US2971929A

US2971929A - Textile treatment with novel aqueous dispersions to achieve flame-resistant and water-repellant finishes

Info

Publication number: US2971929A
Application number: US586382A
Authority: US
Inventors: Nathaniel J Glade
Original assignee: American Cyanamid Co
Current assignee: Wyeth Holdings LLC
Priority date: 1956-05-22
Filing date: 1956-05-22
Publication date: 1961-02-14
Anticipated expiration: 1978-02-14

Description

United States Patent Cfilice 4 2,971,929 Patented Feb. 14, 1961 TEXTILE TREATNIENT WITH NOVEL AQUEOUS DISPERSIONS TO ACHIEVE FLARE-RESISTANT AND WATER-REPELLANI FINISHES Nathaniel J. Glade, Somerville, NJ., assignor to American Cyanamid Company, New York, N.Y., a corporation of Maine No Drawing. Filed May 22, 1956, Ser. No. 586,382

8 Claims. Cl. 260-41) The present invention relates to novel aqueous dispersions, their application to materials and the resulting fireresistant and water-repellent articles. These dispersions have particular application to textile materials containing cellulose fibers.

A wide variety of treatments have been proposed for imparting flame-resistant characteristics to various combustible materials and many others have been suggested for the purpose of rendering porous textile materials water repellent while still retaining a considerable degree of porosity. Although substantial advances have been made, these agents leave much to be desired particularly in maintaining the effectiveness of finish when subjected to dry cleaning or laundering, especially where a harsh alkaline Wash is employed. Cloth treated with many of the so-called permanent or durable finishes must be retreated after a very limited amount of washing or dry cleaning. Further, many of the fire-retardant and waterrepellent compositions are not compatible when with one another and even it compatible, greatly reduce or destroy the effect of the other agent in a combination. Some of the prior art materials must be applied in solution in an expensive or hazardous organic solvent and some release obnoxious or highly poisonous gases while being dried or cured on a textile material. Many combination treatments are complicated by the necessity of using two more treating baths. Accordingly, there is a continuing demand for better flame-retardant and water-repellent finishes for textiles and especially those which can be applied by means of a single aqueous dis persion to provide a finish durable to repeated washing or dry cleaning or both.

An object of the invention is to provide improved compositions for imparting fire-retardant and water-repellent effects.

Another object of the invention is to provide improved durable flame-retardant water-repellent agents for textile materials of a combustible and porous nature. a

A further object of the invention is to provide an improved composition for imparting a flame-retardant water- ;iepellent finish to textile fabrics containing cellulose bers.

Still another object of the invention is to provide an improved method for imparting a flame-resistant waterrepellent finish which is durable to laundering or dry cleaning.

A still further object of the invention is to provide flame-resistant water-repellent textile fabrics containing cellulose fibers which retain their desired characteristics after washing or dry cleaning.

Other objects and advantages of the invention will be apparent to those skilled in the art, especially upon consideration of the detailed disclosure hereinbelow.

The present invention concerns compositions of matter which comprise an aqueous dispersion of an aminotriazine-aldehyde resin; a wax-like compound with a melting point above about 100 F. which contains one or more hydroxylated aliphatic acyl groups of at least 12 carbon atoms; a hydrophilic protective colloid; a dispersing agent of the group consisting of an aliphatic chain of at least 8 carbon atoms, sulfonated lignin, condensation products of polyalkylene polyamines with fatty acids containing at least 8 carbon atoms, dialkyl alkylol alkylamide quaternary ammonium salts and water-dispersible reaction prod ucts of an aliphatic amine containing at least 12 carbon atoms with epichlorohydrin; and an aliphatic phosphoramidate containing from 1 to 6 carbon atoms and having the structural formula:

X/ NHRz wherein R is an alkyl, alkoxyalkyl or halogenated alkyl radical having from 1 to 4 carbon atoms, R is hydrogen or an alkyl radical having from 1 to 4 carbon atoms, and X is OR or NHR The application of these dispersions to materials containing cellulosic fibers and the resulting treated articles are also a part of the invention. Narrower aspects involve the addition of waxes, the incorporation of a long chain fatty alcohol, the preferred constituents and the proportions of the various components.

The resin employed in the novel compositions may be any aminotriazine-aldehyde condensate or mixture of such compounds which is capable of forming either a true solution in water or a colloidal solution exhibiting the characteristic Tyndall haze. These condensates may be either etherified or alkylated with a suitable alcohol, like methanol, or simple unetherified condensates of an aldehyde and an aminotriazine. A wide variety of the unalkylated and alkylated aminotriazine-aldehyde condensates and their preparation are disclosed in Widmer et al. Patents Nos. 2,197,357 and 2,191,362; and hence need not be reiterated here. The triaminoand diaminotriazine derivatives are most readily available, especially melamine and the guanamines such as acetoguanamine and propioguanamine. Of these, the methyl ethers of methylol melamines are greatly preferred as providing outstanding results; and such ethers may contain from 1 to 6 mols of combined formaldehyde and 1 to 6 mols of combined methanol per mol of melamine. The combined methanol content does, of course, not exceed the combined formaldehyde content on a molar basis. For each parts total of the waxy materials described hereinafter, between about 50 and about 1,000 parts of the aminotriazine resin may be employed and the preferred amount is between about 100 and about 600 parts. The aminotriazine-aldehyde condensate may be employed either in essentially monomeric form or in the partially polymerized colloidal state in acid solution as described in Patents Nos. 2,345,543 and 2,609,307. Textile finishing resins of the urea-formaldehyde type are compatible or decrease in the durability or spray rating of textile fabrics finished according to the present invention. Among the suitable agents for decreasing yellowing are essentially monomeric methylated methylol ureas and their water-soluble lower polymers, and the unalkylated and alkylated formaldehyde condensates of alkylene ureas like dimethylol ethylene urea, dimethylol propylene urea, dimethylol trimethylene urea, and their methyl ethers,

These substances and their preparation are well understood and they may contain from 1 to 4 mols of combined formaldehyde per mol of urea or urea derivative as well as a combined methanol content ranging from about up to but not exceeding the formaldehyde content on a molar basis. The water-soluble lower polymers of methylated methylol urea may be easily obtained by refluxing with heating about 2.5 mols of paraformaldehyde per mol of urea in a methanol medium for several hours at an alkaline pH, cooling, adding methanol in stoichiometric excess, adjusting the mixture to a moderately acid pH, refluxing for a short period, then stopping the reaction by cooling and adjusting the pH to a moderately alkaline value. These substance may be employed in quantities ranging up to but not exceeding the weight of aminotriazine resin, and it is generally recommended that at least about 6 and preferably about to 100% (based on the weight of aminotriazine resin) be used when chlorine retention is a significant problem. For producing a water-repellent effeet on porous materials like cloth, leather, etc., it is seldom desirable to have more than a total of 600 parts oi the urea derivative and aminotriazine-aldehyde condensate in a dispersion containing 100 parts of waxy material or materials.

The hydrophobic component of the novel oil-in-water dispersions is, of course, in the dispersed phase. This water-insoluble wax-like material contains a compound with a melting point above 100 F. and preferably above 150 F. which has a hydroxy-lated saturated fatty acyl radical of at least 12 carbon atoms and preferably between 16 and 30 carbon atoms. in these substances, one or more hydroxy ,roups are attached to one or more carbon atoms in the alkyl chain other than the acyl or carboxylic carbon atoms. Thus this component may be a hydroxylated saturated higher fatty acid or an ester thereof with a monohydric or polyhydric alcohol including glycerol. Among the suitable compounds are hydrogenated castor oil'which appears to produce the optimum results, hydrogenated ricinoleic monoand di-glycerides, 9,10-dihydroxystearic acid, methyl, butyl, cetyl and other alkyl esters of hydrogenated ricinoleic acid, laury19,l0-dihydroxy stearate, and mixtures thereof.

A certain percentage of one or more hydrocarbon or ester waxes melting above about 100 F. may be blended with the hydroxylated waxy material with excellent results. In the hydrocarbon category are included various grades of parafiin, ozokerite, scale wax, micro-crystalline waxes, and so forth. A few examples of suitable ester waxes of natural or synthetic origin are carnanba, Japan, montan, candelilla, beeswax and other insect waxes. Refined paraffin wax is preferred when the dispersion is intended for the treatment of light colored textiles and grades melting above about 120 F. are recommended for best results. Mineral waxes are cheaper than hydroxylated fatty acyl compounds; hence, a blend of the two reduces the 'cost of the textile treatment. In addition, it has been found that within proper limits a hydrocarbon wax actually enhances the water-repellent characteristics of the textile finish and somewhat improves its durability to dry cleaning and laundering. Blends of equal parts of the two waxy materials seem to appear to be the optimum. However, the hydrocarbon or ester wax may desirably constitute from about 5 up to about 80% of the weight of the hydrophobic component; beyond that, the dry cleaning durability of the textile finish suflers.

The treating agent also contains a small quantity of one or more hydrophilic protective colloids which serve to stabilize the suspension or dispersion. Polyvinyl alcohol appears to provide the best results and the lower viscosity grades are especially recommended; however, a variety of other materials can be used including carboxymethyl cellulosle, gum ghatti, gum arabic, gelatin, polyacrylamide, polymethylolacrylamide, polymethacrylamide, polymethylolmethacrylamide, and the like. in general,

any hydroph lic protective colloid that ee of rewetting tendencies after drying is suitable in the present invention. Based on the total weight of waxy ingredients, the protective colloids are desirably present in quantities ranging from about basis.

A higher fatty alcohol containing from about 12 up to 30 or more carbon atoms is an optional but often highly desirable component of the mixture, especially where a hydrocarbon wax is present. This alcohol is thought to act as a coupling agent which improves the miscibility of the hydroxylated waxy material and the mineral wax. More importantly, it is a stabilizer which provides long shelf life for the wax dispersion. This obviates any necessity for preparing the wax dispersion at the place it is to be used, a feature which is often important inasmuch as textile finishing plants, etc. are seldom equipped with good emulsification equipment such as homogenizers. Thus it iLpossible to sell the ingredients for preparing the novel dispersions as three items as having a prolonged storage life, namely a resin component, an alkyl phosphoramidate and an aqueous dispersion of the waxy material. In addition, it a pears that the fatty alcohol facilitates the preparation Oi wax dispersions on a large scale and it is well known that large quantities of wax emulsions are often less stable than smaller laboratory batches. Cetyl alco' hol is prefe red for the purpose but one or more other saturated and unsaturated fatty alcohols may be employed, including lauryl, myristyl, stearyl, palmitoleyl, cetoleyl alcohols and the like may be substituted, if desired. The

recommended quantities are from about 1 to 6 parts for each parts of total waxy components.

Many emulsifiers or dispersing agents are unsuitable for the present compositions by reason of incompatibility, a tendency toward rewetting after drying, etc. However, certain classes of wetting or dispersing agents have been discovered which produce good results when one or more are present. Among these are sulfonated or suliated higher fatty acids, alcohols and esters containing an aliphatic chain of at least 8 but seldom over about 30 carbon atoms. Sulfated fatty alcohols are preferred for the purand expression is used herein'to include the alkali metal salts, usually sodium or potassium salts, of such materials since this is the form in which they are commonly available in the market. The many suitable materials encompass esters which term is used herein to include the esters of polyhydrio alcohols such as ethylene glycol, giycerine, etc., as well as monoh-ydric alcohols. Moreover, the aliphatic chains of these materials may be either saturated or unsaturated prior to the sulfonation or sulfation treatment. Among those suitable are caprylyl, capryl, lauryl, myristyl, cetyl and stearyl alcohol sulfates, sulfonated ricinoleyl alcohol, etc., and their alkali salts; methyl, butyl and other alkyl esters of the aforementioned alcohols; sulfated capyrylic, lauric, palmitic, stearic, oleic, linoleic, and linolenic acids as well as sulfonated ricinoleic acid and the corresponding mono, diand triglyceride derivates. For example, good results are also obtainable with sodium glyceryl monolaurate sulfate and sulfonated castor oil. Sodium lignin sulfonate has been used with success. Also polyalkylene polyamine condensates of higher fatty acids like the products of reacting diethylene triamine, hexamethylene tetramine, tetraethylene pentamine, hexaethylene septamine and the like with from about 10% up to a full stoichiometric proportion of a long chain fatty acid (8 to 30 carbon atoms) such as capric, lauric, and stearic acids, frequently accompanied by a lower aliphatic acid such asformic or propionic acid in minor proportion; dialkylalkylol alltylamide quaternary ammonium salts as exemplified by palmitamidoethyl diethyl gamma-hydroxypropyl ammonium chloride, and similar compounds containing two lower alkyl groups of about 1 to 4 carbon atoms, a 1 to 4 carbon alkylol radical, a halogen atom and a radical containing a higher alkylamide 0.5 to about 20% or more on a dry of about 8 to 30 carbons combined with a l to 4 carbon alkyl group; aridithe. water-dispersible reaction products of long chain aliphatic amines containing from 8 to about 22 carbon atoms, like dodecylamine and eicosylamine, with epichlorohydrin can be employed for the purpose. Suitable amine-epichlorohydrin reaction products and their preparation are disclosed in detail in Lundberg application Serial No. 393,246, filed November 19, 1953 (Patent No. 2,753,372) and these may be neutralized with acetic or another lower carboxylic acid for greater stability. The amine-epichlorohydrin molar ratios may range from about 1:2 to 2:1 and this particular group of compounds is preferred for use under acid conditions, as for instance, where the resinous component is in the acid colloid form. Based on the total weight of waxy materials, the dispersing agents described may be present in amounts ranging from about 0.5 to 15%, and for most purposes, between about 1 and about 4% is recommended. A sufficient quantity of the agent should be employed to uniformly disperse the hydrophobic matter throughout the water but large excesses are undesirable and may have a rewetting effect that impairs the water-repellent characteristics of the finish.

To make the stable dispersion mentioned above of the waxlike substances, the hydroxylated waxy material may be melted and thoroughly blended with any hydrocarbon wax or fatty alcohol which may be added at a temperature of 235 F. for example. Meanwhile, the protective colloid may be stirred into about 70 parts by weight of water with heating until it is dissolved; then the dispersing agent may be added and the aqueous phase heated to about 180 F.195 F. Next, about 30 parts of the molten waxy mixture may be combined with the aqueous phase with vigorous agitation followed by passing the crude emulsion through a homogenizer at 3,000 lbs. per square inch.

After this, the suspension of wax-like material is cooled rapidly to a temperature below about 120 F.

In formulating the novel compositions, the alkyl phosphoramidate may be dissolved in water and then the resin is introduced with thorough mixing either in solid form or more usually as a concentrated aqueous solution or dispersion. Then a stable dispersion or suspension of the hydrophobic or wax-like compound or compounds is added with constant agitation to form a homogenous milky emulsion or dispersion with ample stability for textile operations.

The novel compositions maybe used in a variety of applications in the textile, leather, paper, pulp board and carton fields. They are'especially intended for rendering porous combustible materials containing a substantial amount of cellulose fibers both water-repellent and fireresistant. This is accomplished by impregnating the cellulose material with the aqueous dispersion followed by drying and curing to convert the aminotriazine-aldehyde condensate to the substantially water-insoluble state. This curing is accomplished in about 2 to about 15 minutes at elevated temperatures of preferably about 200 to 350 F. or even higher if smoking due to vaporizing a portion of the waxy matter from the impregnated material during curing is not objectionable. In compositions containing a colloidal or partially polymerized aminotriazine resin,

heating is not required to cure the resin but is usually preferred to expedite commercial operations.

The present compositions are particularly adaptable to the finishing of textile fabrics including woven and nonwoven, knitted and felted materials containing cellulose fibers like cotton, linen, flax, viscose and cuprammonium rayons, ramie, jute, and blends thereof. Such treatments are also applicable to blends of any of the aforesaid fibers with any other of the great variety of known textile fibers, but it should be borne in mind that only cellulose fibers are rendered flame retardant by the present treatment; hence, the treatment is effective from a standpoint of flame resistance only to an extent commensurate with the proportion of total fibers in the fabric.

The dispersions may be applied to either fibers or tab rics by any suitable means such as padding, spraying, im-

mersion, roll coating, etc. A typical treatment involves passing a fabric through a dispersion containing from about 4 to about 60%, preferably between about 15 and about 40%, solids with the squeeze rolls adjusted to provide a dry pick up of between about 5 and about 60% solids, about 10 to about 40% being usually recommended, based on the weight of dry cellulose fibers; followed by curing as described above. For good durability of the finish, the dry pick up should amount to at least about 4% of the aminotriazine resin, a similar amount of the alkyl phosphoramidate and at least about 2% of the wax-like component. However, it is also contemplated that the invention may find utility in connection with a lighter deposit on childrens dolls and other toys and accessories. Such a finish would not possess the durability desired herein for most purposes, but nevertheless adequate in the case of materials which are seldom, if ever, washed. It is contemplated that the light treatment would be very desirable for reducing the flammability of highly combustible cottons having a long nap without changing the hand of the material an unacceptable degree.

The lower aliphatic phosphoramidates (which expression is used herein to include the compounds containing monoamide and diamide groups either substituted or unsubstituted) useful in the present invention are set forth in the general formula above. They may be dialkyl phosphoramidates, monoalkyl phosphordiamidates, or the designated substituted alkyl and substituted amide compounds used either alone or in admixture. To retain the desired water-solubility, these substances should contain from 1 to 6 carbon atoms per molecule, and the alkyl group attached to the oxygen atom or replacing one of the hydrogen atoms of an amido group should not exceed 4 carbon atoms. In addition, the organic radical attached to the oxygen atom or atoms may be a halogenated alkyl or an alkoxyalkyl radical containing up to 4 carbon atoms. Suitable compounds include, inter alia, dimethyl phosphora-midate, diethyl phosphoramidate, di-n-propyl phosphoramidate, methyl ethyl phosphoramidate, methyl isopropyl phosphoramidate, .ethyl propyl phosphoramidate, primary, secondary and isobutyl ethyl phosphoramidates, methyl bromoethyl phosphoramidate, chloroethyl bromobutyl phosphoramidate, dimethyl N-ethyl phosphoramidate, diethyl N-butyl phosphoramidate, di-Z- bromoethyl N-isopropyl phosphoramidate and the like as monoamides and Z-methoxyethyl phosphordiamidate, methyl bis-(methylamido)-phosphate, methyl N-sec-butyl phosphordiamidate, methyl N-ethyl-N-isopropyl. phosphordiamidate, ethyl bis(ethylamido) phosphate, 2- chloroethyl N-methyl-N-propyl phosphordiamidate, isopropyl N-methyl-N'-ethyl phosphordiamidate, n-butyl bis- (-methylamido)-phosphate, isobutyl N-ethyl phosphordiamidate, and the like as diamides as well as mixtures of the foregoing compounds.

These and other. suitable phosphoramidates Within the contemplation of this invention are employed within the range of between 25% and 200% of the weight of the aminotriazine-aldehyde resin.

Such compounds may be prepared in the manner described and claimed in Hechenbleikner application Serial No. 403,652, filed January 12, 1954, or according to the methods described in Kaiser et al. application Serial No. 403,653, filed January 12, 1954, which describes and claims aliphatic phosphoramidate. The products of those preparatory methods commonly contain a sufiicient amount of ammonium chloride and ammonium phosphate salts to serve as catalysts for curing the resin-containing mixtures. If desired, however, as for instance where purified phosphoramidates are present, a conventional curing catalyst for aminotriazine-aldehyde condensates may be utilized to expedite the curing operation. Suitable catalysts used in conventional amounts of 0.5% or more based on the resin include oxalic, tartaric or other mild organic acids; diammonium hydrogen phosphate and other I ammonium salts, and acid salts of organic amines such as isopropanolamine hydrochloride.

It is desirable in some instances to prepare an aliphatic phosphorarnidate which is substantially free of these am-v monium salts in order that this material may be mixed with an aminotriazine resin and sold as a combination having a long shelf life without precipitation as a concentrated or dilute aqueous solution. Such a combination reduces the formulating problems of the textile finisher. A relatively pure dialkyl phosphoramidate may be obtained by preparing and purifying the corresponding dialkyl hydrogen phosphite; then introducing either ammonia or the selected lower alkylamine until the mixture is saturated while maintaining the reaction temperature at approximately C. in the presence of a carbon tetrachloride-chloroform mixture as the inert reaction solvent. After filtering out the ammonium chloride and evaporating the solvent, a crystalline mass is obtained which may be purified by recrystallization from acetonitrile, chloroform or othersuitable solvent. However, it is contemplated -that no such purified compound will be required for many applications because the resin and the phosphorus compound maybe added separately to a pad bath at the textile finishing plant and the presence of residual ammonium salts in the alkyl phosphoramidate obviates the need for an additional curing catalyst.

The action of the various components in the new compositions is not fully understood. It appears that the phosphoramidate combines with the arninotriazine resin, possibly by splitting oii either Water or methanol while forming a methylene bridge between aminonitrogens on each of said compounds. Similarly, it is likely that the hydroxylated waxy compound is bound to the resin, perhaps by the reaction of a noncarboxylic hydroxyl group on the former with a hydroxy methyl or methylol radical of the resin with a splitting off of the water or methanol in What would be essentially a transesterification reaction. A single molecule of the resin-forming aminotriazine compound might be involved in both of the proposed reactions. Further, it may be postulated that during curing, such reaction products are linked to cellulosic materials by reaction of the resin with hydroxyl groups on the cellulose. These theories are merely oiiered as possible explanations for the outstanding durability or" the finishes imparted by the present invention to repeated laundering and dry cleaning operations inasmuch as the phosphoramidate and hydroxylated waxy material each display no tendency alone to become firmly attached to cellulose. Moreover, it has been noted that the addition of the phosphoramidate increases the permanency of the waterrepellent characteristics of the articles of the present invention and the presence of the waxy component has the strange eiiect of increasing the durability of the fireretardant eifect. However, the invention is not limited to the, above theories since they have not been established with certainty.

Many benefits result from the present invention in that a simple treatment in an aqueous vehicle with a single impregnating bath produces not only a finish which is both water repellent and flame resistant without any significant tendency toward afterglow but also one which remains efiective after repeated exposure to either dry cleaning solvents or harsh alkaline washes. During processing, no objectionable odors are created as is the case of one'wellknown fire-retardant agent. Nor is any significant foaming encountered as so frequently happens with otherwise good textile treating agents.

The effect of the combination of ingredients is surprising inasmuch as it might be anticipated that the alkyl phosphoramidate would certainly reduce the water repellency of the finish as a diluent or completely destroy it by reason of the water solubility of this constituent, but this does not occur. It could well be anticipated that the addition of hydroxylated fatty material and hydrocarbon waxes would serve as a. fuel which would minimize or eliminate the flame-resistant qualities of the finish, but this does not occur. Also it could easily be predicted that the addition of either of these components would greatly decrease the bonding of the other component through the resin, but each appears to actually supplement or enhance the bonding of the other component.

Textile fabrics, treated according to this invention, may be employed as tarpaulins, tents, boat covers, awnings, stage scenery, upholstery fabrics, slip covers, draperies, batting, insulation, padding, rope, string, twine and wearing apparel for welders, foundrymen, military personnel and the like, as Well as'fabrics for covering the wings and fuselages of airplanes. In the textile industry, and material of appreciable cellulose fiber content (e.g., 5% or more) including raw fibers, carded stock, rovings, threads, yarns and felts may be treated as well as the knitted, woven and unwoven fabrics which appear to provide the largest field of utility.

For a better understanding of the nature and objects of this invention, reference should be had to the following illustrative examples in which all proportions are stated in terms of weight unless otherwise indicated therein. In addition, all testing of fabrics is carried out by standard methods adopted by the American Association of Textile Chemists and 'Colorists unless otherwise stated.

Following the procedure outlined above, a series of aqueous wax dispersions is prepared from the following constituents.

Vvax Dispersions Refined paraflin wax Hydrogenated castor oiL Polyvinyl alcohol Gum ghatti Sodium lauryl sulfate- Sodium ligninsulfonate Cetyl alcohol Water A pad bath is prepared by dissolving in 595 parts of water 180 parts of an alkyl phosphoramidate mixture of the following composition:

7 Percent Diethyl phosphoramidate 62 Ethyl phosphordiamidate 25 Triethyl phosphate 6 Mixed ammonium salts (phosphates, etc.) 7

Next, 225 parts of methylated 'trimethylol melamine (67% methylated) of solids content is added with stirring until a clear solution results. T here is no evidence of a reaction between these two components. Finally, 200 parts of a wax dispersion A is introduced with stirring to produce a, homogeneous, milky emulsion of low viscosity. 7

White mercerized 5.5 ounce cotton poplin is padded through this bath using 2 dips and 2 nips under a pressure of 15 lbs. per square inch per inch of length of the squeeze rolls to obtain awet pick up of approximately The mixture was then dried and cured ina single operation for 6 minutes at 290 F. Charring tests with the fabric disposed vertically in a flame and water repellency tests are run and both are repeated after a dry cleaning operation on onesample and repeated washing tests on another following the standard procedure; of the American Associationofi Textile Chemists. andColorists.

(AATCC). The dry cleaning here is conducted for one hour in ethylene dichloride in a Launder-Ometer. Washing tests are performed with a solution of 0.1% soap and 0.1% sodium carbonate at 160 F. followed by rinsing for a total cycle of one hour. The fabrics are then dried. The results tabulated below show that a high degree of flame resistance in combination with an excellent spray rating are imparted to the fabric and that these effects are durable to both washing and dry cleaning.

Example 2 A pad bath is formulated from of the crude diethyl phosphoramidate, of the methylated trimethylol melamine, water and a suflicient amount of wax dispersion A to introduce-5% waxy solids. An 80 x 80 cotton percale is processed using this bath according to the procedure of Example 1 except that the squeeze rolls are adjusted for 100% expression or wet V 10 V 7 About one-third of these impurities are a mixture of the corresponding alkyl phosphates and various ammonium salts, principally phosphates, which serve to catalyze the curing of the synthetic resin and apparently do not afiect the flame retardant qualities of the final article either adversely or favorably. The remaining two-thirds of impurities are the corresponding diamidates in the case of monoamidates and monoamidates in cases where an alkly phosphorodiamidate is named. These so-called impurities contribute to the flame retardant efiect and may be calculated as part of the flame retardant component for all practical purposes. All samples of treated fabrics display finishes which possess excellent water repellency together with highresistance to flame propagation and afterglow; and these finishes are of a substantially permanent nature in that they possess good durability to harsh alkaline washes of the type described, as Well as to dry cleaning.

cording to the procedure of Example 2 using pad baths of the composition by weight listed below. The various alkyl phosphoramidates employed are crude materials containing up to about 45% impurities on a dry basis.

pick up. A greater number of washing and dry clean- E l 5 ing operations are performed in the same manner except 7 that Varsol H, a Stoddard solvent, is substituted for the Butyl phosphorodlamldate "1 10 ethylene dichloride. The substantially permanent nature Methylated pentamethylol melamme of the highly flame-retardant and water-repellent finish is 50% methylated 1"7 10 apparent from the test results tabulated hereinbelow. $22 sohds (Wax dlsperslon C) Example 3 25 Example 2 is repeated in all details except that wax Example 6 dispersion B is substituted for wax dispersion A on a Ethyl phosphorodiamidate -3 10 basis of equivalent solids, and the treated fabric is dried Methylated trimethylol melamine 15 at 225 F. for 5 minutes prior to curing at 340 F. for Waxy solids (wax dispersion D) 5 1.5 minutes. The test data closely approximate those Water 70 obtained in Example 2.

Example 4 Example 7 A pad bath containing 10% of the crude diethyl phos- Ethyl phosphorodiamidate 10 phoramidate, 16.5% of a heta-cyanopropioguanamine- Methylated trimethylol melamine 15 formaldehyde (123.8 molar ratio) resin and 5% by Waxy solids (wax dispersion E) 5 weight of waxy solids introduced as wax dispersion A is Water 70 used in treating a 5.5 ounce poplin by the procedure E l 8 detailed in Example 2. Again the durable finish im- 7 6 parted is highly repellent to water and resistant to the Diethyl phosphoramidate 10 propagation of flame. Methylated pentamethylol melamine- 50% methylated 15 I Comp anmve Examp [e1 Waxy solids (wax dispersion F) 5 Example 4 is repeated exactly except that the dispersed Wat 70 wax is omitted from the pad bath. By reference to the table immediately below, it is apparent that the finish is Example 9 no longer water repellent and that there is only a minor Beta-chloroethyl phosphordiamidate 5 improvement in flame resistance. The latter effect is Colloidal methylated trimethylol unexpected as it is more logical to presume that the melamine (resin solids) 5 incorporation of the fatty material and hydrocarbon wax Hydrogenated castor oil 2.50 of wax dispersion A in the treatment of Example 4 would Carnauba wax 2.50 greatly impair or totally destroy the flame-resistant char- Polyvinyl alcohol 0.22 acteristics of the flame-proofing agent. Cetyl alcohol 0.14

Vertical Flame Tests, Char Ht. Spray Ratings inIIl.

Example Alter Washing After After Washing After Dry Dry Cleaning Ipitial cl el ln Initial 1hr. 5hrs 1hr. 5hrs. 1hr. 5hrs.

4.1 4.0 (4. 5 3.9 100 100 (90) 100 3. s 3. a 3. 8 3. 6 1o 90 10 so 3.5 3.6 3.6 100 70+ so 70 s. 0 6. 6 6. 6 so 70 5.3 5.8 5.9 0

Values in parentheses relate to 3 rather than 5 wash cycles.

Reaction product of 1 'mol octadecylamine with Unless otherwise stated in Examples 5-18 below, 5.5 70 2 mols of' epichlorohydrin with 75% of the oz. mercerized cotton poplin and a heavy viscose rayon amino groups neutralized with acetic acid 0.19 upholstery fabric are impregnated, dried and cured acwater 34 45- The partially polymerized colloidal melamine resin above is introduced as a 10% aqueous solution exhibiting the characteristic blue Tyndall haze of cationic 11 water-dispersible melamine resin particles aged in acetic acid as described in Patent No. 2,609,307. The fabrics are dried and cured in 9 minutes in a ventilated oven maintained at 225 F. 7

Example 10 Diisopropyl phosphoramidate 10.00. Methylated pentamethylol melamine- 50% methylated 10.00 Hydrogenated castor oil 2.50 Candelilla wax 2.50 Polyvinyl alcohol 0.22 Cetyl alcohol 0.16 Sodium lauryl sulfate 0.09 Water 74.53

Example 11 Methyl phosp-hordiamidate 15.00 Methylated pentamethylol melamine- 50% methylated 15.00 Hydrogenated castor oil 2.50 Beeswax 2.50 Polyvinyl alcohol 0.22 Cetyl alcohol 0.16 Stearamidopropyl dimethyl beta-hydroxyethyl ammonium chloride 0.09 Water 64.53

Example 12 Propyl phosphordiarnidate 5.00 Dimethylol melamine 10.00 Hydrogenated castor oil 2.50 Refined paraifin wax 2.50 Polyvinyl alcohol 0.23 Reaction product of 2.9 mols of technical stearic acid per mol of tetraethylenepentamine plus 1.5% acetic acid 0.56 Water 79.21

Example 13 'Diethyl phosphoramidate 5.00 Methylated trimethylol melamine 10.00 9,10-dihydroxy stearic acid 2.50 Refined paraflin wax 2.50 Polyvinyl alcohol 0.22 Cetyl alcohol 0.16 Sodium lauryl sulfate 0.09 Water 79.53

Example 14 Diethyl phosphoramidate 10.00 Acetoguanamine-formaldehyde (1:2 molar ratio) resin 15.00 Hydrogenated castor oil 2.50 Refined paraffin wax 2.50 Polyvinyl alcohol 0.22 Cetyl alcohol 0.14 Acetic acid neutralized reaction product of 1 mol of octadecylamine with 1.4 mols of epichlorohydrin 0.09 Phosphoric acid 0.02 Water 69.53

In addition to the effects noted above, the fabrics treated with the formulations of Examples 15-18 below have finishes with a low degree of chlorine retention. That is, after the material is exposed to chlorine-containing bleaches such as sodium .hypochlorite, it does not tend to yellow and there is no significant decrease in tensile strength in the scorch test in comparison with an impregnated but unbleached control sample.

12 Example 15 Diethyl phosphoramidate 8.00 Methylated pentamethylol melamine-50% methmethylated 7.50 Partially polymerized. methylated dimethylol urea'--80%'methylated 2.50 Hydrogenated castor oil 3.15 Refined parafiin wax 3.15 Polyvinyl alcohol 0.28 Cetyl alcohol 0.20 Sulfonated castor oil 0.11 Water 75.11

Example 16 Diethyl phosphoramidate 5.00 Methylated trimethylol melamine67% methylated 6.00 Dimethylol ethylene urea 3.00 Hydrogenated castor oil 2.50 Refined paraffin wax (M.P. 133-135 F.) 2.50 Gum ghatti 0.27 Sodium ligninsulfonate 0.16 Water 80.57

Example 17 Diethyl phosphoramidate 5.00 Methylated trimethylol melamine-67% methylated 10.00 Methylated dimethylol trimethylene urea 5.00 Hydrogenated castor oil 5.00 Polyacrylarnide 0.22 Sodium ligninsulfonate 0.16 Water 74.62

Example 18 Diethyl phosphoramidate 5.00 Methylated trimethylol melamine67% methylated 6.00 Monomeric methylated dimethylol urea-% methylated 3.00 Hydrogen-ated castor oil 2.50 Montan wax 2.50 Carboxymethyl cellulose 0.22 Sodium ligninsulfonate 0.16 Water 80.62

Glade et a1. application Serial No. 403,65l, filed January 12, 1954, now Patent No. 2,828,226, relates to flame-retarding treatments without water-repellent qualities and my concurrently filed application Serial No..

stated therein or required by the prior art.

I claim:

1. A composition of matter which comprises an aqueous dispersion of (1) between about 50 and 1000 parts by weight of a resinous component selected from the group consisting of water-solution aminotriazine-aldeh'yde resins and aqueous colloidal aminotriazine-aldehyde resins and mixtures of said aminotriazine-aldehyde resins with a water-soluble textile finishing agent selected from the group consisting of methylated methylol urea, methylol alkylene urea and methylated methylol alkylene urea containing between about 6 and about of said textile finishing agent based on the weight of said aminotriazine-aldehyde resin; (2.) 100 parts of a hydrophobic 13 component selected from the group consisting of a waxlike compound melting above 100 F. containing an bydroxylated aliphatic acyl radical of between about 12 and about 30 carbon atoms and a composition comprising such a wax-like compound and a wax melting above 100 F., said wax in such compositions not being present in an amount exceeding about four times the weight of said wax-like compound; (3) between about 0.5 and about 20 parts of a hydrophilic protective colloid free from rewetting tendencies after drying; (4) between about 0.5 and about 15 parts of an emulsifying agent of the group consisting of sulfonated fatty acids, alcohols and esters containing an aliphatic chain of between 8 and about 30 carbon atoms, sulfonated lignin, condensation products of polyalkylene polyamines with fatty acids containing between 8 and about 30 carbon atoms, dialkyl alkylol alkylamide quaternary ammonium salts and Waterdispersible reaction products of an aliphatic amine containing from 8 to about 22 carbon atoms with epichlorohydrin and (5) an aliphatic phosphoramidate containing from 1 to 6 carbon atoms and having the structural formula:

X \NHRZ wherein R is selected from the group consisting of alkyl, alkoxyalkyl halogenated alkyl radical having from 1 to 4 carbon atoms, R is selected from the group consisting of hydrogen and an alkyl radical having from 1 to 4 carbon atoms, and X is selected from the group consisting of OR and NHR in a quantity equal to between about 25 and about 200% of the weight of the aminotriazine-aldehyde resin.

2. A composition according to claim 1 containing from between about 1 and about 6 parts of a monohydroxy aliphatic alcohol having between about 12 and about 30 carbon atoms.

3. A composition of matter which comprises an aqueous dispersion of 1) between about 100 and 600 parts of a water-soluble methylated methylol melamine; (2) 100 parts of hydrogenated castor oil melting above 100 F.; (3) between about 0.5 and 20 parts of polyvinyl alcohol, between 0.5 and about 15 parts of a sulfated fatty alcohol containing between 8 and about 30 carbon atoms and between about 25 and about 200% based on the weight of the melamine formaldehyde resin of an aliphatic phosphoramidate containing 1 to 6 carbon atoms and having the structural formula:

X NHR wherein R is selected from the group consisting of alkyl, alkoxyalkyl and halogenated alkyl radical having from 1 to 4 carbon atoms, R is selected from the group consisting of hydrogen and an alkyl radical having from 1 to 4 carbon atoms, and X is selected from the group consisting of --OR and -NHR 4. A composition of matter which comprises 1) between about 53 and about 1000 parts by weight of a mixture comprising a minor portion of a. substance of the group consisting of water-soluble methylated methylol urea, methylol alkylene urea and methylated methylol alkylene urea, together with a major proportion amounting to at least 50 parts of a water-soluble methylated methylol melamine; (2) parts of a wax-like substance comprising paraflin wax melting above 100 F. and hydrogenated castor oil meltingabove 100 F. in a weight ratio not exceeding 4:1, said paraffin wax to said hydrogenated castor oil respectively; (3) between about 0.5 and about 20 parts of a hydrophilic protective colloid free from rewetting tendencies; (4) between about 1 and about 6 parts of an aliphatic alcohol containing etween 12 and about 30 carbon atoms; (5) between about 1 and about 4 parts of a sulfated fatty alcohol containing between 8 and about 30 carbon atoms and a quantity of a diethyl phosphoramidate equal to between about 25 and about 200% of the weight of the methylated methylol melamine.

5. A process which comprises treating a material containing cellulose fibers with a composition according to claim 1 and heating the treated material to impart a fire-retardant, water-repellent finish.

6. A process which comprises treating a textile material containing cellulose fibers with a composition accord-- ing to claim 3 in sufiicient amount to deposit thereon at least about 4 percent of methylated methylol melamine, at least about 2 percent of the wax-like substances and at least about 4 percent of diethyl phosphoramidate based on the weight of dry cellulose fibers; heating the treated material to impart a durable fire-retardant water-repellent finish.

7. An article which comprises a material containing cellulose fibers having as a durable fire-retardant waterrepellent finish the heat cured reaction product of a composition according to claim 1.

8. An article which comprises a textile material containing cellulose fibers having as a durable fire-retardant water-repellent finish the heat cured reaction product of a composition according to claim 3 containing at least about 4 percent methylated methylol melamine, at least about 2 percent of the wax-like substances and at least about 4 percent of diethyl phosphoramidate relative to the weight of dry cellulose fibers.

References Cited in the file of this patent UNITED STATES PATENTS 2,191,362 Widmer et al Feb. 20, 1940 2,357,273 Thurston Aug. 29, 1944 2,426,770 Grim Sept. 2, 1947 2,536,978 Fordemwalt Jan. 2, 1951 2,537,667 Harris Jan. 9, 1951 2,702,283 Wilson et al Feb. 15, 1955 2,828,228 Glade et al Mar. 25, 1958 2,835,639 Widmer et al May 20, 1958 FOREIGN PATENTS 729,966 France Aug. 4, 1932 OTHER REFERENCES Bennett: Commercial Waxes, p. 91; 113, Chem. Pub. 00., Brooklyn, N.Y. (1944).

UNITED STATES PATENT OFFICE CERTIFICATIQN 0F CORRECTION Patent No. 2,971,929 February 14, 1961 Nathaniel J. Glade It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Columns 9 and 10, in the table, second column thereof, in the heading, for ".Ipitial" read Initial column 12, line 67, for "solution" read soluble Signed and sealed this 8th day of August 1961'.

(SEAL) Attcst:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents

Claims

1. A COMPOSITION OF MATTER WHICH COMPRISES AN AQUEOUS DISPERSION OF (1) BETWEEN ABOUT 50 AND 1000 PARTS BY WEIGHT OF A RESINOUS COMPONENT SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUTION AMINOTRIAZINE-ALDEHYDE RESINS AND AQUEOUS COLLOIDAL AMINOTRIAZINE-ALDEHYDE RESINS AND MIXTURES OF SAID AMINOTRIAZINE-ALDEHYDE RESINS WITH A WATER-SOLUBLE TEXTILE FINISHING AGENT SELECTED FROM THE GROUP CONSISTING OF METHYLATED METHYLOL UREA, METHYLOL ALKYLENE UREA AND METHYLATED METHYLOL ALKYLENE UREA CONTAINING BETWEEN ABOUT 6 AND ABOUT 100% OF SAID TEXTILE FINISHING AGENT BASED ON THE WEIGHT OF SAID AMINOTRIAZINE-ALDEHYDE RESIN, (2) 100 PARTS OF A HYDROPHOBIC COMPONENT SELECTED FROM THE GROUP CONSISTING OF A WAXLIKE COMPOUND MELTING ABOVE 100*F. CONTAINING AN HYDROXYLATED ALIPHATIC ACYL RADICAL OF BETWEEN ABOUT 12 AND ABOUT 30 CARBON ATOMS AND A COMPOSITION COMPRISING SUCH A WAX-LIKE COMPOUND AND A WAX MELTING ABOVE 100* F., SAID WAX IN SUCH COMPOSITIONS NOT BEING PRESENT IN AN AMOUNT EXCEEDING ABOUT FOUR TIMES THE WEIGHT OF SAID WAX-LIKE COMPOUND, (3) BETWEEN ABOUT 0.5 AND ABOUT 20 PARTS OF A HYDROPHILIC PROTECTIVE COLLOID FREE FROM REWETTING TENDENCIES AFTER DRYING, (4) BETWEEN ABOUT 0.5 AND ABOUT 15 PARTS OF AN EMULSIFYING AGENT OF THE GROUP CONSISTING OF SULFONATED FATTY ACIDS, ALCOHOLS AND ESTERS CONTAINING AN ALIPHATIC CHAIN OF BETWEEN 8 AND ABOUT 30 CARBON ATOMS, SULFONATED LIGNIN, CONDENSATION PRODUCTS OF POLYALKYLENE POLYAMINES WITH FATTY ACIDS CONTAINING BETWEEN 8 AND ABOUT 30 CARBON ATOMS, DIALKYL ALKYLOL ALKYLAMIDE REACTION AMMONIUM SALTS AND WATERDISPERSIBLE REACTION PRODUCTS OF AN ALIPHATIC AMINE CONTAINING FROM 8 TO ABOUT 22 CARBON ATOMS WITH EPICHLOROHYDRIN AND (5) AN ALIPHATIC PHOSPHORAMIDATE CONTAINING FROM 1 TO 6 CARBON ATOMS AND HAVING THE STRUCTURAL FORMULA: