoteric dispersion of an aliphatic hydrocarbon, probably a paraffin wax or a polyethylene wax, sold by Sandoz, under the trademark SANDOLUBE NV.

In each case, the same general process was adopted. The aqueous solution of ammonium polyphosphate, urea and cyclic phosphonate, if present, was prepared and, after dilution with water as desired, were mixed, with stirring, with the softening agent in an amount of 2% (in relation to the total weight) impregnation medium), with the fluoropolymer emulsion, if present, in an amount of 2% by weight in relation to the total weight of the ratio and emulsion, plus 0.5% of a non-remolting agent, sold under the brand name commercial MYKO NRW to give an aqueous medium containing ammonium polyphosphate, urea, wetting and softening agent and, if present, acid phosphonate and / or fluoropolymer. The aqueous medium obtained was stable but was preferably used without undue delay, especially if the fluoropolymer was present. Each (tapestry) fabric was impregnated with the aqueous medium, squeezed and then the impregnated fabric was dried at 90-100 ° C for 1 minute in a forced air dryer or continuous drying oven. Parts of the dry fabric were moved slowly on a carpet but continuously, through a thermostatic continuous oven, with heated air currents directed both to the top and the back of the fabric. The used fabric was then tested, according to the BS 5852 test, Part 1, with ignition sources 0 and 1, for its flammability as a finished product and after washing in hard water at 40 ° C according to BS 5651, Part 1, without final ironing.

Examples 1-6 and Comparative Examples A-E

In Ex. 1-6, the aqueous solution of ammonium polyphosphate (59 parts) and urea (27 parts) and water (139

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-16 parts) and then cyclic phosphonate (15 parts), the fluoropolymer emulsion, the softening agent and the wetting agent were added, obtaining the impregnation medium. The medium, in a padded ironing ironer, was applied to each of the 6 polyester and cotton joining fabrics of 0.270 kg / m, with liquid incorporations of about 80% respectively. The fabrics were made of colored cotton weave (65%) and polyester warp (35%), and were obtained from 3 suppliers. The fabrics were of different styles of use, with different proportions of polyester / cotton on their faces, and with different proportions of polyester / cotton on their faces in relation to their opposite sides. Fabrics A and B had a substantially uniform distribution of polyester / cotton on their faces, while in fabrics C, D, E and Ε, colored cotton was present in many places on the face in a set of relief designs on a background of polyester, while on the reverse the surface fibers were predominantly colored cotton. The impregnated tissues were dried in a continuous forced air oven at 100 ° C for 1 minute and then cured at 150 ° C for 3 minutes in that oven. All finished fabrics and after washing in hard water, passed the BS 5852 test, with Del ignition sources.

In comparative Ex. A-E, the process was repeated without cyclic phosphonate. All fabrics after washing in hard water failed the BS 5852 test with ignition sources 0 and 1, with C-F fabrics being practically instantaneous.

Examples 7-15 and G-0 comparisons

The procedures of Examples 1-6 were repeated without the 1-fluoropolymer emulsion but with different joining tissues and different proportions of cyclic phosphonate. The liquid incorporation was about 80% but the amount of water added to the impregnation medium was adjusted so that, in each case, there was a substantially constant incorporation in the fabric, of ammonium polyphosphate and urea (named 6.9% ammonium polyphosphate and 7.0% urea, solids respectively). The nature of the tissue and the weight of cyclic phosphonate applied to the tissue, were as indicated in the table below

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-17xo. Each fabric had a cotton weave and a polyester warp with a colored cotton embossed warp and a weft design on the face over a polyester background with a significant exposed polyester warp area, but with the average proportion of polyester / a1 cotton on the face being similar to that of the fabric as a whole. The drying and curing conditions were those of Ex. 1-6. The finished fabrics and after washing in hard water, passed all flammability tests before and after washing. In the comparative Ex. G-0, experiments were repeated without cyclic phosphonate and all failed the BS 5852 assay after washing in water.

EX. POLYESTER/ / cotton% % p / p OF PHOSPHONATE IN FABRIC WEIGHT BY AREA D0 FABRIC (Kgm) 7 30: 70 5.4 0.320 8 30:70 5.4 0.400 9 30:70 5.2 0.440 10 35: 65 5.6 0.380 11 35: 65 5.4 0.420 12 39:61 5.8 0.340 1 3 46: 54 5.2 0.520 14 49: 51 6.5 0.300 15 50:50 6.0 0.550

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PR 687 / III / PT / AER

Claims (18)

CLAIMSE5 1 - Process for the preparation of a flame retardant composition, characterized by mixing a condensed organic, quaternary ammonium or ammonium phosphate and at least one cyclic phosphonate ester of formula (A) in which a is 0, 1 or 2; b is 0, 1 or 2; c is 1, 2 or 3 and a + b + c is 3; R is R ¹ , which are the same or different, are alkyl, alkoxy, aryl, aryloxy, alkylaryl, aryloxy, aralkyl, xyloxy or aralkoxy aryl, in which the alkyl portion of these qrj may optionally contain at least a hydroxyl, but not halogen, and the aryl moiety may contain at least one chlorine, bromine or hydroxyl group; R is alkyl, hydroxy 11 or aryl R 4 is lower alkyl or hydroxy 1 4 or 1, or a cyclic phosphonate ester of formula (B) in which d is 0, 1 or 2; e is 1, 2 or 3; d + e is 3; R is like 3 4 orally defined; R is as previously defined; R is lo, aryl, alkylaryl, aralkyl or aryloxyalkyl, in ante rj_alkiquai s 70 424 PR 687 / III / PT / AER The aryl portion may contain at least one bromine, chlorine or hydroxyl; and R4 is an alkyl, alkylene, aryl or arylene, monovalent, divalent or trivalent radical in which the aryl or arylene radical can optionally contain at least one brono, chloro, alkyl or hydroxyl group. Process according to claim 1, character. used by associating an ammonium polyphosphate. Process according to claim 1 or 2, due to the fact that the cyclic phosphonate is of formula A, in which each R and r! represents an alkoxy or lower alkyl group of 1-6 - to 23 carbon atoms, and each of R and R represents an alkyl group of 1-6 carbon atoms. Process according to claim 3, character_i 2 3 used by each of R, R and R represent a methyl or ethyl group and r! represent a methoxy or ethoxy group. 5 - Process according to claim 3 or 4, characterized by associating two phosphonates of formula A in the weight ratio of 25-75: 75-25, one of which has a, b and c equal to 1 and the other has the same a 1, b equals 0 and c equals 2. Process according to any of the preceding claims, characterized in that the weight ratio of the cyclic phosphonate to the condensed phosphate (expressed as ammonium polyphosphate) is 0.1-2: 1. Process according to claim 6, characterized in that the proportion is 0.3-1.0: 1. Process according to any one of the preceding claims, characterized in that a derivative of carbamic acid is also added. Process according to claim 8, characterized in that it comprises 50-200% urea (based on the weight of condensed phosphate, expressed as ammonium polyphosphate). 10 - Process according to any of the claims 3-9, characterized in that the composition contains 8-15% polyphosphate ΊΟ 424 PR 687 / III / PT / AER -20 ammonium, 3-10% cyclic phosphonate and 8-15% urea, with water. Process according to any one of the preceding claims, characterized in that it also comprises the addition of a fluoroacrylic polymer in aqueous emulsion. A flame retardant process for a fabric, characterized in that it comprises the impregnation of a bonding fabric having cellulosic and non-cellulosic fibers, with an aqueous medium containing a composition prepared according to any one of claims 1-11, and, in then drying and curing at a temperature of 130 ° C-180 ° C. 13 - Process characterized by minutes. according to cure with claim 12, 140 ° C-170 ° C for 6-0.5 14 - Process according to claim 12 or 13, characterized in that the bonding fabric has 30-90% cellulosic fibers. 15 - Process according to claim 12 or 13, characterized in that the joining fabric has 50-80% cellulosic fibers and non-cellulosic fibers are polyester or nylon. 16 - Process according to the one characterized by the predominantly polyester fabric. claim 12, union having a 13 or 15, warp Process according to claim 12, 13 characterized in that the fabric has a cotton embossed cotton weave and a polyester warp. or 15, with a 18 - Process according to any one of claims 12-17, characterized in that the fabric is a differential surface fabric.