# Patent

## Title
Sealant application method

## Abstract

This application is a continuation-in-part of copending application Ser. No. 493,815, filed Aug. 1, 1974 now U.S. Pat. No. 3,933,122 which in turn is a divisional application of Ser. No. 244,574 filed Apr. 17, 1972 now U.S. Pat. No. 3,846,155.

## Background
This invention relates to an improved process for rendering textiles materials flame retardant. More particularly, it relates to a more rapid and hence more practical process for polymerizing poly (hydroxymethyl) phosphonium cation on and in cellulose-containing materials with ammonia to render them durably flame retardant. It relates to an apparatus for rapidly and efficiently polymerizing the monomer on and in the cellulose containing materials.

In U.S. Pat. No. 3,607,356, it has been proposed to impregnate cellulose-containing materials with an aqueous solution containing an equilibrium mixture of tris (hydroxymethyl) phosphine ("THP") and tetrakis (hydroxymethyl) phosphonium hydroxide ("THPOH") said solution having a pH of about 7 to about 8. In this process, the impregnated material containing from 10 to about 40 percent by weight of the monomer is dried to about 10 to about 20 percent moisture and then treated with gaseous ammonia in an enclosed cabinet to polymerize the resin monomers. The gaseous ammonia treatment step requires from one or two to 6 minutes exposure time depending upon the character, i.e., the weight, fibrous nature, etc. of the treated material. In many textile processes, the materials are processed in equipment operating at high speed in a continuous manner. Accordingly, operations involving processing times of several minutes duration require either static operation or units of a size wherein such relatively long residence times can be obtained. It is, therefore, desired to process such materials in equipment wherein shorter residence times consistent with high speed continuous operations can be obtained in a practical maner. Moreover, the treatment according to the process of U.S. Pat. No. 3,607,356, when used with available ammonia treatment cabinets, has been found to produce finishes on cellulosic materials which often tended to dust and the durability of the finished materials often failed to meet the stringent government standards (Department of Commerce Standard FF-3-71) which require that the treated materials withstand at least fifty home washing and drying cycles. The enclosed chamber for carrying out the ammonia treatment commonly used in this field comprises a series of perforated pipes housed in a box like enclosure having a large opening in the top. The partially dried impregnated material is passed over the perforated pipes through which ammonia gas is forced. The excess ammonia gas is vented through the opening in the top of the enclosure, and discharged into the atmosphere. This venting of considerable quantities of ammonia gives rise to a severe pollution problem. It can thus be seen that the process disclosed in U.S. Pat. No. 3,607,356 not only results in a highly inefficient utilization of ammonia but also is hardly practical for the lighter, open weave, materials and leaves much to be desired when processing heavier and/or close knit materials.

It is known also, as disclosed in U.S. Pat. No. 2,983,623, to cure further polymerizable methylol-phosphorus polymeric material containing at least one free methylol group attached to a phosphorus atom incorporated in a cellulosic material, by exposing said material in the dry state to the action of gaseous ammonia followed by subjecting it to an aqueous ammonia treatment. In this process, the further polymerizable resins disclosed are solutions of reaction products of tetrakis(hydroxymethyl) phosphonium chloride and urea which solutions are relatively strongly acid and are applied in the presence of buffers which adjust the pH of the solutions to a pH within the range of about 3.5 to 4. The impregnated material is thoroughly dried, exposed to ammonia gas for about 5 to 10 minutes, and then immersed in aqueous ammonia for about 10 more minutes to complete the cure of the resin on and in the material. Such a process also requires relatively long time cycles of treatment especially in the aqueous ammonia hence is hardly applicable with modern high speed processing techniques.

The problem of the long time cycles and efficiency of the polymerization has been substantially overcome by the apparatus and process disclosed in copending application Ser. No. 493,815 filed Aug. 1, 1974. In this application an apparatus and process for imparting flame retardance to cellulose containing materials is disclosed whereby materials which have been impregnated with a solution having a pH of from about 7 to about 9 and a tetrakis (hydroxymethyl) phosphonium hydroxide content of from about 0 to about 8 percent and the monomer is polymerized in and on the cellulose material by exposure in an enclosed chamber to an atmosphere containing from about 50 to about 90 percent by volume of gaseous ammonia for about 5 to about 30 seconds. By this process and with this apparatus the monomer is rapidly and effectively polymerized on and in the cellulose containing material, thereby imparting durable flame retardance to the materials in a rapid and efficient manner. Under certain mill conditions it was found that substantial amounts of formaldehyde was formed during the gaseous ammonia exposure step and when the cured fabric was batched in rolls or on trucks immediately upon exit from the ammonia chamber, it was noted that the odor of formaldehyde rapidly developed in the batched processed materials and also that a considerable exotherm was prevalent in the material. In such materials, i.e., when the odor of formaldehyde and/or exotherm was noted, the durability of the flame retardant character was reduced. It is believed that the formaldehyde produced by decomposition of the polymerized or partially polymerized monomer when confined in the material, reacted with the polymer or partially polymerized polymer to form a moisture sensitive reaction product which may deleteriously affect the durable character of the flame retardant treatment.

The process of the present invention represents an improvement over the process of the aforementioned Ser. No. 493,815 whereby the deleterious effect of the action of formaldehyde is obviated and thus a rapid and effective means of imparting durable flame retardance to cellulose containing materials is provided. Further said improved process is more generally applicable with the currently used high speed textile processing equipment and conditions.

It is, therefore, a principal object of the present invention to provide an improved process for treating textile materials to render them durably flame retardant.

Another object is to provide a more rapid process for imparting flame retardant characteristics to textile materials whereby said materials are impregnated with a solution containing poly (hydroxymethyl) phosphonium cation, dried to remove substantially all of the retained moisture and rapidly and efficiently cured by gaseous ammonia.

A particular object is to provide a process which does not require, in the curing step, prolonged exposure of the impregnated material to either large excesses of gaseous ammonia or aqueous ammonia or both.

A further object is to provide a process which allows operation at low pH, thereby substantially reducing the amount of formaldehyde produced during the process.

An additional object is to provide a process whereby a deleterious effect of polymer degradation products on the treated material is substantially prevented.

These and other objects will be apparent to those skilled in the art by the following description of the present invention.

It has now been found that textile materials can be rapidly and economically rendered durably flame retardant by a process which comprises: phosphonium cation having a pH of from about 2 to about 9, and containing from about 10 to about 40 percent by weight of poly (hydroxymethyl) phosphonium cation; conditions, to a moisture content of from about 0 to about 8 percent by weight; dried material; least about 5 seconds but less than about 60 seconds to an atmosphere containing at least about 50 percent by volume of gaseous ammonia to cure the phosphorus containing resin in and on the material; the material durably flame retardant; and than 1 to about 10 seconds to an atmosphere containing at least about 50 percent by volume of gaseous ammonia.

The curing steps (d), (e), and preferably (f) of the new process are carrried out in an enclosed cabinet which comprises:

a housing;

gas inlet means disposed in the upper portion of said housing;

gas outlet means disposed in the lower portion of said housing;

material inlet means and material outlet means disposed in the lower portion of said housing above said gas outlet means;

partition means disposed in said housing between said gas inlet means and said gas outlet means so as to form a gas treatment chamber in the upper portion of said housing, said partition means including means for permitting the introduction into or removal from said gas treatment chamber of textile material to be treated in said chamber while minimizing the passage of gas into and from said gas treatment chamber;

water inlet means with connecting application means disposed in the upper portion of said housing;

water outlet means disposed in the lower portion of said housing below said gas outlet means; and

means disposed in said gas treatment chamber for supporting textile material to be treated. Cabinets of similar design are disclosed in copending application Ser. No. 493,815 filed Aug. 1, 1974.

The ammonia treated material obtained in accordance with the present invention may be washed and dried numerous times without substantial loss of fire retardancy. In addition, there is an increase in the flame retardant efficiency of the process, together with a decrease of formaldehyde odor from the processing equipment.

In accordance with a preferred mode of carrying out the improved process of this invention, an aqueous solution containing from about 10 to about 40 percent by weight of poly (hydroxymethyl) phosphonium cation and having a pH of from about 2 to about 9 is prepared and used to impregnate a textile material, the impregnated material is dried to about 0 to about 8 percent moisture, the dried material is aerated substantially immediately after leaving the drier by directing a current of air through the material, preferably suction, said material is then exposed for at least about 5 to less than about 60 seconds and preferably for about 10 to about 30 seconds to an atmosphere containing at least about 50 percent by volume of ammonia, preferably from about 70 to about 95 percent of gaseous ammonia, and the material is contacted substantially immediately after ammonia treatment with water, in an amount sufficient to provide a wet pick-up of from about 10 to about 40 percent by weight of water. The material is thereafter again contacted with the gaseous ammonia atmosphere for a short period of time., from about less than 1 to about 10 seconds, and preferably from about less than 1 to about 6 seconds, to further enhance cure. The thus treated material, containing an insoluble polymer of the phosphonium compound in and on the material; is scoured, washed, and dried.

The treatment of the dried impregnated material with ammonia, i.e., the curing step, is carried out in an enclosed chamber wherein the impregnated material is exposed to a gaseous atmosphere containing a high concentration, i.e., above about 50 percent by volume, of ammonia. The material is preferably passed into and out of the chamber, in a continuous manner and at a relatively high speed, so that the material is exposed to the ammonia atmosphere for at least 5 seconds and preferably from about 15 to about 30 seconds.

The improved process of this invention differs from the process disclosed in the aforementioned Ser. No. 493,815 in two respects. In the instant process the impregnated material after being dried is aerated by directing a current of air through the dried material, and also the material, after passing through ammonia curing, is exposed to or contacted by water, while still in the cabinet, and therafter exposed to ammonia gas again. By conducting the process in this manner, the problems caused by the presence of formaldehyde in the dried uncured impregnated material in the curing step and also after the curing of the monomer on and in the cellulosic material can be substantially obviated. It has been found that the pH of the process may be reduced during curing, resulting in the formation of very little formaldehyde and significantly decreasing the formaldehyde odor, which can be sensed in the plant environment outside the ammoniating chamber. In unexpected addition, a higher efficiency of flame retardancy is achieved when the material is a blend of varying cellulosic materials. By the latter, it is meant that a higher add-on of resin occurs resulting in an increase of flame retarding effect together with increased durability, each without adverse effect to the hand of the material.

The materials which can be treated to impart flame retardant properties thereto in accordance with this invention include cottom, rayon, paper, jute ramie, wood, and mixtures thereof, as well as blends of cellulosics such as cotton or rayon with synthetic fibers, such a polyesters, nylons, acrylics, acetate and mixtures thereof or with proteinaceous fibers such as wool, silk, mohair, alpaca, mixtures thereof and the like. The process of this invention is particularly effective when applied to the treatment of cellulosic and cellulosic-blend materials such as cotton and rayon with synthetic materials.

The solution used to impregnate the textile material comprises poly(hydroxymethyl) phosphonium cation of poly(hydroxymethyl) phosphine and poly(hydroxymethyl) phosphonium cation as an equilibrium mixture. Such solutions are well known in the art. One method of preparation is by reacting a solution of tetrakis (hydroxymethyl) phosphonium salt with up to an equivalent quantity of an organic or inorganic base. Typically, any of the tetrakis (hydroxymethyl) phosphonium salts can be utilized to make the solutions of this process. Common salts which may be employed include, for example, the halides, sulfates, acetates, phosphates, carboxylates, oxalates, lactates, formates, sulfonates, and nitrates. The most often used salts are, however, the halides and the sulfates.

The solvent may be water or an appropriate non-aqueous solvent such as alcohol, N,N-dimethyl formamide, dimethyl acetamide, and mixtures thereof and the like. Alternatively, the solution may be in the form of an emulsion. Furthermore, the solution may be a reaction product of the poly(hydroxymethyl) phosphonium cation with an appropriate nitrogen containing material such as urea, guanidines, substituted ureas, melamines, or other amino or amido function containing organic mateials or the reaction product of the previously mentioned nitrogen containing materials with aldehydes, preferably formaldehyde. Especially preferred bases for reaction with the salt are alkaline metal hydroxides, alkaline earth hydroxides, salts of weak acids and strong bases, monoalkaline metal salts of dibasic acids, organic tertiary amines such as triethylamine, trimethylamine, and the like. The pH of the final solution is adjusted to from about 2 to about 9, preferably to from about 5.0 to about 8.1. For the purpose of this invention, the active component of the solution or emulsion is considered to be the poly (hydroxymethyl) phosphonium cation. Hereinafter, the active component will be expressed in terms of this component, although it is probable that there is present a mixture of poly (hydroxymethyl) phosphine and poly (hydroxymethyl) phosphonium cation.

The treating solution may be applied to the textile in any convenient manner. For example, the solution may be applied by padding, dipping, spraying, and the like. After impregnation, the excess solution is preferably removed from the material by passing the material through squeeze rolls, centrifuging, wringing, or other methods. Althrough a wet pick-up of from about 50 to about 200 percent may suitably be used, preferably the material contains about an equal weight, i.e., about 100 percent pick-up, of the treating solutions.

The impregnated material is then dried to a residual content of about 0 to about 8 percent and preferably from about 0 to about 3 percent. The drying is carried out in air or in drying oven at temperatures which may vary from ambient to about 125.degree. centigrade. Excessive drying temperatures and times are to be avoided. The drying time may vary according to the drying temperature and also the weight and fibrous nature of the material, as will be obvious to those skilled in this art. The solvent content of the material may be measured by a suitable manner.

The dried material is then aerated by passing a current of air through the material as soon as possible or convenient after leaving the drier. The aeration step can be carried out by passing the material, after drying, over a perforated plate or pipe through which a strong current of air is continuously blown or sucked. Preferably, the air current is moved by suction. Conveniently, this aeration means is located as close as possible and/or convenient to the material exit of the drier. The material is passed over the perforated or slotted air distribution means, a plate, pipes, or series of pipes extending over the width of the fabric and a current of air, flowing at about 1000 to 3000 cubic feet per minute, is caused to pass through the material. The time required for this operation is not critical, and, in general, the material is exposed to the current of air for about 0.5 to about 2.0 seconds or more. As will be apparent, the speed of the material running through the processing equipment will determine the exposure time, and is a function of the volume of air and speed of the material. By this means, any formaldehyde present in the dried material is rapidly removed by the current of air and also the material is rapidly cooled thereby reducing the formation of additional formaldehyde occaisioned by the probable decomposition of the phosphonium compounds.

The aerated impregnated material next is exposed to gaseous ammonia in an enclosed chamber wherein the resin monomer reacts rapidly and substantially completely to form an insoluble polymer within the material. The gaseous atmosphere which comprises at least about 50 percent of gaseous ammonia, and preferably from about 70 to about 95 percent or more of gaseous ammonia provides an effective, efficient, and suprisingly rapid reactant for the resin curing step. It has been found that the curing step is completed, under these conditions, in less than about 60 seconds and generally less than about 45 seconds, and as low as 5 seconds; whereas, the prior art procedures from about 1 to about 6 minutes were required for substantially complete polymerization and curing of the impregnated composition. Under optimum conditions, the procedure of this invention proceeds with the efficient utilization of the gaseous ammonia charged to the process, whereas prior art processes often preferred up to a 15 fold excess of the ammonia reactant. This huge excess of ammonia presented a serious air pollution problem, which in the present process and apparatus has been eliminated by the highly efficient utilization of the ammonia.

A particularly effective, and hence preferred, apparatus for carrying out the curing step of this process is illustrated by the FIGURE which shows a schematic view of the enclosed cabinet apparatus of this invention.

In this drawing the housing, 1, contains a gas inlet, 2, and a gas outlet 3, which is conviently connected to a suction means, not shown. The housing is provided also with a material inlet, 4, and material outlet, 5, for admitting the dried impregnated material and exiting the cured material. Material guides, 6, are provided for conveying the impregnated material through the cabinet. Partitioning means, 7, extending across the interior of the housing serves to form a chamber in which the material is contacted with the gas. The partitioning means includes flaps, 8 and 9, which permits the material to be treated to enter the gas treatment chamber and the treated material to exit from said chamber, while minimizing the passage of gas into and from the said chamber. A gas distribution device, shown here as a perforated plate, 10, is provided to assist in the distribution of the entering gas stream evenly throughout the gas treatment chamber. Sensing ports, 11, are provided in the gas treatment chamber for removal of samples of the gaseous atmosphere for analysis to monitor the concentration of the treatment gas. Water inlet means, 12, with connecting application means 13, are provided in the gas treatment chamber for the water treatment step.

The housing may be provided with cooling means, not shown, to cool the treatment chamber and to regulate the temperature of the gaseous atmosphere within the treatment chamber. A liquid condensate discharge port, not shown, may be positioned at a convenient place in the housing for removal of condensate from the chamber. Such port should be at a lower point than the material inlet or outlet and the gas outlet, 3.

The housing can be fabricated from conventional materials of construction such as wood, metal, glass, plastic, and the like or any combination thereof.

The partition means, 7, may be constructed from like materials or from rubber. The flaps, 8 and 9, are fabricated from flexible materials such as rubber, leather, plastic film and are attached to the partition means in any convenient manner. It is important that the flaps do not impede the passage of the material therethrough but do substantially prevent the free flow of gas into and out of the treatment chamber.

In operating this apparatus, ammonia gas is fed into the unit through gas inlet, 1, at a rate sufficient to provide an ammonia atmosphere within the gas treatment chamber having at least about 50 percent by volume of ammonia, and preferably from about 70 percent to about 90 percent ammonia by volume. Textile matrerial which has been impregnated with the poly (hydroxymethyl) phosphonium cation and dried to contain from about 0 to about 8 percent moisture is admitted to the apparatus, preferably in a continuous manner, at inlet, 4, and is passed over material guides, 6, through partitioning means, 7, through flap, 8, into the gas treatment chamber wherein the impregnated material is exposed to the ammonia atmosphere. After exposure to the ammonia atmosphere for the requisite time, it is water treated with water application means 13. The material is again exposed to the ammonia atmosphere and therafter leaves the gas treatment chamber passing through flap, 9, of partitioning means, 7, and exits from the housing, 1, at material outlet, 5. The passage of air into the gas treatment chamber is minimized in part by the partitioning means and in part by the withdrawal of gas from the housing through gas outlet, 3, which is connected fto a mild suction means e.g., a vacuum pump.

The rate of flow of ammonia gas into the apparatus is adjusted to provide at least one mol of ammonia per mole of tetrakis (hydroxymethyl) phosphonium hydroxide available for reaction, i.e., curing, on the impregnated material. Preferably about a 20 percent molar excess of ammonia is supplied. This amount of ammonia can be approximated by the following calculation: ##EQU1##

The material is preferably contacted with water within the enclosed chamber. Any convenient method of water application means may be utilized, such as a trough, stream, spray, etc., or any combination thereof, and any convenient location within the chamber would be appropriate; for example, referring to the drawing, a trough may be located above or below the partitioning means or may be an integral portion thereof through which the material is guided with or without an additional material guiding means. In a like manner, a stream or, as illustrated in the drawing, a spray may also be utilized. A combination of means may also be used in application of the water treatment. A preferred method, however, is the application of water in the form of a fine spray. Several means for accomplishing this step will be obvious to those skilled in this art. For example, a spray head or several heads may be positioned convenient to the material exit means from the curing cabinet. Most preferably, the spraying means is one or several air atomizing water spray heads which are used to supply the water in the form of an atomized spray to the material before exiting from the ammonia curing cabinet. Sufficient water should be added to the material to provide a pick-up of about 10 to about 60 percent by weight and preferably from about 20 to about 30 percent by weight pick-up of water. This water not only cools the hot material but also results in the immobilization of formaldehyde and, thus, prevents its further reaction with the phosphonium salt polymer.

It is believed that the water supplied at this stage of the process provides a reaction medium for the formaldehyde to react with ammonia which may be present to form hexamethylene tetramine, which latter product does not react with the phosphonium salt polymer present in and on the material.

It has been found that further treatment with gaseous ammonia, after contact with water, has a further beneficial effect upon the polymerized material. Treatment with gaseous ammonia for from about less than 1 to about 10 seconds and preferable about less than 1 to about 6 seconds reduce further the substantially reduced odor of formaldehyde so that such odor is no longer apparent. To gain such further treatment, placement of the water treatment means at a point away from the material exit, so that the material will remain in the enclosed chamber for a time after water treatment, has been found to be a convenient method of achieving this end. Alternatively, the further gaseous ammonia treatment may be accomplished in a separate chamber.

Where additional ammonia treatment is desired within the chamber after the water treatment step, it might be desirable to maintain a nip roll doctor blade or similarly functioning means immediately after the water treatments means to decrease the amount of water maintained on the material when undergoing the additional ammonia cure. Such means have been found to be effective but are not necessary to the operation of the instant process.

Thereafter, the wetted material which contains about 10 to about 60 percent by weight of moisture pick-up is preferably oxidized or scoured, or washed to remove unpolymerized materials and the like. Where the present invention is carried out on yard goods using mill apparatus, this scouring operation may be effected using any of the conventional scouring, and the like. The scouring may be conveniently carried out using, an aqueous soap solution containing small amounts of sodium carbonate, perborate, or peroxide and synthetic detergents. Preferably this scouring is carried out immediately after the step of contacting the material with water.

Alternatively, the wetted material can be batched in rolls or in trucks and held for extended periods. When also handled, i.e., batched, the material does not develop significant formaldehyde odors nor does a significant exotherm develop. Thus, following the water wetting step of this process, the material is essentially completely processed, except for the normal and conventional scouring, etc. treatments and the flame retardant character is durably imparted thereto. Since in many mills the scouring and other final operations are carried out at points remote from the impregnation drying and curing operations, it is usual in this industry to batch the polymerized or cured materials to the area where the scouring and other finishing operations are carried out. Since hours or days may elapse, it can be seen that the process of this invention provides an efficient and economical means for preventing the deterioration of the flame retardant treatment prior to finishing the material.

The scouring step may be followed by conventional washing and drying operations and thereafter the dried treated material may be subjected to any normal finishing operation such as sanforizing, calendering, and the like.

The flame retardant cellulose-containing materials treated in accordance with the procedures set forth above have been found to be durably flame retardant, even after 50 or more home laundering and drying cycles. Additionally, such materials are substantially free from dust and have a tear resistance, tensile strength, and hand which are substantially unchanged from those of untreated materials.

The process of this invention is readily adaptable to modern high speed commercial textile processing equipment. Substantial savings of time and of consumption of ammonia gas, in the range of about 100 to 200 percent, are effected by this improved process. Addtionally, the present process prevents the deterioration of the flame retardant character imparted to the material which may occur between the curing step and the scouring and other finishing steps.

The following examples will illustrate the process of the present invention. In these examples, as well as in the above specification and the claims hereinafter set out, parts and percentages are by weight and temperatures are given in degrees Fahrenheit, unless otherwise specified. The durability of the flame retardancies reported by accelerated boil test and the 50 home washes test were determined in accordance with the procedure of the United States Department of Commerce test procedure No. DOC FF-3-71.

An aqueous solution containing about 32 percent tetrakis (hydroxymethyl) phosphonim cation and having a pH of 7.4 was used to impregnate 6000 yards of white cotton sheeting material, (3 yards/lb.), at the rate of 60 yards per minute. The impregnated material was passed through squeeze rolls to give a wet pick-up of about 100 percent. the impregnated material was dried in a 225.degree. F oven for 30 seconds and then within about 20 seconds exposed in an enclosed cabinet for about 15 seconds to an atmosphere consisting of 95 percent by volume of ammonia and 5 percent by volume of air. The treated material after emanating from the ammonia treatment cabinet was batched in a roll. After being held in the roll for about 24 hours, the material was tested for flame retardance, after being subjected to the usual oxidation, washing, and drying steps, and failed both the accelerated boil test and the 50 home washes test.

The "accelerated boil test", as a measure of the flame retardant character of the material, is carried out by heating the dried cured material for 45 minutes in a solution containing 90 parts of soap, 90 parts soda ash, and 10 parts of a synthetic anionic detergent in about 50,000 parts of water and rinsed in hot (145.degree. F) water for 15 minutes, repeating the heating and rinsing nine times ("9 boil cycles"). This "accelerated boil" test is roughly equivalent to at least fifty home washing and drying cycles.

A multi-yard run of 35 percent polyester, 65 percent cotton flannel material was continuously processed at the rate of about 60 yards/min. by running into an aqueous bath containing about 28 percent tetrakis (hydroxymethyl) phosphonium cation and having a pH of 7.4. The impregnated material was passed through squeeze rolls to give a wet pickup of about 110 percent and into a 250.degree. F oven (residence time about 30 seconds). The dried material was passed from the oven over a slotted plate about 36 inches long through which air at the rate of about 2,000 cfm was being moved upwardly through the material by suction. The dwell time of the fabric moving at the rate of 60 yards/min. over the slotted plate is about one second. The aerated material was passed into an enclosed cabinet where it was exposed for about 8 seconds to an atmosphere consisting of about 85 percent by volume of ammonia and 15 percent by volume of air. The treated material was contacted substantially immediately after exiting from the cabinet with an air atomized water spray sufficient to result in a pick-up of about 25 percent water. The material was batched in rolls and held for about twenty-four hours, then subject to the usual oxidation, washing, and drying steps. The fabrics were tested according to Federal Regulation FF-3-71 after 50 home washes and 50 tumble dryings with the following result: Run  No. of Samples No. of Samples Avg. Char Length No.  Tested       Burning      (in.) ______________________________________ A    18           3            3.7 B    19           4            3.8 C    15           5            4.0 D    21           1            2.3 E    10           0            2.0 F    12           1            3.2 ______________________________________

A multi-yard run of 35 percent polyester, 65 percent cotton flannel was continually processed by the method of Example II with the exception that the ammonia exposed material was sprayed with water and exposed to an additional atmosphere consisting of about 85 percent by volume of ammonia and 15 percent by volume of air for about 2 seconds. Both of the ammonia gas exposure steps and the water spray were accomplished in the enclosed cabinet. The following results were obtained: Run  No. of Samples No. of Samples Avg. Char Length No.  Tested       Burning      (in.) ______________________________________ G    17           0            2.0 H    19           0            1.9 I     3           0            1.6 J    10           0            2.3 K     6           0            1.9 ______________________________________

Each of the fabrics in both Example II and III were sampled approximately every 1,000 yards with five specimens tested for each sample.

A significant difference was observed in the formaldehyde odor apparent from the batched rolls of Examples I, II, and III. The batched rolls of Example I had an intensive odor, Example II had a significantly reduced odor, and Example III had such a reduced odor as to be not readily apparent.

A precondensate reaction product was prepared by refluxing 1,000 grams of tetrakis(hydroxymethyl) phosphonium chloride and 125 grams of urea in 545 grams of water. The reaction product was thereafter diluted with water to form an aqueous bath containing 36% tetrakis(hydroxymethyl) phosphonium cation concentration.

Cotton flannel material was immersed in the aforesaid aqueous bath and thereafter passed through squeeze rolls to give a wet pickup of about 110 percent. The so impregnated material was oven dried at about 200.degree. F. for a time sufficient to dry the material to a moisture content of less than about b 1 percent and thereafter aerated by the process of Example II. Samples A-D were prepared from the dried and aerated material and subjected to gaseous ammonia cure. Each of the samples were exposed to an atmosphere containing 90 percent by volume ammonia and 10 percent by volume air for varying time periods in an enclosed chamber. In addition, Sample D was also sprayed with water and further exposed to a 90 percent by volume gaseous ammonia atmosphere, all occuring within the enclosed chamber. Each of the samples were subjected to the usual oxidation, washing and drying steps and therafter tested according to Federal Regulation FF-3-71. After 50 home washings and 50 tumble dryings the results were as follows: Exposure           Additional      Char to         Water   Exposure  Resin Length Sample NH.sub.3 (Sec.) Spray   to NH.sub.3 (Sec.) Add-on (in.) ______________________________________ A      9         None    --        19.0  Burn B     18         None    --        19.1  Burn C     36         None    --        21.4  Burn D      9         Yes     3         26.7  1.8 ______________________________________

As can be seen from the aforesaid, Sample D, wherein the material was water sprayed and re-exposed to an ammonia atmosphere, showed an increase in resin add-on and an increased resistance in flammability.

An aquoeus bath was prepared by diluting tetrakis(hydroxymethyl) phosphonium sulfate with sufficient water to provide a tetrakis(hydroxymethyl) phosphonium cation concentration of 36 percent and thereafter neutralizing with sodium hydroxide to a pH of 7.5.

Cotton flannel material was immersed in the aqueous bath, squeezed dried and aerated by the method of Example IV. Samples A and B were prepared and each was exposed to an atmosphere containing 90 percent by volume ammonia and 10 percent by volume air in an enclosed chamber. Sample A was exposed to the ammonia atmosphere for 10 seconds and thereafter subjected to the usual oxidation, washing and drying steps. Sample B was exposed to the ammonia atmosphere for 7 seconds, then water sprayed and re-exposed to the same ammonia atmosphere for 3 seconds in an enclosed chamber. Sample B was thereafter subjected to the usual oxidation, washing and drying steps. After 50 home washings and 50 tumble dryings FF-3-71 results were as follows: Char Length Sample   % Resin Add-On  (in.) ______________________________________ A        17.9            Burn B        19.4            1.7 ______________________________________

A multi-yarn run of cotton flannel fabric was processed by passing it through an aqueous bath containing about 30% tetrakis(hydroxymethyl) phosphonium cation and having a pH of 7.2. The impregnated fabric was passed through squeeze rolls to a wet pickup of about 110 percent then into a 250.degree. F oven (residence time about 30 seconds) and dried to a moisture content of about 0.5%. The fabric was aerated and continually passed into an enclosed ammonia cabinet where it was exposed for about 8 seconds to an atmosphere consisting of about 85 percent by volume gaseous ammonia and 15 percent by volume of air. The fabric was then passed through a kiss roll, contacted with a doctor blade to remove excess water, and passed through a gaseous ammonia atmosphere as above described for about 2 seconds. Each of the aforesaid steps was accomplished within the enclosed ammonia cabinet. Upon exit from the ammonia cabinet, the material was batched in rolls and held for about twenty-four hours, then subjected to the usual oxidation, washing and drying steps. The fabric was tested according to Federal Regulation FF-3-71 and was found to be durably flame retardant as measured by that test.

A tetrakis(hydroxymethyl) phosphonium sulfate urea precondensate was prepared by refluxing 1200 gram of tetrakis (hydroxymethyl) phosphonium sulfate (86% solids), 500 grams of water and 75 grams of urea for 2 hours. The resulting solution was diluted with 1300 grams of water and 77 grams of sodium acetate was added thereto.

Cotton flannel material was immersed in the aforesaid aqueous bath then passed through squeeze rolls to a wet pickup of about 105%. The so impregnated material was oven dried at about 200.degree. F. for a time sufficient to dry the material to a moisture content of about 3-5% and thereafter aerated by the process of Example II. The material was exposed to an atmosphere containing 80 percent by volume ammonia and 20 percent by volume air for 10 seconds, then passed directly into a second chamber, wherein it was immediately sprayed with water and thereafter exposed to an atmosphere containing about 40 percent by volume ammonia gas and 60 percent by volume air fo about 3 seconds. The material was then subjected to the usual oxidation, washing and drying steps. The resin add-on was found to be 23 percent and the fabric was durably flame retardant as measured by Federal Regulation FF-3-71.

The above process was repeated on a cotton flannel material with the exception that no second chmber was utilized and the material was not subjected to a spray and further exposure to gaseous ammonia. The final resin add-on was found to be 16 percent and the fabric burned initially and after testing under FF-3-71.

A pad bath was prepared containing 600 pounds of tetrakis (hydroxymethyl) phosphonium sulfate, 758 pounds of water and 105 pounds of a 50 percent aqueous sodium hydroxide solution.

A desized, scoured 8 oz. sateen material was impregnated with the above solution and squeezed to a wet pickup of about 60 percent. The material was dried at about 200.degree. F to a moisture content of about 5 percent and therafter aerated by the process of Example II. The material was then passed to an ammoniating chamber where it was exposed for about 20 seconds to an atmosphere containing 90 percent gaseous ammonia and 10 percent air, sprayed with water to a wet pick-up of about 40 percent then exposed to the atmosphere containing about 50 percent gaseous ammonia and 50 percent air for about 6 seconds. Each of these steps occured in the ammoniating chamber. The material was then subjected to the usual oxidation, washing and drying steps. The resin add-on was found to be 13 percent and the fabric was durably flame retardant as measured by Federal Regulation FF-3-71.

A desired, scoured and bleached, 5 oz. jean cloth was treated with the solution and process of Example VIII with the exception that wet-pick-up after impregnation was 95%. The final resin add-on was 22% and the jean cloth was found to be durably flame retardant as measured by Federal Regulation FF-3-71.

## Claims

1. A process for rendering cellulosic-containing materials durably flame retardant comprising: solution comprising poly(hydroxymethyl) phosphonium cation having a pH of from about 2 to about 9, and containing from about 10 to about 40 percent by weight of poly(hydroxymethyl) phosphonium cation; about 8 percent by weight; dried material for about 0.5 seconds or more; least about 5 seconds but less than about 60 seconds to an atmosphere containing at least about 50 percent by volume of gaseous ammonia to cure the phosphorus containing impregnant in and on the material; about 10 to about 40 percent by weight of water to render the material durably flame retardant; and about 10 seconds to an atmosphere containing at least about 50 percent by volume of gaseous ammonia.

2. The process of claim 1 wherein said water treatment step (e) occurs within the enclosed chamber of step (d).

3. The process of claim 1 wherein said ammonia atmosphere exposure step (f) occurs within the enclosed chamber of step (d).

4. The process of claim 1 wherein water treatment step (e) and ammonia atmosphere exposure step (f) occur within the enclosed chamber of step (d).

5. The process of claim 1 wherein water treatment step (e) and ammonia atmosphere exposure step (f) occur within a separate enclosed chamber from that of step (d).

6. The process of claim 1 wherein water is sprayed on the material in water treatment step (e).

7. The process of claim 1 wherein the material is passed through a trough of water in water treatment step (e).

8. The process of claim 7 wherein the material is squeezed after passing through said trough.

9. The process of claim 1 wherein the material is water treated by means of a kiss roll in water treatment step (e).

10. The proces of claim 9 wherein water pick-up is regulated by a doctor blade.

11. The process of claim 1 wherein said enclosed chamber comprises: portion of said housing above said gas outlet means;; said gas outlet means so as to form a gas treatment chamber in the upper portion of said housing, said partition means including means for permitting the introduction into or removal from said gas treatment chamber of textile material to be treated in said chamber while minimizing the passage of gas into and from said gas treatment chamber.

12. The process of claim 4 wherein said enclosed chamber comprises: portion of said housing above said gas outlet means; said gas outlet means so as to form a gas treatment chamber in the upper portion of said housing, said partition means including means for permitting the introduction into or removal from said gas treatment chamber of textile material to be treated in said chamber while minimizing the passage of gas into and from said gas treatment chamber; portion of said housing; gas outlet means; and material to be treated.

13. The process of claim 12 wherein said water application means is a spraying means.

14. The process of claim 12 wherein said water application means comprises a trough through which the material is passed.

15. The process of claim 12 wherein said water application means is a kiss roll.

16. The process of claim 1 wherein said cellulosic material is selected from the group consisting of cotton, rayon, paper, jute, ramie, wood, and mixtures and blends thereof.

17. The process of claim 16 wherein said cellulosic material is blended with proteinaceous fibers, synthetic fibers or mixtures thereof.

18. The process of claim 17 wherein said proteinaceous fiber is selected from the group consisting of wool, mohair, alpaca and mixtures thereof.

19. The process of claim 17 wherein said synthetic fiber is selected from the group consisting of polyester, nylon, acrylics, acetate and mixtures thereof.

20. The process of claim 1 wherein said poly(hydroxymethyl) phosphonium cation is prepared by reacting an aqueous solution of poly(hydroxymethyl) phosphonium salt with up to an equivalent quantity of a base.

21. The process of claim 10 wherein said poly(hydroxymethyl) phosphonium salt is selected from the group consisting of halides, sulfates, acetates, phosphates, carboxylates, oxalates, lactates, formates, sulfonates and mixtures thereof.

22. The process of claim 21 wherein said salt is tetrakis(hydroxymethyl) phosphonium sulfate.

23. The process of claim 1 wherein said flame retarding solution comprises a reaction product of a poly(hydroxymethyl) phosphonium cation with a nitrogen containing material selected from the group consisting of urea, guanidines, substituted ureas, melamines and the reaction product of the said nitrogen containing materials with aldehydes.

24. The process of claim 23 wherein said aldehyde is formaldehyde.

25. The process of claim 1 wherein said cellulosic containing material is a cotton/polyester blend.

26. The process of claim 4 wherein said enclosed chamber comprises a first zone wherein the aerated material is initially exposed to said gaseous ammonia atmosphere, a second zone wherein the exposed material is contacted with water and a third zone wherein the material is again contacted with gaseous ammonia.

27. The process of claim 1 wherein water treatment step (e) and ammonia exposure step (f) occur within separate chambers from the enclosed chamber of step (d).

28. The process of claim 5 wherein said separate enclosed chamber comprises a water treatment zone and a gaseous ammonia treatment zone.