US3528849A - Method for imparting oil and water repellency to textile materials - Google Patents

Description

United States Patent 3 528 849 METHoD FOR rMPARTiNG OIL AND WATER REPELLENCY T0 TEXTILE MATERIALS William J. Vullo, Tonawanda, and George M. Wagner,

U.S. Cl. 117-1395 Claims ABSTRACT OF THE DISCLOSURE A process for treating textile materials to impart durable water repellency and durable oil repellency thereto which comprises treating the textile materials with a polyisocyanate or urethanepolyisocyanate and a fluorochemical resin and, thereafter, curing the treated material with water. The isocyanates which may be used include those of the polymethylene polyphenyl type, as well as those of the type formed by reacting a polyhydroxy compound containing 3 to 6 OH groups with a diisocyanate, and may also contain from about 0.05% to 3% by weight of tertiary nitrogen. Additionally, the isocyanate products formed by reacting any of the above isocyanates with a diol may also be used. Various fluorochemical resins, as are known in the art for imparting oil and water repellency to fabrics may be used, such as the fluoroalkyl esters of acrylic and methacrylic acid. The fluorochemical resin is applied either simultaneously with or subsequent to the application of the isocyanate material.

This invention relates to an improved process for treating textile materials and more particularly, it relates to an improved process for treating textile materials to render them durably oil repellent and Water repellent.

Recently, considerable work has been done in the treatment of various textile materials to impart oil and water repellency thereto, thus obtaining a fabric which is stain resistant. Although various types of materials have been utilized, in general, the most successful treatments have been those which have used fluorochemical resins. Various types of these materials, as are known to those in the art, have been used such as the fluoroalkyl esters of acrylic and methacrylic acid. While the fabrics which have been thus-treated have good initial resistance to oil and water, it has frequently been found that after washing or dry cleaning of the fabric, the oil and water repellencies are drastically reduced. It has, therefore, been necessary to periodically retreat such fabrics so as to restore the oil and water repellent properties or to use excessively large amounts of resin in their initial treatment. This is, of course, costly and may, in the former instance, present problems, particularly Where garments are involved which contain different types of materials and/or ornaments or decorations, such as buttons, embroidery, and the like.

It is, therefore, an object of the present invention to provide a process for treating textile materials to render them durably oil repellent and water repellent.

A further object of the present invention is to provide an improved textile material which has been treated so as to render it durably stain resistant, i.e., resistant to wetting by water and solvent based stains.

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 render them durably oil repellent and water repellent which comprises treating the textile material with an isocyanate material selected from the group consisting of polyisocyanates and urethane-polyisocyanates, and a fluorochemical resin, and, thereafter, curing thetreated material with water.

The textile materials produced by this method are found to be durably oil repellent and water repellent and have an excellent ,feel or hand, as compared to an untreated material. Additionally, where the textile material treated is a proteinaceous material, the material is further found to be durably shrinkproof.

More specifially, in the practice of the present invention, the textile materials treated may be formed of any of the various natural or synthetic fibers such as proteinaceous, cellulosic, polyamide, polyester, polyacrylic fibers, or the like. These textile materials may he in various forms, including yard goods, as well as various finished articles, such as articles of clothing, including coates, sweaters, socks, shirts, trousers, skirts, and the like. Preferably, the textile materials treated in accordance with the present method are cellulosic textiles such as cotton, or proteinaceous textiles, such as Wool. This is not, however, to be taken as a limitation on the present invention as other cellulosic textiles, such as those made of rayon, ramie, or jute; other proteinaceous materials, such as alpaca, angora, camel hair, cashmere, huarizo, lama, misti, mohair, suri, viconna, and the like; as well as the various synthetic fabrics indicated hereinabove, may also be treated. Additionally, it is to be appreciated that the method of the present invention may also be utilized with textile materials which are formed of various fiber blends, including blends of suitable natural and/ or synthetic fibers.

In treating the above-described textile materials in accordance with the present method, the materials are desirably impregnated with a polymerizable treating solution or dispersion containing the isocyanate material selected from the group consisting of polyisocyanates and urethane-polyisocyanates. The isocyanate materials used may be of the polymethylene polyphenyl type, or they may be urethane polyisocyanates such as those prepared by the reaction of a polyhydroxy compound and a diiso cyanate and may also contain tertiary nitrogen in an amount of at least 0.05% by weight. Additionally, the isocyanate materials may be the reaction product of any of the above isocyanate materials and a diol.

In general, the polyisocyanates are polyaryl polyisocyanates containing at least three aryl groups and an average of at least three isocyanate groups, a portion of which isocyanate groups may be modified by reaction with an alcohol, a thiol alcohol, an organic acid, an amine, or an amide. For a more specific description of polyisocyanates of this type, reference is made to copending application Ser. No. 510,028, filed Nov. 26, 1965, which application is hereby incorporated into the present disclosure.

In general, the urethane-polyisocyanate type of isocyanates are polyhydroxy modified isocyanates containing (OH) (NCO) and groups wherein n is a number from 0 to 4.5, p is a number from 1.5 to 6 and n+p is a number from 3 to 6. For a more specific description of these urethane-polyisocyanates, reference is made to copending application Ser. No. 510,102, filed Nov. 26, 1965, which application is hereby incorporated in the present disclosure.

In general, the tertiary nitrogen containing isocyanate materials are urethane polyisocyanates which contain (0H) (NCO) and H 0 man).

groups, wherein n is a number from to 4.5, p is a number from 1.5 to 6, q is a number 1 to 20 and ru-I-p is a number from 3 to 6, which compositions contain at least 0.05% of tertiary nitrogen. These compositions may be prepared by reacting a polyhydroxy compound containing from 3 to 6 hydroxy groups with a diisocyanate, wherein from 1 to 100% of the polyhydroxy compound is a tertiary nitrogenous polyol or by reacting a teritary nitrogenius hydroxy compound containing from 1 to 6 OH groups with a polyisocyanate or urethane-polyisocyanate containing from 2 to 6 isocyanate groups. For a specific description of compounds of this type, reference is made to copending application Ser. No. 619,066, filed Feb. 27, 1967, which application is hereby incorporated in the present disclosure.

In general, the diol-isocyanate type of materials are the reaction product of a diol and an isocyanate which is selected from the group consisting of polyisocyanates and urethane polyisocyanates, the resulting reaction product containing (0H),,(NCO) and (lie),

groups, wherein rm is a number from 0 to 4.5, p is a number from 1.5 to 6-, and q is a number from 1 to 20* and n+p is a number from 3 to 6. The isocyanate materials so reacted may be any of the above-indicated isocyanate compositions, including those containing tertiary nitrogen, Whereas the diol may be a dihydroxy alkane containing 2 to 12 carbon atoms; an alkylene diol containing 2 to 12 carbon atoms, polyester diols having a molecular weight of from 200 to 10,000; polyurethane diols having an average molecular weight of 200 to 10,000; and polyether diols having a molecular weight of 62 to 10,000. For a specific description of compounds of this type, reference is made to copending application Ser. No. 622,- 465, filed Mar. 13, 1967, which application is hereby incorporated in the present disclosure.

The fluorochemical resins, with which the textile materials are treated in the practice of the present method, may be any of the various fluorochemical resin materials as are known to those in the art as having utility in imparting oil and water repellency to fabrics treated therewith.

Typically, these fluorochemical resins may be any polymer or copolymer containing a multiplicity of C F groups wherein nl is at least 3 and is preferably a number from 3 to 20. Desirably, the fluorochemical resins are derived from fluoro acids and/or fluoro alcohols, such as polymers of the following:

II (0 F920 F O C CH=CH2 C4F9C O O CH=CH2 wherein n is a number from about 3 to 20 and R is a straight or branched chain aliphatic group containing from about 1 to 4 carbon atoms. In general, the fluorochemical resins may have a molecular weight from about 10,000 to 1 million and are typically described in the following patents: US. 3,102,103; 2,642,416; 2,841,573;

4 2,732,370; 3,034,925; 3,256,230; 3,068,187; British 857,- 689; British 763,674; British 904,262; French 1,308,787; Belgian 635,437.

In preparing the impregnating solutions containing the isocyanate compositions, for use in the present method, the isocyanate material, as has been described above, is dispersed or dissolved in a suitable solvent. Although any solvent in which the isocyanate material will dissolve or may be dispersed without decomposition may be used, in many instances, the aromatic organic solvents, such as benzene, toluene, xylene, and the like, are preferred. Additionally, halogenated aliphatic solvents, such as trichloroethylene, perchloroethylene, carbon tetrachloride, methylene chloride, methyl chloroform, and the like, have also been found to be extremely useful. Moreover, with suitable emulsifying agents, water may also be used as the solvent. The organic solvents may be classified generally as benzene, substituted benzenes containing from 1 to 3 lower alkyl groups of 1 to 6 carbon atoms each, and halogenated lower alkyls containing 1 to 6 carbon atoms and 1 to 8 halogen atoms. The isocyanate material is dispersed or dissolved in the solvent in an amount sutficient to provide the desired resin add-on on the textile material when the material is impregnated with the solution. Concentrations within the range of about 0.5 to about 50% by weight of the solvent composition are typical, but in many instances, higher concentrations are also suitable, up to the maximum solubility of the isocyanate material in the solvent used. Typical of such higher concentrations which may be used are those from to by weight of the solvent composition, or even higher, in those instances where the isocyanate material used is miscible in substantially all proportions with the solvent.

In the preferred method the fluorochemical resins are combined with the isocyanate material so that the application of both of these materials may be carried out simultaneously. In this instance, the preferred solvent is methyl chloroform and the resulting treating solution desirably contains the fluorochemical resin in an amount within the range of about 0.10 to about 10%, with amounts within the range of about 0.5 to about 5% being preferred. It is to be appreciated, of course, that higher concentrations of the fluorochemical resins in the combined treating solutitons may also be used, up to the maximum solubility of the fluorochemical resin material in the solvent which is employed.

The textile material may be impregnated with the polymerizable treating solution, prepared as indicated hereinabove, using any convenient means. For example, the material may be immersed or padded in the treating solution and the fabric then passed through squeeze rolls to remove excess solution. If desired, the treating solution may be applied to the material by spraying, rather than by immersion. Other suitable application techniques, as are known to those in the art, may also be used. After the materials have been impregnated with the solution, they are preferably dried so as to remove the solvent from the material. Desirably, the impregnation is carried out so that the treated material has a total resin add-on within the range of about one to about 15 percent by weight of the material. Higher resin add-ons than 15 percent, e.g., 40 to 50 percent, may be attained in some instances although, generally, it has not been found that such higher add-ons appreciably improve the shrink resistance or oil and water repellency which is obtained. Generally, it has been found that resin add-ons appreciably less than 15 percent, e.g., 2.5 to 8 percent are often sufficient to provide durable shrinkproofing, oil repellency and water repellency of the materials. The relative amounts of isocyanate material and fluorochemical resin in the treating solution are selected and the impregnation is carried out so that the resin add-on of isocyanate material is desirably from about 1 to 10% by Weight and the resin add-on of fluorochemical resin is desirably from about 0.1 to by weight. Preferably the resin add-ons of the isocyanate material and fluorochemical resin are from about 26% by weight and 0.5 to 2.0% by weight, respectively.

Typically, the treating solution is maintained at a temperature within the range of about degrees centigrade to the boiling point of the solvent used, e.g., 120 degrees centigrade for perchloroethylene, and preferably is within the range of about degrees centigrade to about 30 degrees centigrade during the impregnation step. Thereafter, the impregnated material is dried, preferably in an oven, at a temperature within the range of about 20 degrees centigrade to the boiling point of the solvent used, with temperatures within the range of about 65 degrees centigrade to about 125 degrees centigrade being preferred.

Where the fluorochemical resin has not been incorporated in the polymerizable treating solution with the isocyanate materials, it is applied to the textile material after the isocyanate containing composition is applied and the treated fabric has been dried, as has been indicated hereinabove. For such application, the fluorochemical resin is dissolved or dispersed in a suitable solvent, as has been indicated hereinabove, with methyl chloroform being the preferred solvent. Desirably, such treating solutions will contain the fluorochemical resin in amounts within the range of about 0.1 to 10% by weight, with amounts within the range of about 0.5 to 5% being preferred. This treating solution is then applied to the textile material in any convenient manner, such as by padding or by spraying. The application is carried out so that an oil and water repelling amount of the fluorochemical resin is deposited on the fabric, resin add-on amounts within the range of about 0.1 to 5% by weight of the fabric being typical with amounts within the range of about 0.5 to 2% being preferred.

It is to be appreciated that although the sequential application of the isocyanate material, followed by the fluorochemical resin material may be used, the preferred method or carrying out the process of the present invention is by the simultaneous application of the isocyanate material and the fluorochemical resin, as has been indicated hereinabove. It has been found that where the application of these materials is carried out simultaneously, there is an enhancement of both the shrinkproofing and the oil and water repelling properties which are imparted to the fabric, as compared to those obtained in a sequential application. In any event, the fluorochemical resin materials should not be applied prior to the application of the isocyanate material, as such applications has been found to have an adverse effect on both the shrinkproofing properties as well as the oil andwater repellent properties which are imparted to the fabric.

Following these processing steps, the fabric, treated with both the isocyanate material and the fluorochemical resin, is then cured with water. Although various techniques may be utilized in effecting this water cure, the treated material is preferably cured in air, by means of the normal moisture in the atmosphere and any moisture in the fabric. Thereafter, particularly where the textile is a proteinaceous material which is also to be rendered shrink resistant, the material may then be immersed in water and maintained in the water until the curing is complete. Additionally, however, the curing may be effected simultaneously with the application of the fluorochemical resin, e.g., the fluorochemical resin may be applied as an aqueous solution or emulsion and the thustreated fabric then heated. In some instances the isocyanate material and the fluorochemical resin may be applied together as an aqueous emulsion, so that the Water in the emulsion may be used to effect the water cure.

It has been found that the time to effect the desired cure of the materials with which the textile has been impregnated varies with the temperature at which the cure is effected. Accordingly, it is desirable that the liquid water used is at an elevated temperature, temperatures within the range of about 30 degrees centigrade to about degrees centigrade being typical, with temperatures within the range of about 40 degrees centigrade to about 94 degrees centigrade being preferred. When carrying out the water cure at these temperatures, curing times within the range of about one hour to about one minute are typical, with times of 30 minutes to two mintes being preferred. It is to be appreciated, that where the length of curing time is not an important factor, the water cure of the impregnants may be carried. out at room temperature, i.e., about 20 degrees centigrade. Under such condi tions, the curing time may be as long as several days, e.g., 48 hours. There is, however, some indication that the full shrinkproofing effectiveness of the isocyanate compositions may not be attained when the water cure is carried out under these low temperature conditions. Moreover, it has been found that low temperature curing techniques, and particularly those carried out below about 40 degrees centigrade, may not impart to the treated fabric the desired degree of durability to dry cleaning solvents, such as trichloroethylene. In many instances, after curing under these conditions, dry cleaning of the fabric may remove appreciable quantities of the cured materials.

In a preferred embodiment of the present process, the liquid water cure of the treated material is preceded by a preliminary cure or setting of the impregnant in air, i.e., in the presence only of atmospheric moisture and that which may be retained in the fabric. This procedure is desirably effected at room temperatures, i.e., about 20 degrees centigrade, although higher and lower temperatures, as indicated above, may also be used. The length of time for this air cure is generally several hours, e.g., overnight, but is normally carried out to the extent that subsequent wrinkling during the liquid water cure will not result in permanent setting of the wrinkles in the fabric. Additionally, as has been previously noted, in some instances and particularly where the imparting of shrink resistance to the fabric is not a consideration, the water cure may be carried out without immersing the fabric in liquid water, that is by curing with moisture in the atmosphere and in the fabric itself. This may be accomplished by prolonged storage in moist air at ambient conditions or, preferably, by heating the impregnated fabric for a period sufficient to effect the curing.

It is to be further appreciated, that if desired, the water (cure of the impregnants may be effected by substantially pregnants by heating the water-wet, substantially saturated material at an elevated temperature. In such process, curing temperatures within the range of about 40 degrees centigrade to about 177 degrees centigrade for periods of about 30 minutes to about one minute are typical, with temperatures within the range of about 107 degrees centigrade to about degrees centigrade for periods of 10 minutes to about three minutes being preferred. After the Water cure of the impregnated textile material has been completed, the material is then dried to remove any Water which may remain. Frequently, where the water described curing process is used, i.e., water impregnation of the treated fabric, followed by heating at an elevated temperature, the curing and drying of the fabric is effected substantially simultaneously.

It has been found that in some instances the water used to carry out the polymerization of cure of the impregnants in the textile material is desirably slightly alkaline. Typical pH values for the curing water are within the range of about 7.5 to 9. Where the pH of the curing water is below these values, it may be adjusted by adding thereto an alkaline material, such as an alkali metal bicarbonate. Additionally, if desired, the curing water may also contain small amounts of a suitable wetting agent, to in- .sure more thorough and rapid wetting of the impregnated material. Typical wetting agents which may be used are nonionics, such as polyalkylene ethers and anionics, such as alkyl aryl sulfonates and sulfates. These materials are typically present in amounts within the range up to about one percent by weight of the treating water, amounts within the range of about 0.05 to about 0.2 percent being preferred. Additionally, it is to be appreciated that the final liquid water cure of the impregnated fabric may be, at least partially, effected during a subsequent fabric treating process which uses a water containing treating solution, as for example, in a dyeing process.

As has been indicated hereinabove, the process of the present invention may be carried out on textile materials in various forms, including yard goods, finished articles, such as sweaters and the like. It has been found that where proteinaceous textile materials, such as wool, have been treated in accordance with this process, they consitsently show an area shrinkage of less than about six percent, with area shrinkages within the range of about one to three percent being typical. Moreover, it has been found that the shrink resistance and/or oil and water repellency are retained by the treated fabric even after numerous washings in hot water and that the hand and feel of the treated materials are not substantially different from those of untreated material. Additionally, the shrinkproof and/ or oil and water repellent finish is durable to dry cleaning and is found to impart dimensional stability to the fabric.

In order that those skilled in the art may better understand the present invention and the manner in which it may be practiced, the following specific examples are given. It is to be understood that these examples are illustrative of the invention and are not intended to be limitations thereon. In these examples, unless otherwise indicated, temperatures are in degrees centigrade, parts and percentages are by weight of resin or polymer solids, and shrinkages are given as percent change from a treated, unwashed control. Additionally, the oil repellency of the fabrics were tested using the oil repellency test as described by H. G. Bryce in Chapter 4 of Fluorine Chemistry, vol. V, I. H. Simons, ed., Academic Press, New York, 1964, which utilizes a mixture of mineral oil (Nujol) and heptane, the rating scale increasing from to 150, the higher values indicating the greater oil repellency. The water repellency was measured by a similar test, using a mixture of water and methyl alcohol, the rating scale increasing from 0, which resists wetting by water, to 100, water repellent finish is durable to dry cleaning and is cohol.

EXAMPLE 1 A sample of worsted flannel was soaked in a trichloroethylene solution containing 2 percent of polyisocyanate, prepared by condensing 100 parts of polymethylene polyphenylisocyanate and 40 parts of stearyl alcohol, in accordance with the procedure set forth in Ser. No. 510,028, filed Nov.-26, 1965. The fabric was then passed through squeeze rolls to effect a wet pick-u of 120 percent and was then dried in air. Thereafter, the fabric was soaked in a percent, by volume, solution of isobutyl alcohol in water, which solution contained 7.1 percent by weight of a nonionic emulsion containing 28 percent by weight of fluoroalkyl ester of acrylic acid, such as perflurobutyl acrylate, designated by the manufacturer, 3M Company, as FC208. The fabric was then passed through squeeze rolls to effect a 70 percent wet pick-up and then dried for 5 minutes at 35 degrees centigrade in a forced air oven, the water curing of the polyisocyanate impregnant in the fabric being carried out simultaneously by means of the water in the fluorochemical emulsion. Three control samples were also prepared, the first by treatment only with the polyisocyanate solution, followed by treatment with the 5 percent isobutyl alcohol-water solution, Without the fluorochemical resin; the second by treatment only with the fluorochemical resin emulsion; and the third remaining untreated. These four samples were then subjected to repeated 1 hour wash cycles in a center post washer using a commercial detergent, and a water temperature of 60 degrees centigrade. Before washing and after various of the wash cycles, the four samples were tested for oil repellency, water repellency and shrink resistance. Using this procedure, the following results were obtained:

Oil repellency rating... 0

Water repellency rating 50 After 3 wash cycles:

Area shrinkage (percent) 2. 0 2. 7

Oil repellency rating 70 0 Water repellency rating 50 After 5 wash cycles:

Area shrinkage (percent)- 0. 5 9. 6

Oil repellency rating 60 0 Water repellency rating..- 90 50 EXAMPLE 2 A fabric treating solution was prepared made up of methyl chloroform containing 2.5% by Weight of a polyisocyanate prepared by condensing 1 mole of castor oil with three moles of tolulene diisocyanate, according to the process set forth in Serial No. 510,102, filed November 26, 1965, and about 6.67% by weight of a 15% by weight solution in methyl chloroform of fluoroalkyl ester of acrylic acid, such as perfiuorobutyl acrylate, sold under the name FC-310 by the 3M Company. A sample of worsted flannel was impregnated with this treating solution by soaking the fabric in the solution and then passing the fabric through squeeze rolls to obtain a wet pick-up of about The fabric was then dried in air, heated in an over for 5 minutes at degrees centigrade and then cured for 10 minutes in water at 80 degrees centigrade, containing a small amount of a wetting agent and adjusted to pH 8 with sodium bicarbonate. Controls were also prepared by treating similar samples of the worsted flannel with a methyl chloroform solution containing only the polyisocyanate, a methylchloroform solution containing only the fluorochemical resin, and methyl chloroform containing neither the polyisocyanate nor the fiuorochemical resin. A portion of each of the samples was then dry cleaned by shaking the sample for 19 hours in Stoddard solvent at 27 degrees centigrade. The remainder of each of the samples was then given five washings in an automatic home washer, using a commercial detergent and a water temperature of 49 degrees centigrade. Prior to the dry cleaning as well as after dry cleaning and washing, the samples were tested for oil and water repellency and the shrinkage after washing was also determined. Using these procedures, the following results were obtained:

Sample Iolyisocyanate applied (percent by weight of fabric) 3.0 3. 0 0 0 Fluorochemical applied (percent by weight of fabric) 1.2 0 1.2 0 Initial properties:

Measured add-on (percent) 4. 6 3. 4 0 Oil repellency rating 0 140 0 Water repellency rating 100 50 100 30 After 5 home washes:

Area shrinkage (percent) 5. 7 4. 6 26 42 Oil repellency rating 100 O 0 0 Water repellency rating 90 40 70 50 After dry cleaning:

Oil repellency rating 140 0 140 0 Water repellency rating 90-100 40 70 50 EXAMPLE 3 A sample of worsted flannel was treated with the polyisocyanate-fiuorochemical composition as in Example 2 and was then dried, water cured and heated, in accordance with the procedure of that example. A second sample of the worsted flannel was first treated with a methylchloroform solution containing 2.5% of the polyisocyanate set forth in Example 2, following which the sample was dried in air, cured in alkaline water, as in Example 2 and then pressed dry. Thereafter, the sample was further treated with a methyl chloroform solution containing 6.67% by weight of the fluorochemical resin solution composition and the thus-treated sample was then dried for minutes at 135 degrees centigrade in an oven. A third sample was treated only with the methylchloroform solution of the fluorochemical resin and then dried for 5 minutes at 135 degrees centigrade. All of the samples were dry cleaned and then washed, as in Example The samples were treated by soaking the fabric in the various treating solutions, passing the fabric through squeeze rolls to obtain a wet pick-up of about 120% and drying the fabric in air. Thereafter, the fabric is cured using one of the following curing methods:

Cure 1-Heating in an oven for 5 minutes at 135 degrees C.

Cure 2-Curing in alkaline water containing a wetting agent, as set forth in Example 2 Following the cure, the treated fabric samples were subjected to five home washings, using the procedure set forth in Example 2. The treated fabric both before and after the washings were tested for oil repellency and water repellency. Using this procedure, the following results 2 and then tested for oil and water repellency and shrink e Obtained:

Samples Number l 2 3 4 5 6 7 Treatment: I

1st solutlon applled. B A O C Cure 2 1 1 A B ure l Initial Properties:

Oil repellency rating 80 0 0 140 120 140 Water repellency rating 60 0 0 90 90 90 Properties after 5 home washes:

Oil repellency rating 0 0 0 0 100 Water repellency rating 60 0 L80 0 90 9O 90 1 Air dry. 2 2 followed by 1. 3 1 followed by 2. resistance. It was found that the samples treated with the EXAMPLE 5 polyisocyanate and the fluorochemical resin, either simultaneously or consecutively, gave very high levels of both oil and water repellency which were substantially unchanged by dry cleaning and which were only slightly reduced after five home launderings. Additionally, the shrinkage control in these two samples was good. The sample treated only with the fluorochemical material, although showing high initial levels of oil and water repellency lost all of the oil repellency and a substantial amount of the Water repellency after the home laundering. Additionally, this sample had little resistance to shrinkage.

EXAMPLE 4 Samples of 3.1 ounce per square yard of 80 x 80 cotton print cloth were treated with the polyisocyanate and fluorochemical materials as described in Example 2, using one or more of the following treating solutions:

Solution A Trichloroethylene solution containing 5% by weight of the fluorochemical resin material of Example 2 The procedure of Example 4 is repeated with the exception that the samples treated were worsted samples and the treating solutions used were as follows:

Solution A Trichloroethylene solution containing 10% by weight of the fluorochemical resin of Example 2 (PO-310) Solution B Trichloroethylene solution containing 2.5 by weight of polyisocyanate material of Example 2 Solution C The treating solutions were applied to the fabric sample using the procedure of Example 4 and the treated samples were cured using cure 1 and/or cure 2, as set forth in Example 4. Using this procedure, the following results (FC310) were obtained:

Samples Number 1 2 3 4 5 6 7 8 Treatment:

1st solutlon applied A A B B A A C C zndgtt abrsgsirta i 2 1? is (1) (2) cure... QIIIIIIIIIIIIIIII: 1 z'k' f'IIIIIIIIII Properties:

Oilrepelleneyrating 5. 80 8O 70 100 0 0 140 Area Shrinkage (percent) 68 68 6.6 5 .8 20 2.4 2.0 4.6

Air dry. 2 2 followed by 1.

3 1 followed by 2.

Solution B Trichloroethylene solution containing 1.25% of polyisocyanate material of Example 2 Solution C Trichloroethylene solution containing 1.25% by weight of the polyisocyanate material of Example 2 and 5% by weight of the fluorochemical resin of Example 2 (PC-310) of the invention as changes therewithin are possible and it is intended that each element recited in any of the following claims is to be understood and referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly in whatever form its principle may be utilized.

What is claimed is:

1. A method for treating textile materials to render said materials durably oil and water repellent which comprises treating said textile materials with (a) an isocyanate material selected from the group consisting of poly-isocyanates and urethane-isocyanates, and (b) a fluoro-chemical resin selected from the group consisting of polymerizable esters containing fluoro acid moieties, polymeriza'ble esters containing fluoro alcohol moieties and glycidyl ethers of fluorocarbons, or (c) polymeriza ble solutions of (a) and (b), said treatment being such as to provide an addon of isocyanate material of at least about 1 percent by Weight and an add-on of fluorochemical resin of at least about 0.1 percent by weight, based on the weight of said textile material; and thereafter curing the treated textile material with water at a temperature and for a period suificient to effect said cure.

2. The method as claimed in claim 1 wherein the textile material is impregnated with a polymerizable solution of the isocyanate material and the fluorochemical resin.

3. The method as claimed in claim 2 wherein the textile material is treated with the isocyanate material and the fluorochemical resin so as to retain the isocyanate material in an amount of about 0.1 to 10% by Weight of the textile material and the fluorochemical resin in an amount within the range of about 0.1 to 5 percent by weight of the textile material.

4. The method as claimed in claim 3 wherein the isocyanate material is retained in an amount within the range of about 2 to 6 percent by weight of the textile material and the fluorochemical resin is retained in an amount Within the range of about 0.5 to 2.0 percent by weight of the textile material.

5. The method as claimed in claim 4 wherein the fluorochemical resin is a polymerizable fluoroalkyl ester of acrylic or methacrylic acid having at least 7 fluorine atoms and from 3 to 10 carbon atoms in the alcohol portion of the ester.

6. The method as claimed in claim 5 wherein the treated textile material is precured in air at ambient temperatures and in exposure to atmospheric moisture and the final cure is effected by immersing the material in water at a temperature within the range of about 30 degrees Centigrade 12 to about degrees centigrade for a period of from about 1 hour to about 1 minute.

7. An oil and water repellent textile material containing (a) at least about 1 percent by weight, based on the Weight of said textile material, of an isocyanate material selected from the group consisting of polyisocyanates and urethane-isocyanates, and (b) at least about 0.1 percent by weight, based on the weight of said textile material, of a fluorochemical resin resulting from the polymerization of a compound selected from the group consisting of polymerizable esters containing fluoro acid moieties, polymerizable esters containing fluoro alcohol moieties, and glycidyl ethers of fluorocarbons, or (c) polymeriza ble solutions of (a) and (b), wherein the treated textile material has been cured with water subsequent to the application of the isocyanate material and the fluorochemical resin.

8. The textile material as claimed in claim 7 wherein the fluorochemical resin is present in an amount within the range of about 0.1 to 5 percent by weight of the textile material and the isocyanate material is present in an amount within the range of about 0.1 to 10 percent by weight of the textile material.

9. The textile material as claimed in claim 8 wherein the fluorochemical resin is present in an amount within the range of about 0.5 to 2.0 percent by weight of the tex tile material and the isocyanate material is present in an amount within the range of about 2 to 6 percent by weight of the textile material.

10. The textile material as claimed in claim 9 wherein the fluorochemical resin is a polymerizable fluoro-alkyl ester of acrylic or methacrylic acid having at least 7 fluorine atoms and from about 3 to 10 carbon atoms in the alcohol portion of the ester.

References Cited UNITED STATES PATENTS 2,333,914 11/1943 'Berchet 26078 2,642,416 6/1953 Ahlbrecht et al. 26083.5 2,803,615 8/1957 Ahlbrecht et al. 26029.6 2,955,961 10/1960 Koller 117161 X 3,102,103 8/1963 Ahlbrecht et al. 26029.6 3,248,259 4/1966 Borsellino et al. 117139.5

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner U.S. Cl. XQR.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,528,849 Dat d September 15, 1970 Inventor(s) William J. Vullo et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1 line 53: change "in their" to read --in the--- Column 2 line 18: change "coates" to read ---coats---.

Column 6 line 8: change "mintes" to read ---minutes---;

line 66: change "of cure" to read --or cure---.

Column 7 line 16: change "cons itsently" to read ---c0ns istent1y---;

line 4 change "by water to 100, water etc to read ---by water to 100, which indicates resistance to wetting by pure methyl alcohol---.

Signed and sealed this 20th day of April 1971.

(SEAL) Attsst:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attasting Officer Commissioner of Patents FORM PO-105O [IO-69] USCOMM DC 603766569 .1 GOVERNMENT PRINT NG OFFICE II! O-Qii-l!