WO1991016402A1

WO1991016402A1 - Flame-proofing compositions

Info

Publication number: WO1991016402A1
Application number: PCT/US1991/002649
Authority: WO
Inventors: Paul Raymond; Martin Charles Dexter; John Skoufis
Original assignee: Contra-Flame Limited
Priority date: 1990-04-18
Filing date: 1991-04-18
Publication date: 1991-10-31
Also published as: CA2019325A1; GB9008652D0; AU7779391A; EP0525081A4; EP0525081A1

Abstract

Compositions are disclosed for imparting flame-retardant properties to a wide variety of materials including cellulosic materials, such as paper, cotton and wood, and polymeric materials, such as fabrics and other textile articles made from both synthetic and non-synthetic polymers. The compositions are particularly suitable for use on fabrics made from blends of synthetic and non-synthetic fibers, such as polyester silk of the type used in synthetic foliage and artificial flowers. The compositions are aqueous based and comprise an inorganic, flame-retardant ammonium salt and a second component selected from: organic phosphate ester-acids and salts thereof, wherein the ester-acid is an ester of an alkoxylated aliphatic alcohol and phosphoric acid; organic phosphonates and salts thereof; and mixtures of the organic phosphate ester-acids and organic phosphonates and their salts. The compositions are applied by conventional means, such as immersion of the article to be treated, spraying, painting and roller coating.

Description

FLAME-PROOFING COMPOSITIONS

This invention relates to flame-proofing compositions for use in imparting flame-retardant properties to .a variety of flammable articles, and particularly, but not exclusively, for use in indoor environments.

It is well known in the art that the propensity of certain flammable articles to combustion can be.reduced by coating the article with a flame-proofing composition or by incorporating such a composition into the constituent material(s) of the article during its manufacture. The term "flame-proofing" as used herein means a reduction in the flammability of a flammable article and is intended to encompass both a complete and partial reduction in flammability.

It is known, for example, to flame-proof wood and similar porous materials by impregnating the material to be treated with an aqueous solution of a wide variety of inorganic salts and subsequently allowing or causing the impregnated solution to dry. In particular, inorganic ammonium salts, such as ammonium bromide, ammonium chloride, ammonium sulphate, monoammonium phosphate, dia monium phosphate etc., have been widely used alone and in various combinations for this purpose. Such flame-proofing compositions are disclosed, for example, in Japanese Patent No. 56-50985, British Patent Publication No. 2095297 and US Patent Nos. 4223169 and 4239670. Certain surfactants have also been included in these flame-proofing compositions. I particular, non-ionic long chain ethoxylate surfactants hav been recommended for such use. For example, US Patent No. 4212675 discloses flame-proofing compositions comprising an aqueous solution of a flame-retardant water-soluble. inorganic ammonium salt and a surface tension reducing amount of an organic polyphosphoric ester-acid or a salt thereof, wherein the ester-acid is a Coester of an aliphati alcohol and a non-ionic adduct of ethylene oxide and a reactive hydrogen-containing organic compound, in which coesters less than all the phosphate protons are consumed b ester bonds. The amount of surfactant employed is typicall in the range 0.25 to 2% and preferably 0.3 to 1% by volume. The only surfactant exemplified is commonly available under the trade name STRODEX PK-90 from Dexter Chemical Corporation. Although not specifically disclosed, the composition of STRODEX PK-90 is said to be, from US Patent No. 3380927, the potassium salt of a coester of a C₆ to C_₆ aliphatic alcohol and a non-ionic adduct of ethylene oxide and a reactive hydrogen-containing organic compound selecte from the group consisting of C₆ to C₁₈ alkylated phenols, C to C₂5 aliphatic alcohols and C₆ to C_2Q aliphatic monocarboxylic acids, amines or mercaptans. Compositions prepared in accordance with US Patent No. 4212675 are primarily intended for flame-proofing wood, including compressed wood fiber products, e.g. , hardboard, and so called "artificial wood boards", e.g., chipboard. They are not apparently intended for general appliction to a wide variety of materials.

However, known flame-proofing compositions 'have not proven to be entirely satisfactory in that it lias proven difficult to achieve consistently reproducible flame- proofing results. Consequently, the present invention seeks to provide alternative flame-proofing compositions for use in imparting flame-resistant properties to a variety of flammable articles.

According to the present invention there is provided a flame-proofing composition for application to flammable articles comprising an aqueous solution of one or more water-soluble, inorganic, flame-retardant ammonium salts and a second component selected form the group consisting of organic phosphate ester-acids and salts thereof, organic phosphonates and salts thereof and mixtures of organic phosphate ester-acids and organic phosphonates and their salts, wherein said organic phosphate ester-acid comprises an ester of an alkoxylated aliphatic alcohol and phosphoric acid.

Compositions according to the invention are aqueous based and include a water-soluble, inorganic ammonium salt as the primary flame-retardant component. The preferred ammonium salt is ammonium bromide which is commonly used in known fire-proofing compositions. The second component is selected from the group consisting ci : organic phosphate* ester-acids and salts thereof, wherein the ester-acid is an ester of an alkoxylated aliphatic alcohol and phosphoric acid; organic phosphonates and salts thereof and mixtures of the organic ester-acids, organic phosphonates and their salts. The organic phosphate ester-acids and phosphonates used in the practice of the present invention have a flame- retardant effect complementary to that of the inorganic flame-retardant ammonium salt. Moreover, the organic phosphate ester-acid is also believed to aid the penetration of the flame-retardant inorganic salt into the surface of the material to be treated and to prevent recrystallization of the salt once dry. The organic phosphonate is believed to reduce the viscosity of the composition and its tendency to form a visible (crystallized) residue once dry. The aforementioned comments are not intended to be limiting but rather reflect what the applicants believe to be the mechanism responsible for the efficacy of the flame-proofing compositions of the invention. In the most preferred embodiments of the invention, the second component is poly(ethylene oxide) tridecylether phosphate, which can be used alone or more preferably in combination with an organic phosphonate, such as aminotri(methylene-phosphonic acid). The flame-retardant inorganic salt and second component combine to provide a long lasting and effective protective coating on the flammable articles to which they ^'are applied. The flame retarding compositions of the invention are effective in imparting flame-retardant properties to a wide variety of materials including cellulosic materials, such as ^■ paper, cotton fabrics and wood, and to polymeric materials, such as fabrics and films made from both synthetic and non- synthetic polymers. It is also possible to use them on living or preserved plants. The compositions of the invention are particularly effective on fabrics and other textile articles and materials, whether made from synthetic or non-synthetic materials, e.g., carpets, and are especially suitable for use on fabrics made from blends of synthetic and non-synthetic fibers. One preferred application is to polyester silk, of the kind used in the synthetic foliage and artificial flowers commonly adopted for decorations within buildings. Therefore, according to a further aspect of the invention there is provided a method of treating a flammable article to prevent combustion thereof, which method comprises applying to the surface of said article or incorporating into the material from which the article is made a flame-proofing composition.

The second component, that is, the organic phosphate ester-acid, organic phosphonate or mixture thereof, generally comprises not more than 20% and preferably not more than 16% by weight of the composition. Although an amount of the second component greater than 20% may be used in the compositions of the invention, no additional benefit in flame-proofing protection has been observed. Furthermore, too high a loading of the second component may detrimentally affect the performance of the composition in other areas. For example, if the organic phosphate ester- acid is present in amounts greater than about 20% w/w, the increasing viscosity of the composition makes it more difficult to apply and, once applied to the article, imparts a degree of "tackness" to the touch which is for most applications undesirable. Once dry, such compositions also tend to leave a visible residue which mars the appearance of the treated article, which is again normally unacceptable. The second component comprises at least 2%, generally at least 3% and preferably at least 4% by weight of the composition.

It is preferred that the second component is a mixture of the organic phosphate ester-acid and the organic phosphonate as the combined effect of the two components is greater than that observed for compositions incorporating each component individually. For example, comparing formulations containing (i) organic phosphate ester-acid, (ii) organic phosphonate and (iii) a 50:50 mixture of organic phosphate ester-acid and organic phosphonate, then on average from 2 to 6% less of (iii) , based on the dry weight of the coated composition, is required to produce the same degree of flame-retardancy conferred by (i) and (ii) . Moreover, by varying the ratio of organic phosphate ester- acid to organic phosphonate within such a mixture, it is possible to tailor the properties of the composition to suit the intended mode of application. For example, for a given concentration of the ester-acid:phosphonate mixture, a greater proportion of the organic phosphate ester-acid is desirable for spray application since the spray quantity can be controlled to provide optimum softness. For dipping, which necessarily results in a more intense coating, a greater proportion of the organic phosphonate is desirable to reduce the tackiness of the composition. Mixtures comprising from 20 to 60% by weight of the organic phosphate ester-acid and from 40 to 80% by weight of the organic phosphonate are preferred. A mixture comprising about 50% by weight organic phosphate ester-acid and about 50% by weight organic phosphonate has been found to be particularly useful.

The organic phosphate ester-acids used in the present invention comprise esters of an alkoxylated aliphatic alcohol and phosphoric acid. The alkoxylated alcohol is usually prepared by reaction of the aliphatic alcohol with a non-ionic adduct of an alkylene oxide generally comprising up to 5 carbon atoms and preferably up to 3 carbon atoms, e.g., ethylene oxide. The degree of alkoxylation may range from 1 to 6 mole alkoxy groups per mole of alcohol. The aliphatic alcohol generally comprises from 6 to 20 carbon atoms and preferably 10 to 16 carbon atoms, e.g., decanol, undecanol, dodecanol, tridecanol, etc. In the most preferred embodiment of the invention, the organic phosphate ester-acid is poly(ethylene oxide) tridecylether phosphate: Chemical Abstract No. 9046-01-9 (poly(oxy-l,2-ethanediyl)-α- monotridecyl-ω-hydroxyphosphate) . This compound is commercially available under the trade names: PHOENAC T50 from Phoenix Chemicals, Somerville, New Jersey, USA; MONAFAX 410107 from Mona Industries, Patterson, New Jersey, USA and CRODAFOS T5A from Croda Chemicals Ltd, United Kingdom.

A wide range of organic phosphonates are known and useful in the present invention. Such compounds are known in the art as scale deposition inhibitors and generally comprise a hydrocarbon backbone of up to 15, preferably up to 10 carbon atoms, bearing one or more phosphonic acid groups (-P(O) (OH) _ ) • ^Th^e backbone may be branched and it may also contain hetero-atoms such as N, 0, etc.^'. Compounds bearing two or more phosphonic acid groups are.preferred. Highly preferred organic phosphonates are' commercially available from Lonza Inc., Fairlawn, New Jersey, USA, under the trade name UNIHIB and include: l-hydroxyethylidene-1,1- diphosphonic acid (UNIHIB 106); aminotri(methylene- phosphonic acid) (UNIHIB 305) ; the penta sodium salt of aminotri(methylene-phosphonic acid) (UNIHIB 314); diethylene triamine penta(methylene-phosphonic acid) (UNIHIB 905) ; cocoaminodi(methylene-phosphonic acid) (UNIHIB 1304) ; the diammonium salt of cocoaminodi(methylene-phosphonic acid) (UNIHIB 1324) and bis-hexamethylene triamine phosphonic acid (UNIHIB 1704) . Preferably the organic phosphonate is aminotri(methylene-phosphonic acid) or the diammonium or penta sodium salt thereof.

The flame-retardant inorganic salt may comprise any of a wide range of ammonium salts known in the art including: ammonium bromide, ammonium chloride, monoammonium phosphate, diammonium phosphate, ammonium sulphate, ammonium alum and ammonium borate. The flame-retardant additive may also comprise a mixture of such salts. The preferred flame- retardant is ammonium bromide. These and other flame- retardant, water-soluble inorganic salts are well known per se for use in flame-proofing compositions and hence the relative and absolute proportions thereof can readily be determined by those skilled in the art to provide .the desired degree of flame-proofing. These proportions will vary from one material to another depending upon inter alia porosity and inflammability of the material. However, the flame-retardant inorganic salt is generally present in an amount from 8 to 35%, preferably 10 to 30% and more preferably 15 to 25% by weight of the composition, with a typical value of around 21% by weight.

The basic flame-proofing composition of flame- retardant inorganic salt and chosen second component(s) may advantageously include, as an optional but preferred additive, an alcohol, generally in an amount up to 8% by weight of the composition. Ordinarily, the flame-proofing composition will include no more than 4% by weight of the alcohol with typical values being from 1 to 2% by weight of the composition due to the flammable nature of alcohols. The alcohol used is typically ethanol, propan-2-ol (isopropyl alcohol) and propan-l,2-diol (1,2-propylene glycol) .

Another preferred but optional supplementary additive is boric acid. Although the boric acid may be used in amounts up to 10% by weight of the composition, it is preferred to use smaller amounts ranging from 0.05 to 3%, with a typical value in the range from 0.1 to 1% by weight. of the composition. ^{" •}_^•". ^'

The basic flame-proofing compositions may aiso.be supplemented by one or more other additives depending on the intended use, e.g., such as the nature of the material to be treated. A non-exhaustive list of such supplementary additives includes:

(a) sodium phosphate - up to 10% by weight of the composition, usually no more than 8% and typically from 6 to 8%;

(b) organic phosphate (e.g. , GAFEN - available from Avondale Labs.) - up to 20% by weight of composition, usually no more than 16% and typically from 8 to 16%;

(c) phosphorus pentoxide - up to 10% by weight of the composition, usually no more than 8%; (d) wood ash - normally in trace amounts, typically up to 0.03% by weight;

(e) metallic sodium - normally in trace amounts, typically up to 0.003% by weight;

(f) anti-bacterial or fungicidal agents, e.g., acromicine, undecylenic acid and zinc undecylenate, and

(g) a surfactant, e.g., detergent - up to 2% by weight of the composition, usually no more than 1% by weight.

The pH of the aqueous solution is normally adjusted (where necessary) to between 6 and 8 inclusive, preferably 6.5 and 7.5 and more preferably to around pH 7, i.e., neutral pH. Compositions having a pH <6 are undesirable because they can have a corrosive effect on the article to be treated and/or the skin of users causing irritation, etc. Compositions having pH >8 are found to have an unpleasant odor. The desired pH may be achieved using any method of pH adjustment which is compatible with the flame-proofing compositions of the invention including both neutralizing agents and buffers. In the practice of the present inven¬ tion, it is preferred to add a neutralizing agent, e.g., aminoalcohols such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine and mixtures thereof, or an aqueous solution of ammonia (NH OH) .

The aqueous base for compositions according to the invention can be tap water. Although this will necessarily include impurities, we have found that these do not deleteriously affect the performance of the protective coating formed when compositions of the invention are applied to flammable articles.

The compositions of the invention are typically prepared by simple admixture of the constituents to form a homogeneous mixture prior to addition of.the requisite volume of water. The compositions can be applied by conventional means such as immersion of the article, spraying, painting, roller coating or otherwise surface coating the article and the effective life of the coating formed thereby is largely dependent upon the thickness of the coating or in other words the intensity of the application. The composition may be used either as prepared or diluted depending on the desired intensity of coating, the mode of application, the article to be treated, etc. However, above a certain thickness the effectiveness of the coating formed ceases to increase proportionately. It is sometimes desirable to warm the composition prior to its application to the article to be treated as this has been found to improve the flame retardancy and durability of the coating. However, this does vary with the material to be treated. The composition is typically heated until it is lukewarm, although temperatures in the range from 10 to 50°C, more preferably 20 to 40°C may be used.

It is also possible for the flame retardant composition to be incorporated into the material of the article by addition during one of the final stages *_of manufacture, e.g., for articles made of paper o fabric.

The following examples illustrate flame-proofing compositions prepared in accordance with the invention. In each case, the solutions were prepared (unless otherwise indicated) adding the inorganic ammonium salt to tap water and stirring until the salt had dissolved. The remaining ingredients were added to the salt solution. The solutions may be warmed to ensure that all the ingredients have completely dissolved therein.

The aforementioned compositions were applied to various artificial foliage and polyester/cotton fabrics by dipping. All passed conventional "flame-proofed" test protocols including the following:

(1) AS 1530.2 (1973) - Test for Flammability of Materials: conducted by the Australian Wool Testing Authority Limited (AWTA Ltd) , PO Box 740, North Melbourne, Victoria, Australia. Tests were conducted on treated artificial foliage comprising polyester silk leaves and a plastics coated wire stem.

(2) National Fire -Protection Association Standard 701 Small Scale Test: conducted by United States Testing Company Inc., Textile Division, 291 Fairfield Avenue, Fairfield, New Jersey, United States of America._. Tests were again conducted on treated artificial foliage.. ^'• - _. ^{' '}

(3) Rules for the test of Fire Resistive & Flame-proofed materials as specified by the City of New York Board of Standards and Appeals under Calender No. 294-40 SR: conducted by Better Fabrics Testing Bureau, 101 West 31st Street, New York, NY 10001-3583, United States of America. Tests were conducted on: (i) the leaves of an artificial z^~rboricola commercially available from Magic Silk Inc., and (ii) #40 SP Velvette Ribbon In Red commercially available from the Lion Ribbon Company.

(4) Compositions of the invention are Registered Flame Retardant Chemicals (Registration No. C-165.01) as established by the State Fire Marshal for products identified in the California Health and Safety Code Section 13115 .

"CRODAFOS T5A" (Croda Chemicals Ltd.); "GAFEN" (Avondale Laboratories) ; "MONAFAX 410107" (Mona Industries) ; ""PHOENAC T50" (Phoenix Chemicals) ; "STRODEX PK-90" (Dexter Chemical Corporation); and "UNIHIB 106, 305, 314, 905, 1304, 1324 and 1704" (Lonza Inc.) are all trade names.

Example 1

Flame-proofing compositions I to III were prepared according to the following general formulation.

General Formulation A comprising: from 10 to 25% by ^"weight ammonium bromide; from 3 to 20% CRODAFOS T5A (poly(ethylene oxide) tridecylether phosphate) ; from 1 to 2% of an alcohol; up to 3% by weight boric acid; and up to 2% by weight of a surfactant, the balance comprising water and inevitable impurities.

Composition I; 13% by weight ammonium bromide;

6% by weight CRODAFOS T5A; 1% by weight ethanol; 1% by weight boric acid; and 1% by weight detergent, the balance comprising water and inevitable impurities. The pH of the solution was adjusted to about 7.

Composition I was prepared as follows (all percentages are given by weight) :

(i) Ammonium bromide (8%) was added to water (10%) and mixed well.

(ii) Boric acid (1%) was then added to the ammonium bromide solution prepared in step (i) followed by .CRODAFOS T5A (3%) mixed with water (25%) .

(iii) CRODAFOS T5A (3%) followed by industrial detergent (1%) was then added to the mixture prepared in step (ii) . The mixture was then diluted with water (25%) .

(iv) The remainder of the ammonium bromide (5%) with ethanol (1%) was then added to the mixture prepared in step (iii) . The mixture was stirred vigorously while adding the balance of water (18%) until all the ingredients had dissolved.

Composition II: 13% by weight ammonium bromide;

13% by weight CRODAFOS T5A; 1% by weight ethanol; 1% by weight boric acid; and 1% by weight detergent, the balance comprising water and inevitable impurities. The pH of the solution was adjusted to about 7.

Composition II was prepared following the protocol detailed for Composition I above but adding 6% CRODAFOS T5A in step (ii) and 7% CRODAFOS T5A in step (iii) .

Composition III: 21% by weight ammonium bromide;

20% by weight CRODAFOS T5A; 1% by weight ethanol; * 0.5% by weight detergent; and 0.1% by weight boric acid, the balance comprising water and inevitable impurities. The pH of the solution was adjusted to about 7.

Composition III was prepared as follows (all percentages given are by weight) :

(i) Ammonium bromide (11%) was added to water (10%) and mixed well.

(ii) Boric acid (0.1%) was then added to the ammonium bromide solution prepared in step (i) followed by CRODAFOS T5A (7%) mixed with water (15%) .

(iii) CRODAFOS T5A (13%) followed by industrial detergent (0.5%) was added to the mixture prepared in step (ii) . The resulting mixture was then diluted with water ( 25%) .

(iv) The remainder of the ammonium bromide (10%) with ethanol (1%) was then added to the mixture prepared in step (iii) • The mixture was stirred vigorously while adding the balance of water (7.4%) until all the ingredients had dissolved.

Example 2

Flame-proofing compositions IV and V were prepared, .according to the following general formulation.

General Formulation B comprising: from 10 to 25% by weight ammonium bromide; from 3 to 20% by weight pol (ethylene oxide) tridecylether phosphate, aminotri(methylene-phosphonic acid) or a mixture thereof; from 1 to 2% by weight of an alcohol; and up to 3% by weight boric acid, the balance comprising water and any inevitable impurities. The pH of the solution was adjusted to about 7.

Composition IV: 21% by weight ammonium br.omide;

16% by weight CRODAFOS T5A; 1% by weight propan-2-ol; 0.1% by weight boric acid, and diethanolamine in an amount sufficient to provide a pH of about 7, the balance of the composition comprising water and any inevitable impurities.

Composition V: 21% by weight ammonium bromide;

12% by weight UNIHIB 305; 4% by weight PHOENAC T50; * 1% by weight propan-2-ol; ^' 0.1% by weight boric acid, and diethanolamine in an amount sufficient to provide a pH of about 7, the balance of the composition,comprising water and any inevitable impurities.

Composition VI: 21% by weight ammonium bromide;

8% by weight PHOENAC T50;

8% by weight UNIHIB 305;

1% by weight propan-2-ol; and 0.1% by weight boric acid, and diethanolamine in an amount sufficient to provide a pH of about 7, the balance of the composition comprising water and any inevitable impurities. Composition VII: 21% by weight ammonium bromide;

8% by weight CRODAFOS T5A;

8% by weight UNIHIB 305;

1% by weight propan-2-ol; and 0*.1% by weight boric acid, and ammonium hydroxide in an amount sufficient to provide a pH of about 7, the balance of the composition comprising water and any inevitable impurities.

Composition VIII: 21% by weight ammonium bromide;

12% by weight UNIHIB 305; 4% by weight CRODAFOS T5A; 1% by weight propan-2-ol; and 0.1% by weight boric acid, and monoisopropanolamine in an amount sufficient to provide a pH of about 7, the balance of the composition comprising water and any inevitable impurities.

For compositions IV to VIII the following procedure was followed (all percentages given are by weight) : (i) A suitable vessel was charged with all water less about 20%.

(ii) Ammonium bromide (about 15%) followed by boric acid (0.1%) was dissolved in (i) . The solution may be warmed to ensure complete dissolution of all solids.

(iii) The selected second component together with the remainder of the water (about 20%) was then added slowly to the salt solution prepared in step (ii) to avoid excess foaming.

(iv) The mixture was then stirred before addition of the remaining ammonium bromide (about 6%) .

(v) The propan-2-ol was then added to the mixture produced in step (iv) . '.* ^*••

(vi) The requisite neutralizing agent was* then slowly added to the mixture while stirring to complete the formulation.

Example 3

This Example illustrates the flame-retardant properties of flame-proofing compositions prepared in accordance with the^'invention.

The following compositions were prepared using the formulation protocol detailed for Compositions IV to VIII in Example 2. Component Composition

(all percentages are by weight) IX X VIII XI

Ammonium bromide 21 21

CRODAFOS T5A 16

UNIHIB 305 16

Propan-2-ol _.1

Boric acid 0.1 O^'.l

Mono- isopropanolamine

H₂0

The following materials were tested using the National Fire Protection Association Standard 701 Small Scale Vertical Flame Test:

(i) the leaves of an artificial Philodendron commercially available from Magic Silk Inc. ; (ii) the leaves of an artificial Fic ε commercially available from Magic Silk Inc. ;

(iii) the flowers of an artificial .Azalea commercially available from F.P.S.; and

(iv) gold lame, red flock and brocade ribbons commercially available from K. D. Richards. Samples of each material were dipped into individual solutions of Compositions VIII to XI with the excess being wrung/squeezed out of the material. The treated materials were then air-dried for about 24 hours before testing to give a dry coating weight for each composition of between 18 to 20%.

Results

1. All the untreated materials failed the test_* ^*

2. Compositions IX and XI - all samples passed (with the exception of the gold lame ribbon) with results ranging from acceptable to good.

3. Compositions VIII and X - all samples passed with results ranging from good to excellent. Thus, while each of Compositions VIII to XI is at least acceptable in relation to the above materials, compositions incorporating both the organic phosphate ester-acid and organic phosphonate together (Compositions VIII and X) are more effective than those incorporating each component individually (Compositions IX and XI) .

Claims

CLAIMS :

1. A flame-proofing composition for application to flammable articles comprising an aqueous solution of one or more water-soluble inorganic flame-retardant ammonium salts and a second component selected from the group consisting of organic phosphate ester-acids and salts thereof, organic phosphonates and salts thereof and mixtures of organic- phosphate ester-acids and organic phosphonates and their salts, wherein said organic phosphate ester-acid comprises an ester of an alkoxylated aliphatic alcohol and phosphoric acid.

2. A flame-proofing composition as claimed in Claim 1 in which said second component comprises up to 20% by weight of the composition.

3. A flame-proofing composition as claimed in Claim 2 in which said second component comprises up to 16% by weight of the composition.

4. A flame-proofing composition as claimed in any one of Claims 1 to 3 in which said second component is a mixture of organic phosphate ester-acids and organic phosphonates.

5. A flame-proofing composition as claimed in Claim 4 in which the mixture comprises from 20 to 60% by weight of the organic phosphate ester-acid(s) and from 80 to -40% by weight of the organic phosphonate(s) .

6. A flame-proofing composition as claimed in any preceding Claim in which the alkoxylated aliphatic alcohol is the reaction product of an aliphatic alcohol with a non- ionic adduct of ethylene oxide.

7. A flame-proofing composition as claimed in Claim 6 in which the aliphatic alcohol comprises from 6 to 20 carbon atoms.

8. A flame-proofing composition as claimed in Claim 7 in which the aliphatic alcohol comprises from 10 to 16 carbon atoms.

9. A flame-proofing composition as claimed in any preceding Claim in which the organic phosphate ester-acid is poly(ethylene oxide) tridecylether phosphate.

10. A flame-proofing composition as claimed in any preceding Claim in which the organic phosphonate is selected from: aminotri(methylene-phosphonic acid), the diammonium salt of aminotri(methylene-phosphonic acid) , 1- hydroxyethylidene-l,l-diphosphonic acid, diethylene* triamine penta(methylene-phosphonic acid), cocoaminodi(methylene- phosphonic acid) , the diammonium salt of cocoaminodi(methylene-phosphonic acid) and bis-hexamethylene triamine phosphonic acid.

11. A flame-proofing composition as claimed in Claim 10 in which the organic phosphonate is aminotri(methylene- phosphonic acid) .

12. A flame-proofing composition as claimed in any preceding Claim in which the inorganic ammonium salt is selected from: ammonium bromide, ammonium chloride, monoammonium phosphate, diammonium phosphate, ammonium sulphate, ammonium alum and ammonium borate.

13. A flame-proofing composition as claimed in Claim 12 in which the inorganic ammonium salt is ammonium bromide.

14. A flame-proofing composition as claimed in any preceding Claim in which the inorganic ammonium salt is present in an amount from 8 to 35% by weight of the composition.

15. A flame-proofing composition as claimed in Claim

14 in which inorganic ammonium salt is present in an amount from 10 to 30% by weight of the composition.

16. A flame-proofing composition as claimed in Claim ^*

15 in which the inorganic ammonium salt is present in an amount from 15 to 25% by weight of the composition.

17. A flame-*proofing composition as claimed in any preceding claim further comprising an alcohol in an amount up to 8% by weight of the composition.

18. A flame-proofing composition as claimed in Claim 17 in which the alcohol is present in an amount from 1 to 2% by weight of the composition.

19. A flame-proofing composition as claimed in Claim 17 or Claim 18 in which the alcohol is selected from ethanol, propan-2-ol and propan-l,2-diol.

20. A flame-proofing composition as claimed in any preceding Claim further comprising boric acid in an amount up to 10% by weight of the composition.

21. A flame-proofing composition as claimed in any preceding claim further comprising a surfactant in an amount up to 2% by weight of the composition.

22. A flame-proofing composition as claimed in .any. preceding Claim in which the pH of the aqueou≤ so^'ϊμtion* is from 6 to 8. ^' •

23. A flame-proofing composition as claimed in Claim 22 in which the pH of the aqueous solution is about 7.

24. A flame-proofing composition as claimed in Claims 22 or 23 further comprising a neutralizing agent selected from monoethanolamine, diethanolamine, triethanola ine, onoisopropanolamine, diisopropanola ine, triisopropanolamine and mixtures thereof, in an amount sufficient to adjust the aqueous solution to a pH as specified in Claim 21 or Claim 22.

25. A flame-proofing composition as claimed in Claim 1 comprising: from 10 to 25% by weight ammonium bromide; from 3 to 20% by weight polyethylene oxide) tridecylether phosphate; from 1 to 2% by weight of an alcohol; up to 3% by weight of boric acid; and up to 2% by weight of a surfactant, the balance of the composition comprising water and any inevitable impurities.

26. A flame-proofing composition as claimed^' in Claim 1 comprising: from 10 to 25% by weight ammonium bromide; from 3 to 20% by weight poly(ethylene oxide) tridecylether phosphate, aminotri(methylene- phosphonic acid) or a mixture thereof; from 1 to 2% by weight of an alcohol; and up to 3% by weight of boric acid, the balance of of the composition comprising water and any inevitable impurities.

27. A method of treating a flammable article to prevent combustion thereof, which method comprises applying to the surface of said article or incorporating into the material from which the article is made a flame-proofing composition as claimed in any one of Claims 1 to 26.

28. A method as claimed in Claim 27 in which the article comprises artificial foliage and/or flowers.

29. A method as claimed in Claim 27 or Claim '28 in which the article or at least a part thereof is formed from polyester silk.