US3859124A

US3859124A - Durable fire retardant textile materials by anhydrous solvent finishing process

Info

Publication number: US3859124A
Authority: US
Inventors: James M Thompson
Original assignee: Proctor Chemical Co Inc
Current assignee: Proctor Chemical Co Inc
Priority date: 1972-09-25
Filing date: 1972-09-25
Publication date: 1975-01-07
Anticipated expiration: 1992-01-07

Abstract

Anhydrous solvent finishing processes to impart durable fire retardant properties to textile materials, e.g., flat goods or finished garments, made of cellulosic fiber, polyester fiber or fiber blends of such fibers with other fibers, involve (a) impregnating textile material with an anhydrous mixture of trispolyhaloalkyl phosphate, nitrogenous film forming binder resin, organic solvent and organic aminoplast cross-linking catalyst, (b) removing solvent, and (c) heat curing at about 120* to 200*C. The anhydrous organic solvent mixture may include soluble creaseproofing agents so that the resulting fabric acquires both durable press and fire retardant properties.

Description

United States Patent 1191 Thompson 1 1 Jan. 7, 1975 [54] DURABLE FIRE RETARDANT TEXTILE 3,746,572 7/1973 Wei] et al. 117/136 MATERIALS BY ANHYDROUS SOLVENT FOREIGN PATENTS OR APPLICATIONS FINISHING PROCESS 747,014 3/1956 Great Britain 117/136 [75] Inventor: James M, Thompson, Sali b 1,204,163 9/1970 Great Britain NC" 1,241,926 8/1971 Great Britain 117/1394 [73] Assignee: Proctor Chemical Company, Inc., OTHER PUBLICATIONS Salisbury, NC. Chemical Abstracts" by American Chemical Society Volume 47, Number 13, July 10, 1953, pages [22] F1led. Sept. 25, 1972 7230:7231 [21] App]. No.: 292,145

Primary Examiner-William D. Martin Assistant Examiner-Theodore G. Davis 117/136, 117/137,(l);(/11g/91,g Attorney Agent, or Firm Kem0n Palmer & 581 Field 61 Search 117/136, 137, 139.4; Estabmok 106/15 FP; 252/8.1 [57] ABSTRACT 5 References Cited Anhydrous solvent finishing processes to impart dura- UNITED STATES PATENTS ble fire retardant properties to textlle materlals, e.g.,

flat goods or finished garments, made of cellulosic fil f 45 ber, polyester fiber or fiber blends of such fibers with 2887409 41959 fi i 1 5 other fibers, involve (a) impregnating textile material 309l612 5/1963 Stephens "1"l7/132 B with an anhydrous mixture of tris-polyhaloalkyl phos- 313233939 6/1967 Van LOO 117/1394 x P nitrogenous film forming binder resin, Organic 3,434,870 3/1969 Touey et a1 117/1394 x Solvent and Organic aminoplast Cross-linking Catalyst, 3,471,318 10/1969 Redfarn 106/15 FP x (b) ng so and heat curing a about 3,615,743 10/1971 Theuer 106/15 FP X 120 to 200C. The anhydrous organic solvent mixture 3,658,575 4/1972 Tabor et al. 117/136 X may include sgluble crease-proofing agents so that the 0??? resulting fabric acquires both durable press and tire eu er e a. 3,695,926 10/1972 Scarborough 117/136 retardant propemes 3,729,340 4/1973 Powell 117/136 9 Cla ms, No Drawings DURABLE FIRE RETARDANT TEXTILE MATERIALS BY ANHYDROUS SOLVENT FINISHING PROCESS BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to the finishing of fabrics and other textile materials made of cellulosic fibers to impart durable fire retardant qualities thereto. More particularly, it concerns anhydrous solvent finishing methods for textile materials capable of creating good fire retardant ratings for the textile material that are durable to repeated launderings and, in some embodiments, simultaneously also creating durable crease resistance.

2. Description of the Prior Art Textile articles that have fire retardant properties durable even after repeated launderings are much in demand. Federal laws require certain classes of garments to be durably fireretardant and the classes of garments to which these requirements will apply is due to expand (see Chem. & Eng. News, 50 (29), July 17, 1972, p.22).

Fire retardant properties'in textile materials can be obtained in a variety of ways. However, many of the known methods do not create fabrics in which the fireretardancy is capable of withstanding repeated launderings. Cotton fabrics, for example, are relatively easy to treat with ammonium phosphate, ammonium sulfamate and mixtures of boraxand boric acid. Unfortunately, such treatment does not impart durable fireretardancy.

Extensive use has been made of phosphorus and'halogen containing compounds to impart fire retardant properties to textiles and other substrates. In characterizing the ultimate fire-retardancy of such compounds, a convenient notation known as Fire Retardant 1ndex" may be utilized. The indexof any particular material is calculated on a weight basis utilizing the following equation:

FRI (P%) 2(Br%) (Cl%) 2(N%) For example, a compound containing 5%, by weight, phosphorus and 50%, by weight, bromine would exhibit as FRI of 150. It has been determined that for general industrial applications, an FRI of at least about 60 is required to impart satisfactory fire retardance. FRI values of at least about 80 are usually required for use with cellulosic substrates.

One type of compound widely used to impart firere-- tardancy is tris-haloalkyl phosphates. They have been used combined with an organic resin binder and coated on textiles (see U.S. Pat. No. 3,471,318), mixed with phenolic resins to impregnate cellulosic sheets in forming structural laminated panels (see U.S. Pat. No. 3,549,479) and used as an ingredient in aerosol sprays used to fire-proof textilesor other substrates (see U.S. Pat. No. 3,607,745). Bis-haloalkyl phosphates have also been used, e.g., the ammonium salt of bis-(2,3- dibromopropyl) phosphate (see U.S. Pat. No. 3,660,582) and the amides of brominated dialkylene phosphates (see U.S. Pat. No. 2,574,518). A further discussion of the use of the haloakyl phosphates for fire-proofing can be found in Little, Flameproofing.

culty relates to their limited hydrolytic stability. This may be encountered in the utilization of the phosphate on substrates with the result that fire retardant groups are either readily leached from the substrate or converted on the substrate to non-fire retardant alkaline earth phosphate salts during wet landerings.

In order to overcome the problems of the phosphates, phosphonates have been used instead (see U.S. pat. No. 2,803,562 and 3,325,563). Polymerizable phosphonates have been used to impregnate fabrics and form in situ fire retardant polymers, e.g.. wool treated with bis-chloroethyl vinyl phosphonate (see U.S. Pat. No. 3,669,610).

While the phosphonates exhibit greater hydrolytic stability, they are more costly, and at high concentrations required for fire-retardancy, it is difficult to utilize these phosphonates in the treatment of substrates for fire retardance. Hence, there is a need for new methods to use fire-proofing haloalkyl phosphates while avoiding the hydrolytic instability problem so that treated products can be obtained that will retain good fireretardancy even after repeated wet launderings.

OBJECTS A principle object of the present invention is the provision of new methods for durably increasing the fireretardancy of textile products.

Further objects include the provision of:

1. New compositions for treatment of fabrics to im-.

prove their fire retardance properties.

2. New textile products having fire retardance that is durable even to repeated wet launderings of the products.

3. New methods for rendering fabrics both durably fire retardant and durably crease resistant, i.e., for pro ducing durable press fabrics having durable fireretardancy.

4. New anhydrous solution systems and methods for finishing of textile materials to render them durably fire retardant.

Other objects and further scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description, while indicating preferred embodiments of the invention, is given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. It should also be understood the foregoing abstract of the disclosure is for the purpose of providing a non-legal brief statement to serve as a searching-scanning tool for scientists, engineers and researchers and is not intended to limit the scope of the invention as disclosed herein nor is it intended it should be used in interpreting or in any way limiting the scope or fair meaning of the appended claims.

SUMMARY OF THE INVENTION These objects are accomplished according to the present invention by application to a textile product of an anhydrous organic solvent solution-containing (a) polyhaloalkyl phosphate as hereinafter defined and (b) nitrogenous film forming synergistic binder resin as hereinafter defined, evaporation of volatile solvent from the solution containing textile product and heat curing of the reagents retained in the textile product,

preferably promoted by the presence of (c) an aminoplast curing catalyst, to fix the reagents (a) and (b) upon the fibers of the textile product.

Advantageously,.the solution applied to the textile product will contain (d) a nitrogenous crease-proofing agent as hereinafter defined and the solvent-depleted textile material will be subject to a moisture regain step before the heat curing step to provide between about 8 to 15% moisture in cellulosic fiber content of the textile product.

Anhydrous solutions useful in the invention will contain in a volatile organic solvent 550% of ingredient (a) and 220% of ingredient (b)..lf used, ingredient will be present in 0.l% and ingredient (d) in 520%. All such ingredients may consist of a mixture of several reagents.

Application of the anhydrous solution, e.g., by impregnation, to the textile product is conducted to provide in the fabric such quantity of solution that the weight ratio of ingredient (a) to the dry weight of the fabric will be between about 1: 20 and 1: 2. Additionally, the percent add on by weight to the textile product of ingredient (b) will preferably be between about 2 to Stated briefly, processes for the production of durable fire retardant textile materials in accordance with the invention involve the following steps:

A. providing a substantially anhydrous solution comprising:

a. polyhaloalkyl phosphate b. nitrogenous film forming binder resin c. organic solvent having a boiling point below about B. applying said anhydrous solution to a textile product in such quantity that the weight ratio of said ingredient (a) based on the dry weight of the textile product is between 1: and 1: 2.

C. evaporating substantially all volatile organic solvent from the'textile product resulting from step B, and

D. heating the solvent freed textile product to a temperature of between about 120C. to 200C. for a time between about 1 and 30 minutes to cure and fix the ingredients retained in the textile product upon said product.

Preferably, ingredient (a) is tris-2,3-dibromopropyl phosphate and ingredient (b) is an organic solvent soluble melamine or triazine aminoplast resin, especially methoxy methyl melamine or butoxymethyl benzo quanomine.

As the organic solvent of the anhydrous systems used in accordance with the invention, halogenated hydrocarbons are advantageous not only because they are highly effective in the operations but also from a safety viewpoint if non-flammable halogenated hydrocarbons are used. However, the new methods are effective with the use of other water-immiscible organic solvents including hydrocarbons, esters and ethers. The anhydrous solvent may contain up to about 10% of an aliphatic alcohol or an alkoxyalkane to improve the solustrength, color or other desired qualities. By way of example, p-toluene sulfonyl chloride has been found particularly useful. Preferred catalysts are those selected from the group consisting of haloaryllactones, halimides and monocyclic aryl sulfonyl halides.

A mild alkaline afterwash of conventional type may be employed to improve the aesthetics of the final product. Fabric strength degradation by the new processes is less than 15% of the untreated fabric strength.

Success of the invention is, in part, due to the discovery that durable press properties can be produced in cellulosic textile materials simultaneously with fire 'retardant properties using the same anhydrous solvent systems as outlined above relative to the durable press agent. Methylolated carbamates constitute a preferred type of crease-proofing agent for use in these new textile treatments as disclosed hereinafter and also in copending application Ser. No. 215,626, filed Jan. 5, 1972, now US. Pat. No. 3,834,871, the disclosure of which is incorporated herein by reference.

DESCRIPTIONOF PREFERRED EMBODIMENT The following details of operations in accordance with the invention and reported data illustrate the further principles of practice of the invention to those skilled in the art. In these examples and through the remaining specification and claims, all parts and percentages are by weight unless otherwise specified.

Example 1 A clear solution was made by stirring together the following ingredients in the parts specified:

Iris-(2,3-dibromopropyl) phosphate 20 parts tri-(methoxy methyl) melamine 5 parts l,l,l-trichloroethane parts The resulting straw colored solution was used to impregnate viscose rayon fabric to a wet pickup of 70%. The fabric was allowed to air dry at room temperature (20-25C.) for 10 minutes and was then given a hot air cure of 1 minute at C.

Samples of the treated rayon fabric were subjected to (DOC-FF-371) (vertical char method) which gave a char length value of four three-fourth inch with no after flame or after glow. The fabric was then subjected to successive launderings (AATCC Test 124) and was checked for fire retardant properties after 5 and 10 launderings. All such tests gave char lengths of 7 inches or less with no after glow and no after flame.

Example 2 Using the anhydrous solution of Example 1, 100% cotton broadcloth fabric was impregnated to a wet pickup of 80%. The'fabric was allowed'to air dry 10 minutes and then given a hot air cure of one minute at 150C. The resulting fabric gave a value of 5 inch char length on DOC-FF-371 Test (vertical char) with no after flame or after glow. As in Example 1, 5 and 10 launderings (AATCC Test No. 124) gave char lengths of 7 inch or less with no after glow or after flame.

Example 3 Using the anhydrous solution of Example 1, a 50% polyester/50% cotton muslin sheeting fabric was impregnated to a wet pickup of 65%. The fabric was run over low pressure steam drums continuously to effect Example 4 A clear solution was made of the following ingredients:

N,N-dimethylol-Z-methoxyethyl carbamate 125 parts p toluene sulfonyl chloride 10 parts tris-(2,3-dibromopropyl) phosphate 250 parts methoxy methyl melamine 50 parts l,l,l-trichloroethane 565 parts A 100% cotton broadcloth was impregnated with the solution and then pad-squeezed to a wet pickup of 80%. The fabric was air dried at room temperature for 10 minutes and then lightly steamed to produce a moisture regain of l l%. Finally, the fabric was cured for 1 minute at l60l65C. The ambient conditioned fabric when tested produced the following data:

Crease Recovery (AATC No. 66- Recovery Angle: M w n; nslfil rt k 2 8 Durable Press Rating '(AATC No. 124 Durable Press Replica) after one home laundering 4.0

After 50 launderings 3.8-4.0

Vertical Char (DOC-FF-37l) 4.5 inch (one laundering) no flame or after flow Vertical Char 7-8 inch (10 launderings) no flame or after glow Example 5 A clear solution was made of the following ingredients:

N,N-dimethylol-2-methoxyethyl carbamate 150 parts p-toluene sulfonyl chloride 10 parts tris-(2,3 dibromopropyl) phosphate 200 parts methoxy methyl melamine 50 parts l,l,l-trichloroethane 615 parts 3.8 (one laundering) 3.5' (50 launderings) 4.5" (one laundering) no flame or after glow = 7.0 (10 launderings no flame or after glow) Crease Recovery Durable Press Rating Durable Press Rating Vertical Char (DOC-H 371) ll ll ll Vertical Char (DOC-FF-37l) Example 6 As in Example 1, a clear solution was made of the following ingredients:

N,N-dimethylol-2-methoxyethyl carbamate l25 parts p-toluene sulfonyl chloride 10 parts tris (2,3-dibromopropyl) phosphate 350 parts mcthoxy methyl melamine 50 parts l,I,l-trichloroethane 465 parts A 50/50 polyester/cotton prepared sheeting fabric (percale) was impregnated with the solution to a wet pickup of 60% and then allowed to dry at room temper ature by solvent evaporation. The dry fabric was steamed to a moisture regain of 8l5% based upon the weight of the cellulosic component of the fabric. Finally, the fabric was hot air oven cured for 1 minute at l60-l65C. The ambient conditioned fabric when tested produced the following data:

4.5 (one laundering) 4.5 (30 launderings) 5.5" (one laundering) 8-9" (10 launderings) ll ll I! ll ll Example 7 A clear solution was prepared by stirring together the following ingredients in the parts specified:

tris(2,3 dibromopropyl) phosphate 200 parts butoxy methyl urea formaldehyde 50 parts perchloroethylene 750 parts Example 7 A clear solution was prepared by stirring together the following ingredients in the parts specified:

His-(2,3 dibromopropyl) phosphate 200 parts poly-butoxy methyl pentaerythritol tetracarbamate parts l,l.l trichloroethane 720 parts The resultant solution was used to impregnate a rayon drapery fabric to a wet pickup of 90%. The solvent was flashed off by high pressure steam dry cans and the fabric was given a hot air cycle of 1 minute at F.

Samples of the treated fabric were tested for fire retardant properties according to test method DOC-FF- 371, orignally, after 5 launderings and after l0 launderings. In all cases, char lengths were less than 7 inches with no after flame or after glow.

Example 9 A clear solution was prepared by stirring together the following ingredients in the parts specified:

His-(2,3 dibromopropyl) phosphate 350 parts tri (butoxy methyl) melamine 70 parts 1,1,1 trichloroethane 580 parts The resultant solution wasused to impregnate a 35% polyester/65% cotton reverse blend fabric to a wet pickup of 90%. The fabric was allowed to air dry at room temperature for 10 minutes and was given a hot air cure of 1 minute at 160C.

Samples of the treated fabric were tested for fire retardancy according to test method DOC-FF-37 l orignally, after 5 home washings and after home washings. In all cases, char lengths were less than 7 inches with no after glow or after flame.

DISCUSSION OF DETAILS The preferred haloalkyl phosphate for use with the invention is tris-(2,3-dibromopropyl) phosphate. Other tris-haloalkyl phosphates containing six to 24 carbon atoms and at least two chlorine or bromine atoms may be used including: tris-(1,2-dibromoethyl) phosphate; tris-perchloropropyl phosphate; tris-( 1,2-dibromo-l ,2- dichloropropyl) phosphate; tris-(1,1,1-tribromoethyl) phosphate; tris'-( 1,1,2 ,3,3,5-hexabromohexyl) phosphate; tris-perchloramyl phosphate; tris-(1,2,4,4,6,6- hexa bromooctyl) phosphate and like compounds. Advantageously, in the alkyl groups of the phosphate, the ratio halogen atoms to carbon atoms will be atleast 0.5. Mixtures of two or more of the halo-alkyl phosphates may be used and, actually, the commercially available products of this type are usually a mixture of homologs.

The preferred nitrogenous film forming binder resins for use in the invention are tri-methoxymethyl melamine and butoxymethyl benzo quanamine. A variety of comparable solvent soluble nitrogenous resins are available and can be used including: dimethoxymethyl urea-formaldehyde resin, tri-methoxymethyl acetylene diureine, dibutoxymethyl-N-ethyl triazone, N,N'- ethylene-bis-dimethoxymethyl triazone, butyl ethers of methylol urea-formaldehyde polymers, butyl ethers of methylol melamine, meth'oxy or butoxy ethers of polymethylol penta-erythritol tetracarbamate, and the like. Mixtures of two or more such materials may be used.

Halogenated hydrocarbons having a boiling point between about 20-200C. and especially between about 50l50C, are a preferred class of anhydrous organic solvents for use in the new FR fabric treatments, e.g., 1,1,1,-trichloroethane, butyl bromide, perchloroethylene, trichloroethylene, ethylene chloride, ethylene bromide, 1,l, 2-trichloro-l,2,2-trifluoroethane, 1,1,1- trichloro-2,2,2-trifluoroethane, methallyll chloride and 1,1-dichloroethane. Other anhydrous organic solvents of similar boiling range may, however, be used including hexane, pentene-l, methyl ethyl ketone, isopropyl acetate, ethyl acetate, isopropylether, ethyl formate, neohexane, dioxolane, cyclohexane, cyclopentane, benzene, acetone and the like. Mixtures of two or more anhydrous organic solvents may also be used with advantage, particularly where it is desired to control evaporation or drying rate of the fabric treatment solu tion from the impregnated'textile material.

A wide selection of aminoplast catalysts soluble in anhydrous organic solvents are available for use in the new FR treatments. Advantageously, one selects such a catalyst that will not stain or discolor the fabric, cause excessive tendering or present safety or pollution problems. Aromatic sulfonyl halides have been found to be particularly useful, e.g., p-toluene sulfonyl chloride, benzene sulfonyl chloride, 2-chloro-4-ethylphenyl sulfonyl chloride, 2-butyl-4-ethylphenyl sulfonyl chloride, 2-butyl-4-methoxy-phenyl sulfonyl chloride, benzene sulfonyl bromide and the like. The catalyst that is used should be soluble at least to the extent of 1% in the organic solvent hereinbefore described. Advantageously, compounds used as the catalyst are acidic or react with water to form an acidic product. Additional preferred classes of compounds to use as catalysts include halogenatecl aromatic lactones, e.g., chlorophthalide, bromophthalide, iodophthalide, etc. and haloimides, e.g., N-chloro succimide, N.-bromo-a, B-dibromo succimide, N-chloro teraconimide, N-chlorophthalimide and the like. The amount of catalyst used will depend, in part, upon the particular carbamate reagent used, the temperature for curing and similar factors. Generally, the fabric treating solution will comprise 0.1 to 10% of the catalyst and especially 0.1 to 5%.

As illustrated by Examples 4-6, the new anhydrous treating solutions may include a nitrogenous creaseproofing agent as an active ingredient. Unique results are obtained when N,N-dimethylol alkoxy alkyl carbamates, e.g., N,N-dimethylol-2-methoxyethyl carbamate, are used for this purpose. Preferred solutions of this type will contain 550% of the FR phosphate, 5-20% of the binder resin, 5-20% of the creaseproofing agent, 0.1-5% catalyst, 20-80% anhydrous organic solvent and 0-20% of an auxiliary agent.

Auxiliary reagents of various types may be included in the treating solutions, advantageously in amounts between 0.1 to 20% and particularly between 05-15%, especially l-l0%. Such auxiliary reagents include dyes; mildew-proofing agents, sanitizing agents; softening agents; plasticizers; hand-builders and the like.

The FR treatments of the invention are usable will all varieties of cellulosic textile materials. The term cellulosic textile material" as used herein is intended to mean any woven, knit or non-woven fabric as well as garments, bed-clothes, furniture coverings or any other textile material made in whole or in part of cellulosic fibers. Cellulosic fibers include: cotton, linen, viscose rayon, high modulus rayon (polynosic). They may be blended in yarns with synthetic fibers, e.g., nylon, polyester, polyolefin and other fibers or filaments or the textile materials may comprise mixed weaves or knits of cellulosic yarns or filaments and synthetic yarns or filaments. A particular advantage of the invention is the ability of the new operations to impart FR effects to cotton textile materials without undue loss of tensile strength and abrasion resistance. In addition to cellulosic textile materials, the new methods may be applied to 100% polyester fabrics or fabrics made of blends of polyester fibers, e.g., nylon, acrylics and the like.

The anhydrous treating solutions of the invention may be applied in a variety of ways. Dipping and padding, well known in the art, can be used. Additional methods include: spraying, roller coating float coating and the like. However, if enclosed equipment is not used, loss of solvent to. the "atmosphere can be costly and/or present ecological problems. Equipment is commercially available to preform the application of organic solvent treating solutions without loss of solvent to textile material, e.g., see Textile Industries, Oct. 1966, ps. 288-9, 291, 295, 299, 339, and 397.

The amount of solution applied will depend upon the type of fabric, e.g., wherein woven or knit and its weight, the degree of FR effect desired, the concentration of FR phosphate in the solution and similar factors. Under preferred conditions, the amount of solution relative to textile material will be selected to provide in the textile material between about 15()%, especially l20%, of FR phosphate component based upon the dry weight of the cellulosic textile material. Typically, this will involve a wet pickup of treating solution between about 50-150% based upon the dry weight of the textile material.

Following the application of the anhydrous treating solution, the volatile components of the solution are removed, e.g., by evaporation. Passage of the textile material through drying ovens, through infra-red ovens or in any other suitable manner may be used. The evaporated organic solvent is removed and recovered with available solvent handling systems. As a less desirable alternative, the impregnated textile material may be permitted simply to air dry at ambient conditions.

The removal of the organic solvent from the textile material leaves a moisture and solvent depleted fabric. At this point in the new operations, the solvent depleted fabric may be exposed to water vapor to create therein a moisture regain in the cellulosic portion of the fabric of between about 8 and 15%. For 100% cotton, this will mean a total moisture regain of 8-15% while a 50% cotton/50% polyester fabric would involve a total moisture regain of 47.5%. Advantageously, this is accomplished by steaming of the textile material. Exposure tohigh humidity at room temperature or other moisture regain techniques can, however, be used. The moisture regain step is advantageous when durable press effects are also to be imparted to the fabric. More pronounced durable press effects are obtained when the moisture regain step is applied after the solvent evaporation. This also improves solvent recovery operations.

The textile material ultimately is subjected to a heat curing step to cure the resin binder and fix the FR agent sive property or right is claimed are defined as follows:

1. A process for the production of durable fire retardant textile materials which comprises:

A. providing a substantially anhydrous solution comprising the following: i

a. 5-50% of tris-polyhaloalkyl phosphate containing 6 to 24 carbon atoms, and a halogen atom/- carbom atom ratio of at least 0.5,

b. 220% nitrogenous film forming binder resin,

c. 20-80% organic solvent having a boiling point below about 200C,

d. 0.15% organic aminoplast cross-linking catalyst soluble in said organic solvent;

B. impregnating cellulosic textile material with said anhydrous solution to provide therein between about 5 to 50% by weight of said phosphate based upon the dry weight of said textile material;

'C. removing organic solvent from the textile material resulting from step B;

D. thereafter steaming the impregnated textile material to create therein a moisture regain in the cellulosic portion of the fabric of between about 8 and 15%; and

E. heating the textile material resulting from step (D) at a temperature between about and 200C for between about 1 to 30 minutes.

2. The process of claim 1 wherein said resin is selected from the group consisting of methoxy methyl melamine and butoxy methyl benzo quanamine.

3. The process of claim 2 wherein said phosphate is tris-(2,3-dibromopropyl) phosphate.

4. The process of claim 1 wherein said organic solvent comprises at least 90% of a haloalkane or haloalkene containing 1 to 6 carbon atoms.

5. The process of claim 1 wherein said catalyst is selected from the group consisting of haloaryllactones, haloimides and aryl sulfonyl halides.

6. The process of claim 1 wherein said catalyst is a monocyclic aryl sulfonyl chloride.

7. The process of claim 1 wherein said catalyst is ptoluene sulfonyl chloride.

8. The process of claim 1 wherein step B is performed by immersing the textile material in a bath of said mixture and then it is pad-squeezed to a wet pickup of be tween about 50 and of said solution based on the dry weight of the textile material.

9. Fire retardant textile material produced by the process of claim 1.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,859,124 Dated January 7, 1975 Inventor(5) James M. Thompson It is certified that error appears in the above-identified patent and that said Letters Patentere hereby corrected as shown below:

Column 6, line 45, "Example 7" should read -Example 8--;

Column 8, line 39, "will" should be with;

Column 9, line 4, "wherein" should be -whether--;

Column 9, line 48, insert -Claims-;

Signed and sealed this 15th ay of April 1.575.

SEAT...) Attest:

rw rqira'i' VINE; u- U'L1\Ul1. 'u.|.-. HUT C. DIASOTY Commissioner of Patents zattestin; Officer and Trademarks FORM PO-105O (10-59) USCOMM- scans-p59 uvs. eovsnunsu-r PRINTING omc: I969 o-sss-au.

Claims

1. A PROCESS FOR THE PRODUCTION OF DURABLE FIRE RETARDANT TEXTILE MATERIALS WHICH COMPRISES: A. PROVIDING A SUBSTANTIALLY PHOSPHATE CONTAINING 6 TO THE FOLLOWING : A. 5-50% OF TRIS-POLYHALOALKYL PHOSPHATE CONTAINING 6 TO 24 CARBON ATOMS, AND A HALOGEN ATOM/CARBON ATOM RATIO OF AT LEAST 0.5, B. 2-20% NITROGENOUS FILM FORMING BINDER RESIN, C. 20-80% ORGANIC SOLVENT HAVING A BOILING POINT BELOW ABOUT 200*C, D. 0.1-5% ORGANIC AMINOPLAST CROSS-LINKING CATALYST SOLUBLE IN SAID ORGANIC SOLVENT; B. IMPREGNATING CELLULOSIC TEXTILE MATERIAL WITH SAID ANHYDROUS SOLUTION TO PROVIDE THEREIN BETWEEN ABOUT 5 TO 50% BY WEIGHT OF SAID PHOSPHATE BASED UPON THE DRY WEIGHT OF SAID TEXTILE MATERIAL; C. REMOVING ORGANIC SOLVENT FROM THE TEXTILE MATERIAL RESULTING FROM STEP B; D. THEREAFTER STEAMING THE IMPREGNATED TEXTILE MATERIAL TO CREATE THEREIN A MOISTURE REGAIN IN THE CELLULOSIC PORTION OF THE FABRIC OF BETWEEN ABOUT 8 AND 15%; AND E. HEATING THE TEXTILE MATERIAL RESULTING FROM STEP (D) AT A TEMPERATURE BETWEEN ABOUT 120* AND 200*C FOR BETWEEN ABOUT 1 TO 30 MINUTES.

7. The process of claim 1 wherein said catalyst is p-toluene sulfonyl chloride.

8. The process of claim 1 wherein step B is performed by immersing the textile material in a bath of said mixture and then it is pad-squeezed to a wet pickup of between about 50 and 150% of said solution based on the dry weight of the textile material.

9. Fire retardant textile material produced by the process of claim 1.