US3505003A - Method of treating textile materials - Google Patents

Description

United States Patent 3,505,003 METHOD OF TREATING TEXTILE MATERIALS William J. Vullo, Tonawanda, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Filed Apr. 18, 1966, Ser. No. 543,082 Int. Cl. D06m 13/00, 13/26 US. Cl. 8---120 10 Claims ABSTRACT OF THE DISCLOSURE A method for improving wrinkle and flame resistance in textile materials by reacting the textile materials with alkyl vinyl phosphonium salts in the presence of a basic catalyst.

This invention relates to improved textile materials, including methods for preparing the same. More particularly it relates to a method for treating textile materials to impart wrinkle or crease-resistance and flame resistance to the material.

In recent years, increasing emphasis has been placed on the treatment of textile materials so as to render them crease and/ or wrinkle resistant. With many of the compositions which have been proposed for treating textile materials for this purpose, the hand of the material treated may be adversely affected. In other instances, the treating materials used may give satisfactory Wrinkle resistance when the fabric is dry, while imparting only moderate or poor wrinkle resistance when the fabric is wet, or vice versa. Accordingly, in the past it has been very difficult to provide a composition for treating textile materials to render them wrinkle resistant which provides both wet and dry wrinkle resistance without adversely altering the hand or feel of the fabric.

It is, therefore, an object of the present invention to provide an improved wrinkle and flame-resistant textile material.

A further object of the present invention is to provide an improved method for treating textile materials so as to render them wrinkle-resistant and flame-resistant.

These and other objects will become apparent to those skilled in the art from the description of the invention which follows.

Pursuant to the above objects, the present invention includes a process for treating textile materials to impart wrinkle resistance thereto, which process comprises reacting a textile material, in the presence of a basic catalyst, with an alkyl vinyl phosphonium salt. Desirably, the alkyl vinyl phosphonium salt used has the formula:

wherein R is a lower alkyl group, having from about 1 to 6 carbon atoms, n is a number from 1 to 2, and X is halogen.

Textile materials which may be treated in accordance with the present invention include those comprising natural or synthetic polymers or blends of the same, which have functional groups, such as hydroxyl, amino, amido, carboxyl, thiol, and the like, which are capable of reacting with activated vinyl groups. Suitable textile materials include, for example, cellulosic materials, such as cotton, linen, paper, and rayon, and proteinaceous materials such as wool and silk. In many instances, it has been found that the cellulosic materials are preferred for treatment in accordance with the present method and, accordingly, primary reference hereinafter will be made to the treatment of cellulosic materials. The textile materials treated may be in any convenient form, such as fibers, threads, yarns, woven fabric, non-woven fabric, knitted fabric, or

3,505,003 Patented Apr. 7, 1970 the like. At the time of treatment, the fabric may be in the unfinished state or it may have been previously bleached, dyed, printed, or otherwise treated.

It is believed that the modification of the properties of the textile materials which is achieved in accordance with the present invention result from a crosslinking reaction, wherein the vinyl phosphonium compounds of the present invention function as crosslinking agents. In this reaction, these vinyl phosphonium compounds react with the functional groups of the textile being treated, such as with the hydroxyl groups of a cellnlosic material.

The alkyl vinyl phosphonium halides for use in the method of the present invention may be prepared by reacting trivinyl phosphine with an alkyl halide, such as methyl iodide. This preparation is reported in the Journal of the American Chemical Society, volume 79 page 5887. Typical specific alkyl vinyl phosphonium halides, falling within the generic formula which has been set forth hereinabove include methyl trivinyl phosphine iodide, ethyl trivinyl phosphine iodide, butyl trivinyl phosphine iodide, pentyl trivinylphosphine bromides, hexyl trivinyl phosphine chlorides, dimethyl divinyl phosphonium iodide, dibutyl divinyl phosphonium iodide, methyl trivinyl phosphonium chloride, and the like. Of these, the preferred compound for use in the present invention has been found to be methyl trivinyl phosphonium iodide. Accordingly, primary reference hereinafter will be made to this material.

The alkyl vinyl phosphonium halide may be applied to the textile material to be treated in any suitable formulation, for example, as an emulsion or as a solution. Additionally, it may conveniently be applied by dipping, spraying, rolling, padding, or by other suitable application techniques as are known to those in the art. Following the application of the phonsphonium halide modifier, the excess chemical solution may be removed from the textile material by squeezing, centrifuging, pressing, or other similar operations. Thereafter, the material may be dried, if desired, using any convenient drying method, such as a forced air oven, infrared lamps, or evaporation in air at room temperature. Following the drying step, where one is used, the treated fabric is then cured to effect reaction between the modifying agent and the cloth. Depending upon the curing temperatures used, the curing times may take from less than a minute at elevated temperatures, to several hours or more where low temperatudes, e.g., room temperatures are used.

Additionally, it has been found to be desirable to employ a basic catalyst, with the phonsphonium halide modifying material of the present invention, to assist the reaction between the vinyl phosphonium halide and the textile material. Although the catalyst may be applied to the textile material in a separate application step, either before or after the application of the alkyl vinyl phonsphonium halide, it is generally preferred that the basic catalyst be incorporated as a component of the textile treating formulation with the vinyl phosphonium halide. When this is done, the basic catalyst is preferably utilized in an amount which will provide pH in the textile treating formulation of at least about 7 and preferably provide a pH within the range of about 8 to 11.

Various basic material which will provide a desired alkalinity in the treating formulation, without adversely effecting either the treating formulation itself or the textile material treated, may be used. In many instances, basic catalysts such as the alkali metal carbonates and bicarbonates including sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and the like, as well as the alkanol amines, including the mono-, di-, and tri-, alkanol amines, such as triethanolamine, tributanolamine, dimethanolamine, dipropanolamine, are preferred. Although, in some instances, the more basic alkali, such as the alkali metal hydroxide and oxides, may be used, for reasons not clearly understood at the present time, it has surprisingly been found that the crease and wrinkle resistance obtained when using these catalyst is frequently not as great as that obtained when using the preferred catalyst materials indicated hereinabove. Accordingly, hereinafter, primary reference will be made to sodium carbonate, sodium bicarbonate, and triethanolamine, as being the preferred basic catalyst material for use in the present method.

As has been noted hereinabove, the treating formulations for use in the present method are preferably aqueous solutions. Desirably, these solutions will contain the alkyl vinyl phosphonium halide modifying agent in amounts within the range of about 1 to about 40% by weight of the treating solution. In many instances, it has been found that amounts of these modifying agents within the range of about 10 to about 25% by weight of the treating so ution are preferred. Additionally, the basic catalyst is desirably present in the solution in amounts within the range of about 0.5 to about 20% by weight of the treating formulation and in many instances it has been found that molar ratios of the catalyst to the alkyl vinyl phosphonium iodide material within the range of about 0.2 to about 5:1 are preferred.

As set forth hereinabove, the treating formulations are applied to the textile materials using any suitable method. Thereafter, excess formulation is removed from the material, and it may then be dried, after which it is cured to effect the reaction of the vinyl phosphonium halide with the textile. Although the curing may be effected by maintaining the treated fabric at temperatures from about room temperature, i.e., about 20 centigrade, up to about 250 centigrade for a period of time sufficient to effect the desired reaction in the textile material, in many instances, it has been found to be preferable to carry out the curing at temperatures within the range of about 150 to about 185 degrees centigrade for a period of from about 3 to 15 minutes. Although so-called cold curing, i.e. at

about room temperature, may be utilized in some instances, it has been found that frequently this type of curing does not give as good wrinkle resistance as curing operations carried out at higher temperatures.

Generally, it has been found that the treatment of the textile materials should be carried out under conditions and with treating formulations such that the treated textile material, after curing and removal of unreacted modifying agents from the textile material has a resin or chemical add-on of from about 1 to 30% by weight of the textile material. In many instances, add-ons within the range of about 3 to about 15% by weight of the textile material have been found to be preferred. It is to be appreciated that the term add-on as used herein, refers to the modifying agent which has reacted with the textile material and remains as an integral chemical part of the textile material after the material has been cured and then washed to remove any unreacted excess.

If desired, the textile treatment with the alkyl vinyl phosphonium halide compounds of the present invention may be supplemented by treatment with the hand modifier or builder, a softener, a water repellant agent, a dyestuff, or other materials which may further enhance wrinkle resistance or impart or improve other desirable properties in the fabric. Such additional modifying agents may be applied simultaneously, i.e., in the same formulation as the vinyl phosphonium halide compounds, or they may be applied to the fabric before or after the application of the vinyl phosphonium modifiers of the present invention.

In order that those skilled in the art my better understand the present invention and the manner in which it may be practiced, the following specific examples are given. In these examples, unless otherwise indicated, temperatures are in degrees centigrade and parts and percents are by weight. It is to be appreciated, however, that these examples are intended merely as being exemplary of the present invention and are not to be taken as a limitation thereof.

EXAMPLE 1 A swatch of bleached desized, mercerized x 80 threads per inch), cotton print cloth weighing 3.1 ounces per sq. yard, was padded through an aqueous solution containing 20% by weight of methyl trivinyl phosphonium iodide and sodium bicarbonate in a 1:1 mole ratio with the methyl trivinyl phosphonium iodide. This treating solution had a pH of about 8. Thereafter, the fabric was cured for 10 minutes at 160 centigrade, using a forced air oven. The fabric was then hand washed in hot soapy water, rinsed, and pressed flat and dried. The add-on in the fabric was 12.5%. Thereafter, the wrinkle recovery angles of the cloth were determined, using the Monsanto method. The wrinkle recovery angles in the fill direction were found to be 119, dry, and 124, wet, as compared to 67, dry, and 83, wet, for an untreated control. Additionally, in a test for flame resistance, strips of the treated fabric were held in a horizontal position and ignited. After removal of the flame source, there was no propagation of the flame, and the strips were free from after-glow.

The replacement of methyl trivinyl phosphonium iodide in the above examples with an aqueous solution of ethyl trivinyl phosphonium iodide results in a cloth having comparable wrinkle resistance and flame resistance.

EXAMPLE 2 The procedure of Example 1 was repeated with the exception that sodium carbonate, in a mole ratio of 0.5 mole of sodium carbonate to 1 mole of the methyl trivinyl phosphonium iodide was utilized as a catalyst. The treating solution had a pH of 10 and the add-on of the fabric, after curing as in Example 1 was 10.9%. The wrinkle recovery angles in the fill direction, were found to be 133, dry, and wet, as compared to 67, dry, and 83, wet, of an untreated control.

EXAMPLE 3 The procedure of Example 2 was repeated with the exception that the sodium carbonate catalyst was used in a molar ratio of 1.5 moles of sodium carbonate to 1 mole of methyl trivinyl phosphonium iodide and the treating solution contained only 15% by weight of the methyl trivinyl phosphonium iodide. After impregnating the cloth as in the preceding example, the fabric was cured for 10 minutes at 183 centigrade and after washing and drying and pressing, there was an add-on to the cloth of 8.5%. The wrinkle recovery angles of the thus-treated cloth was found to be 128, dry, and 126, wet, as compared to 67, dry, and 83, wet, for the untreated control.

EXAMPLE 4 The procedure of Example 3 was repeated with the exception that the catalyst used was triethanol amine, which material was added to the treating solution in an amount of 0.51 mole of the amine per mole of the methyl trivinyl phosphonium iodide. The pH of the treating solution in this instance was 10. The treated cloth was cured for 2 minutes at centigrade and there was obtained an add-on of 5.7%. The wrinkle recovery angles for this cloth was determined to be 146, dry, and 136, wet, as compared to 67, dry and 83, wet, for an untreated control.

EXAMPLE 5 A treating solution was prepared containing 17% of the methyl trivinyl phosphonium iodide. This solution was applied to the fabric as in Example 1. Thereafter, the fabric was dried and a 10% by weight solution of sodium hydroxide was applied to the dried fabric using a kiss pad. The amount of sodium hydroxide solution applied was such that it provided a mole ratio of sodium hydroxide to methyl trivinyl phosphonium iodide on the fabric of about 4:1. Thereafter, the cloth was placed in a polyethylene bag, held for 30 minutes at 77 Fahrenheit and then washed, and pressed. The wrinkle. recovery an gles of this cloth were determined to be 98, dry, and 127, wet, as compared to 67, dry and 83, wet, for an untreated control.

Following the general procedure of Examples 1 through 4, dimethyl divinyl phosphonium bromide; hexyltrivinylphosphonium iodide; butyl trivinylphosphonium iodide; and methyl trivinylphosphonium chloride, employed in place of the methyl trivinylphosphonium iodide described, produced textile materials having improved wrinkle and flame-resistance.

What is claimed is:

1. A method for imparting improved wrinkle and flame resistance to textile materials having functional groups capable of reacting with activated vinyl groups which comprises reacting said textile material at a pH of from about 7 to about 11 with at least about 1 percent by weight of an alkyl vinyl phosphonium salt having the formula:

wherein R is a lower alkyl group having from 1 to 6 carbon atoms, X is halogen and n is a number from 1 to 2, said reaction conducted in the presence of a basic catalyst.

2. The method as claimed in claim 1 wherein the alkyl vinyl phosphonium salt is methyl trivinyl phosphonium iodide.

3. The method as claimed in claim 2 wherein the textile material treated is a cellulosic textile and the basic catalyst is applied simultaneously with the methyl triviny phosphonium iodide.

4. The method as claimed in claim 3 wherein the basic catalyst is selected .from the group consisting of alkali metal carbonates, alkali metal bicarbonates and lower mono-, diand trialkanol amines, each alkyl group of which contain from 1 to 4 carbon atoms.

5. A textile material, having functional groups capable of reacting with activated vinyl groups, reacted with from about 1 to about 30 percent by weight of an alkyl vinyl phosphonium salt having the formula:

wherein R is a lower alkyl group having from 1 to 6 carbon atoms, X is halogen and n is a number from 1 to 2.

6. The textile material as claimed in claim 5 wherein the alkyl vinyl phosphonium salt is methyl trivinyl phosphonium iodide.

7. The textile material as claimed in claim 6 wherein the textile material is a cellulosic textile.

8. A formulation suitable for imparting wrinkle and flame resistance to textile materials having functional groups capable of reacting with activated vinyl groups consisting essentially of an aqueous solution of from about 1 to about 40 percent by weight of an alkyl vinyl phosphonium salt having the formula:

wherein R is a lower alkyl group containing from 1 to 6 carbon atoms, X is halogen and n is a number from 1 to 2, and a basic catalyst present in an amount sufiicient to impart a pH of at least about 7 to said formulation.

9. The textle treating formulation as claimed in claim 8 wherein the alkyl vinyl phosphonium salt is methyl trivinyl phosphonium iodide and the basic cata yst is selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates and alkanol amines.

10. The textile treating formulation as claimed in claim 9 wherein the methyl trivinyl phosphonium iodideis present in an amount within the range of about 1 to 40% by Weight of the treating solution and the catalyst is present in a mole ratio of from about 0.2 to 5 moles per mole of the phosphonium iodide.

References Cited UNITED STATES PATENTS 2,032,097 2/1936 Piggottetal 8-84 2,044,099 6/1936 Piggott 6t al. 884 2,746,836 5/1956 Rossin 8-84 XR 3,212,842 10/1965 Burkitt s 3,251,642 5/1966 Valentine et al. 8116 XR MAYER WEINBLAT'I, Primary Examiner U.S.Cl.X.R.