US2549060A - Method of treating fibrous cellulosic materials to impart flame resistance thereto, composition therefor, and products thereof - Google Patents

Description

MTFM Q i I A fi ta fet f sacs R OFFICE METHOD OF TREATING FIBROUS CELLU- LOSIC MATERIALS TO IMPART FLAME RESISTANCE THERETO, COMPOSITION THEREFOR, AND PRODUCTS THEREOF Joseph W. Creely, East Bound Brook, N. J), as-

Signor to American Cyanamid Company, New York,'N. Y, a corporation of Maine No Drawing. Application February 1, 1950,

' S erialNo. 141,852

This invention relates to methods of imparting flame resistance to cellulosic material, more par-" ticularly natural or regenerated'cellulosejor mixtures thereof; and specifically to textiles comprising fibers of such cellulosicmaterials. The invention further relates to the" compositions used in such methods and to the. flame-resistant cellulosic products thereof.

In the past, various "compounds and compositions have been used or suggested for use as agents for treating fibrous cellulosic materials and other normally flammable organic materials in order to' render'them' resistant to flame; A e s or trea ments or. m art n am rre st: ance to ordinarily flammable organic materials may be classified as (1) temporary (2) semidurable and (3). permanentv or. durable. This classification is based on the durability. of the treatment in providing continued resistance of the treated textile or. other material to flame during use.

The durable treatments heretofore used orv suggested have been of three general types: (1) urea phosphate (2) double bath precipitation, '(3)m'et'allic oxide-chlorinated 'body. Oneof the main, objections to the urea-phosphate typeof treatment has been its tendering effect on the cellulosic material whereby its tensile strength is reduced considerably. The double bath precipitation and the metallic oxide-chlorinated body types of treatment generally yield cellulosic textiles having a harsh or stiff hand so that the treated textile has a limited field of utility. The above disadvantages have been overcome by processes for impartingfiame resistance to cellulosic textile materials described in the copend ing applications of Anne MacMillan Loukomsky, Roy H. Kienle, and Theodore'R. Cooke, Serial No. 76,644, filed February 15, 1949, now U. S. Patent No. 2,520,103, and Serial No. 64,416, filed December 9, 1948, now U. S.'Patent No. 2,519,388. The first of these applications describes impregnation of fibrous cellulosic materials with a composition containing specified proportions of (1') a finely divided oxide'of antimony, (2) a thermally unstable halogen-containing thermoplastic substance, (3) a water-soluble salt of an oxygencontaining acid of phosphorus in which'phosphorus has a valence of 5, and (4) either cyanamide, dicyandiamide or mixtures thereof, while the latter application discloses a similar use of a composition containing specified proportions of 1) a finely divided oxide of tin, titanium, antimony or bismuth, (2) a thermally unstable halogen-containing thermoplastic substance, (3) a water-soluble salt of 'anoxygen-contiaining acid 17 Claims. (Cl. 1 1'7--103) of phosphorus in which phosphorus has a valence of 5, and (4) urea, biuret, ammonium cyanate or ammonium dicyanimide.

Later it was found that byjudicious selection of the particular, ingredient falling within class (3) of the above identified applications the necessity for including a member of class (4) in compositions for. imparting flame-resistance to cellulose textiles might be eliminated. The three component'compositions and their use for imparting flame-resistance to textiles are described and claimed in my copending "application with Theodore F. C'ooke,Srial No. 141,851, filed Febmay 1', 1950, entitled"Permanent Flameproofing commune-Kim r cedure? It is an objectof the present invention to provide an additional method for, imparting fia-meresistance to cellulosic textile materials which avoids the disadvantages of the urea phosphate, double bath precipitation or metallic oxide-chlorinated body types of treatment. g

It is another object of the present invention to impart flame-resistance to cellulosic textile materials.

It is still another object of the present invention to provide a permanently flame-resistant cellulosic textile material which has an improved hand over that of flame-resistant cellulosic textile materials given a double bath precipitation treatment or a metallic oxide-chlorinated body type of treatment.

Another object of the present invention is to so treat cellulosic textile materials that they be come permanently flame-resistant without excessive tendering.

The above and other objects are attained by impregnating a cellulosic textile material with ingredients comprising (1) a finely divided oxide of tin, ti um, antimony, bismuth, or mixtures thereof, (2) a ing at least 20% by weight of combined halogen and capable of rupturing under heat at carbonhalogen bonds, the ingredients (1) and (2) together being designated hereinafter as (A), and i (B) a water-soluble, metal-free, nitrogencontaining salt of an amino phosphoric acid having 5 an amino nitrogen atom attached directly to a ermoplasticfiu'b'stancemontafin phosphorus atom which salt has 'a' melting point 2 of less than 200 C. The impregnant may be applied to the cellulosic textile material as a single aqueous liquid composition containing the ingredients of both (A) and (B) or as two separately applied aqueous liquid compositions, one containing the ingredients of (A) and the other containing the ingredient (B).

The invention will be described in greater detail in conjunction with the following specific examples in which proportions are given in parts by weight unless otherwise noted. The examples are merely illustrative, and it is not intended that the scope of the invention be limited to th details therein set forth.

ONE BATH APPLICATIONS Example 1 A bath is prepared containing '75 parts of phosphoric acid product #1 (see below), 6.2 parts of antimony oxide (SbzOa), 5.6 parts of polyvinyl 4 A bath (b) containing 5.6 parts of polyvinyl chloride, 6.2 parts of antimony oxide (613203) and 88.2 parts of water is prepared and used to impregnate the padded cloth to give a wet pick-up 5 of about 93%. The treated cloth is then dried in an oven with forced air circulation to give a dry add-on of about 10.9%.

After one wash a char length of 3 inches and no afterglow are observed. After five washes the cloth shows a char length of 3% inches and an after-glow of seconds.

Example 8 is repeated using different impregnating bath with the following results:

Ex. Formulation pH 9 98% #1, 2% HMTA 1 10 50% #1, urea, 2% HMTA..-"

Char Length in Afterglow in Bath (a) Bath (b) Inches secs.

Wet Dry Wet Dry Pickup Addmn Pickup Adchm 1 wash 5 washes 1 wash 5 washes Per cent Per cent Per cent Per cent 123 20.9 94 11 3% 3% none 6 117 16 99 11. 6 3% 3% none 5 105 13 100 11. 7 3 3% none 3 101 13 99 11. 6 3 5 none 6 111 10.8 98 11.5 3% 4 none 6 121 16. 6 93 10.9 3 4% none 5 125 11.2 07 11.3 4 5 none 3 117 20. 3 92 10.8 3% 4% none 5 121 15. 3 93 10. 9 4 4 none 4 119 21. 92 10.8 3% 3% none 5 121 12 90 10.5 3% 3% none 5 125 19. 7 93 10.9 3% 3% none 6 106 8. 7 106 12. 4 4 l 4% none 2 110 8.0 104 12. 2 4 5% none 3 124 18 94 11 3% 5 none 3 118 21 96 11. 2 4 4 none 5 I r 1 HMTA=hexamethylenetetramino.

chloride, and 13.2 parts of water. This solution, which has a pH of about 6.8, is padded on bleached, unmercerized 80 x 80 cotton" cloth to give a wet pick-up of about 125%. The padded cloth is air dried, cured for 15 minutes at 160 C., rinsed and again dried to give a dry add-on of about After one wash a char length of 3 inches is obtained by the vertical flame test, and the cloth has no after-glow. After five washes the char length is 3 inches and the after-glow, 7 secs. Details of both the washing and flame testing procedures used in this and all following examples are given below.

Example 1 is repeated using diiferent impregnating baths with the following results:

Wherever the percentages of ingredients in the formulations appearing in the above tables do not total 100%, the balance is water.

Similar results are obtained when the antimony oxide of the examples is replaced wholly or in part by oxides of bismuth, titanium or tin or by mixtures of two or more of the oxides.

Preparation of phosphoric acid products 1. 2 mols 85% H3PO4 and 6 mols urea are mixed 5 in a glass tray and heated in an oven for one hour at 160 C. A 97.7% yield of a glassy substance is obtained. This is dissolved in sufficient water to make about a 59% solution.

2. 0.5 mol (as H4P2O7) polyphosphoric acid containing 32-50% meta, 47-60% pyro, 3-8% ortho Bath Per One Wash Five Washes Per E Cent Heb Dry Char Aftcr- Char After- Formulation pH u Add- Length, Glow, Length, Glow, p on Inches Secs. Inches Secs.

2-.. 37.5% #1, 2% HMTAJ 18.8% urea, 6.2% SbqOg, 5.6% PVC 7. 3 123 26 3% none 4 5 3... #3, 6.2% 512103, 56% PVC 6. 2 26 3% none 4 5 4... 37.5% #3, 2% IIMTA, 18.8% urea, 6.2% 513203, 5.6% PVC 6. 8 124 31 3 5 none 3% 6 5 37.5% #4, 2% HMTA, 18.8% urea, 6.2% SbzOa, 5.6% PVC 6. 8 124 81 3% none 3% 6 6... 37.5% 18.8 urea, 6.2% Sbg03, 5.6% PVC 6.9 127 3O 3% none 3% 7 7... 37.5% #8, 2% llMlA, 18.8% urea, 6.2% SbzOs, 5.6% PVC 2.4 125 30 4 none 3% 7 l HMTA hexamethylenctetremine. 1 PV C polyvinyl chloride.

TWO BATH APPLICATIONS Example 8 Bleached, unmercerized 80 x 80 cotton cloth is padded with a bath (a) of phosphoric acid product #1 having a pH of about 6.7 to a wet pick-up of about 123%. The cloth is dried in an oven with forced air circulation, cured for 15 minutes at C., rinsed and again dried to give a dry add-on of about 22.6%.

SIEUSS 5. tray and heated for one hour at 160C. An about 84.7 yield of a glassy product is obtained. A 50% solution of this product in Water is made. 4. 2 mols urea and 2 mols monoguanidine phosphate are mixed in a glass-tray and heated for one hour at 160 C." An about 89.4% yield of a glassy product is obtained. This is dissolved in an equal weight of water. i

5. 2 mols urea and 2 mols monoguanidine phosphate are mixed in a glass trayjand heated for 30 minutes at 160 C. in an oven. One-third mol hexamethylenetetramine is stirred in,- and the mixture is heated an additional 20 minutes. The foaming melt is cooled and weighed. Yield: about 95.4% white solid. A 50% solution of this in water is prepared. I v

- 6. 2-mols (as H4P2O1) polyphosphoric acid and 2 mols urea are mixed together-and heatedat 160 C. in an oven.. A white foam forms which solidifies on cooling. Yield: about 87%.

7. '1 mol monoguanidine phosphate, 0.5 mol dicyandiamide and about -6 mols water are heated one hour at 160 C. A white foam results An about 100% yield on the weight of solid reactants is obtained. The product is dissolved in an equal Weight of hot water. I v

8. 1 mol HaPO (85%), 0.5 mol dicyandiamide and about 6 mols water are heated one hour at 160 C.- A white gummy substance results in about a 94% yield.

"FLAME TESTING PROCEDURE Flame tests on the impregnated cotton fabrics of the examples are made following a procedure which is in general that given in ASTM Tentative Specifications Designation: D626-41T issued 1941. Samples 2 /2 inches x 10 inches are cut with the long dimension parallel to the warp. The sample of fabric to be tested is suspended vertically in a shield by means of a clamp at the top and bottom thereof. A Bunsen burner previously regulated to a luminous flame 1 inches high is placed under the suspended sample so that the end of the sample extends A inch into the flame. The flame isheld under thesample for 12 seconds and thenextinguished. The total length of char in inches is measured by the tear length produced with a tearing weight equal to approximately 10 of the tearing strength of the unburned fabric.

WASHING PROCEDURE The washings referred to in the preceding examples are efiected in small oscillating machines. A one pound load is used for each wash, and the fabrics are washed for 15 minutes intervals using 12 liters of 0.5% neutral soap solution at 65-75 C. They are spun and rinsed for from 3-5 minutes in lukewarm water and then spun and rinsed further by hand.

The present inventionis not.limited to the particular polyvinyl chloride of the examples and the thermoplastic substance may be any thermoplastic material containing at least and preferablyatleast 40%, by weight of combined halogen which is capable of rupturing under heat at carbon-halogen bonds. Some examples of such thermoplastic materials are the polyvinyl bromides, the polyvinylidene chlorides, the polyvinylidene bromides, copolymers of vinyl halide and vinylidene halides as, for example, of vinyl chloride and vinylidene chloride, copolymers of vinyl halides and acrylic esters as, for example, of vinyl chloride and methyl, ethyl, propyl, butyl or the like acrylates, halogenated paraffins, halogenated diphenyls as pentachloand the cations of'which contain nitrogen and no metal. Ammonium salts and guanido type salts such as the guanidine, guanylurea and biguanide salts of the following amino phosphoric 'acids are-representative of those which are suitable for use:

. 0% on 7 V s Monoaminodiphosphoric XQ h I O. OH Diaminodiphosphoric P I, o \NH, PN'Hz 0 OH Triaminodipliosphoric PO(OH) P 0(08) Diaminotetraphosphorie PO(OH) Tetraminotetraphosphorlc The monoand poly-salts may be used. I prefer, in general, the ammonium and guanidine salts and more particularly, salts containing a cationic ammonium or guam'dine group for each phosphorus atom in the acid.

The amino phosphoric acid salts may conveniently be prepared by melting together (1) urea or dicyandiamide and (2) phosphoric acid, a polyphosphoric acid or a guanido type salt of phosphoric acid or of a polyphosphoric acid. When the free acid is reacted with urea or dicyandiamide, the ammonium salt of the amino phosphoric acid is obtained. When the urea or dicyandiamide is reacted with the guanido type salt of a phosphoric acid, the corresponding guanido type salt such as the guanidine, biguanide, guanylurea, etc., salt of the amino phosphoric acid is obtained. The invention is not, however, in any way limited to any particular method of preparing the amino phosphoric acid salts.

The cellulosic textile material may be impregnated with the ingredients of the present process in one or more steps or stages as illustrated by the specific examples. It may be impregnated with a dispersion containing all of the necessary ingredients within the range of proportions specified below or it may be given a twobath treatment. If the latter, the textile must be impregnated first with (B), the aqueous solution containing the water-soluble, metal-free, nitrogen-containing salt of an amino phosphoric acid having an amino nitrogen atom attached directly to a phosphorus atom, and then after drying with (A), the dispersion containing the metallic oxide and the thermally unstable thermoplastic substance.

Regardless of the method of impregnation of the fibrous cellulosic textile material it is important that the ingredients of (A) and (B) be employed in a weight ratio of 1 part of the former to from 0.2-8 parts of the latter just as it is important that ingredients (1) and (2) of (A) be employed in a weight ratio of 1 part of the former to from 0.6-20 parts of the latter.

The total amount of the ingredients of (A) and (B) with which cellulosic textile materials are impregnated according to the present process must be sufficient to impart flame-resistance to the materials after heating them within the range of 135-200 C. and thereafter washing to remove any residual water-soluble substances. The total amount of the ingredients of (A) and (B) with which the cellulosic material is impregnated is so controlled that the finished flame-resistant textile contains from about 10 %-50% by weight or, if the hand of the treated material is relatively unimportant, to as high as about 75% by weight, based on the dry weight of the untreated textile, of wash-fast impregnant. During the heat treatment at 135-200 C. a substantial loss of solids takes place which may be as much as of the total weight of the phosphate with which the cellulosic material was initially impregnated. In order to obtain a, finished textile containing from 10%-50%, or in those cases where desired up to 65%-75%, by weight based on the dry weight of the untreated textile, of wash-fast impregnant, the amount of solids in the textile as initially impregnated should be sufiiciently hight to allow for this weight loss of solids during the heat treating and washing steps.

I prefer to employ an aqueous dispersion of the necessary ingredients for treating fibrous cellulosic textile materials in accordance with my invention. The amount of solids in such a dispersion may be varied as described but they will usually constitute from about 40% to about by Weight of the dispersion.

The present invention applies to cellulosic materials of the class consisting of natural celluloses, regenerated celluloses and mixtures thereof and including primarily cotton and viscose rayon.

The textile treating compositions of this invention may be modified by incorporating therein various modifying agents which aid in further improving the flame-resistant characteristics of the treated cellulosic material or which facilitate the technique of application. For instance, the compositions may also contain minor amounts (e. g., from 1% to 30% weight of the total solids content) of such glow retardants as the glow-retarding borates, phosphates, pyrophosphates, etc., e. g., zinc borate, zinc phosphate, zincammonium phosphate, stannic phosphate, phenyl diamido phosphate, melamine pyrophosphate, etc. Agents which have a buffering effect on the composition after being applied to the fabric or other textile, e. g., calcium carbonate, magnesium oxide, urea, hexamethylene tetramine and other polyalkylene polyamines boiling above about 200 C., the amount of said polyamines not exceeding about 7% by weight of ingredient (B), etc., may be incorporated into the treating compositions as desired or as con ditions may require. It is often advantageous to add an agent such as urea which will convert any aminophosphate which may have been hydrolyzed back to the aminophosphate.

Bath (B) in a two-bath process should be adjusted to a pH (glass electrode pH) within the range of from about 3 to about 7 if it is not initially within that pH range. Preferably the pH of the aqueous composition containing ingredient (B) is between about 4 and 6.

The present invention is applicable to the production of a wide variety of flame-resistant cellulosic materials, e. g., wearing apparel of all kinds, especially childrens clothes and clothing used by the armed forces, curtains, draperies, sheeting, furniture coverings, linings for electric blankets, net fabrics, non-woven fabrics, chenilles, etc., which are made of cellulosic textile materials.

The terms flame resistance and flame-rcsistant as used herein and in the appended claims with reference to cellulosic textile materials are used generically to include within their meanings treated cellulosic textile materials,

4 which, after ignition, will continue to burn at a r l l l 9 erly fall: within; the specific-classification ,of fire-resistant cellulosic textile materials.

The terms textile and textile material as used generically herein and in the appended claims include within their meanings filaments, fibers, rovings, slivers,- threads, syarns, twisted yarns, etc.,.as'suchi 'or in. woven, felted or otherwise formed fabrics, sheets, cloths and the like.

Iclaim: I .1 A.

A method orimparting flame-resistance to a cellulosic textile material of the class consisting of natural celluloses, regenerated celluloses and mixtures thereof, which comprises impregnating said material with arr-association of an aqueous liquid.composition containing ingredients comprising (1) .a finely divided oxide of'a metal of the group consisting of antimony, bismuth, tin and titanium and (2) a thermoplastic substance containing at least 20% by weight of combined halogen and capable of rupturing under heat at carbon-halogen bonds, the ingredients of (l) and (2) which together are designated hereinafter as (A) being employed in a weight ratio of 1 part of the former to from 0.6-20 parts of the latter, and of an aqueous liquid composition containing an ingredient comprising (B) a water-soluble, metal-free, nitrogencontaining salt of an amino phosphoric acid having an amino nitrogen atom attached directly to a phosphorus atom, which salt has a melting point of less than 200 C., the ingredients of (A) and (B) being employed in a weight ratio of 1 part of the former to from 0.2-8 parts of the latter, the aqueous composition containing the ingredient (B) having a pH of from about 3 to about 7; heating the impregnated material at a temperature within the range of about 135-200 C'.; and washing the resulting material to remove any residual water-soluble substances therefrom, the total amount of the ingredients of (A) and (B) with which the cellulosic textile material initially is impregnated being such that the finished flame-resistant textile contains from about to about '7 5% by weight, based on the dry weight of the untreated textile, of wash-fast impregnant.

2. A method as in claim 1 wherein the cellulosic textile material is cotton.

3. A method as in claim 1 wherein the cellulosic textile material is viscose rayon.

4. A method as in claim 1 wherein the metal oxide is antimony oxide.

5. A method of imparting flame-resistance to a textile comprising fibers of a cellulosic material of the class consisting of natural celluloses, regenerated celluloses and mixtures thereof which comprises impregnating said textile with an aqueous dispersion having a pH within the range of 3-7 and comprising (1) a finely divided oxide of a metal of the group consisting of antimony, bismuth, tin and titanium, (2) a thermoplastic substance containing at least by Weight of combined halogen and capable of rupturing under heat at carbon-halogen bonds, the ingredients of (1) and (2) which together are designated hereinafter as (A) being employed in a weight ratio of 1 part of the former to from 06-20 parts of the latter, and (B) a water-soluble, metal-free, nitrogen-containing salt of an amino phosphoric acid having an amino nitrogen atom attached directly to a phosphorus atom, which salt has a melting point of less than 200 C., the ingredients of (A) and (B) being employed in a weight ratio of 1 part of the former to from 0.2-8 parts of the latter; heating the impregnated textile at a temperature within the range of about 135- 200 C,; and washing the resulting textile to remove any residual water-soluble substances therefrom, the total amount of the ingredients of (A) and (B) with which the textile initially is impregnatedbeingsuch that the finished flameresistant textile contains from about 10% to about 75% by weight, based on the dry weight of theuntreated textile, of washv-fast impregnant.

.tfipA-method as in claim 5-wherein ingredient (2). is a vinyl chloride polymerization product.

7. A method as in claim 5 wherein ingredient B) is the amino phosphoric acid salt obtained by reaction of urea'with phosphoric acids.

. 8. A method as in claim 5 wherein ingredient (B) is the aminophosphoric acid salt obtained by reaction of urea with pyrophosphoric acid.

9. A method as in claim 5 wherein ingredient (B) is the amino phosphoric acid salt obtained by reaction of urea with monoguanidine phosphate.

10. A method as in claim 5 wherein ingredient (B) is the amino phosphoric acid salt obtained by reaction of dicyandiamide with phosphoric acid.

11. A method as in claim 5 wherein ingredient (B) is the amino phosphoric acid salt obtained by the reaction of dicyandiamide with monoguanidine phosphate.

12. A method as in claim 5 wherein the aqueous dispersion contains a small amount, not exceeding about 7% by weight of the ingredient (B), of a polyalkylene polyamine having a boiling point substantially above 200 C.

13. A method of imparting flame-resistance to a textile comprising fibers of a cellulosic material of the class consisting of natural celluloses, regenerated celluloses and mixtures thereof which comprises impregnating said textile with an aqueous solution having a pH within the range of 3-7 and containing (B) a water-soluble, metal-free, nitrogen-containing salt of an amino phosphoric acid having an amino nitrogen atom attached directly to a phosphorus atom, which salt has a melting point of less than 200 C.; heating the impregnated textile at a temperature within the range of 200 C.; washing the resulting textile to remove any residual water-soluble substances therefrom; impregnating the heated and washed textile with ingredients comprising (1) a finely divided oxide of a metal selected from the group consisting of antimony, bismuth, tin and titanium and (2) a thermoplastic substance containing at least 20% by weight of combined halogen and capable of rupturing under heat at carbon-halogen bonds, the ingredients of (1) and (2) which together are designated hereinafter as (A) being employed in a weight ratio of 1 part of the former to from 0.620 parts of the latter, the ingredients of (A) and (B) being employed in a weight ratio of 1 part of the former to from 0.2-8 parts of the latter; and heating the impregnated material at a temperature within the range of about 135 C. to 200 C., the total amount of the ingredients of (A) and (B) with which the said textile is impregnated being such that the finished flame-resistant textile contains from about 10% to about 75% by weight, based on the dry weight of the untreated textile, of wash-fast impregnant.

14. A flame-resistant cellulosic textile material obtained in accordance with the method of claim 1.

15. A flame-resistant cellulosic textile material obtained in accordance with the method of claim 5.

gether are designated hereinafter as (A) being employed in a weight ratio of 1 part of the former to from 0.6-20 parts of the latter and being dispersed in water containing (B) a water- 15 2,413,163 soluble, metal-free, nitrogen-containing selling. 4 2,75

atom, which salt has a melting point of less than 200 (2., the ingredients of (A) and (B) being employed in a weight ratio of 1 part of the former to from 0.2-8 parts of the latter.

JOSEPH W. CREELY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date Bacon Dec. 24, 1946 Ford et a1 Sept. 27, 1949

Claims (1)

1. A METHOD OF IMPARTING FLAME-RESISTANCE TO A CELLULOSIC TEXTILE MATERIAL OF THE CLASS CONSISTING A NATURAL CELLULOSES, REGENERATED CELLULOSES AND MIXTURES THEREOF, WHICH COMPRISES IMPREGNATING SAID MATERIAL WITH AN ASSOCIATION INGREDIAQUEOUS LIQUID COMPOSITION CONTAINING INGREDIENTS COMPRISING (1) A FINELY DIVIDED OXIDE OF A METAL OF THE GROUP CONSISTING OF ANTIMONY, BISMUTH, TIN AND TITANIUM AND (2) A THERMOPLASTIC SUBSTANCE CONTAINING AT LEAST 20% BY WEIGHT OF COMBINED HALOGEN AND CAPABLE OF RUPTURING UNDER HEAT AT CARBON-HALOGEN BONDS, THE INGREDIENTS OF (1) AND (2) WHICH TOGETHER ARE DESIGNATED HEREINAFTER AS (A) BEING EMPLOYED IN A WEIGHT RATIO OF 1 PART OF THE FORMER TO FROM 0.6-20 PARTS OF THE LATTER, AND OF AN AQUEOUS LIQUID COMPOSITION CONTAINING AN INGREDIENT COMPRISING (B) A WATER-SOLUBLE, METAL-FREE, NITROGENCONTAINING SALT OF AN AMINO PHOSPHORIC ACID HAVING AN AMINO NITROGEN ATOM ATTACHED DIRECTLY TO A PHOSPHORUS ATOM, WHICH SALT HAS A MELTING POINT OF LESS THAN 200* C., THE INGREDIENTS OF (A) AND O(B) BEING EMPOLOYED IN A WEIGHT RATIO OF 1 PART OF THE FORMER TO FROM 0.2-8 PARTS OF THE LATTER, THE AQUEOUS COMPOSITION CONTAINING THE INGREDIENT (B) HAVING A PH OF FROM ABOUT 3 TO ABOUT 7; HEATING THE IMPREGNATED MATERIAL TO REMOVE ANY RETURE WITHIN THE RANGE OF ABOUT 135*-200* C.; AND WASHING THE RESULTING MATERIAL TO REMOVE ANY RESIDUAL WATER-SOLUBLE SUBSTANCES THEREFROM, THE TOTAL AMOUNT OF THE INGREDIENTS OF (A) AND (B) WITH WHICH THE CELLULOSIC TEXTILE MATERIAL INITIALLY IS IMPREGNATED BEING SUCH THAT THE FINISHED FLAME-RESISTANT TEXTILE CONTAINS FROM ABOUT 10% TO ABOUT 75% BY WEIGHT, BASED ON THE DRY WEIGHT OF THE UNTREATED TEXTILE, OF WASH-FAST IMPREGNANT.